• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The presented labeling materials are used to form thick layers 1 to 3 mm thick and have a low viscosity colorant content of 40 to 60% by weight. These color materials consist of fast dry binders, pigments, powder fillers and standard additives based on anionic stabilized emulsion polymers. The remainder is granulated filler having a particle diameter of 0.1 mm or more. Total solids content is 87-93% by weight. The presence of very low proportions of volatiles and fast dry binders reduces the drying time of the applied label as part of the time required for conventional formulations and prevents crack formation.
    公开号:KR19980701768A
    申请号:KR1019970705164
    申请日:1996-02-05
    公开日:1998-06-25
    发明作者:페터-크리스티안 볼트
    申请人:볼라크 모제스；플라스티루테 에스.아.；
    IPC主号:
    专利说明:

    Aqueous labeling substance and preparation method thereof
    The present invention relates to an aqueous label composition for horizontal marking of roads or other traffic destinations comprising anionic stabilized emulsion polymer based dry acceleration binders and color pigments and fillers. In addition, the present invention relates to a method for preparing such an aqueous label composition.
    The expression dry accelerating binder refers to a polymer preparation which ensures, through an integrated physico-chemical mechanism, that a label composition made with such a binder dries much faster than a label composition comprising a conventional binder. Only through such accelerated drying can such label compositions be used in a manner suitable for traffic engineering because long traffic direction roadblocks caused by long drying times can be eliminated.
    Known dry acceleration binders of this kind used for horizontal marking on roads are published in EP-B-0 322 188 and EP-A-0 409 459 and are trademarks PRIMAL from Rohm and Haas (Philadelphia, PA, USA). Available at 2706 and 3031.
    Known polymer preparations for accelerated drying consist of polymer particles of multifunctional water-insoluble or water-soluble amines and water-insoluble and anionically stabilized plastics. These two components are incompatible with each other and cannot react at sufficiently high pH values. However, if the pH value of the preparation drops below a certain value, the physico-chemical reaction of the binder component is ensured and dried. High pH values that initially stabilize are obtained by the addition of volatile bases, in particular ammonia. If the pH value of a paint formulation based on such a binder drops below a certain value through evaporation of the volatile base, the labeling composition solidifies or dries very quickly, regardless of external climatic conditions and layer thickness.
    However, label compositions comprising a suitable combination of known drying accelerated binders such as Primal 2706 and solid inorganic particles such as color pigments, conventional additives and fillers disclosed in this document have so far been sprayed with only at least 20% volatiles. It was prepared and tested only in the form of possible label paints and these sprayable label paints could only be used for label production with a layer thickness of less than 1 mm. The attempt of EP-A-0 409 459 with a dry accelerating binder thus relates to a wet film thickness of about 0.03 mm and a dry film thickness of about 0.09 mm. This is because paint formulations known to date based on accelerated drying binders have severe cracks even at layer thicknesses of less than 1 mm and have surface defects that greatly impair their quality in order to achieve the fast drying speeds required in traffic engineering. .
    Therefore, the rapidly drying label compositions known to date for horizontal labels with a layer thickness of at least 1 millimeter as frequently required are unsuitable.
    Thick layer markers having a layer thickness of about 1 to 3 mm are placed in the so-called drawing shoe method because of their high viscosity. It is also possible to work with a filling knife in the case of work such as the formation of a directional arrow. According to another application, up to 3 mm high is laid on the mark line, for example by a sling, in this way a contour road sign is obtained with improved night visibility in the wet state. In addition, other applications are known for the production of contour markers with a wide variety of contour shapes. Binary systems, in which polymeric methacrylate acts as a binder, are frequently used for thick layer labeling. This material is cured by mixing the composition with a peroxide resulting in the polymerization of the material. The drying time of such a two-component label composition is generally 20 to 35 minutes. The operation is laborious and should be used within 20 to 30 minutes once the composition is combined with the peroxide.
    In addition, thermoplastic compositions have also been used so far, for which thick-layered plastics melt at high temperatures as binders. The composition must be heated on the road for several hours in order to melt the thermoplastic composition before working to obtain working viscosity. It is necessary to maintain a continuous energy supply with a special machine so that the labeling composition can be placed in the course of operation. However, the drying time is very short because the material is cooled immediately to cure. The work is difficult and the main energy consumption is very high.
    According to the state of the art, the possibility of applying a water-dilutable thick layer labeling composition in a much more economical way is almost impossible due to very long drying times when using conventional binders that are not accelerated to drying, and when using the drying accelerated binder mentioned above This is not possible because cracks occur unacceptably.
    The present invention utilizes known drying accelerated binders, in particular binders commercially available under the trademark Primal and utilizes the inherent integrated drying mechanism of these binders and does not compromise their usefulness due to surface defects, cracks or very long drying times. It is an object to produce a dilutable label composition with water for a 3 mm thick layer.
    This object is achieved by the aqueous label composition according to claim 1.
    Therefore, such labeling compositions have an exceptionally high solids content, in particular in granular fillers, low binder ratios and low amounts of volatiles usually present in sprayable label paints. As you know, conventional binders and dry accelerated binders in the form of aqueous dispersions contain about 50% of volatiles, mainly water, so that the labeling composition according to the present invention is only 7 to 13 Contains% volatile components.
    In the case of such a label composition, even at a layer thickness of 3 mm, cracks are completely prevented and there is no defect even when the attached label is magnified 15 times, and drying time is longer than that of a conventional label composition. Although the ratio is small, it is very short (15-30 minutes).
    The low viscosity paint component, which accounts for 40 to 60% by weight of the labeling composition, is known in dry acceleration binders, color pigments, conventional additives and maximum averages as described in EP-A-0 409 459 and EP-B-0 322 188. It is composed of a fine filler having a particle diameter of 0.03 mm. Such low viscosity components constitute a sprayable composition. The remainder consists of granulated fillers having a particle diameter of at least 0.1 mm, in particular 0.1 to 0.7 mm.
    The preparation of the low viscosity paint component is in accordance with the art and the aqueous emulsion paint manufacturing technique.
    The labeling compositions described below are tested as examples and the test results are shown in Tables 1 and 2, which include 50% by weight of low viscosity paint ingredients and granular filler mixtures, the filler mixtures of which are referred to below as crack fillers (AC fillers). Is indicated.
    The low viscosity paint component is constructed as follows and the weight percentages mentioned are for the final label composition:
    The dry accelerating binder used was the commercially available trade name Primal 2706 and the amount used was 18% by weight. As a white finish, titanium dioxide is used in an amount of 7% by weight. The fine filler is calcium carbonate, silicon dioxide or mixtures thereof and the amount used is 23% by weight. All fine fillers with a maximum average particle diameter of 0.03 mm result in substantially the same results. Finally, a conventional additive mixture consisting of dispersant, wetting agent, antifoaming agent, film forming aid and small amount of volatile alcohol is added; These additive components are added to the other components of the labeling composition in an amount of about 2% by weight relative to 100% labeling composition.
    50% by weight of AC filler is added to the prepared low viscosity paint component to form the final label composition. The combination of low viscosity color components and AC fillers is done according to the known art and instructions for the preparation of viscous compositions.
    The binder contains solids, volatiles and water in approximately equal proportions. Similarly, additives such as dispersants and wetting agents consist of approximately equal proportions of solids and volatiles. All remaining components consist of solids and the solids content of the tested samples is about 90% by weight.
    Table 1 shows five different AC filler compositions in rows 1 to 5 where the label composition was tested and the low viscosity paint component was 50% by weight. The various AC filler components used in rows 1, 2 and 3 of Table 1, the drying time in row 4, and the crack test results in row 5 are shown. The results in Table 1 are for a 3 m layer of cover placed on cardboard with so-called drawing shoes.
    Lines 1 to 4 relate to AC fillers treated with particle surfaces and line 5 shows the results when using surface treated AC filler components consisting of particle coatings using organosilane as adhesion promoters between particles and binders. Line 6 shows the comparison results when using a binder which is dried in an accelerated form but in a conventional manner. With conventional compositions, color labels cannot be applied at these layer thicknesses, so comparison with them is not possible.
    Conventional glass beads or reflective beads of 100 to 250 microns and 250 to 500 microns in diameter are used for AC fillers. The quartz sand used has a rutile stone structure and consists of particles of 100 to 400 μm in diameter.
    AC filler composition consisting of fine glass beads 1/3 of 100 to 250μ diameter, granulated glass beads 1/3 of 250 to 500μ, granulated quartz sand 1/3 of 100 to 400μ particle diameter as shown in Table 1 This results in the shortest drying time. However, according to Table 1 all other AC filler compositions have significant results (Table 1, line 6) compared to using a conventional dry binder which requires a 2 to 3 times longer 71 min drying time; Therefore, these conventional binders cannot be applied in a manner suitable for transportation and thus cannot be used for thick layer labeling. In either case no cracking was observed.
    Drying time measurements are performed at constant temperature and humidity in a room with weak air movement. The label composition is applied onto the cardboard substrate using a drawing shoe with a defined layer thickness. The film is then dried. A somewhat absorbent cardboard substrate mimics the absorbent bitumen layer of the road better than the glass plates. The test is considered to be a stable coating if no paint is attached to the thumb when testing by rotating it slightly with pressure on the paint surface. After drying for 60 minutes, the sample is soaked in water for 10 minutes. If the coating is not destroyed by a short, violent rub, the paint is considered water resistant. This applies to all samples.
    Further measurements are made using label compositions of the same composition including the AC fillers indicated in Table 1 for thick layers with thicknesses of 3 mm as well as thick layers with thicknesses of 1 mm and 2 mm. The results are shown in Table 2 and rows 1 to 6 relate to the AC filler compositions specified in rows 1 to 6 of Table 1 and columns 1 to 3 are dried for 1 mm, 2 mm and 3 mm layer thicknesses. Indicates time (minutes). Drying is carried out at 20 ° C. and 70% humidity. Application is made on cardboard. All coatings according to rows 1 to 5 are water resistant after 60 minutes of drying. In contrast, the drying time of a sample comprising the conventional binder is 2-3 times that of the sample according to the invention.
    Generally, the low viscosity component comprises 12 to 24% by weight, in particular 15 to 20% by weight, of the binder based on the final label composition, which comprises 6 to 9% by weight, especially 7 to 8% by weight of color pigments, 20 to 27% Approximately half of the amount of solid material with% fine filler and 1.6 to 2.4% by weight of additives, in particular 2% by weight. In general, it is possible to use carbonates, silicates, talc or sulfates as fine fillers. The nature, purity and granularity of the fine fillers do not need to be further detailed as they have a slight effect on the properties of the low viscosity paint component, and above all, drying time. Of importance is the solids content which should be 87 to 93, in particular 89 to 91% by weight.
    In general, AC fillers comprising granulated mineral and / or organic particles having a minimum particle diameter of 100 μ may be used. In particular, it is possible to use the following fillers:
    Glass beads having a diameter of 100 to 200 mu;
    Glass beads of 100 to 200 microns in diameter mixed with glass beads having 100 to 700 microns in diameter;
    100-400 micron diameter quartz sand and rutile salt mixed with 100-200 micron diameter glass beads;
    Quartz sand and ruckite with a diameter of 100 to 400 mu mixed with glass spheres of 100 to 200 mu diameter and 100 to 700 mu diameter;
    100-400 micron diameter quartz sand and rutile salt mixed with glass beads and water-insoluble carbonates, sulfates or other minerals having a particle diameter of 100-400 microns.
    Suitable organic fillers are hard plastic granulated particles used in aircraft manufacture.
    The labeling composition comprising the AC filler according to Table 1 is highly viscous and can be processed by conventional methods. They have excellent storage stability and can be applied in a simple way. No cracking is observed and after sufficient drying time (20-30 minutes) the paint film has great hardness and good surface adhesion. Drying time is independent of temperature and humidity.
    According to the present invention, the preparation of the aqueous labeling composition is accomplished by first mixing all low viscosity paint components, including the dry acceleration binder provided in a hermetically sealed container, and then mixing the AC filler. Such high viscosity compositions are applied using a drawing shoe. Or the final label composition in such a way that the already mixed low viscosity paint component constituting the sprayable composition is sprayed in the direction of the road surface with a conventional spray layer installed on the label vehicle and adding AC filler particles there before reaching the road surface. Is manufactured; For this purpose, the AC filler particles are fired into the jet leaving the paint spray gun using at least one filler layer. Filler particles are fired onto the paint jet in two directions using two filler guns before the paint jet reaches the road surface. In this way the final label composition is only completed as the paint composition impinges on the road surface. The release of particles into the paint jet is described in EP-B-0 280 102.
    1 (100-250μ beads)2 (250-500μ beads)3 (100-400μ quartz sand)4 (drying time (minutes))5 (cracks) 1) 2) 3) 4) 5) * 6) **16.66% 50.00% ------------ 16.66% 16.66%16.66% ------ 50.00% ------ 16.66% 16.66%16.66% ------------ 50.00% 16.66% 16.66%253122242171None None None None None None * AC filler particles are surface treated ** Samples containing conventional dry binders
    Substances according to Table 1Drying time according to layer thickness (minutes) 1 mm2 mm3 mm 1) 2) 3) 4) 5) 6)7997620171922171643253133242171
    权利要求:
    Claims (10)
    [1" claim-type="Currently amended] In an aqueous label composition for horizontal marking on roads or other traffic areas comprising a dry accelerating binder and a filler based on an anionically stabilized emulsion polymer,
    In order to apply the label with a layer thickness of 1 to 3 mm, the final label composition comprises 40 to 60% by weight of low viscosity components consisting of a drying accelerator binder, color pigments, fine fillers and additives, with the remainder having a particle diameter of at least 0.1 mm. Aqueous emulsion paint, characterized in that it is a phosphorus granular filler and has a total solids content of 87 to 93% by weight.
    [2" claim-type="Currently amended] 2. The aqueous emulsion paint of claim 1, wherein the granular filler comprises 45 to 55%, in particular 50%, by weight of the final label composition and the total solids content is 89 to 91% by weight.
    [3" claim-type="Currently amended] The aqueous emulsion paint of claim 1 or 2, wherein the granular filler is glass beads or consists of a mixture of glass beads and quartz sand.
    [4" claim-type="Currently amended] The method of claim 1 or 2, wherein the granulation filler consists of a mixture of glass beads and quartz sand, wherein 100 parts by weight of the mixture comprises 20 to 70 parts by weight of glass beads having a particle diameter of 0.1 to 0.7 mm, The aqueous emulsion paint, characterized in that the remainder consists of quartz sand having a particle diameter of 0.1 to 0.4 mm.
    [5" claim-type="Currently amended] The granulated filler according to claim 4, wherein the granulation filler is glass beads 1/3 of 0.1 to 0.25 mm particle diameter, glass beads 1/3 of 0.25 to 0.6 mm particle diameter and 1/3 of quartz sand of 0.1 to 0.4 mm particle diameter. Water-based emulsion paint, characterized in that.
    [6" claim-type="Currently amended] The composition according to claim 1, wherein the low viscosity component in the final emulsion is 12 to 24% by weight, in particular 15 to 20% by weight binder, 6 to 9% by weight color pigments, 20 to 27% by weight, in particular 22 to An aqueous emulsion paint comprising 25% by weight fine filler and 2% by weight additive.
    [7" claim-type="Currently amended] The aqueous emulsion paint of claim 3, wherein the granular filler particles are surface treated and coated with organosilane as an adhesion promoter between the particles and the binder.
    [8" claim-type="Currently amended] A method for producing an aqueous emulsion paint according to claim 1, wherein all low viscosity components forming a sprayable composition are mixed and then the sprayable composition is mixed with a coarse filler.
    [9" claim-type="Currently amended] 9. The method of claim 8, wherein the sprayable composition and the granular filler are mixed before the start of the labeling operation.
    [10" claim-type="Currently amended] 10. The assembly filler is sprayed with at least one filler gun so that during spraying the sprayable composition is sprayed in the direction of the road surface with a spray gun and no final emulsion paint is formed until just before it impinges on the road surface. Fired toward the jet leaving the gun.
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    同族专利:
    公开号 | 公开日
    CZ253197A3|1997-11-12|
    HU9702157A3|2001-04-28|
    NO973567D0|1997-08-01|
    NZ300144A|2000-01-28|
    HU9702157A2|1998-04-28|
    WO1996024640A1|1996-08-15|
    DK0808345T3|2000-01-31|
    AU693314B2|1998-06-25|
    US6207742B1|2001-03-27|
    HU224051B1|2005-05-30|
    BG62779B1|2000-07-31|
    CA2211187A1|1996-08-15|
    RO119889B1|2005-05-30|
    LV11955B|1998-03-20|
    FI973006D0|
    NO316225B1|2003-12-29|
    CZ291759B6|2003-05-14|
    BR9607521A|1997-12-30|
    LV11955A|1998-01-20|
    FI105694B|2000-09-29|
    AU4480196A|1996-08-27|
    ES2135865T3|1999-11-01|
    PL182848B1|2002-03-29|
    RU2196155C2|2003-01-10|
    EP0808345B1|1999-07-07|
    SK283085B6|2003-02-04|
    BG101801A|1998-04-30|
    NO973567L|1997-10-08|
    DK808345T3|
    CN1115365C|2003-07-23|
    FI973006A|1997-10-08|
    GR3031132T3|1999-12-31|
    OA10440A|2001-12-07|
    PL321677A1|1997-12-22|
    JPH10513494A|1998-12-22|
    CN1173890A|1998-02-18|
    EP0808345A1|1997-11-26|
    FI105694B1|
    SK107197A3|1998-01-14|
    FI973006A0|1997-07-15|
    DE59602386D1|1999-08-12|
    AT181946T|1999-07-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1995-02-08|Priority to CH36195
    1995-02-08|Priority to CH361/95-8
    1996-02-05|Application filed by 볼라크 모제스, 플라스티루테 에스.아.
    1998-06-25|Publication of KR19980701768A
    2000-04-05|First worldwide family litigation filed
    优先权:
    申请号 | 申请日 | 专利标题
    CH36195|1995-02-08|
    CH361/95-8|1995-02-08|
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