JPS5927971A - Preparation of coating - Google Patents

Abstract

PURPOSE:To prepare a coating excellent in matte effect, film hardness, wear resistance, mar resistance, and fabrication, by adding acrylonitrile polymer particles subjected to steam treatment under special conditions to a coating. CONSTITUTION:Acrylonitrile and an ethylenically unsatd. compd. contg. sulfonic (or sulfonate) groups are polymerized in water to introduce sulfonic (or sulfonate) groups in the resulting polymer and form a water dispersion of polymer drops where polymer particles are in a molten state, said water dispersion being cooled to solidify while stirring and spray-dried to yield acrylonitrile polymer particles with an average particle size of 1-200mu, having pores inside. Said particles are treated by steam at 70-150 deg.C for 1-30min. Then 1-50pts.wt. said polymer particles are added to 100pts.wt. coating and dispersed homogeneously.

Description

DETAILED DESCRIPTION OF THE INVENTION When the present invention is applied to a shade board, it has a lagging effect, the hardness of the coating film is low, and it has excellent abrasion resistance, scratch resistance, and workability. The present invention relates to a method for manufacturing a paint having a sophisticated design.

In recent years, research and development of various paints as resource-saving paints has become an important topic.

- Consumer tastes in paints are becoming more diverse, and one trend is that painted metal sheets with medium to low gloss and muted tones are preferred over high-gloss painted metal sheets. It's here.

Conventionally, a method of adding various solid additives to all paints has been adopted as a method of imparting a matte effect to paints2.
As this solid additive (Ml), inorganic pigments such as calcium carbonate and /recon compounds have generally been used (filtered materials, glass fibers, etc.), but paints with such solid additives have been used. When painted on a metal plate, the paint film is flat, lacks acidity, and has poor design quality.Furthermore, the film performance is poor due to the inclusion of a surfactant. When the particle size of the inorganic material increases to about 10μ or more, the wear resistance and scratch resistance 111 tend to decrease due to the brittleness that is a characteristic of the inorganic material itself. The inorganic materials used in VC coatings have various drawbacks, such as poor adhesion with the organic resin matrix, and the inorganic materials themselves do not have ductility, reducing the processability of VC coatings. When the paint is a water-based paint, since the water-based paint has a relatively low viscosity, the matting additive consisting of an inorganic additive tends to settle out easily, resulting in problems with fractional stability.

As a method to eliminate the disadvantages of using such inorganic materials as matting additives, organic polymer particles consisting of C, such as thermoplastic polymer particles such as polyethylene, polypropylene, and polyester, are used for matting purposes. A method of using it as an additive has also been proposed, but such matting additives made of thermoplastic polymer particles have a disadvantage that they have poor adhesion to water and require some ingenuity when dispersing them in water-based paints. Rarely. - In this method of using organic polymer particles as a total matting agent, acrylonitrile polymer particles have particularly favorable properties such as excellent weather resistance and heat resistance. Acrylonitrile polymers are desirable as additives for stripping because they are not plastic, but the particles of acrylonitrile polymers obtained by commonly used polymerization methods, such as water-thread precipitation polymerization, bath liquid polymerization, or bulk polymerization, are The shape of the acrylonitrile polymer particles is irregular or the particles are porous, so when a metal plate is coated with a paint containing these acrylonitrile polymer particles as a matting additive, it is difficult to achieve a uniform painted surface. It was difficult to obtain.

On the other hand, in order to eliminate the above-mentioned drawbacks of paints in which acrylonitrile polymer particles are added as an additive for completely matting the particles, the present inventors proposed a method in which the average particle diameter was Nitrogen inside the range of 1~20Llμ! A' (Acrylonyl without l-) Fine particles made of IJ l-based polymer (hereinafter referred to as AN-based particles) Full disclosure of the manufacturing method of a paint that is added as a matting additive after dry heat treatment at a specific temperature did.

That is, as AN-based particles, for example, fine primary particles obtained by emulsion polymerization of water particles are made into secondary particles by dry granulation, and dry heat treatment is performed to increase the strength of the secondary particles. This is a method of manufacturing a paint in which the paint is uniformly dispersed in a water-containing paint by using t, and even if the resulting paint is stored for a long period of time, the dichotomous particles will be destroyed and the particles will not change into fine particles. It has a completely long-lasting effect, and when this paint is applied to a metal plate, it is hard to get sun on the paint film, but it is hard to find any effect.

The inventors of the present invention (as a result of repeated various experiments and experiments in order to modify the AN-based particles so that they can be used as a matting additive for the above-mentioned ANN powder particle paints) found that the above-mentioned AN-based particles It has been found that the effect can be further increased by applying steam treatment under Kariashi condition F instead of heat treatment, and that it can be suitably used not only for water-based paints but also for dyestuff yarn paints, and has developed the present invention. It was accomplished.

That is, the present invention provides an acrylonitrile polymer with an average particle size of 2UUμ or less and substantially no voids inside! :
! l) After steam treatment for 1 to 60 minutes at a total temperature of 7 U to 15 U-CI/), an average of 1 to 50 layers of fine particle sonic paint 1011 made of this acrylonitrile polymer was added. The present invention relates to a method for producing a paint characterized by dispersing the paint in the following manner.

Hereinafter, the method for producing the paint according to the F1 invention will be explained in detail.

In the present invention, as described above, after the AN-based particles are subjected to steam treatment under load condition F2,
The present invention relates to a method for producing a paint in which N-based particles are uniformly dispersed in a paint at a predetermined ratio, and the paint may be either water-based or solvent-based.

The purpose of the present invention is to have superior coating film properties, that is, to have a hard coating film with excellent matte effect, and to have excellent abrasion resistance and dust resistance.
/1g and processability.To achieve this purpose, it is necessary to ensure that the erasing additive added to the paint has a uniform particle size, shape, etc. It is necessary that the organic polymer particles are hard particles and are dispersible in water or a bath agent as a medium. Furthermore, this additive for erasing is designed to take into account that the paint coated with this additive for erasing is mainly applied to metal plates used for the exterior facade of buildings. Then,
It is hoped that it can be assembled with a sturdy nail that has good weather resistance! Yes.

As a result of various studies conducted by the present inventors from this viewpoint, the present inventors first discovered that
4-15LILIIJO No. 2 discloses ANN powder particles having an average particle size of 21111 μm or less and having substantially no internal voids. After drying, ANN powder particles are produced by steam treatment under specific conditions F. By adding it to the paint at a predetermined ratio, we discovered that the purpose of the two-layer coating could be achieved.

That is, the above-mentioned Japanese Patent Application No. 12777/1983
-11J6269), the main component of acrylonitrile is gold, and the remainder is a sulfone wave group or an ethylene thread containing an unsaturated olo compound having all its IM bonds.
A sulfonic acid group or its metallurgy is introduced into the polymer produced by polymerization in water, and the aqueous fraction is completely formed at the polymerization temperature in which the fine particles of the polymer are substantially in the 6-1 state. Then, by cooling and solidifying while stirring to prevent the polymer parts from coalescing, it is possible to obtain all spherical AN thread particles with substantially no voids inside. When this ANN powder particle water-dispersed alloy is dried and granulated by the mist drying method, the average particle size is 2L]Oμ or less.
Since it becomes rice particles, the temperature of this ANN powder particle is 70 to 150.
After carrying out the snarm treatment in the range of □C for 1 to 3 minutes, it is sufficient to add it to the paint at a predetermined ratio and disperse it uniformly.

The ANN powder particles obtained in this way are finely spherical fine particles that are transparent with no internal gaps and have a homogeneous structure, and are further transformed by steam treatment. Because the surface is aggravated, the initial particle size can be maintained stably even if it is present in the paint, and the particle surface has a sufficient negative direct load, so it can be dispersed stably in water even when it is not thickened. It is excellent in Therefore, even when this ANN powder particle is added to, for example, a water-based paint, its initial particle size remains stable for a long period of time and is extremely stably dispersed. Also, compared to the inorganic matting additive of IIIm, it has a lower specific gravity, so it tends to settle and its workability is unclear.

Although it is not clear why the predetermined particle size does not return to the original primary particles in the ANN powder particle coating in the ANN powder particle coating by applying the ANN powder particle steam treatment in this way, the present inventors speculate as follows. are doing. That is, if the aqueous dispersion of primary particles of the polymer obtained by polymerization is directly granulated by spray drying, the primary particles coalesce and all spherical secondary particles are formed. In contrast, when the secondary particles are steam-treated, the surface of the primary particles swells with water and the particles are not coagulated sufficiently. This is because the water disappears almost completely, and when it dries in that state, it tightens and becomes firmly connected, and the swelling caused by this moisture is called dry heat treatment.'' It can be inferred that it is.

As a result of various studies on the steam treatment conditions, taking into consideration the degree of coloration of acrylonitrile, reaction form, production composition, economics first grade, etc., we found that
l-1: A range of 1 to 60 minutes is acceptable.

In other words, temperature and time are mutually determined by the shape stability and degree of coloration of the particles, and if the temperature and time are below the respective lower limits, the stabilizing effect of the particles will not be sufficient, and if the temperature exceeds the upper limit of the valley, the effect of stabilizing the particles will be insufficient. This is undesirable because the coloration becomes noticeable and affects the color tone when added to paint, and this is because the heat treatment disclosed in Japanese Patent Application No. 12777/1980 does not allow the ANN powder particles to be uniformly coated. If the color difference is less than 2 compared to the dispersed paint, it can be visually identified. Further, the steam for treating the ANN powder particles may be either superheated steam or saturated steam, and the atmosphere may be either pressurized, normal pressure, or reduced pressure.

In this way, a predetermined number of ANN powder particles are added to the steam-treated paint, and the addition method is the conventional method, for example, the method of adding and mixing during paint manufacturing, or the conventional method. Various methods can be adopted, such as directly adding the diluent to the paint that has been produced by stirring while stirring, or adding the diluent to the obstetric diluent in advance and adding the diluent to the entire paint. Thus, when ANN powder particles are added to a paint, since the ANN powder particles are spherical as mentioned above, even if they are dispersed in the paint, the degree of slipping effect and fringe structure viscosity is small, and the particle surface has a negative charge. Due to its excellent dispersibility, it is possible to pre-contain it, for example, in water-based paints so that the matting effect can be fully exerted.

There is a mutual relationship between the particle size of such ANN powder particles with excellent dispersion performance and the added acid.In order to fully exhibit the particle extinguishing effect, the average diameter should be 810 ~ It is preferable to keep it in the range of IUOμ. In addition, the ANN powder particle compounding ratio for the paint must be in the range of 1 to 50 heavy parts per 1 LILJ vertical part of the head material, and especially if it is 2 to 60 heavy parts, the sound effect can be better produced. It is preferable.

The blending ratio for this ANN powder particle paint, that is, the range of 1 to 50 tons/4 parts to 1UU heavy weight paint, is based on the paint general J Engineering S K541JU-1979F paint general test method Jvc9) A, added heating When measured by a residue test, it usually reaches 40-70%, so the heating residue 1L]O
The blending ratio of AN-based particles to parts by weight is 1.46 to 1.
This corresponds to 25 parts by weight.

Next, the reasons for limiting the numerical values of the ANN powder particle size and the added acid will be explained.

First of all, the reason why the average particle diameter of ANN powder particles is limited to -<2uoμ or less is that if it exceeds 21Julμ, the dispersion state in the paint will deteriorate, reducing painting workability, and furthermore, when processing a painted metal plate, the coating film will be damaged. This is because it is rarely desirable for ANN powder particles to be missing in the processing section.

In addition, the reason why the blending ratio of ANho particles is set at 1 to 50 mounds for the paint ILIIJ heavy ridges is that if the contribution is less than 1 part, the matte effect will be fully exerted on the surface coated on the metal plate. Not only is it impossible to do so, but it is also not favorable because the hardness of the coating film does not improve.If the amount exceeds 1 part to 50 tons, it becomes difficult to obtain a uniform dispersion state in the paint, and the viscosity of the paint increases. This increases the paint workability, and furthermore, the paint coated on the metal plate (the paint forming part decreases, the paint becomes hard and very brittle, and the workability decreases significantly). This is because it is not good.

As explained above, in the present invention, AN particles having an average particle size of 200μ or less and having substantially no internal voids are steam-treated for 1 to 60 minutes at a humidity temperature of U to 150°C. , 1 to 5 Oit parts of the fine particles made of this acrylonitrile thread polymer were added to the heavy free area of the paint ILltJ.
The present invention relates to a method for producing a paint characterized by dispersing the paint into a metal plate, for example, using a roll coater.
This can be done using an appropriate method such as a curtain coater, and even if the original plate of the metal plate to be coated is a hot-dip galvanized steel plate, an electrogalvanized steel plate, an aluminized steel plate, or a tinplate plate, it can be coated using a conventional cold-rolled method. All metal plates that can be coated or printed with paint can be used, even non-plated metal plates such as steel plates, stainless steel plates, and aluminum plates. Note that the scope of application of the paint according to the present invention is limited to metal plates2.
ysa21. There is no point in saying that it is not something that exists.

Next, examples of the method for producing a paint according to the method of the present invention and its usage will be described below, but the scope of the present invention is not limited by the examples listed below. In addition,
In the Examples and Comparative Examples shown below, all numbers in the compounding ratios are heavy masticated portions.

Example 1 450 parts of acrylonitrile, 40 parts of methyl acrylate,
16 parts of sodium p-styrene sulfonate and 1181 parts of arsenic water
After adding 0.5% of di-tert-butyl peroxide as a plate initiator to the total volume of a single mouse, the autoclave was placed in a 2-liter autoclave. Polymerization was carried out at a temperature of 1° C. for 26 minutes. After reaction path r, about 9+J while continuing 1u stirring
After cooling at C-q, the polymerized product 2 was removed from the reactor. This AN yarn polymer dispersion was spray-dried under the following conditions to obtain spherical ANN powder particles with an average particle size of 15 μm and virtually no internal voids. .

Solid content concentration 113 force Spray drying temperature 80℃ Atomizer rotation speed 2LIL] LJLl rpm Supply rate 1t/hr The obtained AN-based particles were subjected to steam treatment under various conditions and further dried at a temperature of 8U℃ for 600 minutes. did.

Table 1 shows the strength and degree of coloration of the AN-based particles that were purified in this way.

1, A for 100 parts of water-based emulsion paint with heating residue of 5 U%, which is mainly composed of acrylic acid ester polymer.
A paint is produced by the method of the present invention by uniformly dispersing N-based particles at a ratio of 10 parts, and this paint is heated at temperatures of 60°C and 50°C.
Table 1 also shows the results of microscopic observation of the dispersion state of AN-based particles in the paint after each paint was allowed to stand for one month under these conditions.

As is clear from the results in Table 1, increasing the temperature and lengthening the steam treatment conditions for AN-based particles increases the strength of the particles and improves the fractional stability in the paint, but the surface temperature and Long-term steam treatment increases the degree of coloration of AN-based particles. If the degree of coloration of the AN type particles is 60 or less, it is acceptable as a dry matting additive for paints. In the range of 7D to 150℃ and the heating time is 1 to
It turns out that 60 minutes is appropriate.

Table 1 (Note 1) The strength of AN-based particles is determined by spreading 2.5-yw of AN-based particles uniformly on a metal plate over an area of 1 ad, placing another metal plate on top, and applying pressure for a total of 1 U seconds on top of it. The state of AN-based particles after being applied was compared.

×: 50% or more of the particles are crushed.

Δ: 6 U% or more of the particles are crushed.

○: Most of the particles are crushed, 0 (Note 2) The degree of coloring is the surface reflectance of AN-based particles made into tablets under the conditions shown below. It was calculated using the following formula using a white board as a standard.

2. As the measuring device, we used a 1-9 spectrometer with a reflection accessory manufactured by Hitachi Co., Ltd., and as a standard white plate, we used an Al ε white plate manufactured by Hitachi Co., Ltd. I regret it.

For molding AN-based particles into tablets, 2°Uy of AN-based particles are put into a molding machine with an inner diameter of 2 cm, and the pressure is 50
The test was carried out under a pressure of KjJ'/cnF for 1 minute.

(Note 3) Stability of AN-based particles in paint 1 Poor: Almost 1
It has returned to the next particle.

Slightly poor: Approximately 5 U% of particles have returned to primary particles.

Good: Almost no return to primary particles Example 2 Among the paints shown in Table 1 of Example 1, No.
315 + 8, No. 1tJ 111 where the strength of the AN-based particles is low and poor stability in the paint, and N'0.719 where the degree of coloring of the AN-based particles is high.
A galvanized iron plate with a thickness of 0.65 mm that has been subjected to a normal phosphate treatment is roll-coated with epoxy thread paint as a primer to a thickness of approximately 5 μm, then baked with IJ treatment, and then coated with a
A coated steel plate was manufactured by applying a-ru coating to a thickness of 5 μm.

Table 2 shows the results of color difference, gloss, straw adhesion resistance, and workability of these coated steel sheets in terms of ml+.

As can be seen from Table 2, if the degree of coloration of the AN-based particles exceeds 60 F''C, the painted metal plate coated with the paint to which the AN-based particles have been added as a matting additive. The color difference is 2 or less, which is acceptable in terms of hue, and a painted surface with a low gloss and uniform appearance can be obtained, and the scratch resistance and processability are also satisfactory. One.

Table 2 (Note 4) Color differences are measured using Color Analyzer 31 manufactured by Hitachi.
It was measured by type 17.

(Note 5) Gloss 1-16 IJ degree with specular reflection distortion and side blemish.

(Chemical 6) Scratch resistance is determined by applying IUKy (
Place 6U5 g/cml of chloride on one semi-reinforced steel plate.9
It was rotated 0 degrees and judged according to the following criteria.

○: Almost no scratches @; Slight scratches △: Significant scratches (Note 7) Workability was determined by the number of sheets that were bent and visually observed without cracks.

T is the thickness of the sample iron plate.

As detailed above, the method for producing a paint according to the present invention not only produces a paint with excellent design, but also has a hardness of the coating. (When manufacturing a durable paint that has excellent abrasion resistance, scratch resistance, and processability, and has a matting effect, AN thread particles created by granulation with a spray dryer etc. are heated to a predetermined temperature. 9r constant time conditions to significantly improve the overall shape stability in aqueous or bath media (C) This is an epoch-making process that provides excellent properties that are stable for a long period of time. It is a method for producing paints that is environmentally friendly, and has the great advantage of expanding the range of applications for paints that do not cause pollution problems, such as water-based paints, and its industrial value is extremely large. There is.

Procedural amendment October 2, 1981 [Japanese Patent Office Commissioner Wakasugi No. 1J Huo 1, Special Application for Indication of Case No. 1982-136282 2,
Name of the invention: Paint manufacturing method 6, relationship with the person making the amendment Patent applicant's office: 2-2-8 Dojimahama, Kita-ku, Osaka-shi, Osaka Name (405) Konosuke Watanabe, representative of Japan Exrane 46 Co., Ltd. Address: 3-4-1 Marunouchi, Chiyoda-ku, Tokyo Address Room 264, Mizu Building, 1-4-5 Marunouchi, Chiyoda-ku, Tokyo
Seigoun 14-2861 bud ((6. Column Z for detailed explanation of the invention in the specification subject to amendment. Contents of amendment 1. The following points in the specification have been amended.

(1) Page 14, line 15 It says "practically" We have corrected the term to "substantially."

(2) Page 20, lines 2 to 6 [@: A little 1 easy is good τJ △: There is a lot of damage 4 = J'< J [△: There is a little hot water X: There is a lot of damage (We will correct it as = J'< J.

Claims (1)

[Claims] 1. Fine particles made of an acrylonitrile polymer having an average particle size of 2 UtJμ or less and having substantially no internal voids are steam-treated at a temperature of 70 to 150°C for 1 to 60 minutes. , the fine particles of this acrylonitrile-based polymer were added in an amount of 1 to 50 parts per 100 parts of the paint.
A method for manufacturing a paint, which is characterized by dispersing the paint into 2. Fine particles made of acrylonitrile polymer? A method for producing a coating material according to claim 1, wherein a coating material having a 'ZJD heat residue in the range of 4U to 70% is used as the coating material to be uniformly dispersed.