JP2000108248A - Resin-coated metallic plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin-coated metallic plate excellent in snow-slipping property, on which a worker does not slip at the time of execution. SOLUTION: A metallic plate has a resin-coated layer having a maximum friction coefficient (μmax) with a cotton cloth of over 0.3 at a load of 200 g/cm2 and a moving speed of 150 mm/min, and a kinetic friction coefficient (μk) with natural snow of less than 0.3 at 0 deg.C, a load of 2 g/cm2 and a moving speed of 10 mm/min, alternatively, a resin-coated metallic plate having a coating of a polyester resin and/or an oil-modified alkyd resin containing a hydrophilic silica having an average particle size of 3-10 μm, or a hydrophilic silica containing an alkali metal ions or aluminum ions on at least one side surface of a resin-coated metallic plate, and the coated surface layer having a maximum surface roughness of 5-20 μm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin-coated metal sheet, and more particularly to a resin-coated metal sheet which is hard to slip during construction but has excellent snow-sliding properties and is suitable as a metal sheet for roofing and other outdoor structures. It is about a board.

[0002]

2. Description of the Related Art Color steel sheets in which a plated steel sheet is coated with a colored resin coating film, so-called pre-coated steel sheets, are widely used in the field of building materials and home electric appliances. Color steel sheets are divided into matte color steel sheets and glossy color steel sheets in terms of design. Among them, matte color steel sheets have been growing as roofing materials in the field of building materials in recent years, due to diversification of tastes and preferences of consumers in recent years.

[0003] The matte effect of a matte steel plate is exhibited by forming fine irregularities on the surface of the coating film by interposing organic or inorganic fine particles in the coating film. Conventionally,
For example, an organic binder and an average particle diameter of 15 to 8
A coating composition containing organic fine particles of 0 μm and an inorganic coating surface modifier having an average particle diameter of 1/3 or less of the organic fine particles and an oil absorption of 80 or more (Japanese Patent Publication No. 6-900); Coating composition in which a silica-based matting agent is blended with a polymer, and a coating in which weather-resistant polymer particles or fine-particle synthetic silica is blended with a vinyl polymer. Composition (JP-A-3-2202)
No. 68), a coating composition containing a fine hollow silica-based powder that has passed through a mesh of 80 mesh (JP-A-63-1894).
No. 74) is known. The gloss of the surface of the coating film formed by these coating compositions is generally in the range of 2 to 50 as measured by 60 ° specular gloss.

[0004]

SUMMARY OF THE INVENTION These prior arts are:
The main focus was on the matting effect on the coating film, and many were related to the constitution of organic and inorganic particles exhibiting a matte color tone. However, these techniques have the following two problems. One is that the surface of the coating film of the matte color steel sheet is slippery. Accordingly, when the matte color steel plate is used as a roof material, the operator can easily slide his / her feet, and as a result, there is a problem that workability is reduced.

Another problem is that when a matte color steel plate is used as a roof material in a snowfall area, snow on the roof is less likely to fall off with a matte color steel plate than with a glossy color steel plate. . In snowfall areas, snow is usually removed from the roof. However, the number of times that the roofing material with insufficient snow sliding property increases the number of times, and the economical and physical burden is large. An object of the present invention is to provide a resin-coated metal plate that suppresses human slipperiness and is excellent in snow slipperiness.

[0006]

Means for Solving the Problems The present inventors have intensively studied to develop a resin-coated metal plate having excellent performance in slipperiness and snow slipping property. A method to evaluate the slipperiness and snow sliding property was studied, and a method to evaluate the slip resistance by the maximum coefficient of friction with cotton cloth and the snow sliding property by the coefficient of kinetic friction with natural snow were established.
Then, it has been found that a resin-coated metal plate having a resin coating layer having the maximum coefficient of friction with a specific cotton cloth and the specific coefficient of dynamic friction with natural snow can achieve the object.

Further, the present inventors have found that hydrophobic silica is useful as a matting agent from the viewpoint of compatibility in paints, but enhances rather than suppresses human slipperiness. It has been found that when a hydrophilic silica having a specific average particle size is used instead of the hydrophobic silica, a metal plate having a resin coating layer with improved human slip resistance can be easily obtained, and the present invention is completed. Reached.

Accordingly, the present invention provides a load of 200 g / c
m ² , the maximum coefficient of friction (μ _max ) with cotton cloth at a moving speed of 150 mm / min exceeds 0.3, and the coefficient of kinetic friction with natural snow at 0 ° C., a load of 2 g / cm ² , and a moving speed of 10 mm / min ( μ _k ) having a resin coating layer of less than 0.3.

Further, the present invention has a resin coating layer containing hydrophilic silica having an average particle diameter of 3 to 10 μm and a polyester resin and / or an oil-modified alkyd resin on at least one surface of the metal substrate, a resin-coated metal sheet, wherein the maximum surface roughness of the resin coating layer (R _max) is 5 to 20 [mu] m.

Preferably, the present invention has a resin coating layer containing hydrophilic silica containing at least one metal ion selected from the group consisting of alkaline earth metals and aluminum. It is a resin-coated metal plate.

Further, the present invention is preferably a resin-coated metal plate characterized in that at least one surface of the metal substrate is subjected to a chemical conversion treatment and / or a primer treatment.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The metal plate of the present invention has one or both surface layers thereof,
200g / cm load^TwoWith a moving speed of 150 mm / min
The maximum coefficient of friction (μ _max)But
More than 0.3 and one or both surface layers
At 0 ° C. under a load of 2 g / cm^Two, Moving speed 10mm / mi
coefficient of dynamic friction (μ_k)
Is less than 0.3. Maximum coefficient of friction with preferred cotton cloth
(Μ_max) Is 0.36 or more, which is preferable for natural snow.
Dynamic friction coefficient (μ_k) Is 0.25 or less.

In order to relatively evaluate the slipperiness of a person at the time of construction, the present inventors have made a resin-coated metal plate having various resin coating layers on a simulated roof having a five-dimensional gradient (26.6 °). And put a sock made of polyester fiber on top of it.
Zero subjects actually stepped on the board in order and evaluated according to the following criteria. Evaluation criteria ○: When 9 or more out of 10 evaluated that they did not slip Δ: When evaluated that 6 to 8 out of 10 did not slip ×: When evaluated that more than 5 out of 10 slipped

Next, for the same resin-coated metal plate, the maximum coefficient of friction (μ _max ) when the cotton cloth was moved under the conditions of a load of 200 g / cm ² and a moving speed of 150 mm / min was measured. Determined that the subject was hard to slip by relative evaluation (○
As shown in FIG. 1, the maximum friction coefficient (μ _max ) under this measurement condition was constant (0.
3), and it was confirmed that the slipperiness of a person at the time of construction can be simulated by the maximum coefficient of friction with the cotton cloth. That is, in order to have good human slip resistance,
It has been found that the maximum coefficient of friction (μ _max ) is more than 0.3, preferably more than 0.36.

Here, the maximum coefficient of friction with the cotton cloth (μ _max )
As shown in FIG. 2, a cotton cloth (length 5 cm; height 1 cm; width 8 cm) 2 is placed on a resin-coated metal plate 1, and a cotton cloth is further placed on the cotton cloth 2. Rolled thing 2
And a weight 3 having a weight of 8 kg (200 g / cm ² load).
The object 2 wound with a cotton cloth was pulled at a rate of mm / min, moved on the resin-coated metal plate 1, and the load F was measured. The maximum value of the measured load F was defined as _Fmax . P is the load (200 g / cm ² ) applied to the cotton cloth. Maximum friction coefficient (μ
_max ) was calculated by the following equation (1). μ _max = F _max / P (1)

Next, the present inventors adhered resin-coated metal plates having various resin coating layers to a simulated roof having a four-dimensional gradient (22 °) in order to evaluate the snow sliding property. Exposure was carried out outdoors in the suburbs of the city, snow was deposited 15 to 20 cm at night, and snowfall was continuously observed by video from 9:00 am the next day when the weather was clear, and the time required from the start of observation to snowfall was measured. Evaluation criteria ：: Snow fell within 3 hours △: Snow fell within 3 hours and more than 6 hours ×: It took more than 6 hours before snow fell or snow did not fall

On the other hand, for the same resin-coated metal plate,
g / cm ² of natural snow on a resin-coated metal plate,
The dynamic friction coefficient (μ _k ) with natural snow at 0 ° C. at a moving speed of 10 mm / min was measured. Evaluation of measured snow sliding properties and 0 ° C
Between the dynamic friction coefficient with the natural snow in, there is a correlation as shown in FIG. 3, in order to snow slipping, mu _k it can be seen that should be less than 0.3.

Here, the coefficient of dynamic friction with natural snow (μ _k )
As shown in FIG. 4, a snow block (15 cm long; 10 cm high; 15 cm wide) is placed on a resin-coated metal plate 11.
And put the weight 13 on the snow block 12,
The total weight of the snow block 12 and the weight 13 is set to 450 g (load P = 2 g / cm ² ), and the snow block 12 is pushed by the load cell 15 via the destination plate 14, and after the snow block 12 starts moving, the moving speed is changed. The load F applied to the load cell 15 while moving at 10 mm / min was measured, and the following equation (2) was obtained.
, The dynamic friction coefficient (μ _k ) was determined. Here, F is the average value of the load during movement. μ _k = F / P (2)

As described above, the resin-coated metal plate of the present invention comprises:
Since the resin coating layer has a maximum friction coefficient (μ _max ) with cotton cloth of more than 0.3 and a kinetic friction coefficient (μ _k ) with natural snow of less than 0.3, it has both human slip resistance and snow sliding property. I have.

Such a resin coating layer is a resin coating layer containing hydrophilic silica having a specific average particle diameter on one or both surfaces of a metal substrate (hereinafter, also referred to as a coating layer or a resin coating film of the present invention). By forming the coating layer to have a specific maximum surface roughness (R _max ). That is, the present invention suppresses the slipping of a resin-coated metal plate by a resin coating layer containing hydrophilic silica which is made to keep hydrophilic by a hydroxyl group on the particle surface, and the maximum surface roughness of the coating layer surface. By controlling (R _max ) to 5 to 20 μm, the snow-slidability of the resin-coated metal plate is improved.

Next, the results of a study on the surface condition of the resin coating layer for improving the snow sliding property will be described. FIG.
The relationship between the maximum surface roughness (R _max ) of the resin coating layer surface and the coefficient of kinetic friction (μ _k ) with natural snow under the above conditions is shown below. This indicates that when the maximum surface roughness (R _max ) is 20 μm or less, the dynamic friction coefficient (μ _k ) between natural snow and the surface of the resin-coated metal plate is less than 0.3. On the other hand, R _max
Is 5 μm, the maximum coefficient of friction (μ _max ) with the cotton cloth becomes too small, and the effect of suppressing human slipperiness cannot be expected. Therefore, if the maximum surface roughness (R _max ) is 5 to 20 μm, it is possible to secure the snow sliding property and the good human slip resistance.

The reason why snow becomes slippery when the maximum surface roughness (R _max ) is 20 μm or less is presumed as follows. For example, when a resin-coated metal plate is used as a roof material, water generated by melting snow on the resin coating layer due to heat from the interior of the house or heat from the sun is in between the resin coating layer and snow. Present in the form of a film. When the water film becomes thicker than the surface roughness of the resin coating layer, the snow is retained by the resin coating layer only by the viscosity of the water, but when the weight of the snow exceeds the viscosity of the water by its own weight. In the meantime, the snow on the resin-coated metal plate begins to slide down naturally. From the above, in order to slide down snow naturally early, maximum surface roughness of the resin-coated metal sheet surface (R _max) in the 20μm or less and a maximum surface roughness (R _max) or more of the thickness of It is considered important to form the water film early.

The hydrophilic silica of the present invention has a hydroxyl group on the particle surface and has an adsorption amount of di-n-butylamine of 100 m
eq / kg, preferably 110-600 meq / k
g, particularly preferably 200 to 500 meq / kg of silica. The hydrophilic silica is produced, for example, by aggregating a silicic acid sol obtained by reacting sodium silicate and sulfuric acid. Alternatively, it is produced by repeatedly treating an aqueous solution of sodium silicate with an ion exchange resin to remove sodium ions. Here, the hydrophilic silica preferably contains one or more metal ions selected from the group consisting of alkaline earth metals and aluminum. The content of the metal ion is adjusted by changing the pH and the temperature when the hydrophilic silica is put into the aqueous solution containing the metal ion and mixed. The content of metal ions is 1 to 1 g of hydrophilic silica.
-100 mg, preferably 1-80 mg, more preferably 1-20 mg. If it is less than 1 mg, the effect of suppressing human slippage is small, and if it exceeds 100 mg, it becomes unstable as a sol.

As the alkaline earth metal, Be, Mg,
Examples include Ca, Sr, Ba and Ra, but practically Mg and Ca are preferred. Be ²⁺ , Mg ²⁺ , Ca ²⁺ , S
By containing r ²⁺ , Ba ²⁺ , Ra ²⁺ , or by containing Al ³⁺ , a positively charged ion having a small valence was substituted at the Si ⁴⁺ site. , Silica will have a negative charge. That is, polarity is given. This enhances the effect of suppressing the human slippage due to the hydroxyl groups of the hydrophilic silica described below. In the case of synthetic silica, for example, in the case of synthetic silica, the surface is prepared by reacting a silanol group on the surface with halosilane, alkoxysilane, or the like. The adsorption amount of di-n-butylamine is 100 meq.
/ Kg or less.

In order to suppress the slipperiness of human beings and to have a matting effect, the content of hydrophilic silica, preferably hydrophilic silica containing metal ions, in the resin coating layer is determined as follows:
It is preferable that the solid content is 1 to 20 parts by weight based on 100 parts by weight of the resin based on the dry coating layer. If it is less than 1 part by weight, there is no effect of suppressing human slipperiness. On the other hand, if it exceeds 20 parts by weight, the effect of suppressing human slip and the effect of matting are saturated, which is not economically preferable. More preferably, it is 2 to 15 parts by weight. The average particle diameter of hydrophilic silica, preferably hydrophilic silica containing metal ions (hereinafter, both may be sometimes referred to as hydrophilic silica) is 3 to 10 μm. If it is less than 3 μm, a sufficient matting effect cannot be obtained. If it exceeds 10 μm, the maximum surface roughness of the coating layer (R _max )
To 20 μm or less. Therefore,
The particle diameter of the hydrophilic silica or the hydrophilic silica containing metal ions is 3 to 10 μm, and more preferably 3 to 8 μm. The average particle size of silica is measured by a Coulter counter method.

Next, the effect of the type of silica in the resin coating layer on human slip resistance will be described. The maximum coefficient of friction between a cotton cloth and a resin-coated metal sheet containing hydrophilic silica, a resin-coated metal sheet containing hydrophilic silica containing metal ions, and a resin-coated metal sheet containing hydrophobic silica (μ)
_max ) is shown in FIG. FIG. 6 shows a polyester resin coating layer containing 5 to 18% by weight of hydrophilic silica having an average particle diameter of 6.0 μm, and M having an average particle diameter of 6.0 μm.
a polyester resin coating layer containing 5 to 18% by weight of hydrophilic silica containing g ions, and an average particle diameter of 6.0 μm
A cotton cloth was applied to a polyester resin coating layer containing 5 to 18% by weight of a hydrophobic silica, and the maximum load was measured under the conditions of a load of 200 g / cm ² and a moving speed of 150 mm / min, and the coating layer calculated from the formula (1). Coefficient of friction (μ
₃ is a graph showing the relationship between _max. ) and the silica content of the coating layer. The asterisk on the vertical axis of the graph indicates the maximum coefficient of friction (μ _max ) of the resin coating layer containing no silica.

FIG. 6 shows that the resin coating layer contains silica.
Is hydrophilic compared to a resin coating layer containing no silica,
Hydrophobicity, maximum coefficient of friction (μ_max) Reduced
However, the resin coating layer containing hydrophilic silica (marked with ●)
More traditionally, hydrophobic silica used as a matting material
The maximum coefficient of friction (μ
_max) Is small and further contains Mg ions.
Maximum friction of resin coating layer containing hydrophilic silica (marked with ○)
Coefficient (μ_max) Is large. That is, it contains hydrophilic silica.
Resin coating layer (marked with ●), especially containing Mg ions
Resin coating layer containing hydrophilic silica (marked with ○) is
Maximum friction from resin coating layer containing hydrophobic silica (marked with □)
Friction coefficient (μ_max) Is large, the cotton cloth is not slippery,
Friction coefficient (μ _max) Can be greater than 0.3
I found it. In other words, the present inventors, as described above,
Slipperiness can be simulated by frictional behavior with cotton cloth
From, containing hydrophilic silica, preferably Mg ions
Suppresses human slippage by utilizing the properties of hydrophilic silica
It was possible to do.

Here, the reason why the maximum coefficient of friction (μ _max ) of the hydrophilic silica with the cotton cloth was considered was considered. The contact angle between water and the polyester-methylated melamine resin coating layer containing silica in the range of 2 to 8% by weight, and the maximum friction between the polyester-methylated melamine resin coating layer and the cotton cloth measured by the same method as described above. FIG. 7 shows the relationship with the coefficient (μ _max ). In the figure, 場合 indicates that the silica contained in the resin coating layer is hydrophilic silica, and □ indicates that the silica is hydrophobic silica. As shown in FIG. 7, it can be seen that the maximum coefficient of friction (μ _max ) with the cotton cloth decreases as the contact angle of the resin coating layer with water increases (as the wettability with water decreases). That is, the maximum coefficient of friction (μ _max ) of the resin coating layer containing hydrophilic silica so that the contact angle is 85 ° or less.
Is large. FIG. 7 shows the results of an experiment on a resin coating layer containing no aggregate.
It was also found that the same tendency was observed in the case where the aggregate was added and the resin coating layer in which the resin was different from that in the case of FIG.

Alkaline earth metals, especially Mg, Ca and A
As described above, the hydrophilic silica has a stronger polarity by substituting a part of the skeleton structure of the silica with l. In FIG. 8, Mg is taken as an example, and M is added to the clear resin coating layer.
surface free energy of a polyester-methylated melamine resin coating layer containing 2 to 8% by weight of each of hydrophilic silica, hydrophilic silica and hydrophobic silica containing g ions, and polyester-methyl measured by the same method as described above. Coefficient of friction of the melamine resin coating layer with cotton cloth (μ
_max ). The surface free energy was determined by measuring the contact angle with water and paraffin. FIG. 9 shows that the clear polyester-methylated melamine resin coating layer is coated with hydrophilic silica containing Mg ions (イ オ ン).
), Hydrophilic silica (●) and hydrophobic silica (□)
The relationship between the surface free energy of the polyester-methylated melamine resin coating layer containing 2 to 8% by weight and the silica content was shown. ☆ mark on the vertical axis of the graph,
4 shows the surface free energy of a resin coating layer containing no silica.

The surface free energy was calculated by the following method.

(Equation 1)

[0031]

(Equation 2)

[0032]

(Equation 3)

From these results, it has been found that hydrophilic silica containing Mg ions increases the surface free energy of the polar component and increases the maximum coefficient of friction (μ _max ) with the cotton cloth as compared with the hydrophilic silica. Was. These show the experimental results for the resin coating layer containing no aggregate, but when the aggregate is further added, the coating layer of a different resin type, alkaline earth metal ions other than Mg and aluminum It was also found that the resin coating layer containing hydrophilic silica containing ions had the same tendency. Even when the hydrophilic silica of the present invention and the metal ion-containing hydrophilic silica are added, the matting effect of the resin coating layer is not different from the case where hydrophobic silica is added.

The metal plate as the substrate used in the present invention is not particularly limited. For example, a cold-rolled steel plate, a hot-dip galvanized steel plate, a hot-dip Zn-Al coated steel plate, a galvanized steel plate, a galvanized steel plate , An aluminum plate, a stainless steel plate, a steel plate, a copper-plated steel plate and the like can be used. Particularly, a hot-dip galvanized steel sheet and a hot-dip Zn-Al coated steel sheet are preferable because of their excellent corrosion resistance and low cost. Further, it may be a band-shaped metal band.

The metal plates used as these substrates are preferably subjected to a known chemical treatment and / or primer treatment in order to improve the adhesion to the resin coating layer of the present invention described later. Examples of the chemical conversion treatment method include a phosphoric acid-based chemical conversion treatment method and a chromic acid-based chemical conversion treatment method.

The primer used in the primer treatment method is appropriately selected depending on the metal plate as the substrate, the chemical treatment method, and the type of the resin coating layer. Particularly, epoxy resins, polyester resins, and modified resins thereof are preferable. Used for These primers may be added with a chromic acid-based rust preventive pigment or a phosphoric acid-based rust preventive pigment for the purpose of improving corrosion resistance. Strontium chromate, zinc chromate, calcium chromate and the like can be mentioned as the chromic acid-based rust preventive pigment, and aluminum polyphosphate and the like can be mentioned as the phosphoric acid-based rust preventive pigment. The amount of phosphoric acid, chromic acid or the like adhered to the metal substrate in the chemical conversion treatment or the amount of the primer applied in the primer treatment can be appropriately selected depending on the type of the metal substrate and the resin coating layer.

The resin used for forming the coating layer of the present invention is a polyester resin and / or an oil-modified alkyd resin. These resins are excellent in processability and durability, low in cost, and preferred. When the resin-coated metal sheet of the present invention is used as a roof metal sheet, it is necessary to select a resin coating layer that can withstand various forming processes. From this point,
The coating layer has a glass transition point or softening point of 10 to 50 ° C.
Of the polyester resin or the oil-modified alkyd resin in an amount of 50% by weight or more.

The polyester resin of the present invention comprises an unsaturated polycarboxylic acid such as maleic anhydride and fumaric acid, a polycarboxylic acid such as phthalic anhydride and isophthalic acid, and a polyhydric alcohol such as propylene glycol and triethylene glycol. Is an unsaturated polyester resin obtained by polycondensation of styrene, and includes a resin obtained by dissolving this in a vinyl monomer such as styrene. The oil-modified alkyd resin of the present invention is obtained by modifying an alkyd resin obtained from phthalic anhydride and a polyhydric alcohol such as glycerin or pentaerythritol with a drying oil such as linseed oil or a non-drying oil such as coconut oil. It is a resin for paint.

As the resin forming the coating layer of the present invention, in addition to the polyester resin and the oil-modified alkyd resin, other resins may be contained as long as the object of the present invention is not impaired. Other resins are also preferably resins having the above-mentioned glass transition point or softening point. The other resin is, specifically, a vinyl resin, an acrylic resin, a fluorine resin, a silicon-modified resin thereof, or the like, and may be a mixture, a copolymer, or a modified product thereof. These resins may be cured by forming a crosslinking bond with various crosslinking agents as necessary.

The dry film thickness of the coating layer is not particularly limited.
10 to 30 μm is preferable, and 10 to 15 μm is more preferable. If it is less than 10 μm, not only a sufficient appearance cannot be obtained, but also durability and peel resistance become insufficient. If it exceeds 30 μm, the appearance is impaired by foaming generated during coating, which is not preferable.

In order to control the maximum surface roughness (R _max ) of the resin coating layer within the range of 5 to 20 μm, an appropriate aggregate can be blended in the resin coating layer. The aggregate is not particularly limited as long as the above-mentioned maximum surface roughness ( _Rmax ) can be controlled. Either organic fine particles or inorganic fine particles may be used, or any one of these may be used, or a combination of two or more thereof may be used. The shape may be spherical or irregular as long as it is a particle, but a fibrous shape is not preferred because it tends to impair snow sliding. The particle size is not particularly limited as long as the maximum surface roughness (R _max ) can be controlled, and examples thereof include an average particle size of 5 to 30 μm usually used as an aggregate. When the average particle diameter exceeds 30 μm, the maximum surface roughness (R _max ) 2
0 μm or less of surface roughness cannot be formed,
When the average particle diameter is less than 3 μm, the maximum surface roughness (R
_max ) is not preferable because 5 to 20 μm cannot be achieved.
Further, two or more kinds having different average particle diameters may be mixed and used.

The aggregate is not particularly limited as long as the above condition is satisfied. Suitable organic fine particles include acrylic resins, polyester resins, nylon resins, resins such as polyacrylonitrile, and inorganic fine particles, as amorphous particles, silica, synthetic mica, mica, talc, alumina, ceramic, Aluminum paste and the like are exemplified, and examples of the inorganic particles having a shape close to a sphere include silica balloons and glass beads. The addition amount of the aggregate is not particularly limited as long as the surface roughness is satisfied, but if the amount of the aggregate is too large, the coating film hardness of the resin coating layer originally required for the metal plate of the present invention, workability, etc. The solid content is preferably 50 parts by weight or less, and more preferably 30 parts by weight, based on 100 parts by weight of the resin. The following is more preferable, and 5 to 20 parts by weight is particularly preferable. In addition, since inorganic fine particles are harder than organic fine particles, they are preferable from the viewpoint of suppressing human slip.

In the present invention, in addition to the above-mentioned hydrophilic silica containing metal ions and hydrophilic silica, a matting material which is usually used may be appropriately added to further improve the matting effect. This is achieved by forming finer irregularities on the surface of the resin coating layer. Hydrophobic silica or hydrophilic silica having a particle diameter of 10 μm or less is preferred.

In the resin coating layer of the metal plate of the present invention, in addition to the above-mentioned hydrophilic silica and hydrophilic silica containing metal ions, the addition of the conventionally used coating materials for paints within the range not impairing the original purpose is provided. For example, coloring agents such as titanium white, iron oxide, and carbon black, extenders such as calcium carbonate, ultraviolet absorbers, abrasion inhibitors, and antioxidants can be added. The resin coating layer of the present invention is provided on one side or both sides of a metal substrate. In the case of one side, the other side may be a metal substrate, or after a chemical conversion treatment, or a chemical conversion treatment and a primer treatment, a coating layer appropriately containing various resins, aggregates and various pigments not depending on the present invention. It may be provided.

The method for forming the resin coating layer of the present invention is not limited. However, from the viewpoint of economy and the like, the resin coating component is made of an organic solvent,
A method in which a paint dispersed or dissolved in water or a plasticizer is applied by a roll coating method, a curtain coating method, or the like is recommended. As a well-known additive in paint, a leveling agent,
An antifoaming agent, a dispersing agent, an anti-repellent agent, an anti-separation agent, an anti-settling agent, and the like can be added as necessary. Heat drying conditions of the resin as a main component are applied to the heating and drying of the paint, and the conditions of 160 to 270 ° C. and 15 to 60 seconds are preferable.

By coating under the above-mentioned preferred conditions, the gloss of the surface can be measured by measuring the specular gloss of 60 ° from 2 to 50.
And a resin-coated metal plate having an excellent matte color tone can be obtained. In addition, at the same time, the slipperiness of a person is suppressed, and the snow slippage is excellent.

The resin-coated metal plate of the present invention has the above-described structure, is excellent in snow sliding property, suppresses slipperiness during construction, and has an excellent matte color. It can be suitably used as a board, especially as a roof material.

[0048]

The present invention will be specifically described below with reference to examples. [Examples 1 to 53, Comparative Examples 1 to 5] As a metal substrate, a hot-dip galvanized steel sheet (sheet thickness 0.35 mm), an aluminum plate (sheet thickness 0.5 mm), a Zn-55 wt% Al-plated steel sheet (sheet thickness 0) .35 mm). The chemical conversion treatment is carried out so that a phosphating solution (Bonderite 3300 manufactured by Nippon Parkerizing Co., Ltd.) is formed at about 1 g / m ² per one side, or a coating type chromate aqueous solution (chromic acid aqueous solution; concentration 3 to 4 weight) %) As a Cr adhesion amount so as to form about 40 mg / m ² per one surface. For the primer treatment, an epoxy resin-based primer (epoxy-melamine-based) or a polyester resin primer (polyester-melamine-based) was used. As the paint, components such as a binder resin shown in Table 1 below are used.
Those obtained by mixing at the ratios shown in Table 2 below were used.

After the surface of the substrate was treated with a chemical conversion treatment agent, a primer was applied to a dry film thickness of 5 μm and baked to a final plate temperature of 210 ° C. after 30 seconds. Continued
The paint is applied so that the dry film thickness becomes 20 μm,
The resin was baked so that the ultimate plate temperature after 230 seconds reached 230 ° C. to obtain a resin-coated metal plate, which was used as a test plate. In the case of one surface, the other surface was subjected only to the chemical conversion treatment or the chemical conversion treatment and the primer treatment, and thereafter, a resin coating layer not appropriately containing the resin not according to the present invention, a surface conditioning aggregate or various pigments was formed. .

[0050]

[Table 1]

With respect to the obtained test plate, the following method was used.
The maximum surface roughness (R _max ) was measured to evaluate the slipperiness of a person, the maximum coefficient of friction with a cotton cloth (μ _max ), the snow sliding property, and the coefficient of dynamic friction with natural snow (μ _k ). The results are shown in Table 2. In the table,
The double-sided material and the single-sided material mean the case where the coating layer of the present invention is applied to both surfaces of the metal plate and the case where it is applied to one surface. (1) Surface roughness Using a surface roughness shape measuring device, a 90 ° conical, 5 μmR diamond needle was used, the measurement length was 10 mm, and the measurement speed was 1.
The maximum surface roughness ( _Rmax ) was measured at 5 mm / sec.

(2) Human Slipperiness (A) A test plate (30 cm in length and 20 cm in width) was placed on a 5-dimensional gradient (26.
6 °), and ten test subjects wearing socks made of polyester fiber stood twice thereon to evaluate the slipperiness. Evaluation criteria ○: When 9 or more out of 10 evaluated that they did not slip Δ: When evaluated that 6 to 8 out of 10 did not slip ×: When evaluated that more than 5 out of 10 slipped

(3) Human Slipperiness (B) The surface free energy was determined by the above method.

(4) Maximum friction coefficient (μ _max ) with cotton cloth The maximum load F _max when the cotton cloth was moved under the conditions of a load of 200 g / cm ² and a moving speed of 150 mm / min using the apparatus shown in FIG. Was measured, and the maximum coefficient of friction (μ _max ) with the cotton cloth was calculated by the equation (1).

(5) Snow sliding property A test plate (length: 1800 cm, width: 90 cm) was inclined by 4 dimensions (2
2 °), and in winter, exposed outdoors in the suburbs of Sapporo city to snow 15 to 20 cm at night. The time required until snowfall was measured. Evaluation criteria ：: Snow fell within 3 hours △: Snow fell within 3 hours and more than 6 hours ×: It took more than 6 hours before snow fell or snow did not fall

(6) Coefficient of kinetic friction with natural snow (μ _k ) When the snow block is moved using the apparatus shown in FIG. 4 under the conditions of 0 ° C., a load of 2 g / cm ² , and a moving speed of 10 mm / min. The coefficient of kinetic friction (μ _k ) with natural snow was measured.

[0057]

[Table 2]

[0058]

[Table 3]

[0059]

[Table 4]

[0060]

[Table 5]

[0061]

[Table 6]

[0062]

[Table 7]

[0063]

[Table 8]

[0064]

[Table 9]

[0065]

[Table 10]

[0066]

The resin-coated metal sheet of the present invention is excellent in snow-slidability while suppressing the slipperiness of a person during construction. Therefore, when used as a roof metal plate, workers can work safely without slipping over or falling down during construction, and because of its excellent snow sliding property, the amount of snow on the roof is greatly reduced Can reduce the task of removing snow,
Economic burden can be reduced. Further, in the resin-coated metal plate of the present invention, in addition to the above effects, has an excellent matte color tone,
It is suitable as a metal sheet for outdoor structures such as roofing materials.

[0067]

[Brief description of the drawings]

FIG. 1 is a graph showing the relationship between the slipperiness of a metal plate having various resin coating layers and the maximum coefficient of friction (μ _max ) with a cotton cloth.

FIG. 2 shows the maximum coefficient of friction (μ) between a resin-coated metal plate and a cotton cloth.
_max ) is a schematic diagram showing a measuring method.

FIG. 3 is a graph showing a relationship between a snow sliding property of a metal plate having various resin coating layers and a dynamic friction coefficient (μ _k ) with natural snow.

Fig. 4 Dynamic friction coefficient (μ) between a resin-coated metal plate and natural snow
It is a schematic diagram showing the measuring method of _k ).

FIG. 5 shows a dynamic friction coefficient (μ) between a resin-coated metal plate and natural snow.
₅ is a graph showing the relationship between _k ) and the maximum surface roughness (R _max ) of the resin coating layer.

FIG. 6 is a graph showing the relationship between the maximum coefficient of friction (μ _max ) between a resin coating layer and a cotton cloth and the content of hydrophilic silica, metal ion-containing hydrophilic silica, and hydrophobic silica in the resin coating layer. is there.

FIG. 7 is a graph showing the relationship between the contact angle between a silica-containing resin coating layer and water and the maximum coefficient of friction (μ _max ) between the silica-containing resin coating layer and a cotton cloth.

FIG. 8 is a graph showing the relationship between the maximum coefficient of friction (μ _max ) between the resin coating layer containing silica and the cotton cloth and the surface free energy of the resin coating layer.

FIG. 9 is a graph showing the relationship between the surface free energy of a resin coating layer and the contents of hydrophilic silica, hydrophilic silica, and hydrophobic silica containing metal ions in the resin coating layer.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Toshiyuki Kato 1 Kawasaki-cho, Chuo-ku, Chiba-shi, Chiba Prefecture Inside the Chiba Works of Kawasaki Steel Corporation (72) Inventor Tatsuyoshi Ito 1025 Hamanocho, Chuo-ku, Chiba-shi, Chiba Steel plate Co., Ltd. (72) Inventor Koji Kobayashi 1025 Kawano Steel, Chuo-ku, Chiba City, Chiba Prefecture Steel plate Co., Ltd. (72) Inventor Hideo Ogishi 1025 Hamano-cho, Chuo-ku, Chiba City, Chiba, Japan F term in product research laboratory (reference) 4D075 BB24X CA09 DB02 DB70 DC01 EA41 EB19 EB35 EB42 EC10 EC11 4F100 AK36D AK41D BA02 BA03 BA04 BA06 GB07 JK14

Claims (4)

[Claims] 1. A load of 200 g / cm ² and a moving speed of 150 m
The maximum coefficient of friction (μ _max ) with cotton cloth at m / min is more than 0.3 and the coefficient of kinetic friction with natural snow at 0 ° C., a load of 2 g / cm ² , and a moving speed of 10 mm / min (μ)
A resin-coated metal sheet having a resin-coated layer in which _k ) is less than 0.3. 2. A resin coating layer containing hydrophilic silica having an average particle diameter of 3 to 10 μm and a polyester resin and / or an oil-modified alkyd resin on at least one surface of the metal substrate, wherein the resin coating layer Wherein the maximum surface roughness (R _max ) of the resin-coated metal sheet is 5 to 20 μm. 3. The method according to claim 2, further comprising a resin coating layer containing hydrophilic silica containing at least one metal ion selected from the group consisting of alkaline earth metals and aluminum. Resin coated metal plate. 4. The resin-coated metal plate according to claim 2, wherein the metal substrate is subjected to a chemical conversion treatment and / or a primer treatment.