KR20120064367A - Methyl methacrylate based reactive resin for anti-skid pavement - Google Patents

Abstract

PURPOSE: An anti-slip methacrylate-based reactive resin composition is provided to enable rapid cure at room temperature and improve shock resistance, low-temperature characteristic, durability, and application property. CONSTITUTION: An anti-slip methacrylate-based reactive resin composition comprises 0.1-5 parts by weight of cross-linking agent and 1-10 parts by weight of polymerization accelerator based on 100.0 parts by weight of mixture. The mixture comprises 20-40 weight% of acrylic polymer, 20-40 weight% of methyl methacrylate, 25-35 weight% of acrylate based monomer except methyl methacrylate, and 5-10 weight% of n-butyl methacrylate monomer. The acrylate-based monomer except methyl methacrylate comprises more than 2 kinds selected from methyl acrylate, ethyl acrylate, N-butyl acrylate, T-butyl acrylate, and 2-ethylhexylacrylate.

Description

Non-slip methacrylate-based reactive resin composition {Methyl methacrylate based reactive resin for anti-skid pavement}

The present invention includes a crosslinking agent and a polymerization accelerator for a mixture of methyl methacrylate, at least two monomers selected from acrylate monomers except methyl methacrylate, and normal butyl methacrylate monomers in an acrylic polymer. The present invention relates to a non-slip packaging material composition having no degradation in physical properties and improved durability.

In general, in downhill or overspeed danger zones such as highways, national roads, and local roads, slippage may occur due to slippery roads or vehicle overturning due to the speed of vehicles. have. In addition, as interest in safety accidents increases, various non-slip structures are used on roads of intersections, sharp curves, and road accidents.

In general, the composition for preventing slipping of the road is made to give a frictional resistance when driving the vehicle. In order to impart such frictional resistance, aggregate, steelmaking slug, silica sand, etc. are used as fillers to impart frictional resistance, and chemical reaction by thermoplastic resin and initiator (curing agent) as binders to firmly bind the fillers that impart frictional resistance. Epoxy resin, urethane resin, and acrylic resin containing methacrylate are used as reactive binders.

In the case of the Republic of Korea Patent No. 0171675, it is proposed a method of fusion to the surface of the road by heating 200-250 degrees by mixing with crushed stone, silica sand using a thermoplastic resin as an anti-slip binder. In the case of such a method, the heat treatment is required in the field, the economical efficiency is reduced, the aggregate distribution is biased, the sliding may occur on the surface of the thermoplastic resin, and its durability is also insufficient.

Recently, non-slip packaging using methacrylate resins as a reactive binder has been widely used. Methyl methacrylate-based resin is excellent in reactivity even at room temperature or low temperature by the peroxide initiator, the non-slip construction time is short, and has excellent characteristics of adhesion and durability with asphalt and concrete surfaces. However, when methyl methacrylate alone is used, its glass transition temperature is high, so that the tensile strength is too high and the elongation is low after curing. If the non-slip construction on the road surface, it may cause tearing or cracking due to shrinkage and expansion by heat of asphalt. In order to solve this problem, it is common to use an acrylic monomer having a relatively low glass transition temperature.

However, when the acrylic monomers are mixed, the acrylic monomers having a slow reaction rate due to the difference in the reaction rates of the two different monomers do not participate in the curing reaction, resulting in a problem of remaining. The acrylic monomer thus retained may be present in the anti-slip composition where the curing reaction is completed to serve as a plastic plasticizer to temporarily improve physical properties. However, these residual acrylic monomers evaporate over time, which results in a drastic deterioration in physical properties, particularly elongation, of the cured composition, which may cause a serious problem that the anti-slip composition is torn or uniform on the road surface. Can be.

The present invention is to solve the problems of the prior art to provide a methacrylate-based non-slip packaging material composition that is capable of rapid curing at room temperature, and to minimize the change of physical properties over time by minimizing the unreacted acrylic monomer. There is a purpose.

The anti-slip packaging composition for solving the above technical problem includes a crosslinking agent and a polymerization accelerator in a mixture consisting of an acrylate monomer and a normal butyl methacrylate monomer except for an acrylic polymer, methyl methacrylate and methyl methacrylate.

Hereinafter, the present invention will be described in more detail.

The non-slip packaging composition of the present invention is 20 to 40% by weight of the acrylic polymer, 20 to 40% by weight of methyl methacrylate, 25 to 35% by weight of the acrylate monomer excluding methyl methacrylate and 5 to normal butyl methacrylate monomer. 0.1 to 5 parts by weight of the crosslinking agent and 1 to 10 parts by weight of the polymerization accelerator, based on 100 parts by weight of the mixture consisting of 10% by weight.

The methyl methacrylate is preferably used 20 to 40% by weight. If the content is less than 20% by weight, there is a problem that the curing is delayed, and if the content exceeds 40% by weight, sufficient elongation characteristics cannot be obtained after curing.

The acrylate monomers other than the methyl methacrylate include two or more acrylate monomers selected from methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate or 2-ethylhexyl acrylate. do.

It is preferable to use 25 to 35% by weight of the two or more monomers selected from the acrylate monomers in the mixture. If the content is less than 25% by weight, the low-temperature properties worsen after curing, and if it exceeds 35% by weight, curing is delayed.

The normal butyl methacrylate monomer is preferably used 5 to 10% by weight. The added normal butyl methacrylate is present between the methyl methacrylate and the acrylic monomer to increase the reaction rate to reduce the unreacted residual acrylic monomer. When the content is less than 5% by weight it is difficult to remove the unreacted acrylic monomer, and when it exceeds 10% by weight it is difficult to secure the required elongation characteristics due to the high glass transition temperature.

The acrylic polymer is methyl methacrylate 30 to 80% by weight; and ethyl methacrylate, n-butyl methacrylate, I-butyl methacrylate, t-butyl methacrylate, lauryl methacrylate, 2-ethyl At least one methacrylate monomer selected from hexyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, at least one acrylate selected from 2-ethylhexyl acrylate Copolymerized with 20 to 70% by weight of one or more comonomers selected from the group monomers or methacrylic acid and acrylic acid.

The acrylic polymer is preferably used 20 to 40% by weight. When the content is less than 20% by weight, the viscosity of the composition is low, the shrinkage problem occurs during curing, and when the content exceeds 40% by weight, the viscosity is high, workability is lowered, and self-leveling is impossible. In addition, the acrylic polymer is characterized in that the glass transition temperature is -20 ℃ ~ 60 ℃.

The crosslinking agent is ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,2-propylene glycol diacrylate, 1,2-propylene glycol dimethacrylate, 1,3-butylene glycol diacrylate, 1, It includes at least one selected from 3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate or 1,6-hexanediol diacrylate.

The crosslinking agent improves chemical resistance by crosslinking in the curing process of the monomer, it is preferable to use 0.1 to 10 parts by weight based on 100 parts by weight of the mixture. If the content is less than 0.1 parts by weight, the curability is lowered, if it exceeds 5 parts by weight there is a problem that the flexibility is lowered after curing is broken.

The polymerization promoter may be used by mixing one kind selected from amine compounds and metal oxides. For example, the amine compound may be N, N-di (2-hydroxypropyl) -p-toluidine, tri-n-butyl amine, N, N-dimethyl-p-toluidine, N-ethyl-N At least one selected from -hydroxy ethyl aniline or N, N-dimethyl aniline.

The polymerization accelerator is preferably used 0.1 to 10 parts by weight based on 100 parts by weight of the mixture. If the content is less than 0.1 parts by weight, the curing reaction is delayed at low temperatures, and if the temperature is higher than 10 parts by weight, the uncured problem occurs.

The present invention may further contain functional additives such as waxes, colorants, colorants or polymerization inhibitors as necessary. The wax is for preventing the surface uncured by blocking the contact of the resin surface and oxygen, the colorant to enable color expression, and polymerization inhibitors such as hydroquinone and topanol-A can impart storage stability. have.

With respect to 100 parts by weight of the mixture, the content of the wax is preferably used 0.1 to 5 parts by weight. If the content is less than 0.1 parts by weight can not be seen, if more than 5 parts by weight of the road surface and adhesion and physical properties are lowered.

The polymerization initiator used in the present invention causes a curing reaction, and organic peroxides can be used, and the organic peroxides are ketone peroxides and diacyl peroxides. It includes one or more selected from hydroperoxides, dialkyl peroxides or peroxy tars. The polymerization initiator is preferably used 1 to 20 parts by weight based on 100 parts by weight of the mixture. If the content is less than 1 part by weight of the reaction rate is difficult to fast hardenability, if it exceeds 20 parts by weight is insufficient flexibility.

Since the non-slip packaging material composition according to the present invention can be cured at room temperature to minimize unreacted acrylic monomers, there is no deterioration of mechanical properties, and thus exhibits excellent physical properties that do not change tensile strength and elongation even after construction. There is no change over time, and excellent impact resistance and low temperature characteristics, it has the advantage of excellent workability.

Hereinafter, the present invention will be described with reference to preferred examples, but the present invention is not limited to the following examples.

[Production Example 1]

Preparation of Acrylic Polymer

0.15 parts by weight of azobisisobutyronitrile (AIBN) as an initiator based on 100 parts by weight of a monomer mixed with 60% by weight of methyl methacrylate, 20% by weight of ethyl acrylate and 20% by weight of butyl acrylate. 0.84 parts by weight of a 5% polyvinyl alcohol solution (Kuraray Co., Ltd. POVAL PVA217) as a dispersant, and 0.36 parts by weight of normal-octylmercaptan as a chain transfer transfer agent at 80 ° C. for 90 minutes. Further reaction was carried out at 120 ° C. for 15 minutes for removal. The polymer polymerized by the above reaction was prepared by washing and drying for 24 hours, and the glass transition temperature of the polymer was 45 ° C.

Preparation of non-slip packaging composition

Prepared in Preparation Example 1 in 30% by weight of methyl methacrylate, 22% by weight of butyl acrylate, 10% by weight of 2-ethylhexyl acrylate, and 8% by weight of n-butyl methacrylate while stirring the stirrer to 60 ° C. A mixture was prepared in which 30 wt% of acrylic polymer A was dissolved. 3 parts by weight of 1,4-butanediol diacrylate, 0.4 part by weight of bis (2-hydroxyethyl methacrylate) acid phosphate and 0.3 part by weight of tri-n-butylamine were added to 100 parts by weight of the mixture. It was reduced to room temperature to prepare a non-slip packaging composition.

[Comparative Production Example 1]

In the non-slip packaging composition in Preparation Example 1, 35 wt% of methyl methacrylate, 22 wt% of butyl acrylate, and 13 wt% of 2-ethylhexyl acrylate without using normal butyl methacrylate. The same preparation was made except that a mixture in which 30 wt% of the acrylic polymer A prepared in 1 was dissolved was used.

Example 1

The specimen was prepared by adding 3% benzolperoxide as a curing initiator to 200 g of the resin composition of Preparation Example 2 and pouring it into a mold having a length of 25 cm x 25 cm thickness 3 mm in a 25-degree constant temperature container. The prepared specimens were processed into dumbbell-type specimens indicated in KS M 3006 standard, and the tensile strength and elongation were measured and shown in Table-1. In addition, in order to analyze the amount of unreacted acrylic monomer present in the cured specimens using gas chromatographies were analyzed and the results are shown in Table 1.

Comparative Example 1

Except for using the anti-slip composition of Comparative Preparation Example 1 was prepared in the same manner as in Preparation Example 1, the physical properties are shown in Table 1 below.

[Table 1]

As shown in Table 1 above, by adding normal butyl methacrylate to an anti-slip composition comprising a methacrylate monomer and an acrylic monomer to increase the reactivity of the methacrylate monomer and the acrylic monomer to minimize the amount of unreacted residual acrylic monomer It can be seen that an excellent anti-slip composition can be produced with little change with time.

Claims (7)

100 weight percent mixture consisting of 20-40 wt% of acrylic polymer, 20-40 wt% of methyl methacrylate, 25-35 wt% of acrylate monomers excluding methyl methacrylate, and 5-10 wt% of normal butyl methacrylate monomer An anti-skid packaging composition comprising 0.1 to 5 parts by weight of the crosslinking agent and 1 to 10 parts by weight of the polymerization accelerator.
The method of claim 1,
The acrylate monomers other than the methyl methacrylate include two or more acrylate monomers selected from methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate and 2-ethylhexyl acrylate. Anti-slip packaging material composition.
The method of claim 1,
The acrylic polymer is methyl methacrylate 30 to 80% by weight; and ethyl methacrylate, n-butyl methacrylate, I-butyl methacrylate, t-butyl methacrylate, lauryl methacrylate, 2-ethyl At least one methacrylate monomer selected from hexyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, at least one acrylate selected from 2-ethylhexyl acrylate A non-slip packaging material composition comprising a copolymer of 20 to 70% by weight of at least one comonomer selected from a monomer, methacrylic acid and acrylic acid.
The method of claim 3, wherein
The acrylic polymer is a non-slip packaging material composition comprising a copolymerization by further reacting at 110 ~ 130 ℃ after the suspension polymerization reaction at 70 ~ 90 ℃.
The method of claim 1,
The acrylic polymer is a slippery packaging material composition having a glass transition temperature of -20 ℃ ~ 60 ℃.
The method of claim 1,
The crosslinking agent is ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,2-propylene glycol diacrylate, 1,2-propylene glycol dimethacrylate, 1,3-butylene glycol diacrylate, 1, Non-slip packaging material composition comprising at least one selected from 3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate or 1,6-hexanediol diacrylate.
The method of claim 1,
The polymerization promoter is N, N-di (2-hydroxypropyl) -p-toluidine, tri-n-butyl amine, N, N-dimethyl-p-toluidine, N-ethyl-N-hydroxyethyl aniline Or N, N- dimethyl aniline non-slip packaging composition comprising at least one selected.