KR20120043351A - Method of preparing photoluminescent retroreflective bead for road sign in the rain - Google Patents

Abstract

PURPOSE: A method for preparing a photoluminescent reflective bead for a road sign is provided to secure night visibility and to prevent drop-out of bead. CONSTITUTION: A core bead and binder are mixed in a container. A fine bead and phosphorescent pigment are mixed in the container and are heated. The binder includes unsaturated ester resin or acrylic resin, reactive monomer, hardener, and reactive catalyst.

Description

Method of preparing photoluminescent retroreflective bead for road sign in the rain}

The present invention relates to a method for manufacturing a road marking photoluminescent reflective bead, and more particularly, to a core label, a binder, a fine bead and a photoluminescent pigment into the container, the mixing and heating step of the photoluminescent reflective bead It relates to a manufacturing method.

Currently, glass beads are widely known as industrial materials in various industrial fields, and typical applications of glass beads commonly encountered in daily life are widely used in traffic safety products such as lanes on road signs and roads.

Background Art Conventionally, a technique of incorporating glass beads having a small diameter into a product for road marking paints and manufacturing them and spraying beads having a relatively large diameter on a coating film during field construction are widely used. This is a product and construction method using the principle of reflex reflection of beads to ensure night visibility by exposing the surface of the beads to the air.

However, the conventional method has a problem that it is difficult to identify the lane because the light is not smoothly irradiated from the vehicle headlights in rainy weather. Excessive bead exposure also weakens the cohesion between the large diameter beads and the paint layer, leading to more bead dropouts due to friction with the car tires, resulting in nighttime visibility falling off over time.

In order to solve this problem, products with small diameter glass beads have been introduced. However, it is difficult to express sufficient retroreflective properties. Also, a protruding construction method is used to improve visibility at night and in rainy weather, but beads are still rainy. Water film is formed on the surface, making it difficult to express sufficient retroreflective function.

In addition, there is a method of adding metal powder, Mica, pearl, etc. as an additive for improving the brightness, but the improvement using these raw materials implies the limitations of lowering the physical properties and compatibility of the paint.

One object of the present invention for solving the problems of the prior art described above is to provide a method of manufacturing a photoluminescent reflective bead for road marking that can ensure night visibility in rainy weather.

Another object of the present invention is to provide a method of manufacturing a photoluminescent reflective bead for road marking that can be maintained for a long time because the beads do not fall even after long use.

One aspect of the present invention for achieving the above object is

Mixing the core beads and the binder in a container; And mixing and heating microbeads and photoluminescent pigments into the container, and the binder relates to a method for preparing photoluminescent reflective beads for road markings comprising an unsaturated ester resin or an acrylic resin, a reactive monomer and a reaction catalyst.

The photoluminescent reflective bead for road marking produced by the present invention can ensure visibility at night even in rainy weather, and also the bead does not drop even after long use, so that the retroreflective performance can be maintained for a long time.

The manufacturing method according to the present invention includes the steps of mixing the core bead and the binder in a container, and mixing and heating the fine bead and the photoluminescent pigment in the container, wherein the binder is an unsaturated ester resin or an acrylic resin, a reactive monomer And a reaction catalyst.

Hereinafter, the present invention will be described in detail.

Core beads  And mixing step of the binder

The step is to mix the core bead and the binder into a container. The binder is coated on each core bead outer surface by the step. There is no restriction on the mixing method of the core beads and the binder. In one example, the container may be rotated to coat the binder on the core beads.

In this step, the mixing temperature in the vessel may be in the range of 15 to 50, preferably 25 to 30 ℃.

With fine beads Luminous pigment  Mixing and heating stage

The step is a step of mixing and heating the photoluminescent pigment and the fine bead in the container after coating the binder on the outer surface of the core bead. In this step, the microbeads and the phosphorescent pigments are partially embedded in the binder and fixed.

In this step, the heating temperature in the vessel may be in the range of 40 to 100 ℃ preferably 70 ~ 80 ℃.

In this step, the mixing time may range from 1-2 hours.

In the present invention, the binder 3 to 10 parts by weight, preferably 5 to 7 parts by weight, the fine bead 3 to 10 parts by weight, preferably 5 to 7 parts by weight and the photoluminescent pigment 3 based on 100 parts by weight of the core bead 10 parts by weight, preferably 5 to 10 parts by weight.

When the content of the binder exceeds 10% by weight in the core bead 100, the microbeads do not adhere to the core and the microbeads are entangled with each other. When using less than the above-mentioned photoluminescent pigment content, the photoluminescent performance is lowered, and in the case of excessive use, only the photoluminescent pigment of the indicated content is attached and the remainder is eliminated, thereby lowering bead adhesion efficiency.

The present invention may further include mixing the binder after the mixing and heating step, and then mixing and heating the microbead and the phosphorescent pigment. By this step, it is possible to effectively prevent the falling of the microbead attached to the core bead primarily.

In addition, since the resin layer becomes thick when coated twice, the mechanical strength between the bead layers is increased and fine beads can be evenly distributed than when coated once.

In the additional coating of the second step, the method is based on 100 parts by weight of the core beads 3 to 10 parts by weight, preferably 5 to 7 parts by weight, 3 to 10 parts by weight of the fine beads, preferably 5 to 7 A part by weight and the phosphorescent pigment 3 to 10 parts by weight, preferably 5 to 7 parts by weight may be further included.

Core beads

Core beads usable in the present invention can be used glass, transparent plastics and the like. The core bead has a refractive index of 1.5 to 1.9. It is preferable that it is spherical particle whose specific gravity is 2.4 or more. The core bead may be elliptical but preferably have no acute protrusions on the particles. In addition, it is preferable that the core bead is not opaque or foreign matter is mixed.

The particle size of the core bead is 600-1200 μm, preferably 800-1000 μm, and when the core bead is a large diameter core bead, the particle size is 1-10 mm, preferably 3-5 mm.

bookbinder

The binder includes an unsaturated ester resin or an acrylic resin, a reactive monomer, a curing agent and a reaction catalyst. The binder is excellent in bead adhesion, high hardness, high gloss, chemical resistance, weather resistance.

The unsaturated ester resin or acrylic resin used in the present invention is a binder resin, and after coating and curing the core bead, it adheres closely to the surface of the core bead so as to remain for a long time, so that fine beads, photoluminescent pigments, etc. are firmly maintained. do.

The unsaturated ester resin can be prepared by polymerized modification of glycol, phthalic acid and methyl methacrylate (MMA). Preferably, glycols having two or more functional groups (Glycol), phthalic acid (Phthalic acid) having two functional groups, and methyl metal acrylate (Methyl metacrylate, MMA) may be obtained by polymerization. The MMA is not environmentally harmful and has excellent elasticity and crack resistance.

The molecular weight of the unsaturated ester resin is 3,000 to 10,000, preferably 6,000 to 7,000. When the molecular weight is less than 3,000, the hardness is high, cracking may occur, and when it exceeds 10,000, it is difficult to control workability due to high viscosity.

The acrylic resin is acrylonitrile, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, acrylic acid, 2-hydroxyethyl (meth) acrylate, methyl (meth) acrylate, styrene monomer, glycy What copolymerized monomers, such as dill (meth) acrylate, isooctyl acrylate, and stearyl methacrylate, can be used.

The acrylic resin has a molecular weight of 50,000 to 60,000, a viscosity of 200 to 1000, preferably 300 to 500 cps (40% in toluene).

As the reactive monomer, one or more selected from methyl metal acrylate (MMA), 2-hydroxyethyl methacrylate (2-Hydroxyethyl metacrylate) and BAM (Butyl acrylate monomer) may be used. In the present invention, the MMA in the reaction monomer can improve gloss, hardness, and weather resistance, and 2HEMA helps to improve hardness and acid resistance, and in the case of BAM, to improve flexibility and adhesion.

The reactive monomer may be 25 to 350 parts by weight based on 100 parts by weight of the unsaturated ester resin or acrylic resin. Curing occurs better in this range. When the reactive monomer is used with the acrylic resin, preferably 100 to 350 parts by weight, and most preferably 150 to 250 parts by weight, based on 100 parts by weight of the acrylic resin. When the reactive monomer is used together with the unsaturated ester resin is preferably 25 to 80, most preferably 40 to 60.

In the present invention, DMA (dimethyl aniline), Co-octate (cobalt octanate), DMPT (N, N-Dimethyl-p-toluidine) may be used as the reaction catalyst. If the reaction catalyst is less than 0.1 parts by weight, the curing time is too late, the working time is long, and the surface is completely hardened, and there is a problem of contamination, and if it is more than 3 parts by weight, the gelling phenomenon is rapidly generated during product storage. As heat progresses, self-heating occurs relatively rapidly due to rapid hardening, which may cause shrinkage and color change.

The curing agent used in the present invention may be granular benzoyl peroxide (hereinafter BPO) or CABPO. The CABPO is in the form of a liquid paste in which the BPO is dispersed in dibutyl phthalate (DBP). The DBP also serves to make the coating film by acting as a plastic film.

It is preferable that the BPO contained in the CABPO is 30 to 80% by weight. The BPO may be in the form of granules (granule) formed in a particle size of 0.01 ~ 0.3mm size. If the particle size of the BPO is less than 0.01mm, it does not flow in the line of the coating equipment, clogged by the surrounding moisture, there is a problem that the solubility is significantly reduced when it exceeds 0.3mm.

The curing agent may be used 10 to 30 parts by weight based on 100 parts by weight of the unsaturated polyester resin. Outside the above range, there is a problem that partial curing or curing is shortened.

In the binder of the present invention, a small amount of a volatile inhibitor (wax) and a storage stabilizer (HQ) may be added.

Fine beads

Microbeads usable in the present invention may be used glass, transparent plastics, 0000 and the like. The fine beads are preferably BaO-ZnO-TiO ₂ And GLASS, and the refractive index is in the range of 1.9 to 2.2 can be used. The size of the fine beads is 20 ~ 100㎛, preferably 45 ~ 90㎛. On the other hand, when the core bead is a large diameter, the size of the fine bead used here may be in the range of 100 ~ 400㎛.

Phosphorescent Pigment

Photoluminescent pigments usable in the present invention are zinc sulfide: copper doped (Zinc Sulfide Copper Doped (ZnS: Cu)), aluminum oxide, aluminum oxide, calcium oxide, strontium oxide, europium oxide. (Europium Oxide), boron oxide (Boron Oxide), alkaline earth aluminate, alkaline earth silicate may be used, preferably ZnS: Cu may be used.

In another aspect, the present invention comprises the steps of mixing the core bead and the binder in a container; Putting a fine bead and a photoluminescent pigment into the container, and mixing and heating the binder, wherein the binder includes an epoxy resin, a melamine resin, and a solvent; It is equipped with the hardening | curing agent containing an amine resin and a solvent, It is characterized by the weight ratio (weight ratio) of the said main body and hardening | curing agent being 100: 40-100.

The method may refer to the above description. However, binder resin can be used including a main body, a hardening | curing agent, and a solvent.

As the said subject, an epoxy resin, a melamine resin, and a solvent can be mixed and used.

Bisphenol-based, ortho-Cresol novolac-based, polyfunctional epoxy, amine-based epoxy, heterocyclic-containing epoxy, substituted epoxy, naphthol-based epoxy may be used as the epoxy resin. It is preferable that the said epoxy equivalent (g / eg) is 450-500 range.

In the present invention, the melamine resin is used together with the epoxy resin, because the melamine resin improves the hardness and adhesion of the epoxy resin.

As said melamine resin, ML-707-60 (Ahae Co., Ltd.) can be used. The content ratio (weight ratio) of the epoxy resin and the melamine resin is 100: 2 to 10.

An amine resin may be used as the curing agent, and examples thereof may include tertiary amines such as benzyldimethylamine, triethanolamine, triethylenediamine, dimethylaminoethanol, and tri (dimethylaminomethyl) phenol.

There is no particular restriction on the solvent. As an example, butanol and xylene can be used.

The ratio of the subject to the curing agent may be in the range of 100: 40 to 100, preferably 100: 50 to 60.

Example  One

Core glass beads (approximately 800 μm particle size, sized by spraying beads used) and binder 1 (see Table 1 below for binder composition) were put in a mixing container in a 100: 5 weight ratio, and the containers were rotated and mixed. Subsequently, 5 parts by weight of fine glass beads (Union, 20-100 μm) and 5 parts by weight of photoluminescent pigment (Hyundai Chemical GSS) were added to a mixing vessel and heated at 80-100 ° C. for about 1 hour. Reflective beads were prepared.

Example  2

It was carried out under the same conditions as in Example 1 except that binder 2 (binder composition is used in Table 1 below) instead of binder 1.

Example  3

The binder was added to the photoluminescent reflecting beads obtained in Example 1 at a weight ratio of 5 (relative to 100 parts by weight of the core beads used in Example 1) and mixed. Subsequently, 5 parts by weight of the fine glass beads and 5 parts by weight of the photoluminescent pigment were added to the mixing vessel with respect to 100 parts by weight of the core glass beads used in Example 1, followed by heating at 80 to 100 degrees for about 1 hour to prepare the photoluminescent reflection beads.

Example  4

The same process as in Example 3 was carried out except that the photoluminescent reflecting beads obtained in Example 2 were used.

Example  5

It carried out under the same conditions as in Example 1 except that the core glass size was 3 to 5 mm and the fine bead size was 20 to 100 μm.

Example  6

It was carried out under the same conditions as in Example 1 except for preparing the main agent and the curing agent as shown in Table 2 and then mixing them with a binder.

Comparative example  One

It carried out except having used the urethane type resin instead of the binder 1 in Example 1.

Binder 1 Binder 2 Acrylic resin
(Neocryl B-725) 100 - Unsaturated ester resin
(SR-S-3000) - 100 Reactive monomo
(MMA) 153.8 35 2-HEMA 28 - BAM - 18 Reaction Catalyst (DMPT) 0.6 - DMA (N, N-Dimethyl aniline) - 1.8 wax 2.8 - Storage Stabilizer (H.Q) 0.3 0.18 Cobalt Octoate 8% - 0.72 BPO 15 15

subject Hardener Epoxy resin
(YD-011X75) 53.3 - Epoxy resin
(YD-128) 7.5 - Melamine resin
(ML-707-60) 3.75 - Amine resin
(good mide 5022X70) - 35.4 Reaction accelerator
(Hiescat-54k) - 0.6 solvent 35.45 14

Experiment 1: Wear resistance  Test

After dropping the photoluminescent reflecting beads of Examples 1 to 6 and Comparative Example 1 on the 400um coating film of the company's road (oil / water) coating products, the bead drop rate was measured through a taber type abrasion test, which is a KS M 6080 road marking paint test method. It was confirmed and shown in Table 3.

Revolutions Comparative Example 1 Example 3 Remarks 50 times 150mg / 50 times 120mg / 50 times 100 times 260mg / 100 times 200mg / 100 times

Experiment 2

In order to measure the luminance in the coating film, the product was applied to one kind of dry white product for road marking (film thickness: 400㎛) and sprayed at 300g / m 2 and measured with a luminance meter, and the results are shown in Table 4.

(mcd / ㎡Lux) KS2 Bead Example 3 When drying 118-120 500-550 Rain 100-120 200-250

※ In the case of rain, the luminance measurement is a European standard.Pure clear water at 0.3m height to make the entire surface of the measurement area saturated, and then measure the luminance in the wet state after 60 ± 5 seconds.

Referring to Table 3, it can be confirmed that Example 3 has a dropout rate of about 20 to 25% less than that of Comparative Example 1 and thus has excellent wear resistance.

In addition, referring to Table 4, it can be seen that Example 3 is about 2 to 5 times better in brightness than KS2 bead, which is a standard standard condition currently used in general.

In the above, preferred embodiments of the present invention have been described in detail, but these are merely for the purpose of explanation and the scope of protection of the present invention is not limited thereto.

Claims (14)

Mixing the core beads and the binder in a container;
Mixing and heating microbeads and photoluminescent pigments into the container, wherein the binder includes unsaturated ester resins or acrylic resins, reactive monomers, curing agents, and reaction catalysts. Manufacturing method. Mixing the core beads and the binder in a container;
And mixing and heating microbeads and phosphorescent pigments in the container, wherein the binder is
The subject containing an epoxy resin, a melamine resin and a solvent;
A curing agent comprising an amine-based resin and a solvent, wherein the weight ratio of the main agent and the curing agent is 100: 50 to 60. The method according to claim 1 or 2, wherein the method further comprises the step of mixing the binder further into the container after the heating step;
And adding the fine beads and the phosphorescent pigment into the container and mixing and heating the fine beads and the phosphorescent pigment. The method according to claim 1 or 2, wherein the method comprises 3 to 10 parts by weight of the binder, 3 to 10 parts by weight of the fine beads and 3 to 10 parts by weight of the photoluminescent pigment based on 100 parts by weight of the core beads. The manufacturing method of the photoluminescent reflective bead for road marking. The method of claim 3, wherein the method further comprises 3 to 10 parts by weight of the binder, 3 to 10 parts by weight of the fine beads and 3 to 10 parts by weight of the photoluminescent pigment based on 100 parts by weight of the core beads. Method for producing photoluminescent reflective beads for road markings. According to claim 1, wherein the binder is 100 parts by weight of unsaturated ester resin or acrylic resin, road markings comprising 25 to 350 parts by weight of reactive monomer, 10 to 30 parts by weight of curing agent and 0.1 to 3 parts by weight of reaction catalyst. Method for producing photoluminescent reflective beads. The method of claim 1, wherein the reactive monomer is one or more selected from methyl methacrylate (MMA), 2-hydroxyethyl methacrylate (2-Hydroxyethyl methacrylate), BAM (Butyl acrylate monomer) The manufacturing method of the photoluminescent reflective bead for a label. The method of claim 1, wherein the unsaturated ester resin is a resin modified by polymerization of glycol, phthalic acid and methyl methacrylate (MMA), the weight average molecular weight of 3,000 ~ 10,000, characterized in that Manufacturing method. The method of claim 1, wherein the acrylic resin has a weight average molecular weight of 50,000 to 60,000. The method of manufacturing a photoluminescent reflective bead for road marking according to claim 1 or 2, wherein the core bead has a size of 800 to 1000 m. The method of manufacturing a photoluminescent reflective bead for road marking according to claim 10, wherein the fine bead has a size of 20 to 100 µm. The method of manufacturing a photoluminescent reflective bead for road marking according to claim 1 or 2, wherein the core bead has a size of 3 to 5 mm. The method of manufacturing a photoluminescent reflective bead for road marking according to claim 12, wherein the fine bead has a size of 100 to 400 mu m. A road marking article comprising a photoluminescent bead prepared according to claim 1.