KR20100066008A - Water-proof materials comprising silicone rubber or butadiene rubber - Google Patents

Abstract

PURPOSE: A water-proof material composition is provided to secure the room temperature rapid curing property and an excellent adhesive force, and to easily construct the composition compared to a guss-based composition. CONSTITUTION: A water-proof material composition is produced by mixing a syrup composition with a polymerization initiator. The syrup composition contains the following: more than two monomer compounds selected from (meth)acrylate monomers; an acrylic polymer capable of dissolving to the monomer compounds; a cross-linking agent; a vinyl monomer containing a phosphorous component; a polymerization promoter mixed with more than one amine system compound or metal oxide; and silicone rubber or butadiene rubber.

Description

Water-Proof Materials Comprising silicone rubber or butadiene rubber

The present invention relates to a one-component acrylic waterproofing material composition to which silicone rubber or butadiene rubber is added.

According to the new construction technology No. 186, there is a waterproofing material that has an epoxy-based resin applied to the upper surface of the steel plate bridge to have waterproof and anticorrosive functions, but epoxy resins have environmental problems due to toxic gases generated during curing. As the temperature increases, the structure stretches, whereas the epoxy resin shrinks, which is not suitable.

In the case of the Republic of Korea Patent 10-1998-0007864 coating film waterproofing material mainly composed of chloroprene rubber, the lifting layer due to the high temperature during asphalt installation and the adhesion of the asphalt and weak adhesive force may cause the waterproof layer to be pushed by the vehicle load. .

In the case of the acrylic waterproof material, the adhesion and waterproof performance is very excellent at room temperature, but in general, the acrylic resin has a weak characteristic at a low temperature, and thus has a disadvantage in that the waterproof layer is damaged by bridge vibration in winter.

In addition, in the case of goose-based asphalt which is usually used for the purpose of waterproofing the steel plate, the waterproof performance is not effective and the construction cost is too high, there may be a problem to apply commercially.

An object of the present invention is to provide a one-component acrylic waterproof material composition capable of rapid curing at room temperature, having excellent adhesion, waterproofing, anticorrosion and low temperature flexibility.

The present invention is a vinyl monomer containing at least two monomer mixtures (a) selected from the (meth) acrylate monomers, an acrylic polymer (b), a crosslinking agent (c), and a phosphorus component that can be dissolved in the component (a). d), a one-component acrylic system prepared by mixing a syrup composition containing a polymerization accelerator (e), a silicone rubber or a butadiene rubber (f) mixed with at least one selected from an amine compound or a metal oxide with a polymerization initiator. It relates to a waterproofing composition.

The present inventors have found that by adding silicone rubber or butadiene rubber to acrylic syrup, it is possible to provide a waterproof material composition having excellent properties of acrylic waterproof material and having flexibility at low temperatures.

Hereinafter will be described in more detail with respect to the present invention.

The mixture of two or more monomers (a) selected from the above (meth) acrylate monomers according to the present invention is 10 to 80% by weight of methyl methacrylate and ethyl methacrylate, n-butyl methacrylate, I-butyl methacryl. One or more methacrylate monomers selected from acrylate, t-butyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, or methyl acrylate, ethyl acrylate, n-butyl acrylate, t It may be prepared by mixing 90 to 20% by weight of one or more acrylate monomers selected from -butyl acrylate, urethane acrylate and 2-ethylhexyl acrylate.

When the methyl methacrylate is used in less than 10% by weight, the curing property is lowered, severe odor may occur after curing, and if it exceeds 80% by weight may be broken by the impact after curing, it is preferable to use in the above range .

The acrylic polymer (b) may be dissolved in at least two monomer mixtures (a) selected from the (meth) acrylate monomers, and selected from methacrylate monomers and acrylate monomers or methacrylic acid and acrylic acid. It may include those copolymerized using one or more types of comonomers capable of copolymerizing on paper.

In the present invention, the methacrylate monomer is ethyl methacrylate, n-butyl methacrylate, I-butyl methacrylate, t-butyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate It may be at least one selected, and the acrylate-based monomer may be at least one selected from methyl acrylate, ethyl acrylate, n-butyl acrylate, t- butyl acrylate, 2-ethylhexyl acrylate. . The methacrylate monomer may impart water resistance, hardness, flexibility, etc. of the one-component acrylic waterproofing material composition according to the present invention.

The acrylic polymer (b) is 30 to 80% by weight of methyl methacrylate and ethyl methacrylate, n-butyl methacrylate, I-butyl methacrylate, t-butyl methacrylate, lauryl methacrylate, 2 -At least one methacrylate monomer selected from ethylhexyl methacrylate or one selected from methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate and 2-ethylhexyl acrylate It is preferable to use the polymer which copolymerized the above acrylate-type monomer or 1 or more types of copolymerizable comonomers chosen from methacrylic acid and acrylic acid at 20 to 70 weight%.

When the methyl methacrylate is used at less than 30% by weight, the surface hardening state is not good, and when the methylmethacrylate is more than 80% by weight, it may be broken by the impact after curing, which may be poor in durability.

The acrylic polymer may be advantageous to low temperature flexibility to use a glass transition temperature of -20 ℃ ~ 60 ℃. The acrylic polymer has excellent adhesion performance and waterproof performance at room temperature.

The crosslinking agent (c) is ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,2-propylene glycol diacrylate, 1,2-propylene glycol dimethacrylate, 1,3-butylene glycol diacrylate Selected from 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, 1,6-hexanediol diacrylate, and 1,4-butanediol diacrylate 1 or more types can be used.

The vinyl monomer (d) containing the phosphorus component is diethyl allyl phosphate, hydroxyethyl methacrylate phosphate, hydroxyethyl acrylate phosphate, bis (2-hydroxyethyl methacrylate) acid phosphate, 2-hydroxy At least one selected from ethyl methacrylate phosphate and tris (2-hydroxyethyl methacrylate) phosphate may be used. The vinyl monomer containing the phosphorus component (d) improves the adhesive strength with the substrate, and can be used to improve the adhesive strength with the existing concrete or steel plate without the usual undercoat.

In the present invention, the polymerization accelerator (e) may be used by mixing one or more selected from amine compounds and metal oxides. As a more specific example of the polymerization accelerator (e), N, N-di (2-hydroxypropyl) -p-toluidine, tri-n-butylamine, N, N-dimethyl-p-toluidine, N- Ethyl-N-hydroxy ethyl aniline, N, N- dimethyl aniline, etc. are mentioned.

In the present invention, the silicone rubber or butadiene rubber (f) may be used by mixing one or two selected from rubbers containing silica or butadiene as a main component. Examples of the silicone rubber include sim 100 (LG Chemical) and butadiene rubber include MUX60 (Mitsubishi Rayon).

Although the composition of the resin of this invention contains (a)-(f) component, if necessary, it can add and use the additive which can be used for the said field | area, such as a wax, a polymerization inhibitor, a coloring agent, etc. as needed. In addition, a polymerization inhibitor such as hydroquinone and topanol-A may be added for storage stability, and color development may be performed by adding a colorant.

The syrup composition is dissolved by mixing 70-5 wt% of the acrylic polymer (b) with 30-95 wt% of the at least two monomer mixtures (a) selected from the (meth) acrylate-based monomers. 0.1 to 10 parts by weight of the crosslinking agent (c), 0.1 to 3 parts by weight of the vinyl monomer (d) containing phosphorus component, 0.1 to 10 parts by weight of the polymerization accelerator (e), and silicone rubber or parts based on 100 parts by weight of the mixture of b). It can be prepared by mixing 3 to 20 parts by weight of tadadiene rubber (f).

The one-component acrylic waterproofing material composition having the above composition and content has a phenomenon of lifting up due to high temperature during asphalt laying and weak adhesion with asphalt, so that the waterproof layer is not pushed due to vehicle load, which is effective for construction as well as rapid curing of the roof. There is a possible advantage.

Hereinafter will be described in more detail the content of the components for forming the syrup composition of the present invention.

The at least two monomer mixtures (a) selected from the (meth) acrylate monomers are 30 to 95 in 100% by weight of the components of the at least two monomer mixtures (a) and the acrylic polymer (b) selected from the (meth) acrylate monomers. A range of weight percent is preferred. If 30% by weight or less is included, the viscosity of the syrup increases and workability is lowered. If it is 95% by weight or more, the degree of polymerization may be lowered and thus curability may be lowered. In addition, the acrylic polymer (b) may be used in 5 to 70% by weight, when using less than 5% by weight, the curability is lowered, and when used in excess of 70% by weight, the viscosity of the syrup increases and workability Can be degraded.

The crosslinking agent (c) is preferably 0.1 to 10 parts by weight, and less than 0.1 part by weight based on 100 parts by weight of the total of at least two monomer mixtures (a) and acrylic polymers (b) selected from the (meth) acrylate monomers. When used as, the curability is lowered, and when used in excess of 10 parts by weight, there may be a problem that the flexibility after curing is lowered and broken.

The vinyl monomer (d) containing the phosphorus component is preferably 0.1 to 3 parts by weight based on 100 parts by weight of the total of two or more monomer mixtures (a) selected from the (meth) acrylate monomers and the acrylic polymer (b). When less than 0.1 part by weight, when used in bridges, the steel plate and the adhesive strength is lowered, if it exceeds 3 parts by weight, the curability may be lowered.

The polymerization accelerator (e) is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the total of two or more monomer mixtures (a) selected from the (meth) acrylate monomers and the acrylic polymer (b). When using less than 0.1 parts by weight, the curing rate is slow, and when it exceeds 10 parts by weight may be broken after curing.

Silicone rubber or butadiene rubber (f) is used 3 to 20 parts by weight based on 100 parts by weight of the total of two or more monomer mixtures (a) and acrylic polymer (b) selected from the (meth) acrylate monomers It is desirable to. When used in 3 parts by weight or less, low temperature properties do not appear sufficiently, and when used in 20 parts by weight or more, it is difficult to secure sufficient physical properties as a waterproofing material by preventing curing.

In addition, in the present invention, the wax may be used in addition to 0.1 to 5 parts by weight based on 100 parts by weight of the sum of the at least two monomer mixtures (a) and the acrylic polymer (b) selected from the (meth) acrylate monomers as necessary. When the amount is less than 0.1 part by weight, the effect is insignificant, and when it is more than 5 parts by weight, the adhesion with the substrate may be reduced.

In the present invention, the syrup composition may be constructed by mixing with a polymerization initiator. When the polymerization initiator is mixed, the syrup composition is cured while polymerizing. The polymerization initiator may use a radical polymerization initiator selected from peroxides, and more specifically, organic peroxides may be used, and ketone peroxides and diacyl peroxides are preferable examples. Hydroperoxides, dialper peroxides, peroxy tars and the like, there may be used benzol peroxide as a preferred example, it may be used alone or in combination.

The polymerization initiator may be used by mixing 1 to 20 parts by weight based on 100 parts by weight of the total syrup composition.

The one-component acrylic waterproofing material composition according to the present invention is capable of rapid curing at room temperature, has excellent adhesion, waterproofing, anticorrosion, and has low temperature flexibility, so that it can be used for construction more easily than a goose-based composition.

More specifically, the one-component acrylic waterproofing material composition according to the present invention not only has excellent physical properties in tensile strength, adhesive strength, adhesive strain, water permeability, etc., but also has excellent elongation and low temperature by adding silicone rubber or butadiene rubber. You can also have flexibility.

In addition, the lifting phenomenon due to the high temperature during the asphalt installation and the adhesive strength with the asphalt is weak, there is no phenomenon that the waterproof layer is not pushed by the vehicle load, it is effective in the construction and has the advantage that can be cured in the roof. Phosphorus-containing vinyl monomer (d), which is included in the present invention, improves adhesion with the substrate, and can be used to improve adhesion with existing concrete or steel plates without the usual undercoat.

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]

Acrylic Polymer Manufacturing

0.15 parts by weight of azobisisobutyronitrile (AIBN), 200 parts by weight of water, based on 100 parts by weight of a monomer containing 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) and 0.36 parts by weight of normal-octylmercaptan, followed by a suspension polymerization reaction at a reaction temperature of 80 ° C. for 90 minutes to remove residual monomers. Further polymerization was carried out at 15 ° C. for 15 minutes. The polymerized acrylic polymer A was washed with a dehydrator and dried in a drier for 24 hours. As a result of analysis by a thermal analyzer, an acrylic polymer A having a glass transition temperature of 45 ° C. was obtained.

Example 1

One component  Acrylic Waterproof Material Composition

While stirring the stirrer at 60 ° C., 60 wt% of methyl methacrylate and 20 wt% of butyl acrylate were added to the stirrer as a mixed monomer. 20% by weight of the acrylic polymer A prepared in Preparation Example 1 was dissolved in the mixed monomer. 3 parts by weight of 1,4-butanediol diacrylate, 0.4 parts by weight of bis (2-hydroxyethyl methacrylate) acid phosphate, tri-n- when the total amount of the mixed monomer and the acrylic polymer A is 100 parts by weight. 0.3 parts by weight of butyl amine and 8 parts by weight of silicone rubber (sim 100, LG Chem) were added, and after the dissolution was completed, the temperature inside the stirrer was reduced to room temperature to prepare a syrup composition. 3 parts by weight of benzol peroxide was mixed with 100 parts by weight of the syrup composition to prepare a one-component acrylic waterproofing material composition. The prepared waterproofing material composition and content are shown in Table 1 below. The prepared waterproofing material composition was measured for physical properties after curing, and the results are shown in Table 2.

[Example 2]

Except for using butadiene rubber (MUX 60, Mitsubishi Rayon) was prepared in one-component acrylic waterproofing material composition in the same manner as in Example 1, the composition and content of the prepared waterproofing material is shown in Table 1 below. The prepared waterproofing material composition was measured for physical properties after curing, and the results are shown in Table 2.

Example 3

While stirring the stirrer at 60 ° C., 50% by weight of methyl methacrylate, 20% by weight of butyl acrylate and 10% by weight of urethane acrylate were added to the stirrer as a mixed monomer. 20% by weight of the acrylic polymer A prepared in Preparation Example 1 was dissolved in the mixed monomer. When the total amount of the mixed monomer and the acrylic polymer A is 100 parts by weight, 2 parts by weight of 1,4-butanediol diacrylate, 0.5 part by weight of bis (2-hydroxyethyl methacrylate) acid phosphate, and tri-n 0.5 parts by weight of -butyl amine and 5 parts by weight of a silicone rubber (sim 100, LG Chemical) were added, and after the dissolution was completed, the temperature inside the stirrer was reduced to room temperature to prepare a syrup composition. 5 parts by weight of benzoleperoxide was added to the prepared syrup composition to 100 parts by weight of the syrup composition to prepare a one-component acrylic waterproofing material composition. The prepared waterproofing material composition and content are shown in Table 1 below. The prepared waterproofing material composition was measured for physical properties after curing, and the results are shown in Table 2.

Comparative Example 1

Except not using a butadiene rubber or silicone rubber, a one-component acrylic waterproofing material composition was prepared in the same manner as in Example 1, and the composition and content of the prepared waterproofing material are shown in Table 1 below. The prepared waterproofing material composition was measured for physical properties after curing, and the results are shown in Table 2.

Comparative Example 2

Except for not using a bis (2-a hydroxyethyl methacrylate) phosphate in Example 1 was prepared in the same manner as in Example 1, the composition and content of the prepared waterproofing material is shown in Table 1 below. The prepared waterproofing material composition was measured for physical properties after curing, and the results are shown in Table 2.

Property evaluation

The physical properties of Examples 1 to 3 and Comparative Examples 1 to 2 were evaluated and shown in Table 2 below.

1) Tensile strength, elongation rate, tensile adhesion strength, shear adhesion strength, shear adhesion strain, water permeability, penetration resistance of chloride ion, resistance to dent and thermal dimension stability were measured by KS F 4932.

2) Tensile adhesiveness was measured after 7 days of immersion according to the highway professional specification.

Table 1

Table 2

Claims (7)

2 or more types of monomer mixtures (a) selected from (meth) acrylate monomers, acrylic polymers (b) soluble in the component (a), crosslinking agents (c), vinyl monomers containing phosphorus components, A one-component acrylic waterproofing material composition prepared by mixing a syrup composition containing a polymerization accelerator (e), a silicone rubber or a butadiene rubber (f) mixed with at least one selected from an amine compound or a metal oxide with a polymerization initiator. The method of claim 1, The mixture of two or more monomers (a) selected from the above (meth) acrylate monomers is 10 to 80% by weight of methyl methacrylate and ethyl methacrylate, n-butyl methacrylate, I-butyl methacrylate, t- One or more methacrylate monomers selected from butyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate or methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate 1-component acrylic waterproofing material composition which mixes 90-20 weight% of 1 or more types of acrylate-type monomers chosen from urethane acrylate and 2-ethylhexyl acrylate. The method of claim 1, The acrylic polymer (b) is 30 to 80% by weight of methyl methacrylate and ethyl methacrylate, n-butyl methacrylate, I-butyl methacrylate, t-butyl methacrylate, lauryl methacrylate, 1 or more methacrylate monomers selected from 2-ethylhexyl methacrylate or 1 selected from methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate A one-component acrylic waterproofing material composition comprising copolymerizing at least one acrylate monomer or at least one copolymerizable comonomer selected from methacrylic acid and acrylic acid at 20 to 70% by weight. The method of claim 3, wherein The acrylic polymer is a one-component acrylic waterproofing material composition having a glass transition temperature of -20 ℃ ~ 60 ℃. The method of claim 1, The crosslinking agent (c) is ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,2-propylene glycol diacrylate, 1,2-propylene glycol dimethacrylate, 1,3-butylene glycol diacrylate 1 selected from 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, 1,6-hexanediol diacrylate, and 1,4-butanediol diacrylate One-component acrylic waterproofing material composition using more than one species. The method of claim 1, The vinyl monomer (d) containing the above-mentioned phosphorus component is diethyl allyl phosphate, hypoxyethyl methacrylate phosphate, hydroxyethyl acrylate phosphate, bis (2-hydroxyethyl methacrylate) acid phosphate, 2-hydroxy A one-component acrylic waterproofing material composition using at least one selected from ethyl methacrylate phosphate and tris (2-hydroxyethyl methacrylate) phosphate. The method according to any one of claims 1 to 6, The syrup composition is dissolved by mixing 70-5 wt% of the acrylic polymer (b) with 30-95 wt% of the at least two monomer mixtures (a) selected from the (meth) acrylate monomers, and (a) and (b 0.1 to 10 parts by weight of the crosslinking agent (c), 0.1 to 3 parts by weight of the vinyl monomer (d) containing phosphorus component, 0.1 to 10 parts by weight of the polymerization accelerator (e), or silicone rubber A one-component acrylic waterproofing material composition comprising a diene rubber (f) 3 to 20 parts by weight.