CN114539939A

CN114539939A - Environment-friendly reflective marking capable of being constructed quickly and preparation method thereof

Info

Publication number: CN114539939A
Application number: CN202210282407.2A
Authority: CN
Inventors: 赵爽; 张会建; 吴荣生
Original assignee: Zhejiang Tongyi Transportation Technology Co ltd
Current assignee: Zhejiang Tongyi Transportation Technology Co ltd
Priority date: 2022-03-22
Filing date: 2022-03-22
Publication date: 2022-05-27

Abstract

The invention provides an environment-friendly reflective label tape capable of being quickly constructed and a preparation method thereof, wherein the reflective label tape comprises a reflective layer, a base belt layer, an adhesive layer and a release layer, the reflective layer, the base belt layer, the adhesive layer and the release layer are sequentially stacked from top to bottom, the thickness of the reflective layer is 0.01 mm-1 mm, and the reflective layer comprises glass beads, high-reflective water-based pigment, water-based paint and functional auxiliary agent; the thickness of the base belt layer is 0.05 mm-2 mm, and the base belt layer comprises a high-performance thermoplastic high polymer material, nano calcium carbonate, paraffin, naphthenic oil petroleum resin and a functional auxiliary agent; the thickness of the adhesive layer is 0.05 mm-2 mm, and the adhesive layer comprises an acrylic block copolymer, SBS, a plasticizer, tackifying resin and a functional auxiliary agent; the release layer comprises release paper or a release plastic film. Solvent adhesive is not used in the production process of the reflective label tape, so that the production process is safer and more environment-friendly; during construction, the release film is directly torn and is pasted on the asphalt pavement, curing is not required to be waited, and the release film is glued for many times, so that the construction is more convenient and rapid.

Description

Environment-friendly reflective marking capable of being constructed quickly and preparation method thereof

Technical Field

The invention relates to a road reflective marking, in particular to an environment-friendly reflective marking capable of being constructed quickly and a preparation method of the reflective marking.

Background

The reflective marking tape is mainly used for road surface indication: such as zebra stripes, center double solid lines, lane lines, text, arrows, etc. It is suitable for various road surfaces and wall surfaces such as asphalt, cement, concrete, marble and the like. The existing road marking, warning marking and the like have the disadvantages of unsafe and environment-friendly production process and construction process, complex steps, long time consumption, high price and cost, and general pain points in the bonding strength of ground such as high-polishing marble, ceramic tile, asphalt and the like.

CN207833866U discloses a method for making a high wear-resistant reflective marking tape, which comprises: the adhesive is formed by sequentially adhering and curing a reflective layer, an adhesive layer, a coating layer, a base material layer, an adhesive layer and a primer layer from top to bottom, wherein a formaldehyde solvent adhesive using oligomeric polyamide is used as the adhesive in the process. The method has the defects of complex manufacturing process, long time consumption, use of solvent adhesive and insecurity and environmental protection;

CN104710720B discloses a substrate of a reflective label tape, and a method for manufacturing the substrate and the reflective label tape: cleaning the pavement to be adhered with the mark, drawing the contour line of the mark pattern by using the mark, painting the adhesive with moderate thickness uniformly on the back of the mark and the contour line of the ground, airing for a certain time after coating, contacting the adhesive layer with fingers to rub the adhesive layer with force, and adhering when the fingers are completely dried without adhesive. The method has complex construction steps and long waiting time, and cannot meet the requirements of rapid, simple and convenient and high-quality road construction;

the method of brushing paint on the ground is easy to wear and fade, has common light reflection effect and shorter service life; in addition, abrasion resistant preformed retroreflective markings successfully developed by 3M corporation in the United states are too expensive to be widely used.

Disclosure of Invention

In order to solve the technical problems, the first purpose of the invention is to provide an environment-friendly reflective label tape which can be quickly constructed, solvent adhesive is not used in the production process, and the production process is safer and more environment-friendly; during construction, the release film is directly torn and is pasted on the asphalt pavement, curing is not required to be waited, and the release film is glued for many times, so that the construction is more convenient and rapid.

The second purpose of the invention is to provide a preparation method of the environment-friendly reflective label tape capable of being constructed quickly.

In view of the above objects, an aspect of the present invention provides an environment-friendly reflective label tape capable of being rapidly constructed, the reflective label tape comprising a reflective layer, a base tape layer, an adhesive layer and a release layer, the reflective layer, the base tape layer, the adhesive layer and the release layer being sequentially stacked from top to bottom, wherein,

the thickness of the reflecting layer is 0.01 mm-1 mm, and the reflecting layer comprises glass beads, high-reflection water-based pigment, water-based paint and functional auxiliary agent;

the thickness of the base belt layer is 0.05 mm-2 mm, and the base belt layer comprises a high-performance thermoplastic high polymer material, nano calcium carbonate, paraffin, naphthenic oil petroleum resin and a functional auxiliary agent;

the thickness of the adhesive layer is 0.05 mm-2 mm, and the adhesive layer comprises an acrylic block copolymer, SBS, a plasticizer, tackifying resin and a functional auxiliary agent;

the release layer comprises release paper or a release plastic film.

Preferably, the high-performance thermoplastic polymer material comprises LDPE or star SBS.

Preferably, the hard segment monomer of the acrylic block copolymer is styrene, and the soft segment monomer is acrylate.

In another aspect of the present invention, there is provided a method for preparing the environment-friendly reflective tape capable of being rapidly constructed, comprising:

preparation of the base tape layer:

adding 20-35 parts by mass of a high-performance thermoplastic polymer material, 0-20 parts by mass of paraffin, 0-20 parts by mass of naphthenic oil and 10-20 parts by mass of petroleum resin into an internal mixer for mixing at the temperature of 80-120 ℃ for about 1 hour, adding 20-40 parts by mass of nano-scale calcium carbonate powder, 0.1-1.0 part by mass of an antioxidant, 0.1-1.0 part by mass of an anti-ultraviolet agent and 0-10 parts by mass of quartz sand into the internal mixer for mixing for about 30 minutes, pouring the materials into a mold, and performing press molding to obtain a sheet-shaped molding base band;

preparing a light reflecting layer:

adding 70-90 parts by mass of high-wear-resistance high-strength water-based paint into a stirring kettle, adding 0.1-1.0 part of high-light-reflection water-based pigment and 0.1-1 part of ultraviolet-resistant agent, and mixing at the normal temperature and pressure and at the rotating speed of 60-120 r/min for 20-30 min to be uniform; selecting one surface of a base band layer as a reflective surface, brushing or blade-coating a mixed water-based paint on the reflective surface, uniformly scattering 10-20 parts of glass beads on the surface of the paint, drying the paint by using a drying tunnel, and rolling and forming the paint after the paint is completely dried;

preparing an adhesive layer and coating the adhesive layer:

adding 15-35 parts by mass of an acrylic block copolymer, 5-15 parts by mass of an SBS elastomer, 15-25 parts by mass of a plasticizer, 10-15 parts by mass of a natural resin and a modified resin thereof, mixing in an internal mixer at the mixing temperature of 140-160 ℃ for 40-70 min, adding 20-30 parts by mass of a petroleum resin, 0-10 parts by mass of a coumarone resin, 1-5 parts by mass of an antioxidant and 1-5 parts by mass of an anti-ultraviolet agent, and continuously mixing in the internal mixer for 30-60 min; adding the mixed hot-melt pressure-sensitive adhesive into a hot-melt adhesive box of a hot-melt adhesive coating machine, setting the temperature of the hot-melt adhesive box to be 160-180 ℃, and installing the previously finished base band coiled material on the coating machine for coating operation; the selected gluing surface is a non-reflective layer of the base band, and the release layer is synchronously compounded on the gluing surface while the coating operation is carried out, and the coating machine is wound at the tail end.

Compared with the prior art, the invention has the beneficial effects that:

solvent adhesive is not used in the production process, so that the production process is safer and more environment-friendly;

the adhesive layer is made of hot-melt pressure-sensitive adhesive mainly made of acrylic block copolymer, the release film is directly torn off during construction, and the adhesive layer is pasted on the asphalt pavement without waiting for solidification and gluing for multiple times, so that construction is more convenient and quicker;

the base band main body material used by the invention is a high-performance thermoplastic polymer material, and has the advantages of stable chemical performance, acid and alkali corrosion resistance, good tensile property, good yellowing resistance and good aging resistance. In addition, compared with the wear-resistant preformed reflective marking of 3M company, the price is lower, and the service life is long;

the glass beads and the reflective pigment are used as reflective materials, and compared with the traditional paint marked lines, the glass beads have a scattering effect on light, the refractive index of the marked lines can be improved, and the reflective effect is better;

the adhesive layer has excellent bonding effect: compared with the traditional hot-melt pressure-sensitive adhesive, the acrylic block copolymer is selected as the main material, and the main chain of the acrylic block copolymer does not have carbon-carbon double bonds, so that the acrylic block copolymer has excellent aging resistance and weather resistance; the hard segment monomer of the acrylic block copolymer is preferably styrene, so that excellent tensile strength and structural strength are provided for the polymer, the soft segment monomer of the acrylic block copolymer is acrylate, so that the acrylic block copolymer has excellent adhesive property for high-polishing ceramic tiles, marbles, asphalt and other difficult-to-adhere pavements, and meanwhile, the SBS elastomer is added, so that the compatibility and adhesive property of the adhesive layer to the base band and the asphalt are improved. In addition, the hot-melt pressure-sensitive adhesive prepared by taking the hot-melt pressure-sensitive adhesive as a main material has double glass transition temperatures, and the glass transition temperature range is-40-100 ℃, so that the hot-melt pressure-sensitive adhesive has excellent high and low temperature performance; the acrylate block copolymer has high adhesion to the base material, the formed molecular level adhesive bonding interface has fewer pore passages compared with the traditional pressure-sensitive adhesive, and water molecules and metal salt ions are less likely to enter the adhesive bonding interface to damage the adhesive bonding strength, so that the acrylate block copolymer has good water resistance and weather resistance.

Detailed Description

The present invention will be further described with reference to the following examples.

It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.

It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.

The embodiment provides an environment-friendly reflective target tape capable of being rapidly constructed, which comprises a reflective layer, a base tape layer, an adhesive layer and a release layer, wherein the reflective layer, the base tape layer, the adhesive layer and the release layer are sequentially stacked from top to bottom,

the release layer comprises release paper or a release plastic film.

As a preferred embodiment, the high-performance thermoplastic polymer material comprises LDPE or star SBS.

In a preferred embodiment, the hard segment monomer of the acrylic block copolymer is styrene and the soft segment monomer is acrylate.

preparation of the base tape layer:

preparing a light reflecting layer:

preparing an adhesive layer and coating the adhesive layer:

Specifically, the method comprises the following steps: examples 1-3 preparation of reflective landmark base band layer:

the raw materials selected in the examples 1-3 are as follows: the low density polyethylene is LD104BR of Exxon Mobil; EVA is a tabbed UE 629; SBS is medium petrochemical 792; the paraffin is Kunlun 58# semi-refined wax; c5 Petroleum resin is dicyclopentadiene of Henghe; the nano calcium carbonate powder is CAN-6600 of Shimianmei conducted in Guangdong province; the quartz sand is British quartz sand with 200 meshes; the antioxidant is German Pasteur Irganox 1010; the UV resistant agent is Pasteur Tinuvin 326, Germany.

Examples 1-3 methods for preparing a base tape:

adding high-performance thermoplastic high-molecular material, paraffin, naphthenic oil and petroleum resin into a mansion Weibull 110L internal mixer, mixing at the temperature of 80-120 ℃ for about 1h, adding nano-scale calcium carbonate powder, an antioxidant, an anti-ultraviolet agent and quartz sand into the internal mixer, and mixing. Mixing for about 30min, pouring the materials into stainless steel molds customized by corresponding customers, and press-molding. A sheet-shaped molded base tape is obtained.

Example 1 base tape layer formulation was:

name (R)	Mass portion of
		Low density polyethylene	25
Paraffin wax	15
		C5 Petroleum resin	15
Nano-grade calcium carbonate powder	40
		Quartz sand	5
Antioxidant agent	0.5
		Anti-ultraviolet agent	0.5

Example 2 base tape layer formulation was:

example 3 base tape layer formulation:

name (R)	Mass portion of
		EVA	10
SBS	25
		Paraffin wax	5
Naphthenic oil	10
		C5 Petroleum resin	10
Nano-grade calcium carbonate powder	35
		Quartz sand	5
Antioxidant agent	0.2
		Anti-ultraviolet agent	0.5

Examples 4-6 preparation of light-reflective layers:

the raw materials selected in the examples 4 to 6: the high-wear-resistance high-strength water-based paint is Wanhua water-based polyurethane dispersoid 8408 with solid content of 60% and British water-based acrylic block copolymer paint T780 with solid content of 60%; the ultraviolet-proof agent is German Pasteur Tinuvin 326; the water-based White pigment is a Pasteur 0022 titanium White paste Dispers White 0022.

Examples 4 to 6 preparation methods: adding the high-wear-resistance high-strength water-based paint into a 100L stainless steel stirring kettle, adding the high-light-reflection water-based pigment and the anti-ultraviolet agent, and mixing at normal temperature and normal pressure at the rotating speed of 60 r/min-120 r/min for 20 min-30 min to be uniform. Selecting one surface of the first prepared base band as a reflective layer, brushing or blade-coating a mixed water-based coating on the reflective surface, uniformly scattering glass beads on the surface of the coating layer, drying the reflective layer by using a drying tunnel, and rolling and molding the base band sheet after the reflective layer is completely dried.

Example 4 the formulation of the reflective layer was:

example 5 the retroreflective layer formulation was:

example 6 the retroreflective layer formulation was:

example 7-9 preparation of adhesive layer:

the raw materials selected in examples 7 to 9:

the acrylic ester block copolymer is M03 of British Innovative materials; the SBS elastomer is medium petrifaction 792; trioctyl phosphate, naphthenic oil and dioctyl phthalate are products of national medicine group, and rosin glyceride and polymerized rosin are products of Guangdong Ke Maolin chemical industry Co., Ltd; the C5 petroleum resin, C9 petroleum resin and coumarone resin are American Isyman products; the antioxidant is German Pasteur Irganox 1010; the UV resistant agent is Pasteur Tinuvin 326, Germany.

The preparation method of the embodiment 7-9 comprises the following steps:

adding the acrylic block copolymer, the SBS elastomer, the plasticizer, the natural resin and the modified resin thereof into a mansion Weibull 110L internal mixer, mixing at the temperature of 140-160 ℃ for 40-70 min, adding the petroleum resin, the coumarone resin, the antioxidant and the anti-ultraviolet agent, and continuously mixing in the internal mixer for 30-60 min. And adding the mixed hot-melt pressure-sensitive adhesive into a glue melting box of the Chinese Taiwan terahertz hot-melt adhesive coating machine, setting the temperature of the glue melting box to be 160-180 ℃, and mounting the previously finished base band coiled material on the coating machine for coating operation. The selected gluing surface is a non-reflective layer of the base band, and the release layer is synchronously compounded on the gluing surface while the coating operation is carried out, and the coating machine is wound at the tail end.

Example 7 the adhesive preparation formulation was:

name(s)	Mass portion of
		Acrylic block copolymer	30
SBS elastomer	10
		Phosphoric acid trioctyl ester	15
Naphthenic oil	5
		Polymerized rosin	15
Maleic anhydride grafted C5 petroleum resin	10
		Coumarone resin	10
Antioxidant agent	3
		Anti-ultraviolet agent	2

Example 8 the adhesive preparation formulation was:

name (R)	Mass portion of
		Acrylic block copolymer	35
SBS elastomer	10
		Dibutyl phthalate	17
Naphthenic oil	5
		Rosin glyceride	15
Maleic anhydride grafted C9 petroleum resin	10
		Coumarone resin	10
Antioxidant agent	3
		Anti-ultraviolet agent	2

Example 9 the adhesive preparation formulation was:

examples 10-12, preparation of reflective landmark base bands with 3 properties:

any of the embodiments in the retroreflective layer 3 set can be combined with any of the embodiments in the base belt layer 3 set to produce retroreflective landmark base belts with different properties. 3 groups of samples were arbitrarily selected and confirmed as examples 10 to 12.

Examples 10 to 12 preparation methods:

a base tape was prepared according to the method described in examples 1 to 3, and a light reflecting layer was formed on the base tape by the method described in examples 4 to 6.

Formulation of example 10:

the base band formula is example 1, and the reflective layer formula is example 4;

formulation of example 11:

the base band formula is example 1, and the reflective layer formula is example 5;

formulation of example 12:

the base band formula is example 1, and the reflective layer formula is example 6;

example 13-15 preparation of retroreflective landmark adhesive tapes of 3 Properties:

any embodiment in the 3 groups of the reflective layer, any embodiment in the 3 groups of the base band layer and any group in the 3 groups of the adhesive layer can be freely combined to produce the finished reflective landmark adhesive tape with different performances. At present, 3 groups are randomly selected for testing as follows;

examples 13 to 15 preparation methods:

preparing a base tape according to the method of the above embodiments 1 to 3, and preparing a light reflecting layer on the base tape according to the method of the above embodiments 4 to 6; with reference to the methods described in examples 7-9, adhesives were prepared and size coated on top of the retroreflective base tape.

Formulation of example 13:

the base band formula is embodiment 1, the reflective layer formula is embodiment 5, and the adhesive formula is embodiment 7;

formulation of example 14:

the base band formula is embodiment 1, the reflective layer formula is embodiment 5, and the adhesive formula is embodiment 8;

formulation of example 15:

the base tape formulation is example 1, the retroreflective layer formulation is example 5, and the adhesive formulation is example 9.

The test method comprises the following steps:

and (3) thickness testing: selecting 5 points by a thickness gauge, testing and taking an average value;

testing the flexibility of the base band: selecting a round bar with the diameter of more than 3mm to wind the base band for one circle, and if the winding process is soft and easy to bend, the base band is qualified;

and (3) testing the water resistance of the base band: soaking the base band in tap water for 72h at room temperature, observing the state of the base band after being taken out, and if the base band does not have obvious phenomena of cracking, fading, peeling and the like, the base band is qualified;

and (3) testing the high and low temperature resistance of the baseband: placing the base band in a circulating oven capable of automatically adjusting the temperature, setting the temperature of-20-60 ℃ as a temperature adjusting period, setting the time of one period to be 4 hours, circulating for 3 periods, taking out the base band, and determining the base band to be qualified if the phenomena of obvious cracking, fading, peeling and the like do not exist;

testing longitudinal tensile strength of a base band: HG/T3849-2008 is adopted;

and (3) testing the anti-skid and light-reflecting performance and water resistance of the base band: the same as the base band water resistance test method;

testing the heat resistance of the anti-skid and light-reflecting performance of the base band: same as the baseband heat resistance test method;

and (3) testing the skid resistance of the anti-skid and light-reflecting performance of the base band: the GB/T16311-2009 is adopted, and the product is qualified when the BPN is more than 45;

testing the dry initial retroreflection brightness coefficient of the base band antiskid and light reflection performance: GB/T21383-^-2·lx^-1；

Viscosity retention: GB/T2792-;

180 ° peel strength: adopting GBT 31125-2014, selecting an asphalt slab prepared by asphalt pavement pressing and synthesizing and an adhesive tape coated in the embodiment as a test base material;

testing the initial viscosity of the ring: the initial adhesion test of GB31125-2014 is adopted, and the test material is the adhesive tape coated in the embodiment;

and (3) hot shearing of the structural adhesive: according to HG/5052-2016, an asphalt plate prepared by laminating an asphalt pavement and the adhesive tape coated in the embodiment are selected as test substrates;

testing the water resistance of the reflecting marking adhesive tape: and (3) bonding the light-reflecting marking adhesive tape to the surface of the stainless steel plate to prepare a sample, placing the sample in water, soaking the sample for a period of time, taking the sample out, and respectively testing the shear strength and the 180-degree peel strength.

And (3) testing results:

1. and base band performance test results:

2. testing the anti-skid and light-reflecting performance of the base band:

3. the basic performance test result of the reflecting marking adhesive tape is as follows:

4. the water resistance test result of the reflecting marking adhesive tape is as follows:

in conclusion, the production process of the embodiment does not use solvent adhesive, so that the production process is safer and more environment-friendly;

Although the embodiments of the present invention have been shown and described, it is understood that the above embodiments are illustrative and not restrictive, and that those skilled in the art can make changes, modifications, substitutions and alterations to the above embodiments without departing from the spirit and scope of the invention, and any simple modifications, equivalent changes and modifications to the above embodiments according to the technical spirit of the present invention are still within the technical scope of the present invention.

Claims

1. An environment-friendly reflective label tape capable of being rapidly constructed is characterized by comprising a reflective layer, a base tape layer, an adhesive layer and a release layer, wherein the reflective layer, the base tape layer, the adhesive layer and the release layer are sequentially stacked from top to bottom,

the release layer comprises release paper or a release plastic film.

2. The environment-friendly reflective sign tape capable of being rapidly constructed according to claim 1, wherein the high-performance thermoplastic polymer material comprises LDPE or star SBS.

3. The environment-friendly reflective marker band capable of being rapidly constructed according to claim 1, wherein the hard segment monomer of the acrylic block copolymer is styrene, and the soft segment monomer is acrylate.

4. A method for preparing the environment-friendly rapidly-constructed reflective marking tape according to any one of claims 1 to 3, comprising:

preparation of the base tape layer:

adding 20-35 parts by mass of a high-performance thermoplastic polymer material, 0-20 parts by mass of paraffin, 0-20 parts by mass of naphthenic oil and 10-20 parts by mass of petroleum resin into an internal mixer, mixing at 80-120 ℃ for about 1 hour, adding 20-40 parts by mass of nano-scale calcium carbonate powder, 0.1-1.0 part by mass of an antioxidant, 0.1-1.0 part by mass of an anti-ultraviolet agent and 0-10 parts by mass of quartz sand into the internal mixer, mixing for about 30 minutes, pouring the materials into a mold, and press-molding to obtain a sheet-shaped molding base band;

preparing a light reflecting layer:

preparing an adhesive layer and coating the adhesive layer: