KR101542577B1 - Eco-friendly nonslip paving material composition - Google Patents

Abstract

The present invention relates to an anti-slip pavement material composition. The anti-slip pavement material composition includes: (1) copolymers; (2) fillers; (3) silica; (4) a cross-linking agent; and (5) a promoter. The promoter can be dimethyl aniline or N.N′-trimethyl aniline. The anti-slip pavement material composition has excellent low-temperature curability, slip resistance, curing rate, and wear resistance as well as storage stability. The composition also does not crack, thereby being used as an anti-slip pavement material for a road.

Description

{ECO-FRIENDLY NON SLIP PAVING MATERIAL COMPOSITION}

The present invention relates to an environmentally friendly non-slip wrapping material, and more particularly, to an environmentally friendly anti-slip wrapping material which is quick in curing, can be cured at low temperatures, has excellent chemical resistance and weatherability, And a manufacturing method thereof.

Non-slip packaging materials are applied to prevent the risk of safety accidents by preventing slippery roads, sidewalks, bike roads, children's protection areas, slip areas, parking lots, parks, The non-slip wrapping material is formed on a road surface such as a road so that a frictional force acts between the non-slip wrapping material and the vehicle tire to prevent slippage.

The non-slip wrapping material is required to have excellent adhesion strength to meet the purpose of the application, and to have excellent physical properties in terms of slip resistance and abrasion resistance. In addition, there is no change in appearance due to aging, and it is required that the environment also does not contain heavy metals or volatile organic compounds (VOC).

Conventional non-slip packaging materials mainly contain epoxy-based synthetic resin, but epoxy resin requires a lot of time for curing in winter and opening the vehicle after completion of construction. This characteristic is caused by time constraints .

In order to improve the curing rate and low-temperature curing property, a slip-resistant packaging material including methyl methacrylate and capable of opening the roadway quickly after construction even during the winter roadway construction has been developed. However, There is a problem that cracks are generated after opening, resulting in serious consequences such as road breakage.

Korean Patent Registration No. 10-1014423 discloses a room temperature curing type non-slip wrapping material excellent in curing rate and low temperature curing property including polymethyl methacrylate, methyl methacrylate and ethylhexyl acrylate, .

However, such a non-slip packaging material containing methyl methacrylate is disadvantageous in that the storage stability is very disadvantageous, and cracks and end portions of the coating film occur at the time of construction.

Therefore, there is a need for the development of a novel anti-slip packaging composition that is excellent in curing speed, low temperature curability, slip resistance, and abrasion resistance, has excellent storage stability, and is free from cracking of the coating film.

An object of the present invention is to provide a non-slip packaging composition excellent in curing speed, low temperature curability, slip resistance and abrasion resistance, excellent in storage stability, and free from cracking of the coating film.

In accordance with the above object,

(1) a copolymer; (2) fillers; (3) silica sand; (4) a crosslinking agent and (5) an accelerator,

Wherein the accelerator is dimethylaniline or N, N'-trimethylaniline.

The anti-slip packaging composition of the present invention is excellent in storage stability and excellent in curing speed, low temperature curability, slip resistance, and abrasion resistance, and is free from cracking of the coating film, so that it can be effectively used as a slip resistant packaging material for roads.

The anti-slip package composition of the present invention comprises (1) a copolymer; (2) fillers; (3) silica sand; (4) a crosslinking agent, and (5) an accelerator, and optionally (6) a coloring agent; (7) auxiliary filler; (8) catalyst and / or (9) other additives.

Hereinafter, the constituent components of the present invention will be described in detail.

(1) Copolymer

The copolymer (1) is preferably a copolymer comprising a structural unit derived from (1-1) an unsaturated acid, an unsaturated acid anhydride, or a mixture thereof, (1-2) a structural unit derived from a saturated polybasic acid, a saturated polybasic acid anhydride, , And (1-3) a polyhydric alcohol having a valence of 2 or more, and may further include (1-4) a crosslinking agent.

(1-1) a structural unit derived from an unsaturated acid, an unsaturated acid anhydride, or a mixture thereof

In the present invention, the constituent unit (1-1) is derived from an unsaturated acid, an unsaturated acid anhydride, or a mixture thereof, and the unsaturated acid, the unsaturated acid anhydride, or a mixture thereof may be, for example, maleic acid, maleic anhydride, fumaric acid, Itaconic anhydride, citraconic acid, citraconic anhydride and mesaconic acid, and preferably at least one selected from the group consisting of maleic acid, maleic anhydride, and fumaric acid.

The content of the constituent unit (1-1) may be 5 to 50 mol%, preferably 10 to 40 mol%, of the total constituent units constituting the copolymer.

(1-2) a structural unit derived from a saturated polybasic acid, a saturated polybasic acid anhydride, or a mixture thereof

In the present invention, the constituent unit (1-2) is derived from a saturated polybasic acid, a saturated polybasic acid anhydride, or a mixture thereof, and the saturated polybasic acid, the saturated polybasic acid anhydride, or a mixture thereof is selected from the group consisting of phthalic anhydride, isophthalic acid, Terephthalic acid, hexachloronendomethylenetetrahydrophthalic acid (HET acid), chlorendic acid, and adipic acid, and preferably at least one selected from the group consisting of phthalic anhydride, isophthalic acid, tetrahydrophthalic anhydride, terephthalic acid, Hexachloroindomethylenetetrahydrophthalic acid, and the like.

The content of the constituent unit (1-2) may be 10 to 70 mol%, preferably 20 to 50 mol%, more preferably 40 to 50 mol%, based on the total constituent units constituting the copolymer %. ≪ / RTI >

(1-3) a structural unit derived from a polyhydric alcohol having two or more hydroxyl groups

In the present invention, the constituent unit (1-3) is derived from a polyhydric alcohol having a valence of two or more, and the polyhydric alcohol having a valence of two or more is ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, -Hexanediol, glycerin, diglycerol, monopentaerythritol, and dipentaerythritol, and preferably at least one selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, and neo Pentyl glycol, and the like.

The content of the constituent unit (1-3) may be 5 to 50 mol%, and preferably 10 to 40 mol%, of the total constituent units constituting the copolymer.

The (1) copolymer may be prepared by reacting the unsaturated acid, the unsaturated acid anhydride, or a mixture thereof, the saturated polybasic acid, the saturated polybasic acid anhydride, or a mixture thereof, and the dihydric or higher polyhydric alcohol in a solvent . At this time, the solvent is used to reflux during the production of the copolymer and recovered when the reaction is terminated. Any solvent may be used as long as it is used in the production of the copolymer, but it may preferably be xylene. The above (1) copolymer can be produced, for example, by the reaction shown in the following reaction formula (1).

[Reaction Scheme 1]

The (1) copolymer may be contained in an amount of 0.1 to 50% by weight, preferably 5 to 40% by weight, more preferably 10 to 30% by weight based on the slip resistant packaging composition (based on the solid content).

(2) Filler

The anti-slip package composition of the present invention comprises a filler material, which can perform the function of increasing the strength of the anti-slip material.

The filler may be calcium carbonate and the calcium carbonate may be a grit calcium carbonate, a light calcium carbonate, or a mixture thereof.

The calcium carbonate may have a particle diameter of 0.01 to 0.2 탆, preferably 0.03 to 0.15 탆, more preferably 0.04 to 0.1 탆.

The hard calcium carbonate may have a particle diameter of 10 탆 or less, preferably from 0.5 to 5 탆, and more preferably from 1 to 3 탆.

The filler may be one surface-treated with soybean oil, dehydrated castor oil, flaxseed oil, or tung oil. When the surface is treated with the oils, the dispersibility of the filler increases, and the weatherability, tensile strength and abrasion resistance Can be improved.

(3) Silica sand

The anti-slip package composition of the present invention comprises silica sand to impart anti-slip and abrasion resistance to the anti-slip package.

The quartz sand may be a quartz aggregate that is obtained by physically crushing silica to separate particles according to the particle size standard. For example, quartz sand (aggregate of quartz aggregate) of No. 3 (1.5 to 2.0 mm) to No. 8 (less than 0.2 mm) Can be used.

The silica sand may have a different grain size depending on the application. For example, the silica sand may be mixed with a No. 3 or No. 4 silica (0.8 to 1.5 mm) having a relatively large grain size in a steeply sloping region or a region requiring a large frictional force.

When using only silica sand having a uniform particle size, the silica sand may have a problem in terms of durability such as dislocation of the silica sand due to the continuous load application and breakage of the coating film due to increased internal voids during the application, It is possible to reduce the internal void by including sandpaper having a small particle diameter such as a filament. Therefore, the non-slip pavement composition of the present invention preferably comprises 1 to 50% by weight, preferably 5 to 30% by weight, more preferably 10 to 20% by weight of the silica sand of the above (6) to It can be included in quantity.

(4) Crosslinking agent

The non-slip packaging composition of the present invention comprises a crosslinking agent, which may be a combination of a monomer having a high transition temperature and a monomer having a low transition temperature.

The monomer having a high transition temperature may be at least one member selected from the group consisting of styrene, styrene having an alkyl substituent, methyl (meth) acrylate, and ethyl (meth) acrylate, time, can be a methyl methacrylate acrylic acrylate or methacrylate.

The monomer having a low transition temperature may be at least one selected from the group consisting of butyl acrylate 2-ethylhexyl acrylate, and propyl acrylate, preferably butyl acrylate.

The monomer having a high transition temperature and the monomer having a low transition temperature can be used in an amount of 50:50 to 95: 5, preferably 60:40 to 90:10 by weight. When the ratio of the monomer having a high transition temperature is more than 95, the toughness of the non-slip wrapping material becomes excessive and cracks or breaks. When the ratio of the monomer having the low transition temperature is more than 50, It is difficult for the packaging material to exhibit proper carriage force.

The crosslinking agent may be contained in an amount of 0.1 to 40% by weight, preferably 1 to 30% by weight, more preferably 3 to 20% by weight, based on the anti-slip packaging composition (based on the solid content).

(5) Accelerator

The anti-slip packaging composition of the present invention comprises an accelerator for promoting the curing of the anti-slip package, wherein dimethylaniline or N, N'-trimethylaniline is used as the accelerator.

Generally, a cobalt-based promoter is mainly used as a promoter in a slip-resistant packaging material. However, the cobalt-based promoter has a short heat generation and gradually cures, and takes a long time until complete curing in a thick film and hardly causes surface hardening, I have. In addition, the cobalt-based accelerator has a problem that it is affected by moisture and humidity. Accordingly, the anti-slip package composition of the present invention comprises dimethylaniline or N, N'-trimethylaniline as an aniline accelerator as an accelerator.

The accelerator may be used in an amount of 0.01 to 1% by weight, preferably 0.02 to 0.5% by weight, more preferably 0.03 to 0.1% by weight based on the anti-slip package composition (based on the solids content). When the promoter is contained in an amount of not less than 0.01% by weight, an appropriate curing accelerating effect can be exhibited. When the accelerator is contained in an amount of not more than 1% by weight, yellowing of the packaging material can be prevented while exhibiting an appropriate curing promoting effect.

(6) Coloring

The anti-slip packaging composition of the present invention may contain a coloring agent to impart an effect such as an improvement in the visibility of the anti-slip wrapping material and / or a beautiful appearance, if necessary.

The coloring agent may be, for example, a pigment, and is not particularly limited as long as it can be usually used in a non-slip packaging material. Examples of the pigment include a blue pigment and a red pigment, and may be iron oxide, chromium oxide, or barium carbonate, for example.

The coloring agent may be used in an amount of 0.1 to 5% by weight, preferably 0.1 to 4% by weight, more preferably 0.5 to 3% by weight based on the antistatic agent composition (based on the solid content).

When the coloring agent is used in an amount of 0.1 wt% or more, the effect of imparting appropriate color to the non-slip packaging material can be exhibited. If the coloring agent is used in an amount of 5 wt% or less, the physical properties of the non-slip packaging material may not be affected.

(7) Auxiliary filler

The anti-slip packaging composition of the present invention may further include auxiliary fillers as needed in order to increase the bonding force between the components and solve problems such as cracking or breaking of the anti-slip wrapping material.

The auxiliary filler may be, for example, polyvinyl alcohol (PVA) yarn, nylon yarn, polyester yarn, or a mixture thereof and has a length of 1 to 20 mm, preferably 2 to 10 mm, more preferably 3 to 5 mm mm.

The auxiliary filler may be used in an amount of 0.01 to 5% by weight, preferably 0.05 to 1% by weight, more preferably 0.1 to 0.3% by weight based on the composition of the anti-slip material (based on the solid content).

(8) Catalyst

The catalyst is included for curing of the anti-slip package composition, and benzo-peroxide may be used.

The benzoyl peroxide is not particularly limited, but it is possible to use those having a purity of 50% to 99%, and considering that the benzoyl peroxide is liable to explode by impact or heat, preferably 50% .

(9) Other additives

The anti-slip package composition of the present invention may further comprise waxes, anti-settling agents, dispersants, adhesion promoters, and the like, if necessary.

The wax may be included for oxygen blocking, coating protection, scratch resistance, abrasion resistance, stain resistance improvement, and the like. The wax may be used in an amount of 0.01 to 2 wt%, preferably 0.02 to 1 wt%, more preferably 0.05 to 0.5 wt%, based on the anti-slip package composition (based on the solids content).

The anti-settling agent may be added to prevent sedimentation of the coloring agent included in the anti-slip packaging composition and to prevent sagging of the anti-slip packaging composition. The anti-settling agent may be used in an amount of 0.01 to 2% by weight, preferably 0.02 to 1% by weight, more preferably 0.05 to 0.5% by weight based on the anti-slippery package composition (based on the solid content).

The process of curing the anti-slip packaging composition of the present invention can be described as follows.

For example, if (1) the copolymer (1) is diluted to 30 to 50% by weight in the crosslinking agent (4), addition polymerization occurs in the unsaturated group portion of the copolymer and the vinyl period of the crosslinking agent, And forms a high-molecular-weight high-molecular-weight resin. At this time, a catalyst and an accelerator are added, and the catalyst and the accelerator are added just before the polymerization.

Since the reaction is an exothermic reaction and the solvent may volatilize during the polymerization reaction, it is preferably carried out at a temperature of about 20 to 60 ° C, preferably at room temperature.

Example

Hereinafter, the present invention will be described in more detail with reference to the following Preparation Examples and Examples, but the present invention is not limited thereto.

Manufacturing example  : Preparation of Copolymer

44.2 parts by weight of triethylene glycol, 11.6 parts by weight of ethylene glycol, 8.4 parts by weight of propylene glycol, 63.0 parts by weight of tetrahydrophthalic anhydride, 67.0 parts by weight of fumaric acid and 12 parts by weight of xylene were fed into a reactor, Lt; RTI ID = 0.0 >%< / RTI >

Example  1: Preparation of slip resistant packaging composition

194.2 parts by weight of the resin prepared in the above Production Example was diluted at 30 캜 or lower, and then diluted with 55 parts by weight of methyl methacrylate and 20 parts by weight of butyl acrylate.

Wherein the diluted resin in 21 parts by weight, N, N- trimethyl-aniline and 0.07 parts by weight of a light calcium carbonate as a promoter (TALC POWDER (zeolite planar # 325 pass product), ㈜ Cotswold Co., Ltd.) 21 parts by weight of colloidal calcium carbonate (CaCO ₃ (K-LON 1000, NIKKON CO., LTD.) Having a length of 3 to 6 mm, 4.5 parts by weight of a coloring agent (POWDER CO., LTD.), 1.8 parts by weight of iron oxide , 0.1 part by weight of wax (Cepaflour 914, manufactured by BYK), 44.12 parts by weight of No. 6 silica (manufactured by Kyokin Kagaku Kagaku Co., Ltd.), 6 parts by weight of silica gel No. 8 ) Were mixed to prepare an anti-slip package composition.

Example  2 to 5: Manufacture of anti-slip package composition

A non-slip packaging composition was prepared in the same manner as in Example 1, except that the content of each component was changed as shown in Table 1 below.

Example  One Example  2 Example  3 Example  4 Example  5 Example  6 Example  7 Suzy 21 21 21 21 21 21 21 Accelerator (aniline system) 0.07 0.07 0.07 0.07 0.07 - - Accelerator (cobalt) - - - - 0.07 0.08 CaCo3 21 15 15 21 21 21 15 Colloidal calcium carbonate 4.5 10.5 10.5 4.5 4.5 4.5 10.5 ColorPaste 1.8 1.0 1.0 1.0 1.8 1.8 1.0 BYK410 0.1 0.1 - 0.2 0.1 0.1 0.1 Auxiliary filler
( PVA fiber reinforcing agent ) 0.1 0.1 - 0.2 0.1 0.1 0.1 WAX 0.1 - - - 0.1 0.1 - No. 6 silica sand 30.12 35.12 40.12 44.12 44.12 44.12 35.12 No. 8 Silk 20 15 10 6 6 6 15 Bemgoic Peroxide  (50%) 1.0 1.0 1.0 1.2 1.2 1.2 1.0

Experimental Example  : Property evaluation

The non-slip packaging compositions of Examples 1 to 5 were stirred at a high speed within a temperature range of 20 to 40 DEG C within 10 minutes using a hand mixer.

The primer (T-44, KAN-KA Hwasung, KUT-11, Kolon) was applied thinly on the construction surface to a thickness of 0.5 mm or less by using a roller. Within 30 minutes, each of the anti- And then uniformly coated with a mortar and then uniformly coated in a second order using a roller. At this time, the thickness was set to be in the range of 2 to 3 mm. The properties were evaluated according to the following methods, and the results are shown in Table 2

Drying time: KS M 5000

Absorption Rate: SPS-KTS.1102-1890: 2012

Flame resistance: KS M ISO1514

Compressive strength: KS F 2476

Adhesive strength: KS F 2386

Accelerated weathering: KS ISO 1514

Abrasion resistance: KS M 6080

Slip resistance: KS F 2375

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Drying time (Solidification) 120 minutes or less 50 45 40 40 40 45 50 Absorption rate 1.0 (%) or less 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Saltwater 3% saline 96 hours
Discoloration, no parts no problem no problem no problem no problem no problem no problem no problem Compressive strength 20MPa or more 35 30 35 37 40 37 30 Adhesive strength
(MPa) concrete
1.5 or more 2.5 2.7 3.0 3.3 3.5 3.0 2.5 asphalt
1.0 or higher 2.3 2.5 2.8 3.0 3.4 2.4 2.3 Accelerated weathering No more than 300 hours no problem no problem no problem no problem no problem no problem no problem Abrasion resistance Wear rate less than 1% 0.5 0.6 0.6 0.5 0.5 0.5 0. Slip resistance 500,000 times
55BPN or more 55 56 57 57 58 57 56

As a result of evaluation of the physical properties, the non-slip packaging materials prepared using the non-slip packaging compositions of Examples 1 to 5 were presented in the group standard [non-slip packing agent (SPS-KTS. 1102-1890: 2012) It was confirmed that the physical properties satisfying the above were satisfied.

mixture Drying time (solidification) min 120 or less Absorption% 1.0 or less Saltwater It should be soaked in 3% (w / v) saline solution for 96 hours. Impact resistance There should be no cracking or peeling due to the impact of the weight. Compressive strength (1 day at a time) MPa 20 or more Adhesive strength
MPa concrete 1.5 or more asphalt 1.0 or higher Accelerated weathering After 300 hours of testing, there should be no discoloration or discoloration. Abrasion test
(500,000 times) Wear rate% 1 or less Slip Resistance BPN 55 or more

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is clearly understood that the same is by way of illustration and example only and is not to be taken by way of limitation, It is to be understood that the invention may be practiced within the scope of the appended claims.

Claims (10)

(1) a copolymer;
(2) fillers;
(3) silica sand;
(4) a crosslinking agent; And
(5) contains an accelerator,
Wherein the accelerator is dimethylaniline or N, N'-trimethylaniline,
Wherein the filler comprises a gypsum calcium carbonate,
Wherein said calcium carbonate is surface-treated with soybean oil, dehydrated castor oil, linseed oil, or tung oil.
The method according to claim 1,
Wherein the copolymer (1) comprises a structural unit derived from (1-1) an unsaturated acid, an unsaturated acid anhydride, or a mixture thereof, (1-2) a structural unit derived from a saturated polybasic acid, a saturated polybasic acid anhydride, , And (1-3) a structural unit derived from a polyhydric alcohol having two or more hydroxyl groups.
3. The method of claim 2,
Wherein the (1-1) unsaturated acid, the unsaturated acid anhydride, or a mixture thereof is selected from the group consisting of maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and mesaconic acid At least one non-slip packaging composition.
3. The method of claim 2,
Wherein the saturated polybasic acid, the saturated polybasic acid anhydride, or the mixture thereof is at least one selected from the group consisting of phthalic anhydride, isophthalic acid, tetrahydrophthalic anhydride, terephthalic acid, hexachloroendomethylenetetrahydrophthalic acid (HET acid, chlorenedic acid, Wherein the composition is at least one selected from the group consisting of polypropylene, polypropylene, and polypropylene.
3. The method of claim 2,
The polyhydric alcohol of (1-3) bivalent or higher is preferably at least one selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, butanediol, 1,6-hexanediol, glycerin, diglycerol, And at least one member selected from the group consisting of dipentaerythritol.
delete The method according to claim 1,
Wherein said gelled calcium carbonate has a particle size of from 0.01 to 0.2 占 퐉.
The method according to claim 1,
Wherein the anti-slip packaging composition further comprises (5) 0.01 to 5% by weight of auxiliary filler,
Wherein the auxiliary filler is polyvinyl alcohol, nylon or polyester or mixtures thereof.
9. The method of claim 8,
(7) The anti-slip package composition as described in (7), wherein the auxiliary filler has a size of 3 to 5 mm.
The method according to claim 1,
(1) the copolymer, (2) the filler, (3) the silica, (4) the crosslinking agent, and (5) the accelerator are added to the non-slip packaging composition in an amount of 0.1 to 50 wt. %, 0.1 to 50 wt%, 5 to 60 wt%, 0.1 to 40 wt%, and 0.01 to 1 wt%, based on the total weight of the composition.