KR20200110515A - Packing material for slip prevention Packing material using resin composition - Google Patents

Abstract

The present invention provides a resin composition for a slip prevention packing material, comprising: 100 parts by weight of a main material including a mixture of a methyl methacrylate (MMA) monomer and a polymethyl methacrylate (PMMA) resin; 10 to 40 parts by weight of a reactive monomer; 40 to 60 parts by weight of non-slip material including at least one component of silica sand and a metal oxide; and 1 to 10 parts by weight of rocky fibers. The non-slip packaging material prepared by using the composition has very excellent slip prevention properties as well as abrasion resistance, durability and weather resistance.

Description

Packing material for slip prevention Packing material using resin composition}

The present technology is a technology related to road pavement, specifically, a technology in the field of a pavement resin composition for preventing slipping.

In general, anti-slip packaging materials are constructed by using epoxy and MMA-based organic compounds as a binder and mixing silica sand, which is a non-slip material. These anti-slip packaging materials are excellent in wear resistance, chemical resistance, and light resistance, and have the advantage of being able to express a variety of colors. The phenomenon of breaking and peeling of the anti-skid packaging material frequently occurs due to passage and external impact.

In addition, the anti-slip material used in the existing crosswalks and walkways has a problem in that the thickness of the coating film is thin, so that the durability is low, and the service life is short, which causes excessive maintenance costs. In addition, due to low impact resistance, adhesion to the road surface, and low-temperature flexibility, cracks are frequently generated due to repeated vehicle operation and the adhesion is weak, resulting in a problem that the anti-slip packaging material is removed and peeled off.

Accordingly, the problems of the anti-slip surface treatment material (raised, cracked, cracked, low slip resistance, etc.) are improved through the high-adhesive binder composition and the anti-slip material optimization design process to reduce the braking distance of the vehicle on the road surface, and within the school zone or silver zone. There is an urgent need to develop an anti-skid packaging composition to reduce the occurrence of slipping safety accidents occurring in pedestrian paths.

In general, the anti-skid packaging material is the most widely used method of construction by adding a curing agent, BPO (benzoyl peroxide), using MMA resin with excellent adhesion strength and fast curing speed. MMA resin binder contains pigments (red, black, blue, etc.) to visually distinguish that the packaging material is installed, and non-slip materials (silica sand, alumina, steel slag, etc.) to impart anti-slip performance. This is a technology that solves the problem of traffic congestion since it is cured after forming a coating film on the road surface, so that vehicle traffic can resume in a short time.

Existing non-slip packaging materials using MMA resin alone have various defects such as poor mixing ratio of hardener, surface lift due to shrinkage of packaging material due to rapid exothermic reaction due to curing of binder, and decrease in adhesion strength of packaging materials due to excessive use of fillers. Has become. In particular, due to the low viscosity of the pavement, the binder flows down from the slope of the road, difficulty in forming a certain thickness of the coating, and the slipping phenomenon of the non-slip material occurs. It has a technical problem that occurs.

In addition, Korea's climate is a high temperature and high humidity environment in summer and a low temperature dry environment in winter, and the temperature change on the surface of concrete and ascon is -20~60℃, which is exposed to very extreme environments. However, typical MMA and epoxy resin binders have a high and narrow glass transition temperature (Tg) area, which causes the anti-slip packaging material to be lifted and peeled off due to the difference in thermal expansion coefficient from the base body. Surface cracks are occurring due to impact.

The object of the present invention is an invention conceived to solve the above problems, and can be applied to various temperature changes by securing slip resistance, abrasion resistance, weather resistance, high adhesion performance, and securing a wide and low glass transition temperature (Tg) range. It is to provide a resin composition for a non-slip packaging material in the form of a fast curing reactive resin as possible.

Another object of the present invention is to provide a road pavement material capable of constituting a region of a road surface by curing the composition to be formed.

The non-slip packaging material resin composition according to an embodiment of the present invention comprises 100 parts by weight of a main substance consisting of a mixture of a methyl methacrylate (MMA) monomer and a polymethyl methacrylate (PMMA) resin, 10 to 40 parts by weight of a reactive monomer, and silica sand And 30 to 60 parts by weight of a non-slip material including at least one component of metal oxide, and 1 to 10 parts by weight of rocky fibers.

Examples of the reactive monomer include 2-ethylhexyl acrylate (2-EHA), 2-hydroxyethyl acrylate (2-HEA), 2-hydroxyethyl methacrylate (2-HEMA), and n-butyl acrylate (n -BA, acrylic acid (AA), methacrylic acid (MAA), vinyl acetate, acrylamide, glycidyl methacrylate (GMA), and the like may be used.

The PMMA resin may be mixed with the MMA monomer in a form melted in the MMA monomer so as to have a weight of 10 to 30% based on the weight of the MMA monomer.

As the metal oxide, aluminum oxide or titanium oxide may be used.

Basalt fiber may be used as the rocky fiber, and the basalt fiber is used in the form of a chop-shaped section having a length of 4 mm or less.

The anti-slip packaging material resin composition may further include an adhesion enhancer to improve adhesion to the road surface, and as the adhesion enhancer, EVA, a rosin ester compound, a rosin ester acid compound, an acrylate polyester compound, etc. It may be, and may be used so as to be from 05 to 5 parts by weight based on 100 parts by weight of the subject.

The non-slip packaging material resin composition may further include 15 to 25 parts by weight of filler components such as aerosol, calcium carbonate, and meerschaum.

Another object of the present invention is to provide a non-slip packaging material comprising a cured product formed by curing the above-described non-slip packaging material resin composition by a curing reaction under the addition of a curing agent, and at least a part of the rocky fiber is exposed to the surface of the packaging material. will be.

The road surface constructed by the resin composition for anti-slip packaging material according to the present invention is excellent in resistance to slip, abrasion resistance, and adhesion, and excellent durability against various climate changes, especially temperature changes. It can maintain homeostasis such as anti-slip performance and surface smoothness. In addition, the composition can be applied universally even in climatic regions having extreme environments.

In addition, according to the composition, it can be cured in a short time, thereby maximizing the construction efficiency of road construction.

On the other hand, in the case of the packaging material formed by the composition, rocky fibers such as basalt are included, and thus incineration is possible and thus has an advantageous advantage in terms of environment.

1 is a cross-sectional view conceptually showing a cross-section of a non-slip packaging material according to an embodiment of the present invention.
2 is a graph showing the results of FT-IR analysis after curing the MMA/PMMA binder.
3 is a graph showing the results of FT-IR analysis after curing the MMA/BA/2-EHA/AA/vinyl acetate binder.
4 and 5 are graphs showing DSC analysis results after curing of the MMA/PMMA binder and DSC analysis results after curing of the MMA/PMMA/BA/2-EHA/AA/vinyl caetate binder, respectively.
6 and 7 are graphs showing tensile strength test results at room temperature and low temperature (-20°C), respectively.

Hereinafter, a resin composition for an anti-slip packaging material according to an embodiment of the present invention will be described in detail with reference to the accompanying drawings.

The non-slip packaging material resin composition according to an embodiment of the present invention comprises 100 parts by weight of a main substance consisting of a mixture of a methyl methacrylate (MMA) monomer and a polymethyl methacrylate (PMMA) resin, 10 to 40 parts by weight of a reactive monomer, and silica sand And 30 to 60 parts by weight of a non-slip material including at least one component of metal oxide, and 1 to 10 parts by weight of rocky fibers.

The resin composition, as a subject serving as a binder, includes 100 parts by weight of a mixture of a methyl methacrylate (MMA) monomer and a polymethyl methacrylate (PMMA) resin.

By adding PMMA resin powder, heat stabilizer, and other additives to the MMA monomer and melting at 70 to 80° C. for about several hours, the MMA/PMMA subject can be prepared. As such, preparing the subject composition through a preemptive heating and melting process is to induce a rapid curing reaction at room temperature and minimize exothermic reactions during construction.

The PMMA resin powder is used to be 10 to 30% by weight based on the weight of the MMA monomer.

The composition is a thermoplastic mixture and contains a reactive monomer. The reactive monomer is included in order to secure low temperature flexibility of the packaging material by reducing the glass transition temperature (Tg) of the non-slip packaging material. Due to the high glass transition temperature (Tg) of the existing MMA binder, defects due to breakage and lifting of the packaging material frequently occur due to the impact load of the vehicle passage under low temperature conditions. In general, when the strength of the anti-slip packaging material increases, the tensile strength increases, but the elongation rate decreases, causing the packaging material to be destroyed by an external impact. On the other hand, even if the tensile strength is slightly reduced, it maintains a high adhesion to the base surface, and thus shows a tendency to secure more excellent durability.

Therefore, the functional monomer is included in order to improve the low temperature flexibility and adhesion of the composition.

As the reactive monomer, 2-ethylhexyl acrylate (2-EHA), 2-hydroxyethyl acrylate (2-HEA), 2-hydroxyethyl methacrylate (2-HEMA), n-butyl acrylate ( n-BA, acrylic acid (AA), methacrylic acid (MAA), vinyl acetate, acrylamide, glycidyl methacrylate (GMA), etc. The monomer may be used alone in some cases. It can be mixed and used in various combinations for designing composition characteristics having various glass transition temperatures.

The reactive monomer may be included in an amount of 10 to 40 parts by weight relative to 100 parts by weight of the subject, and the amount of the reactive monomer may be variously changed according to the glass transition temperature of the subject and the type of the monomer. Furthermore, the usage amount can be optimally designed in consideration of the specificity of the construction area and the condition of the floor.

Silica sand, metal oxide, etc. may be used as the non-slip agent, and aluminum oxide and titanium oxide may be used as the metal oxide. The non-slip agents may be used alone or in combination of different types. The non-slip material may improve slip resistance and abrasion resistance by controlling the content of each type and size. In practice, the anti-slip performance is determined by the type, particle size and settling stability of the non-slip material. The non-slip material is used so as to be 30 to 60 parts by weight based on 100 parts by weight of the subject. When the content of the non-slip material is less than 30 parts by weight, the non-slip material is not evenly distributed on the surface of the packaging material, so that it cannot exhibit uniform anti-slip properties.On the other hand, when the content exceeds 60 parts by weight, agglomeration of the non-slip material occurs. As a result, the uniformity of the sliding characteristics cannot be ensured.

In order to secure the sedimentation stability of the non-slip material, the packaging material resin composition of the present invention contains rocky fibers. In addition to rocky fibers, glass fibers may be used in parallel. As the rocky fiber, basalt fiber may be used. This inorganic fiber-type anti-settling material not only prevents the sedimentation of the non-slip material with a high specific gravity, but also prevents abrasion of the packaging material by being exposed to the surface of the non-slip packaging material, and increases the frictional force with the automobile tire to shorten the braking distance. In addition, the inside of the anti-slip packaging material is reinforced to form a more dense structure of the binder, thereby preventing the occurrence of microcracks due to external impacts and changes in the coefficient of thermal expansion.

It is preferable that the rocky fiber such as the basalt fiber and the additionally included glass fiber are chop-shaped section fibers having a length of 4 mm or less.

1 is a cross-sectional view conceptually showing a cross-section of a non-slip packaging material according to an embodiment of the present invention.

Referring to FIG. 1, in the non-slip packaging material 100 according to an embodiment of the present invention, the non-slip material 120 is uniformly dispersed in the cured binder resin 110. The non-slip material 120 is distributed not only inside the packaging material 100 but also on the surface thereof, thereby inducing non-slip characteristics of the packaging material 100. The rocky fiber or glass fiber 130, such as basalt fiber, prevents the sedimentation of the non-slip material 120 to achieve uniform dispersion of the non-slip material 12. In addition, the rocky fiber 130 may be partially exposed to the surface of the packaging material 100, and thus may play a role of reinforcing non-slip properties by itself.

The non-slip packaging material resin composition may include an adhesion enhancer for improving adhesion to the road surface and a curing accelerator for promoting curing.

As the adhesion enhancer, EVA, a rosin ester compound, a rosin ester acid compound, and an acrylate polyester compound may be used. The content of the adhesion enhancer is preferably 05 to 5 parts by weight based on 100 parts by weight of the subject. If the content of the adhesion enhancer is less than 05 parts by weight, it does not affect the adhesion and curing reaction of the binder. On the other hand, if it exceeds 5 parts by weight, it may become thick on the surface of the binder, causing foreign matter and surface damage to the packaging material surface. I can.

As the curing accelerator, a thiol-based additive or trimethylolpropane triacrylate (TMPTA) having a monofunctional or polyfunctional structure may be used. As the curing accelerator, a compound represented by the following formula (1) or formula (2) may be used.

Formula 1

Formula 2

On the other hand, the anti-slip packaging composition may include a filler component such as aerosol and calcium carbonate. The filler component is preferably included in 15 to 25 parts by weight based on 100 parts by weight of the subject. If the content of the filler is less than 15 parts by weight, the viscosity may be low and flow down may occur. On the other hand, if the content exceeds 25 parts by weight, the viscosity of the vinduck increases, but the packaging material causes voids in the tissue. There is.

Although not mentioned above, the anti-slip packaging composition may further include various commercially available functional additives such as antioxidants.

The non-slip packaging material formed by curing the non-slip packaging material resin composition has a form in which at least a part of the rocky fiber is exposed to the surface of the packaging material.

MMA/PMMA combination experiment

The basic binder resin (subject) of the anti-slip packaging material was prepared by adjusting the contents of MMA monomer and PMMA powder to improve curing drying time, adhesion to the road surface, and workability. In order to reduce the heat of curing reaction and develop a binder having a determined physical property, the amount of the MMA monomer used was fixed, and the amount of PMMA powder was increased, and the experiment was conducted as shown in Table 1 below.

Table 1

Meanwhile, a binder was prepared by mixing a curing agent with the prepared binder resin.

2 is a graph showing the results of FT-IR analysis after curing the MMA/PMMA binder.

Referring to Figure 2, the reaction of the MMA monomer can be confirmed by the disappearance of the C = C double bond absorption band, it was confirmed that the C = C double bond absorption band disappeared at 1636 cm-1. In addition, by observing the COC absorption band in the CH ₂ absorption band, 1242cm-1 and 1149cm-1 in the C = O, 1453cm-1 and 756cm-1 in the aliphatic CH, 1728cm-1 at 2947cm-1, 1481cm-1 to MMA the curing agent It was confirmed that it was synthesized as PMMA.

In addition, it was confirmed that increasing the content of PMMA, which is not reactive in the MMA monomer, lowers the heat of reaction and decreases the cure shrinkage rate. On the other hand, when the PMMA content was decreased, the viscosity of the binder decreased, but the cure shrinkage due to the reaction heat increased. This resulted in improved packaging material deformation due to exothermic reaction and curing shrinkage and lifting on the road surface, and some improvement in performance against yellowing.

Functional monomer mixing experiment to improve low temperature flexibility and adhesion

To improve low-temperature flexibility, n-BA (n-Butyl acrylate), 2-EHA (2-ethylhexylacrylate), 2-HEA (2-Hydroxyethyl acrylate), etc., with a low glass transition temperature (Tg) were added, and In order to improve adhesion performance, functional monomers such as MAA (methacrylic acid), AA (Acrylic acid), vinyl acetate, acrylamide, and GMA (Glycidyl methacrylate) were added to design the optimal composition of the anti-slip binder as shown in Table 2.

Table 2

3 is a graph showing the results of FT-IR analysis after curing the MMA/BA/2-EHA/AA/vinyl acetate binder.

3, the reaction of MMA/BA/2-EHA/AA/vinyl acetate was confirmed by the disappearance of the C=C double bond absorption band at 1636 cm-1. In addition, the alkyl group CH ₃ of acrylic in the 2947cm-1 absorption band, the aliphatic CH in the 1481cm-1 absorption band, C=O in 1728cm-1, the CH ₂ absorption band in 1453cm-1 and 756cm-1, COC in 1242cm-1 and 1149cm-1 By observing the absorption band, it was confirmed that the reaction of the anti-slip packaging material was completed by the curing agent.

In general, the higher the glass transition temperature (Tg) of acrylic, the higher the hardness of the coating film, so the low-temperature flexibility of the binder decreases, and the lower the glass transition temperature (Tg) is, the more advantageous it is to form the binder, but becomes flexible, resulting in a thickness difference. First, in order to improve the low-temperature flexibility of the non-slip packaging binder, a binder was prepared by adding a BA/2-EHA monomer having a low glass transition temperature (Tg). In this case, the low-temperature flexibility improved as the amount of BA at -54℃ and 2-EHA at -85℃ increased to the MMA/PMMA binder with a glass transition temperature (Tg) of 105℃. However, if more than 25% of MMA/PMMA was added A crackling occurred on the surface, and B-3 secured low temperature flexibility and did not generate a crackling.

In addition, when BA/2-EHA/AA/vinyl acetate is added to the MMA/PMMA binder with a glass transition temperature of 105℃, the adhesion strength with the substrate increases as the amount of AA/vinyl acetate increases, but due to the low glass transition temperature (Tg) B-8 composition, which improves low-temperature flexibility and adhesion strength at the same time, was selected as a non-slip packaging binder because some jitteriness occurs on the surface, and it was confirmed that the glass transition temperature (Tg) was lowered to 62°C. Since the glass transition temperature (Tg) appears in a single region rather than individually, the acrylic binder forms an integrated uniform structure. In the entire temperature range, the DSC graph showed that MMA, BA, 2-EHA, AA, and vinyl acetate did not appear individually, but that the glass transition temperature (Tg) appeared in a single region. This can be seen that the acrylic binder forms a stable bonding structure.

4 and 5 are graphs showing DSC analysis results after curing of the MMA/PMMA binder and DSC analysis results after curing of the MMA/PMMA/BA/2-EHA/AA/vinyl caetate binder, respectively.

In summarizing these results, as the glass transition temperature (Tg) increases, the binder becomes too hard in a low-temperature environment, and a large amount of cracks due to external impact is generated. Therefore, as a monomer with a low glass transition temperature such as BA/2-EHA is added, It was confirmed that the flexibility was increased, and the adhesion performance increased as the amount of AA/vinyl acetate was increased.

Next, changes in tensile strength, elongation rate, and physical properties under low temperature conditions were confirmed according to the functional monomer content of the composition for improving the low temperature flexibility and adhesion of the non-slip packaging binder.

A binder composition was designed by adding AA/vinyl acetate monomer to improve adhesion by adding AA (acrylic acid) at a glass transition temperature (Tg) of 70°C and vinyl acetate at 30°C. According to ASTM D 638-"Standard test method for properties of plastic" test method, after leaving Type IV test piece in standard condition (23±2℃) and low temperature environment -(20±2℃) for 1 hour or more, test speed 50mm/ The test was carried out in min. The MMA/PMMA binder showed a hard and brittle property, but when a monomer having a low glass transition temperature (Tg) such as BA/2-EHA was added, the tensile strength decreased but the low temperature flexibility was increased.

When vinyl acetate monomer having a glass transition temperature of 30°C was added instead of AA (acrylic acid) having a glass transition temperature of 70°C, as the vinyl acetate content increased, the tensile strength of the binder decreased and the elongation rate increased. Optimal binder composition B-8 showed physical properties such as tensile strength (7.5N/), elongation (151%) at room temperature, tensile strength (28.7N/) and elongation (3.2%) at low temperature (-20±2°C). .

6 and 7 are graphs showing tensile strength test results at room temperature and low temperature (-20°C), respectively.

Evaluation of non-slip material

In order to select the optimum blending ratio for anti-slip performance, a test specimen was prepared according to the type and particle size of non-slip materials (silica sand, aluminum oxide) in a binder, and the slip resistance (BPN) was evaluated. As a result, as the particle size of the non-slip material increased, the slip resistance performance increased.When less than 30% of the non-slip material was mixed, the non-slip material was not evenly distributed on the surface, so it was not possible to secure a certain non-slip. Agglomeration of the non-slip material occurred, resulting in inconsistent non-slip properties on the surface. Table 3 below is a table showing the slip resistance performance test results.

Table 3

However, when silica sand No. 3 was added, the dispersion was not uniform on the surface due to the particle size, and the occurrence of fine cracks and the anti-slip performance were partially uneven.In the case of using No. 8, the binder was added to the binder due to the small particle size. The phenomenon that the non-slip material was buried partially occurred. In addition, when aluminum oxide was added rather than silica sand, the slip resistance performance increased. Therefore, silica sand No. 4 and No. 8 are mixed to be used as a non-slip material, and aluminum oxide #30 having excellent abrasion resistance is added to prevent the occurrence of abrasion of the non-slip material due to vehicle traffic on the surface of the packaging material to improve the anti-slip performance. Was designed.

Hereinafter, the present invention will be described in detail with examples of construction of a specific packaging material resin composition. However, the technical idea of the present invention is not limited by the following examples, and the technical idea of the present invention is only determined by the claims to be described later.

Example

Example 1

In accordance with the mixing ratio shown in Table 4 below, a non-slip packaging material was constructed.

Table 4

In the anti-slip packaging material, MMA and PMMA powder are first added to the reactor, then melted at 75°C for 2 and a half hours, and then cooled to a temperature below 50°C to obtain functional acrylic monomers (BA, 2-EHA, AA, vinylacetate, etc.). It was added and stirred for 1 hour. At this time, 1 part by weight or less of an adhesion enhancer was added and stirred with respect to 100 parts by weight of the binder composition. Next, a filler, an anti-settling material, a pigment, a non-slip material, and the like were added in a certain ratio and stirred to be homogeneously dispersed.

As for the anti-skid pavement construction method, clean/arrange the concrete or asphalt concrete surface and perform primer treatment. After adding the curing agent at a certain mixing ratio, uniformly apply 1 mm of the first anti-slip packaging material for ground application, and carry out the work of applying 2 mm of the second non-slip equipment packaging material. If more than 3mm is applied at a time, cracks are generated on the surface and the non-slip material is buried in the binder, so it is impossible to secure a certain anti-slip performance on the surface. Therefore, it is difficult to slip by using a roller, rubber rake, or scraper. A re-homogeneous dispersion operation was carried out.

Evaluation of properties of non-slip packaging materials

The physical properties of the anti-slip packaging material were evaluated as shown in Table 5 below.

Table 5

Claims (7)

Methyl methacrylate (MMA) monomer and polymethyl methacrylate (PMMA) resin powder is mixed and preemptively heated and melted to prepare 100 parts by weight of the main body;
10 to 40 parts by weight of a reactive monomer including 2-ethylhexyl acrylate (2-EHA), n-butyl acrylate (n-BA), acrylic acid (AA), and vinyl acetate;
40 to 60 parts by weight of a non-slip material containing at least one component of silica sand and metal oxide;
1 to 10 parts by weight of rocky fibers; And
As an adhesion enhancer for improving adhesion to the road surface, a non-slip packaging resin comprising 05 to 5 parts by weight of at least one compound selected from the group consisting of EVA, rosin ester compounds, rosin ester acid compounds, and polyester acrylate compounds Composition. The method of claim 1,
The PMMA resin is melted in the MMA monomer so as to have a weight of 10 to 30% based on the weight of the MMA monomer. The method of claim 1,
The metal oxide is a non-slip packaging resin composition, characterized in that aluminum oxide or titanium oxide. The method of claim 1,
The rocky fiber is a non-slip packaging resin composition, characterized in that the basalt (basalt) fiber. The method of claim 5,
The basalt fiber is a non-slip packaging resin composition, characterized in that the chop (chop)-shaped section fiber having a length of 4 mm or less. The method of claim 1,
Non-slip packaging resin composition, characterized in that it further comprises 15 to 25 parts by weight of at least one filler component selected from the group consisting of aerosil, calcium carbonate and meerschaum. An anti-slip packaging material comprising a cured product formed by curing the resin composition for an anti-slip packaging material according to claim 1 under the addition of a curing agent, wherein at least a portion of the rocky fiber is exposed to the surface of the packaging material.

Images