KR20180053135A - Composition for construction materials and construction materials having the same - Google Patents

Abstract

The present invention relates to a composition for building materials, composed of a dry mixture containing an inorganic binder and an aggregate, a polysaccharide derivative, and a phase change material. The present invention further relates to a building material containing the same. According to the present invention, it is possible to provide building materials with excellent adhesive strength at room temperature as well as under high temperatures and underwater environment.

Description

TECHNICAL FIELD [0001] The present invention relates to a composition for building materials and a construction material containing the same. BACKGROUND ART [0002]

The present invention relates to a composition for building materials and a construction material containing the same, and more particularly, to a composition for building materials having a high adhesive strength under a high temperature environment and minimizing a decrease in adhesive strength during immersion in water, To compositions and building materials comprising them.

Building materials such as tile cement mortar, masonry mortar, and repair mortar use polysaccharide derivatives such as cellulose ether to prevent detachment of materials, extend working time, and maintain water retention necessary for curing.

However, the polysaccharide derivatives alone are limited to meet the requirements of building materials used in various environments. For example, the cellulose ether has a limitation in improving the problem of deterioration of adhesive strength caused by dry shrinkage of mortar under a high temperature environment, and thus tiles, masonry, repair mortar, etc. adhering to the construction surface may be dropped have.

As a conventional method for solving the problem of lowering the adhesive strength of the mortar, a method of using a re-melting type powder resin is known.

For example, Patent Document 1 (Domestic Registration No. 10-0782044) is composed of cement, water, fine aggregate and admixture, and the admixture is composed of 1.5 to 5.0 parts by weight of calcium sulfaaluminate-based expanding agent, 0.5 to 4 parts by weight of shrinkage reducing agent 1.0 to 4.0 parts by weight of a fluidizing agent, 4.0 to 10.0 parts by weight of a hydroxyethylcellulose thickener, 0.6 to 1.0 part by weight of a defoaming agent, 2.0 to 8.0 parts by weight of a re-firing powder resin, 1.0 to 1.7 parts by weight of a reinforcing fiber, To 10.0 parts by weight of an inorganic polymer mortar, and the mortar is described as an inorganic polymer mortar having an ability of repairing a section of a deteriorated portion of a reinforced concrete structure and having water resistance. In particular, Patent Document 1 exemplifies ethylvinyl acetate powder resin or SBR powder resin as the re-oiling type powder resin, and describes that the powder resin plays a role in improving adhesion between aggregates.

In Patent Document 2 (Korean Patent Laid-Open Publication No. 10-2012-0075698), any one selected from 35 to 45 wt% white Portland cement or 1 ordinary Portland cement, 25-40 wt% of 60-100 mesh silica, 10 to 20% by weight of 100 to 200 mesh silica sand, 0.2 to 0.5% by weight of methyl cellulose as a thickener, 0.05 to 0.3% by weight of starch as an auxiliary thickener, 0.02 to 0.2% by weight of a polycarboxylic acid and a cellulose content of at least 99.6% 0.3 to 2.0% by weight of fibers, 0.3 to 1.0% by weight of calcium sulfoaluminate as an accelerator, 5 to 10% by weight of a re-oiled EVA powder resin and 5 to 10% by weight of an elastic powder. According to the Patent Document 2, the re-melting type EVA powder resin is an agent for imparting adhesive strength and flexibility, and has an advantage of improving adhesion strength under adverse conditions of a construction environment to improve stability of tile attachment.

However, when a building material such as the inorganic polymer mortar or tile adhesive described in Patent Documents 1 and 2 is immersed in water, the re-melting type powder resin contained in the building material is eluted and the adhesive strength of the building material is lowered Problems can arise.

KR 100782044 B KR 1020120075698 A

A problem to be solved by the present invention is to provide a composition for a building material which contains a polysaccharide derivative and a phase transition material and has an excellent adhesive strength under a high temperature environment and minimizes a decrease in adhesive strength during immersion in water.

Another object to be solved by the present invention is to provide a building material comprising the composition.

In order to solve the above problems, the present invention provides a dry mixture comprising an inorganic binder and an aggregate; Polysaccharide derivatives; And a phase change material.

Wherein the dry mixture is selected from the group consisting of calcium formate, calcium chloride, calcium acetate, calcium nitrate, calcium nitrite, calcium thiocyanate, sodium acetate, sodium nitrate, sodium nitrite sodium thiocyanate, potassium acetate, potassium nitrate, potassium Nitrite, and potassium thiocyanate. The curing accelerator may further include a curing accelerator.

The polysaccharide derivative may include one or more selected from the group consisting of cellulose ether, starch ether, cellulose ester and modified starch.

The cellulose ether includes one or more selected from the group consisting of methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, ethyl hydroxyethyl cellulose and methyl ethyl hydroxyethyl cellulose can do.

The content of the polysaccharide derivative may be 0.05 to 1.0 part by weight based on 100 parts by weight of the dry mixture.

The phase transition temperature of the phase change material is preferably 50 to 80 ° C. and the phase change material is selected from the group consisting of paraffinic hydrocarbons, halogenated hydrocarbons, fatty acids, waxes, and polyethylene glycols glycol, and the like.

The amount of the phase change material may be 0.001 to 0.45 parts by weight based on 100 parts by weight of the dry mixture.

The polysaccharide derivative and the phase change material may be contained in a weight ratio of 10: 0.2 to 10: 4.5.

The composition for building materials according to the present invention may further comprise a re-melting type powder resin.

The re-fusing type powder resin may be 0.1 to 10.0 parts by weight based on 100 parts by weight of the dry mixture, and the re-fusing type powder resin may contain one or more kinds selected from the group consisting of ethylene-vinyl acetate, acrylic latex and styrene-butadiene rubber .

The phase change material contained in the composition and the re-powdered powder resin may be contained in a weight ratio of 1: 400 to 400: 1.

On the other hand, the present invention provides a building material comprising the composition for building materials.

The building material may be any one selected from the group consisting of tile cement mortar, masonry mortar and repair mortar.

According to the present invention, since a polysaccharide derivative and a phase transition material are contained, it is possible to prevent a decrease in adhesive strength due to drying shrinkage at a high temperature, and at the same time, for a building material in which deterioration of adhesive strength due to elution of additives, Composition can be provided.

Therefore, the present invention can provide a building material having excellent adhesive strength not only at room temperature but also under high temperature and underwater environment.

The present invention relates to a dry mixture comprising an inorganic binder and an aggregate; Polysaccharide derivatives; And phase change materials, and a construction material containing the same.

The inorganic binder binds the aggregates and enhances the strength of the building material. Examples of such binders include hydraulic cements such as white cement, ordinary Portland cement, fly ash cement and aluminum containing cement, semi-gypsum, slaked lime, dolomite plaster and clay May be used.

The aggregate serves as a skeleton of the building material. The aggregate serves to improve the mechanical strength of the building material, and a rigid and chemically stable material should be used. As such an aggregate, at least one selected from the group consisting of river sand, mountain sand, silica sand, calcium carbonate and light aggregate (e.g., pearlite) may be used.

The dry mixture may further include a hardening accelerator in addition to the binder and the aggregate. The curing accelerator promotes the hydration reaction and increases the initial strength. The curing accelerator is a compound which enhances the initial strength by increasing the initial strength. Examples of the curing accelerator include calcium formate, calcium chloride, calcium acetate, calcium nitrate, calcium nitrite, calcium thiocyanate, sodium acetate, Nitrate sodium thiocyanate, potassium acetate, potassium nitrate, potassium nitrite and potassium thiocyanate may be used.

The polysaccharide derivative may include one or more selected from the group consisting of cellulose ether, starch ether, cellulose ester, and modified starch, and may be preferably a cellulose ether.

The cellulose ether is derived from cellulose, which is a vegetable material, and is a cellulose derivative in which a hydroxyl group of cellulose is etherified with an etherifying agent.

Specifically, the cellulose ether is selected from the group consisting of alkyl cellulose, hydroxyalkyl cellulose, hydroxyalkyl alkyl cellulose, and alkylalkyl hydroxyalkyl cellulose. And may contain more than one kind of cellulose, such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, ethyl hydroxyethyl cellulose and methyl ethyl hydroxyethyl cellulose And may include more than one kind selected.

Preferably, the methyl cellulose may have a degree of methyl group substitution (DS) of 0.27 to 2.0, and the hydroxyethyl cellulose may have a degree of substitution (MS) of 0.3 to 5.0, and the hydroxyethyl methyl cellulose (DS) of 0.27 to 2.40 and a degree of substitution (MS) of hydroxyethyl group of 0.03 to 1.3, and the hydroxypropylmethyl cellulose has a methyl group substitution degree (DS) of 0.27 to 2.50 and a hydroxypropyl group substitution degree The MS may be 0.02 to 1.1, but is not limited thereto. In the present specification, the degree of methyl group substitution (DS) means the average number of hydroxyl groups substituted with a methyl group per anhydrous glucose unit, and the degree of hydroxyalkyl group substitution (MS) means the average number of hydroxyl groups substituted with a hydroxyalkyl group per anhydrous glucose unit do. The degree of substitution (MS) of the hydroxyethyl group of the hydroxyethyl cellulose is a value obtained by adding the number of hydroxyl groups substituted with hydroxyethyl groups and the number of hydroxyethyl groups bonded to carbon per anhydroglucose unit.

When the degree of substitution of the methyl group is high, the hydrophobicity is high, and when the hydroxyalkyl group is small, the hydrophobicity is high. Therefore, when cellulose ether having a degree of methyl group substitution of more than the upper limit value or a degree of substitution of hydroxyalkyl group of less than the lower limit value is used, the water retention of the cellulose ether becomes insufficient and the workability of the building material containing the cellulose ether may become poor. On the other hand, when the degree of substitution of the methyl group is less than the lower limit of the above range or the degree of substitution of the hydroxyalkyl group is more than the upper limit, there is a fear that the change in the fluidity with time becomes large, and the necessary pot life can not be obtained.

The modified starch is a starch derived from various grains or rootstocks treated with a small amount of chemical substance and chemically modified by reaction between the hydroxy group of the starch and the reactant, It is an improvement. Specifically, the modified starch may be at least one selected from the group consisting of oxidized starch, acetyladipic acid starch, acetyl phosphate pre-starch, octyl stannous sodium starch, pre-phosphate, pre-phosphate, pre-phosphoryl phosphate, acetic acid starch, Hydroxypropyl starch, and hydroxypropyl starch.

The content of the polysaccharide derivative may be 0.05 to 1.0 part by weight based on 100 parts by weight of the dry mixture. If the content of the polysaccharide derivative is less than 0.05 part by weight, the addition effect may be insufficient. On the other hand, if the content of the polysaccharide derivative exceeds 1.0 part by weight, excessive retention of the polysaccharide derivative may accelerate the decrease of adhesive strength when drying shrinkage occurs at a high temperature.

The phase change material (PCM) is a solid material at room temperature or a liquid material having fluidity at high temperature. The phase transition material serves as a filler in building materials such as mortar at room temperature, thereby enhancing the bonding strength during standard curing and filling voids in which water evaporates at high temperatures, thereby preventing a decrease in adhesive strength due to drying shrinkage.

The phase transition temperature of the phase transfer material may be 50 to 80 캜. Specifically, the phase transition material may include a paraffinic hydrocarbon, a halogenated hydrocarbon, a fatty acid, a wax, and a polyethylene glycol polyethylene glycol, and the like. For example, the paraffinic hydrocarbon may be one or more selected from the group consisting of compounds represented by the formula C _n H _{2n + 2} (wherein n is 24 to 34), and the halogenated hydrocarbon is p-dichlorobenzene (p dichlorobenzene, chlorowax, p-bromophenol and o-xylene dichloride. The fatty acid may be at least one selected from the group consisting of CH ₃ ( CH ₂ ) _2n COOH wherein n is 12 to 20, and the wax may be at least one selected from the group consisting of bees wax, candelilla wax, Carnauba wax, shellac wax, and the like.

Particularly, when a paraffinic hydrocarbon, halogenated hydrocarbon or wax having high water resistance as the phase change material is used, it is possible to further suppress the elution of additive such as re-oil type powder resin or the like contained in the building material during immersion in water, It is possible to minimize the deterioration of the bonding strength.

The amount of the phase change material may be 0.001 to 0.45 parts by weight based on 100 parts by weight of the dry mixture. If the content of the phase change material is less than 0.001 part by weight, there is a fear that the adhesive strength at high temperature and in water may be lowered. On the other hand, if the content is more than 0.45 part by weight, the water retention property may deteriorate.

At this time, the polysaccharide derivative and the phase change material may be contained at a weight ratio of 10: 0.2 to 10: 4.5. If the phase transition material is contained in a less amount than the polysaccharide derivative out of the above range, the effect of suppressing lowering of adhesive strength at high temperature and in water may be insignificant. On the other hand, if the phase transition material is excessively contained, water retention may be deteriorated.

Meanwhile, the composition for building materials according to the present invention may further comprise a re-melting type powder resin. The re-melting type powder resin is added in order to prevent drying shrinkage of the building material at a high temperature. The re-melting type powder resin may be 0.1 to 10.0 parts by weight based on 100 parts by weight of the dry mixture. If the content of the powdery resin is less than 0.1 part by weight, the effect of preventing the drying shrinkage may be insufficient. On the other hand, if the amount exceeds 10.0 parts by weight, the amount of the powdery resin to be eluted during immersion in water may be excessively increased.

 The re-fusing powder resin may include one or more selected from the group consisting of ethylene-vinyl acetate, acrylic latex and styrene-butadiene rubber, preferably ethylene-vinyl acetate.

The phase change material contained in the composition for building material and the re-oil type powder resin may be contained in a weight ratio of 1: 400 to 400: 1, preferably in a weight ratio of 1:60 to 1: 350, By weight in the weight ratio of 1: 65 to 1: 170. If the phase transition material is out of the above range and the phase transition material is excessively larger than the powder resin, the bonding strength at room temperature and high temperature may be somewhat lowered. On the other hand, when the powder resin is excessively larger than the phase transition material, The elution amount of the powdery resin becomes large and the adhesive strength in water may be lowered.

The present invention provides a building material comprising the composition for building materials.

Since the building material according to the present invention is excellent in bonding strength under normal temperature, high temperature and underwater environment, it can be suitably used for any one selected from the group consisting of tile cement mortar, masonry mortar and repair mortar, , Flooring materials, soundproof walls, and the like.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these embodiments.

Example 1

35% by weight of Portland cement (1 kind of KS L 5201 manufactured by Tong Yang Cement Co., Ltd.), 32.25% by weight of silica sand # 6 (particle size 60 μm or less, average particle size 300 μm) Mu m, average particle size of 150 mu m) (Kyungin material, No. 7) and 0.5 wt% of calcium formate were mixed by dry mixing to prepare 1 kg of a dry mixture.

Then, 0.3 part by weight of hydroxyethyl methyl cellulose (HEMC) as a cellulose ether, 0.03 part by weight of paraffin wax powder as a phase transition material and 24.5 parts by weight of water were added to 100 parts by weight of the dry mixture, The tile cement mortar was prepared by kneading. At this time, the viscosity of the tile cement mortar is 500 kcps as measured by a Brookfield viscometer at 20 ° C and 20 rpm.

Examples 2 to 5 and Comparative Examples 1 to 5

The same procedure as in Example 1 was carried out except that the amount of the HEMC, paraffin wax powder and water were adjusted as described in the following Table 1, and the re-powdered powder resin was added thereto in an amount as shown in the following Table 1 Tile cement mortar. At this time, the respective doses are parts by weight introduced into the outer barrel based on 100 parts by weight of the dry mixture. At this time, the viscosity of each tile cement mortar is 500 kcps as measured by a Brookfield viscometer at 20 ° C and 20 rpm.

≪ Evaluation method of adhesive strength &

The sample curing and measurement methods for measuring the adhesive strength of the tile cement mortar prepared according to Examples 1 to 5 and Comparative Examples 1 to 5 were conducted in accordance with KS L ISO 13007.

Concretely, a trowel (saw blade size 6 mm x 6 mm) is used to form a bone on a concrete plate of 40 cm x 40 cm. Next, after leaving the concrete plate for 5 minutes, a 5 cm x 5 cm ceramic tile was attached to the concrete plate, and the tensile adhesion strength, the heat aging adhesion strength, and the water resistance of the tiles were measured using an adhesive strength tester (Shin Kagaku Kogyo Co., The immersion adhesive strength was measured. At this time, the adhesive strength to ten tiles was measured for each example or comparative example, and the average value of the remaining adhesive strengths was calculated, except for the values exceeding the standard deviation of the average strength of 占 20% Are shown in Table 1 below.

However, the respective adhesive strengths were measured after the following procedure.

- Tensile bond strength

The tensile bond strength is a value measured after allowing the ceramic tile attached on the concrete plate to stand in a standard state (temperature: 23 ° C, relative humidity: 50%) for 28 days.

- Heat aging adhesive strength

The heat aging adhesion strength was measured after 14 days of curing the ceramic tiles attached to the concrete plate for 14 days in a standard condition and leaving them in an air circulating dryer at 70 ° C for 14 days.

- Underwater immersion bond strength

The underwater dipping adhesion strength is a value measured after dipping the ceramic tile attached on the concrete plate for 7 days in a standard state and immersing in water for 20 days.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 HEMC
(Parts by weight) 0.27 0.285 0.27 0.285 0.27 0 0 0.3 0.3 0.3 Paraffin wax powder
(Parts by weight) 0.03 0.015 0.03 0.015 0.03 0 0.03 0 0 0 Re-melting type powder resin (parts by weight) 0 2 2 5 5 0 0 0 2 5 water
(Parts by weight) 24.5 24.5 24.5 24 24 20 20 24.5 24.5 24 Seal
Adhesive strength
(N / mm ² ) 0.96 1.3 1.42 1.33 1.49 N.A N.A 0.85 1.08 1.1 Heat aging
Adhesion strength (N / mm ² ) 0.52 1.16 1.27 1.58 2.03 N.A N.A 0.31 0.78 1.15 Underwater immersion adhesive strength (N / mm ² ) 0.91 0.72 0.81 0.69 0.86 N.A N.A 0.8 0.60 0.53

* HEMC: MECELLOSE ^® EMA-70U / Lotte Fine Chemicals

* Paraffin wax powder: Zefeng 64/66 # / Zefeng (Melting point: 64 ~ 66 캜, Oil content ≤ 0.5%)

* Resuspended Powder Resin: Vinnapas 5044N / Wacker

As shown in Table 1, the tile-cement mortar prepared according to Example 1 including HEMC and paraffin wax powder exhibited the best underwater immersion adhesive strength. In the case of the tile-cement mortar prepared according to Examples 2 to 5 further comprising the re-oiling type powder resin together with the HEMC and the paraffin wax powder, the underwater immersion adhesive strength was somewhat lower than that of the tile-cement mortar of Example 1 , The tensile bonding strength and the heat aging bonding strength are excellent.

The effects of the HEMC and paraffin wax powder addition are as follows.

First, in the case of the tile-cement mortar prepared according to Example 1 including the HEMC and the paraffin wax powder when the re-oiling type powder resin was not contained, the tile-cement mortar prepared according to Comparative Example 3 which did not contain paraffin wax powder The tensile bond strength, the heat aging bond strength, and the underwater immersion bond strength are superior to those of the other examples. At this time, in the case of Comparative Examples 1 and 2 which did not include cellulose ether in addition to the re-melting type powder resin, the tile was detached from the concrete plate during the testing process, and the adhesion strength could not be measured.

On the other hand, in the case of the tile-cement mortar prepared according to Examples 2 to 5 including the HEMC and the paraffin wax powder when the re-oiling type powder resin was included, the tile-cement mortar prepared according to Comparative Examples 4 to 5 containing no paraffin wax powder The tensile bond strength, the heat aging bond strength and the underwater immersion bond strength are superior to those of the tile cement mortar.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, Should be construed as being included in the scope of the present invention.

Claims (14)

A dry mix comprising an inorganic binder and aggregate;
Polysaccharide derivatives; And
A composition for building materials comprising phase change materials. The method according to claim 1,
Wherein the dry mixture is selected from the group consisting of calcium formate, calcium chloride, calcium acetate, calcium nitrate, calcium nitrite, calcium thiocyanate, sodium acetate, sodium nitrate, sodium nitrite sodium sodium thiocyanate, calcium nitrate and calcium nitrite Wherein the composition further comprises one or more curing accelerators selected from the group consisting of potassium acetate, potassium nitrate, potassium nitrite, and potassium thiocyanate. The method according to claim 1,
Wherein the polysaccharide derivative comprises at least one selected from the group consisting of cellulose ether, starch ether, cellulose ester and modified starch. The method of claim 3,
The cellulose ether includes one or more selected from the group consisting of methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, ethyl hydroxyethyl cellulose and methyl ethyl hydroxyethyl cellulose By weight based on the total weight of the composition. The method according to claim 1,
Wherein the content of the polysaccharide derivative is 0.05 to 1.0 part by weight based on 100 parts by weight of the dry mixture. The method according to claim 1,
Wherein the phase transition temperature of the phase change material is 50 to 80 占 폚. The method according to claim 1,
Wherein the phase change material includes at least one selected from the group consisting of paraffinic hydrocarbons, halogenated hydrocarbons, fatty acids, waxes, and polyethylene glycols Compositions for building materials. The method according to claim 1,
Wherein the amount of the phase change material is 0.001 to 0.45 parts by weight based on 100 parts by weight of the dry mixture. The method according to claim 1,
Wherein the polysaccharide derivative and the phase change material are contained in a weight ratio of 10: 0.2 to 10: 4.5. The method according to claim 1,
Characterized in that the composition further comprises a re-firing powder resin. 11. The method of claim 10,
Wherein the amount of the re-fusing powder resin is 0.1 to 10.0 parts by weight based on 100 parts by weight of the dry mixture, and the re-fusing powder resin includes one or more selected from the group consisting of ethylene-vinyl acetate, acrylic latex and styrene-butadiene rubber By weight based on the total weight of the composition. 11. The method of claim 10,
Wherein the phase transition material contained in the composition and the re-fired powder resin are contained in a weight ratio of 1: 400 to 400: 1. A building material comprising the composition for building materials according to any one of claims 1 to 12. 14. The method of claim 13,
Wherein the building material is any one selected from the group consisting of tile cement mortar, masonry mortar and repair mortar.