JP6201616B2 - Antifouling display for road - Google Patents

Description

  The present invention relates to an antifouling road display body, and more particularly to an antifouling and road marking body having flexibility.

  Road signs (road sign pillars) are used for gaze guidance and vehicle entry control, on roads such as sidewalks, median strips, center lines (lane separation), diversion points, parking lots, parks, entrances to facilities, etc. It contributes to smooth traffic every day. Since it is installed outdoors, dirt adheres to the surface due to dust, exhaust gas, or the like after a long period of use, and visibility, which is the main function, is reduced.

  Therefore, various methods such as a film or sheet having a self-cleaning action on the surface of the road marking body, surface treatment (painting treatment), etc. have been taken (Patent Documents 1 and 2).

JP 2004-285625 A JP-A-7-76808

  However, in the method of sticking a film or sheet to the road marking body, the film or sheet is only stuck to the road marking body after being attached to the road marking body, and the adhesiveness to the road marking body is low. It was a problem because it was easy. On the other hand, the surface treatment of the silicate-containing fluororesin paint has a drawback that the base polymer is expensive.

  Then, this invention makes it a subject to provide the sign body for roads which has antifouling property and a softness | flexibility.

  Other problems of the present invention will become apparent from the following description.

  The above problems are solved by the following inventions.

1. A urethane resin is mixed with an alkoxysilane or an organosilicate compound that is a multimer thereof, and a part or all of the surface of a road marking body is coated with a hydrolyzed silanol group paint. A sign for roads,
The organosilicate compound is blended in the range of 10.0 to 58.0% by weight with respect to the total weight of the solid content weight of the urethane resin and the organosilicate compound in the paint,
A road marking body characterized in that a high-hardness and a low-hardness urethane resin are used in combination.

  2. 2. The road sign according to claim 1, wherein the organosilicate compound is an organosilicate compound in which two or more silanol groups are generated by hydrolysis of alkoxysilane.

  3. The sign for road according to 1 or 2, wherein the organosilicate compound is an alkoxysilane which is a difunctional to tetrafunctional hydrolyzable silane compound.

4). 2. The sign for road according to 1 above, wherein the organosilicate compound is obtained by hydrolysis of an alkoxysilane having a structure represented by the following formula (1).
Formula (1)

（式中、ｍは２〜１００を表す。）

(In the formula, m represents 2 to 100.)

  5. 5. The road marking body according to any one of 1 to 4, wherein the paint has a thickness of 1 to 15 μm.

  According to the present invention, a road marking body having antifouling properties can be provided.

  Further, according to the present invention, since it is excellent in flexibility (flexibility), it is possible to provide a road marking body that does not cause cracks even if it is bent 180 degrees.

  Furthermore, according to the present invention, since a urethane resin is used for the paint instead of the conventional fluororesin, there is an advantage that the cost is low.

  Embodiments of the present invention will be described below.

  The road marking body of the present invention is formed by coating a part or all of the surface of the road marking body main body with a specific paint.

  The specific coating material used in the present invention comprises a urethane resin and an organosilicate compound which is an alkoxysilane or a multimer thereof, and has a silanol group obtained by hydrolyzing the organosilicate compound.

<Urethane resin>
The urethane resin that is the raw material of the paint is not particularly limited, but is a two-component type that is synthesized by reacting two components consisting of a main component mainly composed of polyol and a curing agent mainly composed of an isocyanate compound. And a one-component type in which a urethane prepolymer having an isocyanate group as a main component reacts with moisture in the air and cures at room temperature to form a urethane resin. In the present invention, any of them can be used, and each of them can be used alone. However, two liquid types can be used in combination of two or more types such as two liquid types and one liquid type.

  Preferred examples of the isocyanate compound include bifunctional or higher isocyanate compounds.

  Examples of the bifunctional isocyanate compound include tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, naphthylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, tetramethylxylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane. Examples of the polyisocyanate compound include diisocyanate and norbornane diisocyanate.

  The trifunctional or higher functional isocyanate compound is synthesized using the above diisocyanate as a starting material, and examples thereof include a burette body, a trimethylolpropane adduct body, an isocyanurate body, and an allophanate body.

  The polyol is not particularly limited, and a known polyol can be used.

  As a compounding quantity of the urethane resin in a coating liquid, the range of 40 to 90 weight% is preferable as solid content weight%, More preferably, it is the range of 50 to 80 weight%.

  As the urethane resin used in the present invention, a high hardness resin and a low hardness resin are used in combination.

  If the coating liquid does not contain a high-hardness urethane resin, the antifouling property is low, and if the coating liquid does not contain a low-hardness urethane resin, flexibility is lost, which is not preferable.

  The urethane resin is available as a commercial product, and as a high-hardness urethane resin, for example, DM-653, DM-675, DM-677, DM-678 manufactured by DIC, and the like can be preferably used. As a low-hardness urethane resin, DF-407, 16-411, 16-416, 18-472, DN-980, DN-981, etc. can be preferably used.

  When the road marking body of the present invention is cracked or cracked due to impact or bending, dirt enters the site. Therefore, when used as a road marking body, it is preferable to use a flexible urethane resin. Moreover, in this invention, when using as a road sign body, it is preferable to use the urethane resin which is hard to produce yellowing (non-yellowing).

  In the present invention, when the road marking body main body is formed of urethane resin, since the urethane resin is used for the polymer serving as the base of the paint, it is preferable because of its good adhesion to the main body.

<Organosilicate compound>
In the coating material of the present invention, an alkoxysilane or an organosilicate compound that is a multimer thereof is added to a urethane resin, and the organosilicate compound has a hydrolyzed silanol group.

  As for the content of the organosilicate compound, the organosilicate compound is blended in the range of 10% by weight or more with respect to the total weight of the solid content of the urethane resin and the organosilicate compound. In particular, the organosilicate compound is preferably blended in the range of 10 to 70% by weight with respect to the total weight of the solid content of the urethane resin and the organosilicate compound.

  By containing the organosilicate compound at a certain ratio, the surface of the urethane resin paint can be hydrophilized. By making such a surface hydrophilic, it is possible to prevent adhesion of smoke and soot, which are hydrophobic substances, and soil and dust, which are hydrophilic substances, can have a self-cleaning action of washing away with water due to rain. it can.

  The antifouling property in the present invention has a self-cleaning action that can prevent adhesion of smoke and soot, which are hydrophobic substances, and can wash soil and dust, which are hydrophilic substances, together with water due to rain. Say.

  In the present invention, the organosilicate compound is preferably an organosilicate compound in which two or more silanol groups are generated by hydrolysis of alkoxysilane.

  In the present invention, the organosilicate compound is more preferably an alkoxysilane which is a bifunctional to tetrafunctional hydrolyzable silane compound, such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane. And methyltriethoxysilane.

  Examples of the alkoxy include methyl silicate oligomer and methoxy. For example, when methoxysilane is used, a methyl silicate oligomer having a high hydrolysis rate and high reactivity can be obtained. The methyl silicate oligomer can be obtained as a commercial product, and for example, MS-51, MS-56, MS-57, MS-56S manufactured by Mitsubishi Chemical Corporation can be preferably used.

  Furthermore, in the present invention, the organosilicate compound obtained by hydrolysis of the alkoxysilane represented by the formula (1) is also preferable. In this example, methyl silicate oligomer and the like are obtained by hydrolysis of methoxysilane.

<Other ingredients>
In the above-mentioned paint, other optional components may be blended as necessary within the range not impairing the problems and objects of the present invention. Examples of such optional components include ultraviolet absorbers and light stabilizers.

<Manufacture of paints>
In order to obtain a paint containing each of the above components, the concentration of the component is about 5 to 20% by weight in a single solvent or mixed solution such as toluene, butyl acetate, cyclohexanone, acetone, methyl ethyl ketone, and methyl isobutyl ketone. It is used as an organic solvent solution so dissolved.

<Manufacture of the road marking body of the present invention by application>
The road marking body of the present invention is obtained by covering part or all of the surface of the road marking body main body (base material) with the obtained paint.

  Specifically, a urethane resin paint is applied onto a road sign body made of urethane resin, dried, and subjected to a surface treatment that volatilizes the solvent and hardens the paint, thereby obtaining the road sign body of the present invention. It is done.

  Although the coating method is not particularly limited, it can be performed by a known coating method such as a dipping method, a spray method, a roll coating method, a doctor blade method, or a flow coating method.

  Although a drying method can be set suitably, it is preferable that drying temperature is room temperature-120 degreeC, and drying time is performed for 30 to 90 minutes.

  It is preferable that the specific coating material used by this invention is apply | coated with the thickness of 1-15 micrometers as a thickness of a coating film with respect to the road marking body of this invention.

  When it is thicker than 15 μm, the surface is uneven, and the flexibility of the coating film is lowered, which is not preferable. On the other hand, if the thickness is less than 1 μm, the urethane layer of the road marking body (base material) is exposed, the amount of coating components received is reduced, the wear resistance is lowered, and the antifouling property is weakened.

  As an application of the paint according to the present invention, it can be preferably used as an antifouling paint by being applied not only to road marking bodies but also to indoor and outdoor installations.

  Examples of the present invention will be described. The present invention is not limited to the embodiments.

Example 1
<Blend ingredients and blending amounts>
-High hardness urethane resin (DIC-made "DM-653" (solid content concentration 55.0% by weight) 3.8 parts by weight Low hardness urethane resin (DIC-made "DM-407" (solid content concentration 25.0 (Weight%) 2.2 parts by weight-Organosilicate (tetramethoxysilane) (solid content) 0.3 parts by weight-Cyclohexanone 11.5 parts by weight-Butyl acetate 11.5 parts by weight

  Various blends according to Example 1 were mixed and dissolved uniformly to prepare a urethane resin paint.

  Moreover, the compounding ratio of the organosilicate compound solid content weight to the total measurement of the solid content weight of the urethane resin and the organosilicate compound was as shown in Table 1.

  A urethane resin paint was spray-coated on a road sign body body made of urethane resin, dried at 120 ° C. for 60 minutes, volatilized from the solvent, and subjected to a surface treatment to cure the paint.

  The thickness of the paint after curing was 8 μm.

<Evaluation method>
The following items were evaluated for the antifouling coating film obtained in Example 1, and the results are shown in Table 1.

(1) Initial adhesiveness of coating film Based on JIS K5400-8-5 (1990), a cross-cut test was performed using a 100-th cross-cut, and peeling of the adhesive tape was evaluated according to the following criteria.
A: No peeling B: Separation of 1st to 10th eyes was confirmed.
(Triangle | delta): 11-60 eyes peeling was able to be confirmed.
X: 61-100 eyes peeling was confirmed.

(2) Antifouling property After rubbing carbon black (EC600JD manufactured by Lion Corporation) on the antifouling coating film and applying carbon black suspension (Pigdai Black LN-720N manufactured by Resino Color Industry Co., Ltd.) to the antifouling coating film The antifouling coating film was shower-washed with ion exchange water (pressure: 0.3 MPa), and the antifouling property was evaluated according to the following criteria.
A: Self-cleaning effect, no dirt
○: There is minute dirt.
Δ: Partially dirty
X: There is no self-cleaning effect, and there is a stain on the entire surface.

(3) Flexibility (flexibility)
Based on JIS K5600-5-1 (1999), after a 180 degree | times bending test, it observed with the stereomicroscope and evaluated the presence or absence of a crack and a crack.
A: No crack.
○: There are minute cracks.
Δ: Partially cracked
X: There are cracks on the entire surface.

(4) Hydrophilicity The contact angle with water was measured with an automatic contact angle meter (Kyowa Interface Science CA-V type).
The contact angle is preferably 65 ° or less, and more preferably 50 ° or less. If the contact angle is 65 ° or less, it is excellent in hydrophilicity and can prevent adhesion of smoke, soot, etc., which is a hydrophobic substance, and soil and dust, which are hydrophilic substances, can be washed away together with water due to rainfall. .

(Example 2)
In Example 1, 0.3 parts by weight of organosilicate was changed to 2.2 parts by weight, 11.5 parts by weight of cyclohexanone was changed to 20.0 parts by weight, and 11.5 parts by weight of butyl acetate was changed to 20.0 parts by weight. Except for the above, a urethane resin paint was molded in the same manner.
Thereafter, in the same manner as in Example 1, a surface treatment was performed on the road sign body body made of urethane resin. The obtained antifouling coating film was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

(Example 3)
In Example 1, 0.3 parts by weight of organosilicate was changed to 3.4 parts by weight, 11.5 parts by weight of cyclohexanone was changed to 25.0 parts by weight, and 11.5 parts by weight of butyl acetate was changed to 25.0 parts by weight. Except for the above, a urethane resin paint was molded in the same manner.
Thereafter, in the same manner as in Example 1, a surface treatment was performed on the road sign body body made of urethane resin. The obtained antifouling coating film was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Example 4
In Example 1, 3.8 parts by weight of urethane resin (“DM-653” manufactured by DIC (solid content concentration 55.0% by weight)) was changed to 3.9 parts by weight, and urethane resin (“DM-407” manufactured by DIC). (Solid concentration 25.0% by weight) 2.2 parts by weight, 1.0 part by weight of organosilicate, 2.0 parts by weight, 11.5 parts by weight of cyclohexanone, 18.0 parts by weight Further, a urethane resin paint was molded in the same manner except that 11.5 parts by weight of butyl acetate was changed to 18.0 parts by weight.
Thereafter, in the same manner as in Example 1, a surface treatment was performed on the road sign body body made of urethane resin. The obtained antifouling coating film was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

(Example 5)
In Example 1, 3.8 parts by weight of urethane resin (“DM-653” manufactured by DIC (solid content concentration 55.0% by weight)) was changed to 2.6 parts by weight, and urethane resin (“DM-407” manufactured by DIC). (Solid concentration 25.0% by weight) 2.2 parts by weight, 2.4 parts by weight of organosilicate, 1.7 parts by weight, 11.5 parts by weight of cyclohexanone, 11.0 parts by weight In addition, a urethane resin paint was molded in the same manner except that 11.5 parts by weight of butyl acetate was changed to 11.0 parts by weight.
Thereafter, in the same manner as in Example 1, a surface treatment was performed on the road sign body body made of urethane resin. The obtained antifouling coating film was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

(Comparative Example 1)
In Example 1, except that 0.3 parts by weight of organosilicate was changed to 0 parts by weight, 11.5 parts by weight of cyclohexanone was changed to 10.0 parts by weight, and 11.5 parts by weight of butyl acetate was changed to 10.0 parts by weight. Similarly, a urethane resin paint was molded.
Thereafter, in the same manner as in Example 1, a surface treatment was performed on the road sign body body made of urethane resin. The obtained antifouling coating film was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

(Comparative Example 2)
In Example 1, 0.3 parts by weight of organosilicate was changed to 4.0 parts by weight, 11.5 parts by weight of cyclohexanone was changed to 28.0 parts by weight, and 11.5 parts by weight of butyl acetate was changed to 28.0 parts by weight. Except for the above, a urethane resin paint was molded in the same manner.
Thereafter, in the same manner as in Example 1, a surface treatment was performed on the road sign body body made of urethane resin. The obtained antifouling coating film was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

(Comparative Example 3)
In Example 1, 3.8 parts by weight of urethane resin (“DM-653” manufactured by DIC (solid content concentration 55.0% by weight)) was changed to 4.0 parts by weight, and urethane resin (“DM-407” manufactured by DIC). (Solid content concentration 25.0% by weight) 2.2 parts by weight, 0 parts by weight of organosilicate 0.3 parts by weight, 11.5 parts by weight of cyclohexanone 12.0 parts by weight, A urethane resin paint was molded in the same manner except that 11.5 parts by weight of butyl acetate was changed to 12.0 parts by weight.
Thereafter, in the same manner as in Example 1, a surface treatment was performed on the road sign body body made of urethane resin. The obtained antifouling coating film was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

(Comparative Example 4)
In Example 1, 3.8 parts by weight of urethane resin (“DM-653” manufactured by DIC (solid content concentration 55.0% by weight)) was changed to 0 part by weight, and urethane resin (“DM-407” manufactured by DIC (solid) (Partial concentration 25.0 wt%) 2.2 parts by weight, 6.2 parts by weight of organosilicate, 1.3 parts by weight, 11.5 parts by weight of cyclohexanone, 7.0 parts by weight, A urethane resin paint was molded in the same manner except that 11.5 parts by weight of butyl acetate was changed to 7.0 parts by weight.
Thereafter, in the same manner as in Example 1, a surface treatment was performed on the road sign body body made of urethane resin. The obtained antifouling coating film was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

<Evaluation>
From the above results, Examples 1-5 and Comparative Examples 2 in which the organosilicate compound is blended in an amount of 10.0% by weight or more based on the total weight of the solid content of the urethane resin and the organosilicate compound in the paint. Regarding No. 4, it was confirmed that the hydrophilicity was good as compared with Comparative Example 1 containing no organosilicate compound.

  However, in Comparative Example 2 in which the organosilicate compound was blended in an amount exceeding 58.0% by weight, since a large amount of the organosilicate was blended, cracking occurred in the flex test, and the flexibility was x. It was. In Comparative Example 2, the glossiness was remarkably reduced.

  Further, the comparative example 3 shows poor flexibility when the paint does not contain a low hardness urethane resin, and the comparative example 4 shows that the paint does not contain a high hardness urethane resin. It was confirmed that the soiling deteriorated.

  Since the specific paint used in the present invention has the effects as described above, it can be preferably used for road signs, and various coatings such as a dipping method, a spray method, a roll coating method, a doctor blade method, a flow coating method, etc. Since it can apply | coat by the method, unlike the antifouling process by a film or a sheet | seat, it can utilize preferably in various outdoor installations regardless of the shape of installation objects.

Moreover, since the specific coating material used in the present invention has an effect of easily removing dirt, it can be preferably used in indoor installations.

Claims (5)

A urethane resin is mixed with an alkoxysilane or an organosilicate compound that is a multimer thereof, and a part or all of the surface of a road marking body is coated with a hydrolyzed silanol group paint. A sign for roads,
The organosilicate compound is blended in the range of 10.0 to 58.0% by weight with respect to the total weight of the solid content weight of the urethane resin and the organosilicate compound in the paint,
A road marking body characterized in that a high-hardness and a low-hardness urethane resin are used in combination.   2. The road sign according to claim 1, wherein the organosilicate compound is an organosilicate compound in which two or more silanol groups are generated by hydrolysis of alkoxysilane.   The sign for road according to claim 1 or 2, wherein the organosilicate compound is an alkoxysilane which is a bifunctional to tetrafunctional hydrolyzable silane compound. The said organosilicate compound is obtained by hydrolysis of the alkoxysilane which is a structure of following formula (1), The sign for roads of Claim 1 characterized by the above-mentioned.
Formula (1)

(In the formula, m represents 2 to 100.) The road marking body according to any one of claims 1 to 4, wherein the paint has a thickness of 1 to 15 µm.