KR102221314B1 - Braille block composition for handicapped person containing urethane acrylic polymer - Google Patents

Abstract

According to the present invention, a blind person guiding block sheet includes acrylic polyols, polyester polyols, diisocyanates, disulfide diol compounds, and surface-modified heat-insulating pigments, wherein the surface-modified heat-shielding pigments are surface-modified with a surface modifier containing an isocyanate group at the end, thereby having excellent durability and heat-insulating properties.

Description

Block sheet for inducing the visually impaired made of urethane acrylic resin {Braille block composition for handicapped person containing urethane acrylic polymer}

Block sheet for inducing the visually impaired made of urethane acrylic resin {Braille block composition for handicapped person containing urethane acrylic polymer}

In recent years, as social interest in the facilities for the disabled has increased, the installation of structures for the convenience of various disabled people is increasing. Among them, structures for the visually impaired include guidance blocks, braille guide boards, sound signals, and guidance signals.

Among these, induction blocks are the most commonly used for the convenience of the visually impaired, and are blocks with protruding projections so that the visually impaired can check the shape through the touch of the sole or cane in the normal walking state. And walking direction can be guided.

Such guidance blocks may be installed parallel to a crosswalk or a pedestrian movement line, or may be installed to indicate the location of a crosswalk in a place where facilities such as a crosswalk are present.

Conventional induction blocks are largely divided into indoor and outdoor use, and in the case of outdoor use, concrete or aggregate was bonded to the underside of the polymer material to construct the sidewalk block together, and in the case of indoor use, only the sheet upper plate made of synthetic wood was attached. It was common.

However, in recent years, in order to improve the convenience of construction, in the case of outdoor guidance blocks, only the top of the sheet is attached, and an outdoor guidance block is required for construction by applying an adhesive on the crosswalk, concrete and asphalt substrates, and attaching the guidance blocks. .

However, in the case of attaching the guide blocks on the crosswalk, concrete and asphalt substrates, the adhesive strength with concrete and asphalt is low, and thus durability degradation problems such as being easily separated from concrete and asphalt and damaged occurred. There is a need to develop a block sheet for induction of the visually impaired with excellent adhesion.

Korean Patent Publication No. 10-1168905

An object of the present invention is to provide a block sheet for induction of the visually impaired having excellent adhesion to crosswalks, concrete and asphalt.

Another object of the present invention is to provide a block sheet for induction of the visually impaired having excellent durability and self-healing ability.

Another object of the present invention is to provide a block sheet for induction of the visually impaired, which has excellent heat shielding properties and can prevent problems such as a decrease in durability due to heat.

The block sheet for induction of the visually impaired according to the present invention includes an acrylic polyol, an isocyanate, a disulfide diol compound, a surface-modified heat shielding pigment and a surface-modified extender pigment,

The surface-modified heat-shielding pigment or the surface-modified extender pigment is characterized in that the surface is modified with a surface modifier containing an isocyanate group at the terminal.

In the block sheet for inducing the visually impaired according to an embodiment of the present invention, the surface-modified heat shielding pigment may be at least one selected from 3-isocyanate propyltrimethoxysilane and 3-isocyanate propyltriethoxysilane.

In the block sheet for inducing the visually impaired according to an embodiment of the present invention, the acrylic polyol may have a weight average molecular weight of 120,000 to 1,100,000.

In the block sheet for inducing the visually impaired according to an embodiment of the present invention, the acrylic polyol may have a glass transition temperature of 30 to 80°C.

In the block sheet for inducing the visually impaired according to an embodiment of the present invention, the heat shielding pigment may include one or more metal oxides selected from titanium, iron, zinc, chromium, and antimony.

In the block sheet for induction of the visually impaired according to an embodiment of the present invention, the block sheet for induction of the visually impaired is 50 to 90 parts by weight of isocyanate, 1 to 10 parts by weight of disulfide diol compound, 0.5 to 10 parts by weight of a heat shielding pigment based on 100 parts by weight of the acrylic polyol. It may contain 5 parts by weight and 3 to 20 parts by weight of an extender pigment.

The present invention also includes a block sheet for inducing the visually impaired, and the block sheet for inducing the visually impaired according to the present invention may be manufactured including a block sheet for inducing the visually impaired according to an embodiment of the present invention.

The block sheet for induction of the visually impaired according to the present invention includes an acrylic polyol, an isocyanate, a disulfide diol compound, a surface-modified heat-shielding pigment and a surface-modified extender pigment, and the surface-modified heat-shielding pigment or the surface-modified extender pigment is at the end. By using a surface-modified agent containing an isocyanate group, it has excellent adhesion to a substrate such as asphalt or concrete, and has excellent durability and heat shielding properties.

1 shows a block sheet for induction of the visually impaired manufactured according to an embodiment of the present invention.
2 and 3 show the construction process of the block sheet for induction of the visually impaired manufactured according to an embodiment of the present invention.
Figure 4 is a view and shows after the construction of the block sheet for induction of the visually impaired manufactured according to an embodiment of the present invention.

Advantages and features of the embodiments of the present invention, and a method of achieving them will become apparent with reference to the embodiments described below in detail together with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in a variety of different forms, and only these embodiments make the disclosure of the present invention complete, and are common knowledge in the technical field to which the present invention pertains. It is provided to completely inform the scope of the invention to those who have, and the invention is only defined by the scope of the claims. The same reference numerals refer to the same components throughout the specification.

In describing the embodiments of the present invention, if it is determined that a detailed description of a known function or configuration may unnecessarily obscure the subject matter of the present invention, a detailed description thereof will be omitted. In addition, terms to be described later are terms defined in consideration of functions in an embodiment of the present invention, which may vary according to the intention or custom of users or operators. Therefore, the definition should be made based on the contents throughout this specification.

The block sheet for induction of the visually impaired according to the present invention includes an acrylic polyol, an isocyanate, a disulfide diol compound, a surface-modified heat shielding pigment and a surface-modified extender pigment,

The surface-modified heat-shielding pigment or the surface-modified extender pigment is characterized in that the surface is modified with a surface modifier containing an isocyanate group at the terminal.

Block sheets for guiding the visually impaired are installed in front of a crosswalk and are used to guide the walking of the visually impaired. The block sheet for induction of the visually impaired is attached using an adhesive on a substrate such as asphalt. Conventional block sheets for induction of the visually impaired often contain an unsaturated polyester resin, and in this case, the adhesion to the asphalt substrate is significantly low, and when used for a long time, the block sheet for induction of the visually impaired may fall or be damaged on the asphalt. .

However, in the case of the block sheet for induction of the visually impaired according to the present invention, acrylic polyol, isocyanate and disulfide diol compound are polymerized, and by including a surface-modified heat-shielding pigment and a surface-modified extender pigment, adhesion to a substrate such as asphalt or concrete is remarkably There is an advantage to be improved.

The surface-modified heat-shielding pigment or the surface-modified extender pigment according to the present invention may be surface-modified with a surface modifier containing an isocyanate group at the end. Preferably, both the heat shielding pigment and the extender pigment are surface-modified with an isocyanate group at the end. It may be modified.

The heat shielding pigment or extender pigment according to the present invention is surface-modified with a surface modifier containing an isocyanate group at the terminal, so that it partially participates in the polymerization reaction in the polymerization process of isocyanate and acrylic polyol, or is produced by polymerization of isocyanate and acrylic polyol even if it does not participate. There is a characteristic that compatibility with polyurethane is remarkably improved. The physical properties of the entire block sheet for induction of the visually impaired by such improved compatibility can be improved, and mechanical strength can also be improved.

Specifically, the surface modifier may be at least one selected from 3-isocyanate propyltrimethoxysilane and 3-isocyanate propyltriethoxysilane, and the modification efficiency may be improved by using such a surface modifier.

At this time, the surface modification of the heat shielding pigment or the extender pigment may use a conventional method for modifying the surface of particulate matter, and the present invention is not limited thereto. As a specific and non-limiting example, a method of dissolving the surface modifier in an alcohol or ketone-based solvent, impregnating a heat shielding pigment or extender pigment, and separating and drying the solid may be used, but the present invention is limited thereto. It does not become.

In the block sheet for induction of the visually impaired according to an embodiment of the present invention, the heat-shielding pigment shows a heat-shielding effect by blocking infrared rays, etc., and can be used without limitation if the pigment exhibits a color suitable for the induction block sheet for the blind. And, the present invention is not limited thereto.

As a specific and non-limiting example, the heat shielding pigment may include an oxide of a metal selected from titanium, iron, zinc, chromium, and antimony, or a composite oxide thereof, but the present invention is not limited thereto. In addition, as the heat shielding pigment, a commercial heat shielding pigment may be used, and the scope of the present invention is not limited thereto.

The block sheet for inducing the visually impaired according to an embodiment of the present invention includes 0.5 to 5 parts by weight, preferably 1 to 4 parts by weight, based on 100 parts by weight of the acrylic polyol. When a small amount of heat shielding pigment is included, it is difficult to produce sufficient color, and when a large amount of heat shielding pigment is included, the weather resistance and mechanical strength of the entire block sheet for visually impaired induction may be deteriorated.

The block sheet for inducing the visually impaired according to the present invention includes a constitutive pigment. These extender pigments may be mixed with the above-described heat shielding pigment to exhibit uniform color development. In this case, the extender pigment may be used without limitation in the case of a white extender pigment that is commonly used, and the present invention is not limited thereto.

As a specific and non-limiting example, the extender pigment may include one or more selected from titanium dioxide, calcium carbonate, barium sulfate, magnesium hydroxide, and talc, but the present invention is not limited thereto.

In the block sheet for induction of the visually impaired according to an embodiment of the present invention, the extender pigment may have an average particle diameter of 1 to 10 μm, and if the average particle diameter is too small, aggregation of the extender pigment may occur, and the average particle diameter is too large. In this case, there is a problem that may affect the color development of the heat shielding pigment.

The block sheet for induction of the visually impaired may include 3 to 20 parts by weight, preferably 5 to 15 parts by weight of an extender pigment based on 100 parts by weight of acrylic polyol. If a small amount of the extender pigment is included, the color development of the heat shielding pigment may decrease, and if a large amount of the heat shielding pigment is included, the block sheet for induction of the visually impaired may be cracked.

The block sheet for induction of the visually impaired according to the present invention includes an acrylic polyol, and a urethane resin can be prepared by reacting and polymerizing the hydroxy group of the acrylic polyol with an isocyanate.

In this case, the acrylic polyol may be polymerized by mixing an acrylic monomer containing a hydroxyl group and a conventional acrylic monomer not containing a hydroxyl group.

Specifically, the acrylic monomer containing a hydroxy group may be one or two or more selected from 2-hydroxy ethyl (meth) acrylate and 2-hydroxy propyl (meth) acrylate, and the acrylic monomer not including the hydroxy group Monomers are methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate And one or two or more selected from pentyl (meth)acrylate, and the like, but the present invention is not limited thereto.

More preferably, the acrylic polyol is polymerized by mixing methyl (meth) acrylate: n-butyl (meth) acrylate: 2-hydroxyethyl (meth) acrylate in an amount of 1: 0.8 to 1.2: 0.8 to 1.2 In this range, acrylic polyol can perform sufficient polymerization with isocyanate.

In the block sheet for inducing the visually impaired according to an embodiment of the present invention, the acrylic polyol may have a molecular weight of 120,000 to 1,100,000. When the weight average molecular weight is low, it is difficult to maintain the shape of the block sheet for induction of the visually impaired, and when the weight average molecular weight is high, a problem of lowering the smoothness may occur.

In addition, the acrylic polyol may have a glass transition temperature of 30 to 80°C. If the glass transition temperature is low, problems such as deformation of the shape during storage of the block sheet for induction of the visually impaired may occur. If the glass transition temperature is high, cracks This can easily happen.

The block sheet for induction of the visually impaired according to the present invention includes an isocyanate, and the isocyanate reacts with the acrylic polyol to form a block sheet for induction of the visually impaired.

Specifically, the isocyanate may be used without limitation if it is an isocyanate compound known in the art that can react with a polyol to form a polyurethane, and the present invention is not limited thereto. As a specific and non-limiting example, the isocyanate is isophorone diisocyanate (IPDI), dicyclohexylmethane-4-4-diisocyanate (H ₁₂ MDI), hexamethylene diisocyanate (HDI), 1,3-bis (Methyl isocyanate) Cyclohexane (H ₆ XDI) and m, o, P -may contain one or two or more selected from xylene diisocyanate, etc., preferably a biuret or trimer type of hexamethylene diisocyanate, and , More preferably, it may be a hexamethylene diisocyanate trimer, and if a burette type or trimer of hexamethylene diisocyanate is used, there is an advantage that it is possible to manufacture a block sheet for induction of the visually impaired with improved weatherability.

The block sheet for inducing the visually impaired according to an embodiment of the present invention may contain 50 to 90 parts by weight, preferably 60 to 75 parts by weight of isocyanate, based on 100 parts by weight of the acrylic polyol. In the case of containing a large amount of isocyanate, unreacted isocyanate may remain, leading to a decrease in weather resistance of the block sheet for induction of the visually impaired, and if a small amount of isocyanate is included, it is difficult to secure sufficient strength of the block sheet for induction of the blind.

The block sheet for inducing the visually impaired according to the present invention includes a disulfide diol compound. The block sheet for induction of the visually impaired according to the present invention may include a disulfide diol compound, so that self-healing ability may be added. Specifically, the hydroxy group at the end of the disulfide diol compound may be added to the polymer by participating in the polymerization process of the acrylic polyol and isocyanate, and the disulfide diol is added to the polyurethane, thereby heat treatment or ultraviolet rays by disulfide metathesis of the disulfide group. There is an advantage that the durability can be further improved by adding self-healing capability without irradiation.

Specifically, the disulfide diol compound includes two hydroxyl groups at the terminal, and in the case of a compound including a disulfide group (-S-S-), it can be used without limitation, and the present invention is not limited thereto. Preferably, the disulfide diol compound may be bis(4-hydroxyphenyl) disulfide.

The block sheet for inducing the visually impaired according to an embodiment of the present invention may include 1 to 10 parts by weight, preferably 2 to 8 parts by weight of the disulfide diol compound, based on 100 parts by weight of the acrylic polyol. When a small amount of the disulfide diol compound is included, the above-described self-healing ability may not be exhibited, and when a large amount of the disulfide diol compound is included, the weather resistance and mechanical properties of the coating film may be deteriorated.

The block sheet for induction of the visually impaired according to an embodiment of the present invention may further include additives such as ultraviolet stabilizers and antioxidants, and the additives added at this time may be used without limitation if they are additives commonly used in polyurethane. And the present invention is not limited thereto.

Specifically, the antioxidant may include one or two or more selected from quinones, amines and phenols, and preferably at least one antioxidant selected from aromatic amines and phenols may be used, but the present invention is limited thereto. no. The antioxidant may be included in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the acrylic polyol, but it is obvious that the amount of the antioxidant may vary depending on the type of antioxidant.

In addition, the ultraviolet stabilizer may be used without limitation, if it is a stabilizer commonly used in polyurethane, and the present invention is not limited thereto. Specifically, the UV stabilizer may include one or two or more selected from benzotriazole-based, benzophenone-based, hydroxybenzoate-based, and diphenyl acrylate-based, but the present invention is not limited thereto. The UV stabilizer may be included in an amount of 0.1 to 2 parts by weight relative to 100 parts by weight of acrylic polyol, and it is apparent that the amount of the UV stabilizer may vary depending on the type of the added UV stabilizer and the environment of use of the block sheet for inducing the blind.

The block sheet for induction of the visually impaired according to an embodiment of the present invention may have irregularities and the like to assist the walking of the visually impaired, and the size and height of the irregularities may be based on related regulations, but the present invention It is not limited.

Advantageously, the block sheet for induction of the visually impaired according to an embodiment of the present invention can be attached to substrates such as crosswalks, concrete and asphalt through a water-soluble acrylic adhesive, and when attached using a water-soluble acrylic adhesive, the adhesion is remarkably It is improved and has an advantage of excellent durability.

The present invention also provides a method of constructing a block sheet for inducing the visually impaired, wherein the block sheet for inducing the visually impaired may be made of a block sheet for inducing the visually impaired according to an embodiment of the present invention.

The construction method of the block sheet for inducing the visually impaired according to the present invention comprises a washing step of washing the road surface; A pretreatment step of applying a primer; An adhesive application step of applying an adhesive on the primer; And attaching the block sheet for induction of the blind. At this time, the washing step and the pretreatment step may generally follow a construction method of constructing on a crosswalk, concrete, and asphalt, and the present invention is not limited thereto. In addition, the adhesive used in the adhesive application step of applying the adhesive on the primer may be a water-soluble acrylic adhesive. When using a water-soluble acrylic adhesive, not only excellent adhesion to asphalt but also visually impaired persons including acrylic polyol There is a feature of remarkably high adhesion to the induction block sheet, and accordingly, there is an advantage that a problem such as lifting does not occur even when used for a long time.

Hereinafter, the present invention will be described in detail by examples and comparative examples. The following examples are only intended to aid understanding of the present invention, and the scope of the present invention is not limited by the following examples.

[Production Example 1]

1. Manufacture of surface-modified heat-shielding pigment and extender pigment

A mixed pigment was prepared by mixing 10 g of a heat shielding pigment (ASAHI Yellow 5970) and 30 g of an extender pigment having an average particle diameter of 1.5 μm (Rutile TiO _{2 ).} Separately, 10 g of 3-isocyanate propyltrimethoxysilane was dissolved in 100 ml of methyl ethyl ketone to prepare a surface modifier solution, and the mixed pigment was immersed and stirred at 100 rpm for 2 hours, and then the solid content was separated. It was dried at 35 ℃ to prepare a mixture of the surface-modified heat-shielding pigment and extender pigment.

2. Manufacturing of block sheets for induction of the visually impaired

The weight ratio of methyl methacrylate: butyl methacrylate: 2-hydroxyethyl methacrylate is mixed at a weight ratio of 35: 30: 35, and the weight average molecular weight measured through GPC is about 300,000, and the glass transition temperature is about To prepare an acrylic polyol of 75 ℃.

Prepared acrylic polyol 100 g, 1,6-hexamethylene diisocyanate trimer (Soya) 72 g, bis(4-hydroxyphenyl) disulfide 5 g, surface-modified heat-shielding pigment and extender pigment mixture 12 g, phenolic oxidation 1 g of an inhibitor (SONGNOX 1076) and 1 g of a benzotriazole-based UV stabilizer were mixed, heated to about 90° C., and then injection-molded to prepare a block sheet for induction of the visually impaired. The manufactured block sheet for induction of the visually impaired has a thickness of about 2 mm excluding irregularities and a width x length of 300 x 300 mm.

[Production Examples 2 to 11]

It was prepared in the same manner as in Preparation Example 1, but after mixing in different compositions as shown in Table 1 below, a block sheet for induction of the visually impaired was prepared through injection. The composition of Table 1 was added in g units, and antioxidants and ultraviolet stabilizers were omitted for convenience among the composition of the block sheet for induction of the blind, and were added in the same amount as in Preparation Example 1.

Preparation Example 9 was polymerized by adding the same amount of acrylic polyol having an average molecular weight of 100,000, and Preparation Example 10 was polymerized by adding the same amount of acrylic polyol having an average molecular weight of 1,250,000. In the case of Preparation Example 11, a block sheet for induction of the visually impaired was prepared by mixing equal amounts of a heat-shielding pigment and an extender pigment without surface modification.

Manufacturing example Acrylic polyol tHDI Disulfide Heat shielding pigment Extender pigment Remark One 100 72 5 3 9 2 100 70 4.5 3.5 10 3 100 72 0 3 9 4 100 90 5 3 9 5 100 72 0.5 3 9 6 100 72 10 3 9 7 100 72 5 11 9 8 100 72 5 0.4 9 9 100 72 5 3 9 Use of low molecular weight acrylic polyol 10 100 72 5 3 9 High molecular weight acrylic polyol used 11 100 72 5 3 9 No surface modification of heat shielding and extender pigments

The tensile strength

The tensile strength of the block sheet for induction of the blind prepared in Preparation Example was measured according to KS M ISO 527-1, and the results are shown in Table 2.

Accelerated weathering

After applying the WS type of KS F 2274 and exposing it to the accelerated weathering test environment for 250 hours, the tensile strength was measured again and the rate of change was calculated compared to the initial tensile strength, and the results are shown in Table 2.

Adhesive strength

Using W-310SE, a block sheet for induction of the visually impaired was attached to the asphalt specimen and the adhesion strength was measured. The adhesive strength was based on the tensile adhesive strength, and the adhesive strength was measured according to KS F 4931, and the results are shown in Table 2.

Heat shielding performance evaluation

Each prepared specimen prepared in Preparation Example was cut into a size of 150×150 mm, and the specimen was loaded in a styrofoam box with a width × length × height of 300 × 300 × 300 based on the inside and a thickness of 1 cm, and infrared rays. After irradiating the lamp for 2 hours, the temperature change of the specimen was measured, and the results are shown in Table 2.

Manufacturing example Tensile strength (MPa) Weather resistance (%) Adhesive strength (N/㎟) Heat shielding performance (℃) One 13.2 95 1.3 15.5 2 12.9 94 1.3 15.1 3 12.0 85 1.1 15.2 4 12.5 80 1.2 16.5 5 12.4 87 1.2 15.2 6 10.6 90 0.9 18.4 7 11.4 79 1.0 12.6 8 13.0 92 1.2 20.3 9 10.6 85 1.3 15.9 10 13.3 83 1.1 15.4 11 10.3 88 1.0 17.4

Referring to Table 2, based on 100 parts by weight of acrylic polyol, isocyanate 60 to 75 parts by weight, disulfide diol compound 2 to 8 parts by weight, heat shielding pigment 1 to 4 parts by weight, and extender pigment 5 to 15 parts by weight induction prepared including It can be seen that the used block sheet has excellent tensile strength, weather resistance, and adhesive strength, so that it can be used without deformation for a long time.

Claims (6)

Including acrylic polyol, isocyanate, disulfide diol compound, surface-modified heat shielding pigment and surface-modified extender pigment,
The surface-modified heat-shielding pigment or the surface-modified extender pigment is characterized in that the surface is modified with a surface modifier containing an isocyanate group at the end,
The acrylic polyol has a weight average molecular weight of 120,000 to 1,100,000,
Characterized in that it comprises 60 to 75 parts by weight of isocyanate, 2 to 8 parts by weight of a disulfide diol compound, 1 to 4 parts by weight of a surface-modified heat shielding pigment, and 5 to 15 parts by weight of a surface-modified extender pigment based on 100 parts by weight of the acrylic polyol. Block sheet for guiding the visually impaired. The method of claim 1,
The surface modifier is a block sheet for induction of the visually impaired, characterized in that at least one selected from 3-isocyanate propyltrimethoxysilane and 3-isocyanate propyltriethoxysilane. delete The method of claim 1,
The acrylic polyol is a block sheet for induction of the visually impaired, characterized in that the glass transition temperature is 30 to 80 ℃. The method of claim 1,
The heat shielding pigment is a block sheet for induction of the visually impaired, characterized in that it comprises at least one metal oxide selected from titanium, iron, zinc, chromium and antimony. delete

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