JPH07116392B2 - Paint containing FRP fine powder - Google Patents

Description

Detailed Description of the Invention

[0001]

Invention BACKGROUND OF THE INVENTION This application relates to additive material <br/> consisting FRP fine powder used in paints and paint filled with fine powder of FRP (fiber reinforced plastic) as an additive material. In this application, with FRP fine powder
Crush the FRP with a pulverizer into a fine powder.
It is a thing.

[0002]

2. Description of the Related Art Generally, a paint is a fluid substance, and if it is spread on the surface of the substance, it will solidify into a thin continuous film after a certain period of time. It acts to beautify and protect the object to be coated. The paint has the following three functions. (1) Protection of objects (moisture prevention, rust prevention, corrosion prevention, oil resistance, acid resistance, alkali resistance, etc.) (2) Prevention of changes in appearance and shape (beauty, coloring, signs, camouflage, surface flattening, three-dimensional decoration) (3) Addition of special functions (adjustment of heat and electric conductivity and absorption / reflection of light rays, prevention of attachment of organisms, sterilization, insecticide, absorption of sound waves, reflection, divergence, temperature indication by color change Etc.) The paint is composed of a coating film element (non-volatile component) and a coating film auxiliary element (solvent or diluent). The coating film element is made up of a coating film main element (drying oil, natural resin, processed resin, cellulose derivative, rubber derivative, etc.) and a coating film sub-element (plasticizer, curing agent, dispersant, emulsifier). However, paints consisting solely of coating elements and coating aids give a clear coating when applied, making the article appear dull. Hide painted green body of the article to be coated, in order to obtain a colored coating must be added to the pigment to the transparent coating. Pigments are classified into (a) colored pigments, (b) extender pigments, and (C) special pigments.
Color pigments are inorganic pigments (white titanium, zinc white, red iron oxide,
Dark blue, etc.), organic pigments (carbon black, phthalocyanine green, etc.), metal powder pigments (aluminum powder, brass powder, etc.). However, in many cases, the coloring pigment is used in combination with the extender pigment shown below. The extender pigment itself does not have the effect of coloring the coating film and hiding the surface to be coated, but it adjusts the viscosity of the coating, improves the dispersibility of the pigment in the coating, increases the flesh of the coating, and increases the gloss. It has the effect of adjusting. These include chalk, clay, barite, diatomaceous earth, silica white and talc.
By the way, protection of the global environment and effective utilization of limited global resources are important issues not only in Japan but also internationally. One of those issues is the processing and recycling of plastic waste. Various investigations have been made to solve this problem, some of them have been solved, and the reuse of thermoplastic resins and thermosetting resins has become technically possible. However, one of the most difficult problems among plastics is fiber reinforced plastics such as glass fiber reinforced plastics (FR
Since this FRP, which is P), is a non-destructible resin, it has many technical problems regarding the recycling of its waste , and now it is unavoidable that it must be disposed of by landfill or incineration.
Only reason is taken. The inventors of the present application are concerned about such a current situation, and have been conducting basic research for many years for the purpose of overcoming these technical problems. As a result of extensive studies to develop an effective milling device, were successfully <br/> the finally grinding hard FRP in ultrafine powder having an average particle size of 15 [mu] m. (Japanese Patent Application No. 3-126957)

[0003]

A paint is added with a pigment according to the purpose. In many cases, an extender pigment is added together with a coloring pigment, which contributes to viscosity and dispersibility according to the purpose, and gloss. I am adjusting the degree. Therefore, it is a fact that the paint-related persons desire a new additive (filler) that retains the function as an extender pigment. Therefore,
As a result of earnest research on these points, the present inventor has discovered that FRP fine powder obtained from a good quality and uniform FRP waste material has an excellent function as an extender pigment. The invention of this application is based on the discovery, and uses fine powder of FRP obtained by crushing FRP waste generated as industrial waste as an additive, and makes use of its excellent function as an extender pigment. A paint having high film strength is provided.

[0004]

The coating additive of the invention of this application is composed of FRP fine powder, and the coating is prepared by adding this coating additive as an extender pigment.

[0005]

[Function] When FRP fine powder is added as an extender pigment to a paint, it serves to reinforce and increase the amount of the coating, and the characteristics of the coating are FR
It was not affected by the type of P (hand layup method, SMC method, etc.). On the other hand, the mechanical properties of the coating film are
Differences were seen depending on the type of paint. More than that, the particle size of the additive, that is, F
The fineness of the RP fine powder. The coating film made only of FRP fine powder having a particle size of 75 μm or less had a tensile strength three times higher and a Young's modulus four times higher than in the case where no additive was added. These values were not obtained when a fine inorganic compound powder (calcium carbonate or the like) was added. Further, by adding the FRP fine powder, the obtained coating film had less gloss and increased hardness.

[0006]

EXAMPLES Examples of the invention of this application will be described.
F made by hand lay-up molding method or SMC molding method
Using RP waste material as a raw material, it was pulverized by the fine pulverizer. The produced FRP fine powder was a micro powder having an average particle size of about 15 μm. The ingredients of this fine powder are
When the FRP waste material produced by the former hand lay-up method was used, it was about 50% unsaturated polyester resin and about 50% glass fiber. Also, in the latter FRP of the SMC method,
Unsaturated polyester resin approx. 30%, glass fiber approx. 30%
Besides, it contained calcium carbonate. These FR
P fine powder was added to the synthetic resin paint and mixed thoroughly. F
The coating material containing the RP fine powder was applied on a glass plate with a brush and dried to form a coating film. Made coating (thickness about 200
μm) was measured for pencil hardness and gloss, and was peeled from the glass plate to measure the tensile strength of the coating film. The properties of the coating film showed similar characteristics even when the type of FRP was different. However, the properties of the coating film differed depending on the type of paint (water-based acrylic paint, oil-based alkyd paint). In the case of the coating film made of the former water-based acrylic paint and FRP fine powder, the gloss decreased as the amount of FRP added increased, but the surface hardness increased. Also, the tensile strength and elongation of the coating film were both low. In addition, in the coating film in which FRP fine powder is mixed in the alkyd coating for metal coating, the tensile strength and hardness do not change even if the addition amount is increased, but the Young's modulus becomes high and the elongation and gloss are It became low. In the case of a long oil phthalic acid resin paint, which is a general oil paint, the coating film to which FRP fine powder was added had low tensile strength, elongation and gloss, but increased hardness.
As described above, the characteristics of the coating film to which the FRP fine powder was added differed depending on the type of resin and the addition amount of the FRP fine powder.
The tensile strength and gloss were low, and the coating film was matte, but the coating film hardness tended to increase. The strength of the coating film itself was considered to be related to the particle size of the FRP fine powder added. For that purpose, the FRP fine powder finely divided by a pulverizer is sieved, and 75 μm or less, 75 μm to 150 μm,
It was classified into three types of 150 to 300 μm. They were added separately to the paint to make coatings and their tensile strength was determined. The tensile strength of the coating film made only from the paint in which the FRP fine powder is not dispersed is 31.8 kg / cm ² , whereas when 20% of the paint weight of the FRP fine powder of 75 μm or less is added, It showed 92.4 kg / cm ^2, and the strength was increased about 3 times. Moreover, the hardness of the coating film does not change, and the Young's modulus is 230 kg / cm ² to 380 kg.
/ Cm ² It became large. Further, in order to investigate whether the tensile strength was increased by adding a fine substance, calcium carbonate having an average particle size of about 10 μm was added to the coating to form a coating film, and FRP fine powder-added coating film was formed. The same measurement as in the above case was performed. However, the tensile strength of the coating film was decreased by the addition, and tended to decrease as the amount increased, and it was not enough to increase the tensile strength. Hereinafter, specific examples of the present invention will be described in detail.

[Example 1] Hand layup method or SM
FRP fine powder obtained by crushing an FRP molded body prepared by the method C was used. A predetermined amount (for example, 1 g to 5 g) of this is weighed out by an analytical balance, added to the paint (10 g), and sufficiently (1
Mixed for about a minute). The amount added was from 10% to 50% of the paint weight. The paint used was a synthetic resin paint (water-based, kk Asahipen) containing white pigments for buildings. The coating film containing the FRP fine powder was manufactured as follows. Put 4 pieces of cellophane tape on a glass plate (35 cm, 35 cm, thickness 5 mm) and stick it,
It was used as a spacer (thickness 0.4 mm) for adjusting the film thickness. Approximately 10 g of paint (only the actual liquid and a predetermined amount of FRP fine powder mixed and dispersed) was spread on this glass plate, and a glass rod (diameter 10 mm) was used to smooth it so that the width was 10 c.
It was spread to about m and a length of about 20 cm. Even if FRP fine powder was added to the paint, the workability at the time of producing the coating film was not deteriorated. Further, the viscosity of the mixture containing the FRP fine powder was naturally increased as the amount thereof was increased.
The coated glass plate was placed in a dryer heated to 50 ° C. and kept for 150 minutes. After cooling, the coating film was peeled off from the glass plate. The peeled coating film was turned over so as to be sufficiently dried, and further dried in a dryer at 50 ° C. for 90 minutes. The dried coating film was cut into a predetermined shape and the following measurements were performed. (1) Tensile strength The tensile strength of the coating film was measured using a universal tensile tester. Measurement sample (width 15 mm, length 50 mm, thickness 0.2
(mm) was attached to a testing machine, and the tensile strength was determined by applying a load at a gripping interval of 15 mm and a pulling speed of 20 mm / min. Simultaneously with the measurement, Young's modulus and elongation were calculated. (2) Measurement of coating film hardness (pencil hardness) The pencil hardness of the coating film adhering to the glass plate was determined. For the measurement, the pencil was held by hand with the surface of the pencil tilted at 45 degrees, and a load of 1 kgf was applied thereto. The pencil was continuously moved to measure the hardness according to the state of scratch formation on the coating film surface. At that time, even if the pencil was moved continuously, the film was not scratched, but among the pencils having holes when moved intermittently, the hardness of the softest pencil was defined as the pencil hardness of the coating film. The moving speed of the pencil was 1 cm / 1 second. The pencils (made by Mitsubishi Pencil kk) used for measurement are 4B, 3B, 2B, B, H.
There were 9 types of B, H, 2H, 3H and 4H. The pencil lead was sharpened with a cutter knife. (3) Measurement of coating film glossiness Using a glossiness meter (Suga Tester kk, HG-6 type), the coating film (width 15 m, incident angle 60 °, reflection angle 60 °)
m, length 50 mm, thickness 0.2 mm) was measured. Table 1 shows the measurement results of the coating film obtained by dispersing the fine powder made from the FRP waste produced by the hand lay-up method in the water-based paint. As the amount of FRP fine powder added increases,
The tensile strength, elongation and gloss of the coating film were low, but the pencil hardness tended to be high.

[0008]

[Table 1]

Next, a fine powder obtained by finely pulverizing the FRP waste material produced by the SMC method was used and mixed into an aqueous paint (acrylic paint) to form a coating film. Table 2 shows various properties of the obtained coating film. In this case as well, the tendency was almost the same as in Table 1.

[0010]

[Table 2]

Example 2 As the paint, a synthetic resin-based alkyd resin paint (manufactured by kk Asahipen, containing white pigment), which was manufactured for the iron part and to which an organic solvent was added, was used. In the same manner as in Example 1, a finely crushed FRP waste material molded by the hand layup method and the SMC method was used, and a predetermined amount thereof was added to prepare a coating film. Even if the paints were different, no difference was found in the production status of the coating film. With respect to this coating film, the tensile strength (the tensile speed in this case was 5 mm was measured in the same manner as in Example 1).
/ Min) Young's modulus, elongation, gloss and pencil hardness were measured. The characteristics of a coating film made from fine powder of FRP waste made by hand lay-up method and alkyd resin paint,
It shows in Table 3. Due to the different paint, different results were obtained than in Example 1. As the amount of FRP fine powder added increased, the tensile strength of the coating film did not change, but the Young's modulus increased. On the contrary, the elongation and the gloss were low. Therefore, in the case of this paint, even if about 30% of the weight of the paint was added to the FRP fine powder, its mechanical properties were not significantly affected. This is a very interesting point.

[0012]

[Table 3]

Then, a fine powder obtained by finely pulverizing the FRP waste material produced by the SMC method was used and mixed into an oil paint (alkyd resin) to form a coating film. Table 4 shows various properties of the obtained coating film. In this case as well, the tendency was almost the same as in Table 3.

[0014]

[Table 4]

[Example 3] The paint is a synthetic resin-based long-oil phthalate resin paint (made by kk Asahipen, containing white pigment)
I used the one that was manufactured for the building and added the organic solvent. In the same manner as in Example 1, a finely crushed FRP waste material molded by the hand layup method and the SMC method was used, and a predetermined amount thereof was added to prepare a coating film. Even if the paints were different, no difference was found in the production status of the coating film. With respect to this coating film, tensile strength (pulling rate: 5 mm / min) Young's modulus, elongation, glossiness and pencil hardness were measured by the same method as in Example 1. Table 5 shows various characteristics of the coating film made from the fine powder of FRP waste material produced by the hand lay-up method and the phthalic acid resin paint. Due to the different paints, different results were obtained than in Examples 1 and 2. As the amount of FRP fine powder added increased, the tensile strength, Young's modulus, elongation and gloss of the coating film decreased, but the hardness increased. A similar experiment was conducted to examine the reproducibility of this experiment, and the results are shown in Table 6.

[0016]

[Table 5]

[0017]

[Table 6]

Next, a fine powder obtained by finely pulverizing the FRP waste material produced by the SMC method was used and mixed into an oil paint (long oil phthalic acid resin) to form a coating film. Table 7 shows various properties of the obtained coating film. In this case as well, there was almost the same tendency as in Tables 4 and 5.

[0019]

[Table 7]

The same synthetic resin type long-oil phthalic acid resin paint as in Example 3 (made by kk Asahipen,
(With white pigment) was used. In the same manner as in Example 1, a finely crushed FRP waste material molded by the hand lay-up method was used, and a predetermined amount thereof was added to form a coating film. At that time, it is considered that the fineness of the additive, that is, the particle size of the additive affects the properties such as the tensile strength of the coating film. Fine powder from FRP waste made by hand lay-up method,
It was further classified into three types using a sieve. It is 75 μm
Hereinafter, it was 75 to 150 μm and 150 to 300 μm. 20% of the weight of the coating material was added and mixed well, and a coating film was prepared in the same manner as in Example 1. With respect to this coating film, the tensile strength (pulling speed in this case: 5 mm / min), Young's modulus, elongation, glossiness and pencil hardness were measured by the same method as in Example 1. Table 8 shows those characteristics. Although the addition amount of the FRP fine powder was all the same as 20%, the characteristics of the coating film were greatly influenced by the particle size of the FRP fine powder. When the particle size of the FRP fine powder was large, the characteristics of the coating film were almost the same as those of the non-added one. However, as the particle size of the FRP fine powder became smaller, the tensile strength of the coating film became higher. The tensile strength of the coating film in which FRP fine powder is not dispersed is 31.8 kg /
cm ² is 61.4 kg when 75 to 150 μm FRP fine powder is added at 20% of the coating weight.
/ ^Cm 2, when adding the following FRP fine powder 75μm is, 92.4kg / cm ² are shown respectively, each about twice or about three times the strength is increased. Further, the Young's modulus of the coating film was 230 kg / cm ² in the case of no addition,
When FRP fine powder of 75 μm or less is added, 10
It was 60 kg / cm ² and was 5 times as large. Therefore, the characteristics of the coating film indicate that the finer the particle size of the additive, that is, the particle size of the FRP fine powder, the denser the coating film formed, and the higher the tensile strength.

[0021]

[Table 8]

Further, in order to examine whether or not the mechanical properties of the coating film are improved even if fine powder other than FRP is added to the coating material, it is usually used as an extender pigment in the coating material. A coating film was prepared by adding and mixing fine powder of calcium carbonate which is the main component of chalk. The coating method is FRP
The same as in the case of fine powder. Table 9 shows various properties of the obtained coating film. The mechanical properties of the coating film in this case showed the same tendency as in the case of the FRP waste material produced by the SMC method. However, even if the amount of calcium carbonate added was increased, the tensile strength of the coating film was not significantly increased. Therefore, F
When the RP fine powder was added, the mechanical properties of the formed coating film were improved as compared with the case where the fine inorganic powder (calcium carbonate) was added. This means that FRP fine powder
It can be considered that not only the action as an additive, a viscosity modifier, or a bulking agent, but also a chemical reaction with the paint itself, thereby improving the mechanical properties of the coating film. The smaller the particle size of the FRP fine powder, the higher the strength of the coating film, which means that the finer the particles, the easier the reaction with the paint. From these facts, it was found that FRP fine powder has many desirable points as an extender pigment for paints and is a very practical and useful material as an additive for paints.

[0023]

[Table 9]

[0024]

According to the invention of this application, the FRP waste material is made into a fine powder, and the FRP fine powder is used as a paint additive and added as an extender pigment to the paint. Can be reused as
It is possible to provide a coating material that not only serves to increase the amount of the coating material, but also provides a coating film having excellent mechanical strength such as tensile strength and Young's modulus as compared with other extender pigments that have been conventionally used.

Claims (2)

[Claims] 1. Fine powder obtained by crushing FRP as an extender pigment
Paint with the addition of FRP fine powder to end form 2. A FR obtained by crushing FRP into a fine powder.
Paint additive consisting of P fine powder