WO2014007486A1 - Method for preparing environmentally-friendly inorganic resin composition and composition prepared thereby - Google Patents

Method for preparing environmentally-friendly inorganic resin composition and composition prepared thereby Download PDF

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Publication number
WO2014007486A1
WO2014007486A1 PCT/KR2013/005631 KR2013005631W WO2014007486A1 WO 2014007486 A1 WO2014007486 A1 WO 2014007486A1 KR 2013005631 W KR2013005631 W KR 2013005631W WO 2014007486 A1 WO2014007486 A1 WO 2014007486A1
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WIPO (PCT)
Prior art keywords
cellulose
water
alkoxysilane
alkoxysilane compound
resin composition
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PCT/KR2013/005631
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French (fr)
Korean (ko)
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임헌영
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Lim Heon Young
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Publication of WO2014007486A1 publication Critical patent/WO2014007486A1/en

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
    • C04B41/61—Coating or impregnation
    • C04B41/62—Coating or impregnation with organic materials
    • C04B41/64—Compounds having one or more carbon-to-metal of carbon-to-silicon linkages
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
    • C04B12/04—Alkali metal or ammonium silicate cements ; Alkyl silicate cements; Silica sol cements; Soluble silicate cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C04B26/22—Natural resins, e.g. rosin
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/30—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Other silicon-containing organic compounds; Boron-organic compounds
    • C04B26/32—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Other silicon-containing organic compounds; Boron-organic compounds containing silicon
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/49—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
    • C04B41/4905—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
    • C04B41/4922—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as monomers, i.e. as organosilanes RnSiX4-n, e.g. alkyltrialkoxysilane, dialkyldialkoxysilane
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
    • C09D101/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds

Definitions

  • the present invention relates to a method for producing an environmentally friendly inorganic resin composition and a composition therefrom, and more particularly, to reduce the volatile organic solvents that cause environmental pollution to ensure environmental friendliness, and concrete surface adhesion due to the concrete and similar components
  • the present invention relates to a method for preparing an environmentally friendly inorganic resin composition capable of increasing the durability and preventing yellowing as well as the composition thereof.
  • the coating on the coating layer of concrete or mortar can be classified into dry method and wet method.
  • solvent-type urethane, epoxy, rubber asphalt, etc. are applied to the surface of concrete or mortar, which is the coating layer, or sheets.
  • Weak especially when installed outdoors there is a problem that easily neutralized, corrosion, aging due to acid rain.
  • a coating agent As a coating agent, a two-component or one-component urethane, and an epoxy coating agent, which are used after dissolving rubber asphalt, butyl rubber, chloroprene, chlorosulfonated polyethylene, etc. in a solvent or mixed with a curing agent, are mainly used.
  • Most solvents are solvents, which adversely affects environmental pollution and is not environmentally friendly. Therefore, as the solvent type coating waterproofing agent has increased interest in the environmental protection of the international community, it is necessary to take into account environmental pollution or work safety due to the toxicity of the solvent. Recently, volatile organic solvents that are harmful to the human body and cause environmental pollution ( There is a shift to environmentally friendly wet methods that do not use volatile organic compounds.
  • These paints are organic paints mainly composed of organic resins such as polymer resins. They are excellent in processability, adhesiveness, oxygen permeability resistance, and flame retardancy, while moisture is stagnated at the interface between the coating material and the structure, so that the coating material is dropped or promotes corrosion of steel. There is a fear of causing, yellowing phenomenon caused by ultraviolet rays, aesthetic problems occur, and the joint mortar portion of the tile or stone joint is deteriorated. Of course, it is necessary to secure durability due to internal and external environmental factors, and volatile organic compounds are released.
  • titanium dioxide which exhibits photocatalysts or various characteristics, hardly exhibits its characteristics in the shade without sunlight or at night, and because of its high price, titanium dioxide has limitations in economics for general use in concrete structures.
  • the first technical problem to be solved by the present invention is to reduce the volatile organic solvents that cause environmental pollution to ensure environmental friendliness, to increase the adhesion of the concrete surface due to the concrete and similar components, durability and prevention of yellowing It is to provide a method for producing an environmentally friendly inorganic resin composition and a composition thereby.
  • the second technical problem to be solved by the present invention is to reduce the volatile organic solvents that cause environmental pollution to ensure environmental friendliness, to increase the adhesion of the concrete surface due to the concrete and similar components, durability and prevention of yellowing It is to provide an environmentally friendly inorganic resin composition that can be.
  • the present invention maintains a constant reaction temperature, hydrolyzes the alkoxysilane in an acidic atmosphere to produce a water-soluble alkoxysilane compound, and adds cellulose to the water-soluble alkoxysilane compound and stirs it.
  • the aqueous cellulose alkoxysilane compound of step S1 is separately reacted with an alkoxysilane and ammonia in an acidic aqueous solution, and then added to prepare an alkoxysilane mixture.
  • the silicate compound and the alcohol are separately added to the alkoxysilane mixture with water, hydrochloric acid and S2 step of reacting with oxalic acid to add and stir the mixture to prepare a modified silicate alkoxysilane compound; And a step S3 of mixing the modified silicate alkoxysilane compound of step S2 with the water-soluble cellulose alkoxysilane compound of step S1.
  • the silicate compound is an alkali silicate salt, wherein alkali metal ions, alkaline earth metal ions, earth metal ions and / or transition metal cations, and anions of the silicates are isolated, cyclic, grouped, chained. It may be a die, band, layered or three-dimensional silicate or a combination thereof.
  • the silicate compound may be an alkyl silicate.
  • the acid component of the step S1 may be due to hydrochloric acid and water.
  • the concentration of the hydrochloric acid may be 0.1 to 2wt%.
  • the silicate compound and the alcohol may be mixed with the reactant of step S2 while maintaining a predetermined acidity.
  • the predetermined acidity may be due to water, hydrochloric acid and oxalic acid.
  • the acidic aqueous solution of step S2 may be due to boric acid and water.
  • the alkoxysilane may be at least one selected from the group consisting of r-glyciroxypropyltrimethoxysilane, methyltrimethoxysilane and r-glycidoxypropylmethyldiethoxysilane. have.
  • the cellulose is nitro cellulose, triacetate cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose At least one selected from the group consisting of cellulose, ethyl hydroxyethyl cellulose, hydroxypropyl cellulose and sodium carboxymethyl cellulose.
  • the present invention provides an environmentally friendly inorganic resin composition characterized in that it is manufactured by the above-described manufacturing method in order to solve the above-described second technical problem.
  • the manufacturing method of the environmentally friendly inorganic resin composition according to the present invention and the composition thereby it is possible to reduce the volatile organic solvents causing environmental pollution, to ensure the environment-friendly, and to increase the adhesion of the concrete surface due to the concrete and similar components Durability as well as yellowing can be prevented.
  • Figure 2 is a photograph of whether the damage after dropping water on the concrete surface is coated with the composition according to Example 1,
  • Figure 4 is a photograph of the cracks and traces of contamination of the coating film formed by adding the composition according to Example 2,
  • FIG. 5 is a photograph of the cracks and traces of contamination of gambling formed by adding the composition according to Comparative Example 1.
  • the present invention maintains a constant reaction temperature, hydrolyzing the alkoxysilane in an acid atmosphere to produce a water-soluble alkoxysilane compound, adding cellulose to the water-soluble alkoxysilane compound and stirring to produce a water-soluble cellulose alkoxysilane compound S1 step;
  • the alkoxysilane and ammonia are separately added to the water-soluble cellulose alkoxysilane compound in an acidic aqueous solution and then added to prepare an alkoxysilane mixture.
  • the silicate compound and the alcohol are separately reacted with water, hydrochloric acid and oxalic acid at room temperature.
  • the step S1 is a step of hydrolyzing the alkoxysilane and mixing cellulose.
  • the alkoxysilane may be at least one selected from the group consisting of r-glycileoxypropyltrimethoxysilane, methyltrimethoxysilane, and r-glycidoxypropylmethyldiethoxysilane.
  • the hydrolysis may be carried out in an acid crisis with hydrochloric acid and water, wherein the concentration of hydrochloric acid may be 0.1 to 2wt%, if less than 0.1wt%, durability and water resistance improvement may be insignificant, on the contrary, 2wt When it exceeds%, storage stability is impaired and crack failure may occur after construction.
  • the concentration of hydrochloric acid is based on the entire mixture of the alkoxysilane, water and hydrochloric acid, and chlorine (Cl ⁇ ) of hydrochloric acid is substituted with the alkoxysilane through a hydrolysis reaction.
  • cellulose is nitrocellulose , Triacetate cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, hydroxypropyl cellulose and sodium carboxy It may be at least one selected from the group consisting of methyl cellulose.
  • the constant reaction temperature here means a temperature in which this step is exothermic and thus does not use external heat separately using heat at this time.
  • step S2 is a step of adding an alkoxysilane and ammonia to the hydrolyzed reactant in step S1 after the reaction in an acidic aqueous solution.
  • the alkoxysilane is prepared separately from the alkoxysilane of step S1, and induces a reaction in an acidic aqueous solution of boric acid and water, and through this process, the composition according to the present invention is applied to the surface to be cracked. It is given the property to prevent.
  • ammonia here is used to ensure storage stability, which is a property necessary for storage until the production process step or post-construction of the inorganic resin composition according to the present invention, and is used for compatibility with other additives.
  • the silicate compound and alcohol may be added to the reactant of step S2 while maintaining the acidity at room temperature, followed by mixing.
  • the silicate compound and the alcohol exothermically react, thereby interfacial affinity with concrete to be a conductor. Can be secured.
  • the room temperature refers to a temperature that does not apply a special external heat of about 20 to 30 °C, at a temperature higher than the room temperature may reduce the generation of cracks or water resistance after construction, and maintains the room temperature in the subsequent process.
  • the predetermined acidity may be due to water, hydrochloric acid and oxalic acid.
  • the silicate compound is an alkali silicate salt, wherein alkali metal ions, alkaline earth metal ions, earth metal ions and / or transition metal cations, and anions of the silicates are isolated, cyclic, grouped, chained, banded, layered or It may be a three-dimensional silicate or a combination thereof, and through such a configuration, it is possible to solidify the adhesion or penetration force to the concrete or mortar as the conductor.
  • the silicate compound may be an alkyl silicate, in particular ethyl silicate may be used.
  • the step S3 is a step of mixing the reactants of the step S2 with the reactants of the step S1.
  • Hydrolysis reaction was carried out while stirring 5 parts by weight of water and 2 parts by weight of hydrochloric acid at 500 rpm for 3 hours to 100 parts by weight of r- glycidoxy propyl trimethoxysilane.
  • 10 parts by weight of ammonia, 30 parts by weight of water and 30 parts by weight of boric acid were stirred at 500 rpm for 3 hours to 100 parts by weight of r-glycidoxy propyl trimethoxysilane, and 50 parts by weight of the hydrolysis reactant was 100 parts by weight.
  • the mixture was stirred at 500 ° C. at 25 ° C. for 1 h at room temperature.
  • Ethyl silicate compound was prepared by stirring 400 parts by weight of ethyl silicate, 350 parts by weight of ethyl alcohol (99 wt% purity), and 50 parts by weight of water, 5 parts by weight of hydrochloric acid, and 10 parts by weight of oxalic acid at 500 rpm for 3 hours. 50 parts by weight of the ethyl silicate compound was stirred at 500 rpm at room temperature for 1 hour to 100 parts by weight of the mixture of Preparation Example 1 to prepare an environmentally friendly inorganic resin composition according to the present invention.
  • Example 1 The inorganic resin compositions prepared in Example 1 and Comparative Example 1 were each applied to the concrete surface, and then cured for 7 days to form a coating film. Then, water was dropped onto the paper on which the coating film was formed, and the coin was used to observe whether the coating film was damaged. The results are shown in FIGS. 2 and 3.
  • Example 2 After applying the inorganic resin composition prepared in Example 2 and Comparative Example 1 on the concrete surface, respectively, it was cured for 7 days to form a coating film and the surface of the coating film was taken close-up. The results are shown in FIGS. 4 and 5.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Disclosed are a method for preparing an environmentally-friendly inorganic resin composition and a composition prepared thereby, the method comprising: step 1 (S1) in which, while maintaining a predetermined reaction temperature, alkoxysilane is hydrolyzed in an acid atmosphere to prepare a water-soluble alkoxysilane compound, and cellulose is added to the water-soluble alkoxysilane compound and is stirred to prepare a water-soluble cellulose alkoxysilane compound; step 2 (S2) in which alkoxysilane and ammonia, having been separately reacted with each other in an acidic aqueous solution, are added to the water-soluble cellulose alkoxysilane compound to prepare an alkoxysilane compound, and a silicate compound and alcohol, having been separately reacted with water, chloride, and oxalic acid at room temperature, are added to the alkoxysilane compound, and are mixed and stirred to prepare a modified silicate alkoxysilane compound; and step 3 (S3) in which the modified silicate alkoxysilane compound of S2 is mixed with the water-soluble cellulose alkoxysilane compound of S1. Thus, the composition is environmentally-friendly due to the reduction of volatile organic compounds that can cause environmental pollution, has enhanced adhesive force to a concrete surface due to having similar components as concrete, has improved durability, and can prevent yellowing.

Description

환경친화성 무기계수지 조성물의 제조방법 및 그에 의한 조성물Method for producing environmentally friendly inorganic resin composition and composition therefrom
본 발명은 환경친화성 무기계수지 조성물의 제조방법 및 그에 의한 조성물에 관한 것으로, 더욱 상세하게는 환경오염을 유발시키는 휘발성 유기용매를 저감시켜 친환경성을 확보하고, 콘크리트와 유사성분으로 인해 콘크리트 표면 부착력을 증가시킬 수 있고, 내구성은 물론 황변을 방지할 수 있는 환경친화성 무기계수지 조성물의 제조방법 및 그에 의한 조성물에 관한 것이다.The present invention relates to a method for producing an environmentally friendly inorganic resin composition and a composition therefrom, and more particularly, to reduce the volatile organic solvents that cause environmental pollution to ensure environmental friendliness, and concrete surface adhesion due to the concrete and similar components The present invention relates to a method for preparing an environmentally friendly inorganic resin composition capable of increasing the durability and preventing yellowing as well as the composition thereof.
콘크리트나 몰탈의 피도막층에 대한 피복은 통상 건식법과 습식법으로 분류할 수 있는데, 이중 건식법은 피도막층인 콘크리트나 몰탈의 표면에 용제타입의 우레탄, 에폭시, 고무아스팔트 등을 도포하거나, 또는 시트를 중첩하여 접착시키는 방법으로서 피도막층인 콘크리트나 몰탈 표면의 청소 상태, 평활도, 건조 상태 등이 불량하면 시공후 콘크리트나 몰탈 표면과의 접착이 불량하여 들뜸, 박리 현상이 발생하고, 내구수명이 약하여 특히 옥외에 시공하는 경우에는 쉽게 산성비에 의한 중화, 부식, 노화되는 문제점이 있다.The coating on the coating layer of concrete or mortar can be classified into dry method and wet method. In the double dry method, solvent-type urethane, epoxy, rubber asphalt, etc. are applied to the surface of concrete or mortar, which is the coating layer, or sheets. Is a method of superimposing and bonding the surface of concrete or mortar, which is the layer to be coated, if the cleaning state, smoothness, or dry state is poor, adhesion to the surface of concrete or mortar is poor after construction, causing lifting and peeling. Weak, especially when installed outdoors there is a problem that easily neutralized, corrosion, aging due to acid rain.
고무아스팔트, 부틸고무, 클로로프렌, 클로로설폰화폴리에틸렌 등을 용제에 용해시켜 단독 또는 경화제와 혼합하여 사용하는 도막제, 이액형 또는 일액형의 우레탄, 에폭시의 도막제가 주로 많이 사용되고 있는 바, 이들의 용매가 대부분 용제(솔벤트)이므로 환경공해에 악영향을 미치며 환경친화적이지 못하다. 따라서 이러한 용제형 도막방수제가 국제사회의 환경보호의 관심이 증대됨에 따라 환경공해나 용제의 독성에 인한 작업 안전성 등을 고려하지 않을 수 없는 바 최근에는 인체에 유해하며 환경오염을 유발시키는 휘발성 유기용매(Volatile organic compounds)를 전혀 사용하지 않는 환경 친화적인 습식법으로의 전환이 대두되고 있다.As a coating agent, a two-component or one-component urethane, and an epoxy coating agent, which are used after dissolving rubber asphalt, butyl rubber, chloroprene, chlorosulfonated polyethylene, etc. in a solvent or mixed with a curing agent, are mainly used. Most solvents are solvents, which adversely affects environmental pollution and is not environmentally friendly. Therefore, as the solvent type coating waterproofing agent has increased interest in the environmental protection of the international community, it is necessary to take into account environmental pollution or work safety due to the toxicity of the solvent. Recently, volatile organic solvents that are harmful to the human body and cause environmental pollution ( There is a shift to environmentally friendly wet methods that do not use volatile organic compounds.
종래에는 내구성, 내오염성, 내수성과 같은 시공 후 특성에 대한 기능을 부여하고, 외부 충격에 의한 긁힘, 크랙과 같은 손상을 방지하기 위하여 피도막층의 표면에 위 기능에 부가된 특성을 가진 도료를 피복하거나 코팅하는 기술이 사용되고 있다Conventionally, in order to impart functions on post-construction properties such as durability, stain resistance, and water resistance, and to prevent damages such as scratches and cracks caused by external impacts, paints having properties added to the above functions on the surface of the coating layer are applied. Coating or coating technology is used
이러한 도료들은 고분자수지계 같은 유기 수지를 주성분으로 하는 유기도료로 가공성, 접착성, 산소투과저항성과 차염성 등이 우수한 반면에, 피복재와 구조체 계면에 수분이 정체되어 피복마감재가 탈락하거나 철로부식을 촉진 시킬 우려가 발생하고, 자외선 등에 의한 황변현상 발생으로 미관상의 문제가 발생하며 타일이나 석재이음새의 줄눈 모르타르 부위는 열화되는 부작용이 발생된다. 물론 내외적 환경적 요인으로 인한 내구성 확보가 필요하고 휘발성 유기화합물 등이 방출되는 문제점도 발생한다.These paints are organic paints mainly composed of organic resins such as polymer resins. They are excellent in processability, adhesiveness, oxygen permeability resistance, and flame retardancy, while moisture is stagnated at the interface between the coating material and the structure, so that the coating material is dropped or promotes corrosion of steel. There is a fear of causing, yellowing phenomenon caused by ultraviolet rays, aesthetic problems occur, and the joint mortar portion of the tile or stone joint is deteriorated. Of course, it is necessary to secure durability due to internal and external environmental factors, and volatile organic compounds are released.
근래에는 광촉매나 다양한 특성을 나타내는 이산화티탄은 태양광이 없는 그늘이나 야간에는 그 특성을 거의 나타낼 수 없으며, 가격이 고가이기 때문에 콘크리트 구조물에 범용적으로 사용하기에는 경제성 부분에서 한계를 지니고 있다.In recent years, titanium dioxide, which exhibits photocatalysts or various characteristics, hardly exhibits its characteristics in the shade without sunlight or at night, and because of its high price, titanium dioxide has limitations in economics for general use in concrete structures.
실란과 실리케이트를 사용한 콘크리트 침투성 표면보호재의 자기세정 및 내구성능에 대한 연구가 있으나, 내수성 부분과 자기 세정성의 효과를 지속하기 위한 추가연구의 필요성이 대두되고 있는 실정이다.Although there are studies on the self-cleaning and durability of concrete permeable surface protective materials using silane and silicate, there is a need for further research to maintain the water-resistant part and self-cleaning effect.
이에 따라 콘크리트 구조물에 용이하게 침투되고, 대기의 산성화 및 이산화탄소 오염에 의하여 중성화되는 콘크리트 구조물을 효과적으로 보호하며. 콘크리트의 표면 강화를 통한 수밀성 확보와 함께 오염방지와 자기세정 기능을 장기적으로 발현하는 경제성 있는 환경친화성 무기질계 콘크리트 표면 보호재가 필요한 실정이다.Therefore, it easily penetrates the concrete structure and effectively protects the concrete structure neutralized by the acidification of the atmosphere and carbon dioxide pollution. In addition to securing watertightness by strengthening the surface of concrete, there is a need for economical and environmentally friendly inorganic-based concrete surface protection materials that exhibit pollution prevention and self-cleaning functions over the long term.
따라서, 본 발명이 해결하고자 하는 첫번째 기술적 과제는 환경오염을 유발시키는 휘발성 유기용매를 저감시켜 친환경성을 확보하고, 콘크리트와 유사성분으로 인해 콘크리트 표면 부착력을 증가시킬 수 있고, 내구성은 물론 황변을 방지할 수 있는 환경친화성 무기계수지 조성물의 제조방법 및 그에 의한 조성물을 제공하는 것이다.Therefore, the first technical problem to be solved by the present invention is to reduce the volatile organic solvents that cause environmental pollution to ensure environmental friendliness, to increase the adhesion of the concrete surface due to the concrete and similar components, durability and prevention of yellowing It is to provide a method for producing an environmentally friendly inorganic resin composition and a composition thereby.
또한, 본 발명이 해결하고자 하는 두번째 기술적 과제는 환경오염을 유발시키는 휘발성 유기용매를 저감시켜 친환경성을 확보하고, 콘크리트와 유사성분으로 인해 콘크리트 표면 부착력을 증가시킬 수 있고, 내구성은 물론 황변을 방지할 수 있는 환경친화성 무기계수지 조성물을 제공하는 것이다.In addition, the second technical problem to be solved by the present invention is to reduce the volatile organic solvents that cause environmental pollution to ensure environmental friendliness, to increase the adhesion of the concrete surface due to the concrete and similar components, durability and prevention of yellowing It is to provide an environmentally friendly inorganic resin composition that can be.
본 발명은 상술한 첫번째 기술적 과제를 달성하기 위하여, 일정 반응온도를 유지하며, 알콕시실란을 산성분위기에서　가수분해하여 수용성알콕시실란화합물을 제조하고, 상기 수용성알콕시실란화합물에 셀루로오스를 가하고 교반하여 수용성셀루로오스알콕시실란화합물을 제조하는 S1단계; 상기 S1단계의 수용성셀루로오스알콕시실란화합물에 별도로 알콕시실란과 암모니아를 산성수용액에서 반응시킨 후 첨가하여 알콕시실란혼합물을 제조하고, 상기 알콕시실란혼합물에 별도로 실리케이트화합물과 알콜을 상온에서 물, 염산 및 옥살산과 반응시켜 첨가하고 혼합교반하여 개질된 실리케이트알콕시실란화합물을 제조하는 S2단계; 및 상기 S1단계의 수용성셀루로오스알콕시실란화합물에 S2단계의 개질된 실리케이트알콕시실란화합물을 혼합하는 S3단계;를 포함하는 것을 특징으로 하는 환경친화성 무기계수지 조성물의 제조방법을 제공한다.In order to achieve the first technical problem described above, the present invention maintains a constant reaction temperature, hydrolyzes the alkoxysilane in an acidic atmosphere to produce a water-soluble alkoxysilane compound, and adds cellulose to the water-soluble alkoxysilane compound and stirs it. S1 step of preparing a water-soluble cellulose alkoxysilane compound; The aqueous cellulose alkoxysilane compound of step S1 is separately reacted with an alkoxysilane and ammonia in an acidic aqueous solution, and then added to prepare an alkoxysilane mixture. The silicate compound and the alcohol are separately added to the alkoxysilane mixture with water, hydrochloric acid and S2 step of reacting with oxalic acid to add and stir the mixture to prepare a modified silicate alkoxysilane compound; And a step S3 of mixing the modified silicate alkoxysilane compound of step S2 with the water-soluble cellulose alkoxysilane compound of step S1.
본 발명의 일 실시예에 의하면, 상기 실리케이트화합물은 알칼리실리케이트염으로서, 알칼리 금속 이온, 알칼리 토금속 이온, 토금속 이온 및/또는 전이금속 양이온과, 실리케이트의 음이온이 고립형, 고리형, 그룹형, 사슬형, 밴드형, 층형 또는 3차원 실리케이트 또는 그들의 조합일 수 있다.According to an embodiment of the present invention, the silicate compound is an alkali silicate salt, wherein alkali metal ions, alkaline earth metal ions, earth metal ions and / or transition metal cations, and anions of the silicates are isolated, cyclic, grouped, chained. It may be a die, band, layered or three-dimensional silicate or a combination thereof.
본 발명의 다른 실시예에 의하면, 상기 실리케이트화합물은 알킬실리케이트일 수 있다.According to another embodiment of the present invention, the silicate compound may be an alkyl silicate.
본 발명의 또 다른 실시예에 의하면, 상기 S1단계의 산성분위기는 염산과 물에 의한 것일 수 있다.According to another embodiment of the present invention, the acid component of the step S1 may be due to hydrochloric acid and water.
본 발명의 또 다른 실시예에 의하면, 상기 염산의 농도는 0.1 내지 2wt%일 수 있다.According to another embodiment of the present invention, the concentration of the hydrochloric acid may be 0.1 to 2wt%.
본 발명의 또 다른 실시예에 의하면, 상기 S2단계의 반응물에 실리케이트화합물, 알콜은 소정 산도를 유지하며 반응시킨 후 혼합할 수 있다.According to another embodiment of the present invention, the silicate compound and the alcohol may be mixed with the reactant of step S2 while maintaining a predetermined acidity.
본 발명의 또 다른 실시예에 의하면, 상기 소정 산도는 물, 염산 및 옥살산에 의한 것일 수 있다.According to another embodiment of the present invention, the predetermined acidity may be due to water, hydrochloric acid and oxalic acid.
본 발명의 또 다른 실시예에 의하면, 상기 S2단계의 산성수용액은 붕산과 물에 의한 것일 수 있다.According to another embodiment of the present invention, the acidic aqueous solution of step S2 may be due to boric acid and water.
본 발명의 또 다른 실시예에 의하면, 상기 알콕시실란은 r-글리시르옥시프로필트리메톡시실란, 메틸트리메톡시실란 및 r-글리시드옥시프로필메틸디에톡시실란으로 이루어진 군으로부터 선택된 적어도 하나일 수 있다.According to another embodiment of the present invention, the alkoxysilane may be at least one selected from the group consisting of r-glyciroxypropyltrimethoxysilane, methyltrimethoxysilane and r-glycidoxypropylmethyldiethoxysilane. have.
본 발명의 또 다른 실시예에 의하면, 상기 셀루로오스는 니트로셀루로오스, 트리아세테이트셀루로오스, 하이드록시프로필메틸셀루로오스,카르복시메틸셀루로오스,메틸셀루로오스, 히드록시에틸셀루로오스, 에틸히드록시에틸셀루로오스, 히드록시프로필셀루로오스 및 소디움카르복시메틸셀루로오스로 이루어진 군에서 선택된 적어도 하나일 수 있다.According to another embodiment of the invention, the cellulose is nitro cellulose, triacetate cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose At least one selected from the group consisting of cellulose, ethyl hydroxyethyl cellulose, hydroxypropyl cellulose and sodium carboxymethyl cellulose.
한편, 본 발명은 상술한 두번째 기술적 과제를 해결하기 위하여 상기한 제조방법에 의하여 제조되는 것을 특징으로 하는 환경친화성 무기계수지 조성물을 제공한다.On the other hand, the present invention provides an environmentally friendly inorganic resin composition characterized in that it is manufactured by the above-described manufacturing method in order to solve the above-described second technical problem.
본 발명에 따르는 환경친화성 무기계수지 조성물의 제조방법 및 그에 의한 조성물에 의하면 환경오염을 유발시키는 휘발성 유기용매를 저감시켜 친환경성을 확보하고, 콘크리트와 유사성분으로 인해 콘크리트 표면 부착력을 증가시킬 수 있으며, 내구성은 물론 황변을 방지할 수 있다.According to the manufacturing method of the environmentally friendly inorganic resin composition according to the present invention and the composition thereby, it is possible to reduce the volatile organic solvents causing environmental pollution, to ensure the environment-friendly, and to increase the adhesion of the concrete surface due to the concrete and similar components Durability as well as yellowing can be prevented.
도 1은 본 발명에 따르는 제조방법을 공정단계별로 나타내는 순서도이며,1 is a flowchart showing a manufacturing method according to the present invention for each process step,
도 2는 실시예 1에 의한 조성물이 도포된 콘크리트 표면에 물을 떨어뜨린 후 손상여부를 촬영한 사진이고, Figure 2 is a photograph of whether the damage after dropping water on the concrete surface is coated with the composition according to Example 1,
도 3은 비교예 1에 의한 조성물이 도포된 콘크리트 표면에 물을 떨어뜨린 후 손상여부를 촬영한 사진이며, 3 is a photograph of the damage after dropping water on the concrete surface is coated with the composition according to Comparative Example 1,
도 4는 실시예 2에 의한 조성물을 첨가하여 형성한 도막의 크랙 및 오염의 흔적을 촬영한 사진이고, Figure 4 is a photograph of the cracks and traces of contamination of the coating film formed by adding the composition according to Example 2,
도 5는 비교예 1에 의한 조성물을 첨가하여 형성한 도박의 크랙 및 오염의 흔적을 촬영한 사진이다.5 is a photograph of the cracks and traces of contamination of gambling formed by adding the composition according to Comparative Example 1. FIG.
이하, 본 발명을 상세하게 기술한다.Hereinafter, the present invention will be described in detail.
여기서, 본 발명은 다양한 변경을 가할 수 있고 여러 가지 형태를 가질 수 있다. 그러나, 이는 본 발명을 특정한 개시 형태에 대해 한정하려는 것이 아니고, 본 발명의 사상이나 기술 범위에 포함되는 변경, 균등물 또는 대체물을 모두 포함하는 것으로 이해되어야 할 것이다.Herein, the present invention may be variously modified and may have various forms. It is to be understood, however, that the intention is not to limit the invention to the particular form disclosed, but to include all modifications, equivalents, or substitutes included in the spirit or scope of the invention.
본 발명은 일정 반응온도를 유지하며, 알콕시실란을 산성분위기에서　가수분해하여 수용성알콕시실란화합물을 제조하고, 상기 수용성알콕시실란화합물에 셀루로오스를 가하고 교반하여 수용성셀루로오스알콕시실란화합물을 제조하는 S1단계; 상기 수용성셀루로오스알콕시실란화합물에 별도로 알콕시실란과 암모니아를 산성수용액에서 반응시킨 후 첨가하여 알콕시실란혼합물을 제조하고, 상기 알콕시실란혼합물에 별도로 실리케이트화합물과 알콜을 상온에서 물, 염산 및 옥살산과 반응시켜 첨가하고 혼합교반하여 개질된 실리케이트알콕시실란화합물을 제조하는 S2단계; 및 상기 S1단계의 수용성셀루로오스알콕시실란화합물에 S2단계의 개질된 실리케이트알콕시실란화합물을 혼합하는 S3단계;를 포함하는 것을 특징으로 하는 환경친화성 무기계수지 조성물의 제조방법에 관한 것이다.The present invention maintains a constant reaction temperature, hydrolyzing the alkoxysilane in an acid atmosphere to produce a water-soluble alkoxysilane compound, adding cellulose to the water-soluble alkoxysilane compound and stirring to produce a water-soluble cellulose alkoxysilane compound S1 step; The alkoxysilane and ammonia are separately added to the water-soluble cellulose alkoxysilane compound in an acidic aqueous solution and then added to prepare an alkoxysilane mixture. The silicate compound and the alcohol are separately reacted with water, hydrochloric acid and oxalic acid at room temperature. S2 step of preparing a modified silicate alkoxysilane compound by adding and mixing and stirring; And an S3 step of mixing the modified silicate alkoxysilane compound of the S2 step with the water-soluble cellulose alkoxysilane compound of the S1 step; and a method for producing an environmentally friendly inorganic resin composition.
이하에서는, 본 발명에 따른 환경친화성 무기계수지 조성물의 제조방법을 도 1을 참고하여 설명하면 다음과 같다.Hereinafter, a method for preparing an environmentally friendly inorganic resin composition according to the present invention will be described with reference to FIG. 1.
상기 S1단계는 알콕시실란을 가수분해하고, 셀루로오스를 혼합하는 단계이다.The step S1 is a step of hydrolyzing the alkoxysilane and mixing cellulose.
여기서, 상기 알콕시실란은 r-글리시르옥시프로필트리메톡시실란, 메틸트리메톡시실란 및 r-글리시드옥시프로필메틸디에톡시실란으로 이루어진 군으로부터 선택된 적어도 하나일 수 있다.Here, the alkoxysilane may be at least one selected from the group consisting of r-glycileoxypropyltrimethoxysilane, methyltrimethoxysilane, and r-glycidoxypropylmethyldiethoxysilane.
상기 가수분해는 염산과 물에 의한 산성분위기에서 수행될 수 있으며, 이때, 염산의 농도는 0.1 내지 2wt%일 수 있는데, 만일 0.1wt%미만이면, 내구성과 내수성 개선이 미미할 수 있고, 반대로, 2wt%를 초과하면, 저장안정성이 저해되며, 시공후 크랙(crack) 불량이 발생될 수 있다.The hydrolysis may be carried out in an acid crisis with hydrochloric acid and water, wherein the concentration of hydrochloric acid may be 0.1 to 2wt%, if less than 0.1wt%, durability and water resistance improvement may be insignificant, on the contrary, 2wt When it exceeds%, storage stability is impaired and crack failure may occur after construction.
여기서 염산의 농도는 상기 알콕시실란과 물, 염산의 혼합물 전체를 기준으로 하는 것이며, 가수분해반응을 통하여 염산의 염소(Cl-)가 알콕시실란에 치환되게 된다.The concentration of hydrochloric acid is based on the entire mixture of the alkoxysilane, water and hydrochloric acid, and chlorine (Cl − ) of hydrochloric acid is substituted with the alkoxysilane through a hydrolysis reaction.
여기서 상기 S1단계의 반응물에 셀루로오스를 가하여 교반하는 공정은 시공후 크랙불량 방지와 경화를 유도하도록 하고, 시공시 도포되는 두께의 일정성을 확보할 수 있으며, 셀루로오스는 니트로셀루로오스, 트리아세테이트셀루로오스, 하이드록시프로필메틸셀루로오스,카르복시메틸셀루로오스,메틸셀루로오스, 히드록시에틸셀루로오스, 에틸히드록시에틸셀루로오스, 히드록시프로필셀루로오스 및 소디움카르복시메틸셀루로오스로 이루어진 군에서 선택된 적어도 하나일 수 있다.Here, the process of adding cellulose to the reactant of step S1 to induce stirring to prevent cracking and hardening after construction, and to ensure the uniformity of the thickness applied during construction, cellulose is nitrocellulose , Triacetate cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, hydroxypropyl cellulose and sodium carboxy It may be at least one selected from the group consisting of methyl cellulose.
또한, 여기서의 일정 반응온도는 본 단계가 발열반응이어서 이때의 열을 이용할 뿐 별도로 외부의 열을 가하지 아니하는 온도를 의미한다.In addition, the constant reaction temperature here means a temperature in which this step is exothermic and thus does not use external heat separately using heat at this time.
다음으로, 상기 S2단계는 상기 S1단계에서의 가수분해된 반응물에 알콕시실란과 암모니아를 산성수용액에서 반응시킨 후 첨가하는 단계이다.Next, step S2 is a step of adding an alkoxysilane and ammonia to the hydrolyzed reactant in step S1 after the reaction in an acidic aqueous solution.
여기서의 알콕시실란은 S1단계의 알콕시실란과는 별도로 준비하는 것으로, 붕산과 물의 산성수용액 분위기에서 반응을 유도하게 되며, 이 공정을 통하여 본 발명에 따르는 조성물이 피도면에 도포된 후 갈라짐(crack) 불량을 방지할 수 있는 특성이 부여된다.Herein, the alkoxysilane is prepared separately from the alkoxysilane of step S1, and induces a reaction in an acidic aqueous solution of boric acid and water, and through this process, the composition according to the present invention is applied to the surface to be cracked. It is given the property to prevent.
여기서의 암모니아는 본 발명에 따르는 무기계수지 조성물의 제조공정단계나 제조후 시공전까지 보관에 필요한 특성인 저장안정성을 확보하고, 다른 첨가제와의 상용성을 위하여 사용되는 것이다.The ammonia here is used to ensure storage stability, which is a property necessary for storage until the production process step or post-construction of the inorganic resin composition according to the present invention, and is used for compatibility with other additives.
또한, 상기 S2단계의 반응물에 실리케이트화합물과 알콜을 상온에서 소정 산도를 유지하며 반응시킨 후 가하여 혼합할 수도 있는데, 실리케이트화합물과 알콜은 발열반응을 하며, 이에 의하여 피도체인 콘크리트와의 계면 친화성을 확보할 수 있다.In addition, the silicate compound and alcohol may be added to the reactant of step S2 while maintaining the acidity at room temperature, followed by mixing. The silicate compound and the alcohol exothermically react, thereby interfacial affinity with concrete to be a conductor. Can be secured.
여기서 상온은 20 내지 30℃ 정도의 특별한 외부 열을 가하지 아니한 온도를 의미하는 것으로, 상온보다 높은 온도에서는 시공후 크랙발생이나 내수성이 저감될 수 있으며, 이후 공정에서도 상온을 유지한다.Here, the room temperature refers to a temperature that does not apply a special external heat of about 20 to 30 ℃, at a temperature higher than the room temperature may reduce the generation of cracks or water resistance after construction, and maintains the room temperature in the subsequent process.
또한, 상기 소정 산도는 물, 염산 및 옥살산에 의한 것일 수 있다.In addition, the predetermined acidity may be due to water, hydrochloric acid and oxalic acid.
아울러, 상기 실리케이트화합물은 알칼리실리케이트염으로서, 알칼리 금속 이온, 알칼리 토금속 이온, 토금속 이온 및/또는 전이금속 양이온과, 실리케이트의 음이온이 고립형, 고리형, 그룹형, 사슬형, 밴드형, 층형 또는 3차원 실리케이트 또는 그들의 조합일 수 있는데, 이러한 구성을 통하여 피도체인 콘크리트나 몰탈에 부착력이나 침투력을 공고히 할 수 있게 된다. In addition, the silicate compound is an alkali silicate salt, wherein alkali metal ions, alkaline earth metal ions, earth metal ions and / or transition metal cations, and anions of the silicates are isolated, cyclic, grouped, chained, banded, layered or It may be a three-dimensional silicate or a combination thereof, and through such a configuration, it is possible to solidify the adhesion or penetration force to the concrete or mortar as the conductor.
또한, 상기 실리케이트화합물은 알킬실리케이트일 수 있으며, 특히, 에틸실리케이트를 사용할 수 있다.In addition, the silicate compound may be an alkyl silicate, in particular ethyl silicate may be used.
다음으로, 상기 S3단계는 상기 S1단계의 반응물에 상기 S2단계의 반응물을 혼합하는 단계이다.Next, the step S3 is a step of mixing the reactants of the step S2 with the reactants of the step S1.
한편, 상기한 제조방법에 의하여 제조되는 환경친화성 무기계수지 조성물을 볼 수 있다.On the other hand, it can be seen an environmentally friendly inorganic resin composition prepared by the above production method.
본 발명은 이하 제조예, 실시예 및 실험예를 통하여 좀 더 구체적으로 설명될 것이다. 이러한 제조예, 실시예 및 실험예는 단지 본 발명이 좀더 이해될 수 있도록 예시적으로 제시되는 것이므로, 이들 실시예로서 본 발명의 범위를 한정해서는 안 될 것이다.The present invention will be described in more detail through the following Preparation Examples, Examples and Experimental Examples. These preparations, examples and experimental examples are only presented by way of example so that the invention can be more understood, these examples should not limit the scope of the invention.
제조예 1Preparation Example 1
r-글리시드옥시프로필트리메톡시실란 100중량부에 물 5중량부, 염산 2중량부를 3시간 동안 500rpm으로 교반하며 가수분해 반응을 수행하였다. 다음으로, r-글리시드옥시프로필트리메톡시실란 100중량부에 암모니아 10 중량부, 물 30중량부, 붕산 30중량부를 3시간 동안 500rpm으로 교반하여, 이의 50중량부에 상기 가수분해 반응물 100중량부를 1시간 동안 25℃ 상온에서 500rpm으로 교반하며 혼합물을 제조하였다.Hydrolysis reaction was carried out while stirring 5 parts by weight of water and 2 parts by weight of hydrochloric acid at 500 rpm for 3 hours to 100 parts by weight of r- glycidoxy propyl trimethoxysilane. Next, 10 parts by weight of ammonia, 30 parts by weight of water and 30 parts by weight of boric acid were stirred at 500 rpm for 3 hours to 100 parts by weight of r-glycidoxy propyl trimethoxysilane, and 50 parts by weight of the hydrolysis reactant was 100 parts by weight. The mixture was stirred at 500 ° C. at 25 ° C. for 1 h at room temperature.
제조예 2Preparation Example 2
제조예1의 가수분해 반응물 100중량부에 하이드로에틸셀루로오스 5중량부를 1시간 동안 25℃ 상온에서 500rpm으로 교반하며 혼합한 것을 제외하고는 제조예 1과 동일하게 제조하였다.5 parts by weight of hydroethyl cellulose in 100 parts by weight of the hydrolysis reaction product of Preparation Example 1 was prepared in the same manner as in Preparation Example 1, except that the mixture was stirred at 500 rpm at 25 ° C. for 1 hour.
실시예 1Example 1
에틸실리케이트 400중량부, 에틸알콜(순도 99wt%) 350중량부를 교반하고 여기에 물 50중량부, 염산 5중량부, 옥살산 10중량부를 3시간 동안 500rpm으로 교반하여 에틸실리케이트화합물을 준비하였다. 상기 제조예 1의 혼합물 100중량부에 상기 에틸실리케이트화합물 50중량부를 1시간 동안 상온에서 500rpm으로 교반하여 본 발명에 따르는 환경친화성 무기계 수지 조성물을 제조하였다.Ethyl silicate compound was prepared by stirring 400 parts by weight of ethyl silicate, 350 parts by weight of ethyl alcohol (99 wt% purity), and 50 parts by weight of water, 5 parts by weight of hydrochloric acid, and 10 parts by weight of oxalic acid at 500 rpm for 3 hours. 50 parts by weight of the ethyl silicate compound was stirred at 500 rpm at room temperature for 1 hour to 100 parts by weight of the mixture of Preparation Example 1 to prepare an environmentally friendly inorganic resin composition according to the present invention.
실시예 2Example 2
제조예 2의 혼합물을 사용한 것을 제외하고는, 실시예 1과 동일하게 하여 본 발명에 따르는 환경친화성 무기계수지 조성물을 제조하였다.Except for using the mixture of Preparation Example 2, an environmentally friendly inorganic resin composition according to the present invention was prepared in the same manner as in Example 1.
비교예 1Comparative Example 1
r-글리시드옥시프로필트리메톡시실란 100중량부에 물 5중량부, 암모니아 10중량부, 염산 2중량부를 3시간 동안 500rpm으로 교반하고, 여기에 하이드로에틸셀루로오스 5중량부, 물 100중량부를 사용하여 무기계수지 조성물을 제조하였다.5 parts by weight of water, 10 parts by weight of ammonia, and 2 parts by weight of hydrochloric acid were stirred at 500 rpm for 3 hours to 100 parts by weight of r-glycidoxy propyl trimethoxysilane, and 5 parts by weight of hydroethyl cellulose and 100 parts by weight of water were added. The inorganic resin composition was manufactured using the part.
실험예 1 : 내구성, 내수성, 내스크래치성 평가Experimental Example 1 Evaluation of Durability, Water Resistance, and Scratch Resistance
실시예 1 및 비교예 1에 의해 제조된 무기계수지 조성물을 콘크리트 표면에 각각 도포한 후, 7일 동안 경화시켜 도막을 형성하였다. 그런 다음 상기 도막이 형성된 지재에 물을 떨어뜨리고 동전을 사용하여 도막의 손상 여부를 관찰 하였다. 그 결과를 도 2 및 도 3에 나타내었다.The inorganic resin compositions prepared in Example 1 and Comparative Example 1 were each applied to the concrete surface, and then cured for 7 days to form a coating film. Then, water was dropped onto the paper on which the coating film was formed, and the coin was used to observe whether the coating film was damaged. The results are shown in FIGS. 2 and 3.
실험 결과, 실시예 1에 의해 제조된 조성물이 도포된 콘크리트 표면은 7일이 경과한 후에도 용해되어 생기는 현상이 발생되지 않고 표면에 물이 굴러가는 발수현상이 발생하는 것을 관찰하였다. 그러나 비교예 1에 의해 제조된 조성물이 도포된 콘크리트 표면의 경우 도포 후 1시간 정도가 경과되면서 도막의 일부가 물에 용해되고, 쉽게 표면이 긁힘이 발생한 것을 볼 수 있었다.As a result of the experiment, the concrete surface to which the composition prepared in Example 1 was applied was observed after 7 days elapsed, and the phenomenon of dissolution did not occur, and it was observed that water repellent phenomena of rolling on the surface occurred. However, in the case of the concrete surface to which the composition prepared by Comparative Example 1 was applied, a portion of the coating film was dissolved in water as the elapse of about 1 hour after the coating, it was seen that the surface was easily scratched.
실험예 2 : 크랙방지 및 오염물 제거 평가Experimental Example 2: Evaluation of Crack Prevention and Contaminant Removal
실시예 2 및 비교예 1에 의해 제조된 무기계수지 조성물을 각각 콘크리트 표면위에 도포 한 후, 7일 동안 경화시켜 도막을 형성하고 도막 표면을 근접 촬영하였다. 그 결과를 도 4 및 도 5에 나타내었다.After applying the inorganic resin composition prepared in Example 2 and Comparative Example 1 on the concrete surface, respectively, it was cured for 7 days to form a coating film and the surface of the coating film was taken close-up. The results are shown in FIGS. 4 and 5.
실험 결과, 실시예 2에 의해 제조된 조성물을 포함하여 형성된 도막의 경우 갈라짐과 같은 손상도 없고, 오염물도 잘 지워지거나 없음을 알 수 있었으나, 비교예 1에 의해 제조된 조성물을 포함하여 형성된 도막의 경우 갈라짐(크랙)이 미세하게 발생하였음을 보여 주었고, 오염의 흔적도 남아 있음을 볼 수 있었다.As a result of the experiment, it was found that the coating film formed by the composition prepared in Example 2 had no damage such as cracking, and contaminants were not easily removed, but the coating film formed by using the composition prepared by Comparative Example 1 In the case of cracks (cracks) was shown to occur finely, it could be seen that the traces of contamination remain.
본 발명에 의하면 환경오염을 유발시키는 휘발성 유기용매를 저감시켜 친환경성을 확보하고, 콘크리트와 유사성분으로 인해 콘크리트 표면 부착력을 증가시킬 수 있고, 내구성은 물론 황변을 방지하는 환경친화성 무기계수지 조성물을 제조할 수 있다. According to the present invention to reduce the volatile organic solvents that cause environmental pollution to ensure eco-friendliness, to increase the adhesion of the concrete surface due to the concrete and similar components, environmentally friendly inorganic resin composition to prevent yellowing as well as durability It can manufacture.

Claims (9)

  1. 일정 반응온도를 유지하며, 알콕시실란을 산성분위기에서　가수분해하여 수용성알콕시실란화합물을 제조하고, 상기 수용성알콕시실란화합물에 셀루로오스를 가하고 교반하여 수용성셀루로오스알콕시실란화합물을 제조하는 S1단계; Maintaining a constant reaction temperature and hydrolyzing the alkoxysilane in an acid atmosphere to produce a water-soluble alkoxysilane compound, and adding cellulose to the water-soluble alkoxysilane compound and stirring to prepare a water-soluble cellulose alkoxysilane compound;
    상기 수용성셀루로오스알콕시실란화합물에 별도로 알콕시실란과 암모니아를 산성수용액에서 반응시킨후 첨가하여 알콕시실란혼합물을 제조하고, 상기 알콕시실란혼합물에 별도로 실리케이트화합물과 알콜을 상온에서 물, 염산 및 옥살산과 반응시켜 첨가하고 혼합교반하여 개질된 실리케이트알콕시실란화합물을 제조하는 S2단계; 및 The alkoxysilane and ammonia are separately added to the water-soluble cellulose alkoxysilane compound in an acidic aqueous solution, and then added to prepare an alkoxysilane mixture. The silicate compound and the alcohol are separately reacted with water, hydrochloric acid and oxalic acid at room temperature. S2 step of preparing a modified silicate alkoxysilane compound by adding and mixing and stirring; And
    상기 S1단계의 수용성셀루로오스알콕시실란화합물에 S2단계의 개질된 실리케이트알콕시실란화합물을 혼합하는 S3단계;를 포함하는 것을 특징으로 하는 환경친화성 무기계수지 조성물의 제조방법.And a step S3 of mixing the modified silicate alkoxysilane compound of step S2 with the water-soluble cellulose alkoxysilane compound of step S1.
  2. 제 1 항에 있어서,The method of claim 1,
    상기 실리케이트화합물은 알칼리실리케이트염으로서, 알칼리 금속 이온, 알칼리 토금속 이온, 토금속 이온 또는 전이금속 양이온과, 실리케이트의 음이온이 고립형, 고리형, 그룹형, 사슬형, 밴드형, 층형 또는 3차원 실리케이트 또는 그들의 조합인 것을 특징으로 하는 환경친화성 무기계수지 조성물의 제조방법. The silicate compound is an alkali silicate salt, wherein alkali metal ions, alkaline earth metal ions, earth metal ions or transition metal cations, and anions of the silicates are isolated, cyclic, group, chain, band, layered or three-dimensional silicates or It is a combination thereof, The manufacturing method of an environmentally friendly inorganic resin composition.
  3. 제 1 항에 있어서,The method of claim 1,
    상기 실리케이트화합물은 알킬실리케이트인 것을 특징으로 하는 환경친화성 무기계수지 조성물의 제조방법. The silicate compound is a method for producing an environmentally friendly inorganic resin composition, characterized in that the alkyl silicate.
  4. 제 1 항에 있어서,The method of claim 1,
    상기 S1단계의 산성분위기는 염산과 물에 의한 것을 특징으로 하는 환경친화성 무기계수지 조성물의 제조방법.The acid component of the step S1 is a method for producing an environmentally friendly inorganic resin composition characterized in that the hydrochloric acid and water.
  5. 제 4 항에 있어서,The method of claim 4, wherein
    상기 염산의 농도는 0.1 내지 2wt%인 것을 특징으로 하는 환경친화성 무기계수지 조성물의 제조방법.The concentration of the hydrochloric acid is 0.1 to 2wt% method for producing an environmentally friendly inorganic resin composition.
  6. 제 1 항에 있어서,The method of claim 1,
    상기 S2단계의 산성수용액은 붕산과 물에 의한 것을 특징으로 하는 환경친화성 무기계수지 조성물의 제조방법.The acidic aqueous solution of step S2 is a method for producing an environmentally friendly inorganic resin composition, characterized in that by boric acid and water.
  7. 제 1 항에 있어서,The method of claim 1,
    상기 알콕시실란은 r-글리시르옥시프로필트리메톡시실란, 메틸트리메톡시실란 및 r-글리시드옥시프로필메틸디에톡시실란으로 이루어진 군으로부터 선택된 적어도 하나인 것을 특징으로 하는 환경친화성 무기계수지 조성물의 제조방법.The alkoxysilane is at least one selected from the group consisting of r- glycyroxy propyl trimethoxy silane, methyl trimethoxy silane and r- glycidoxy propyl methyl diethoxy silane of the environmentally friendly inorganic resin composition Manufacturing method.
  8. 제 1 항에 있어서,The method of claim 1,
    상기 셀루로오스는 니트로셀루로오스, 트리아세테이트셀루로오스, 하이드록시프로필메틸셀루로오스,카르복시메틸셀루로오스,메틸셀루로오스, 히드록시에틸셀루로오스, 에틸히드록시에틸셀루로오스, 히드록시프로필셀루로오스 및 소디움카르복시메틸셀루로오스로 이루어진 군에서 선택된 적어도 하나인 것을 특징으로 하는 환경친화성 무기계수지 조성물의 제조방법.The cellulose is nitro cellulose, triacetate cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, A method for producing an environmentally friendly inorganic resin composition, characterized in that at least one selected from the group consisting of hydroxypropyl cellulose and sodium carboxymethyl cellulose.
  9. 제 1 항의 제조방법에 의하여 제조되는 것을 특징으로 하는 환경친화성 무기계수지 조성물.An environmentally friendly inorganic resin composition, which is prepared by the method of claim 1.
PCT/KR2013/005631 2012-07-02 2013-06-26 Method for preparing environmentally-friendly inorganic resin composition and composition prepared thereby WO2014007486A1 (en)

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JPH1111983A (en) * 1997-06-19 1999-01-19 Matsushita Electric Ind Co Ltd Production of water-repellent glass coating
KR20060118906A (en) * 2005-05-17 2006-11-24 엘지전자 주식회사 Warer-repellent coating composition containing surface-modified nano particles and method for forming a coating layer with a contrilled transparency and contact angle using the composition
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JPH1029847A (en) * 1996-07-16 1998-02-03 Daicel Chem Ind Ltd Method for reducing shrinkage and cracking of mortar or concrete due to drying
JPH1111983A (en) * 1997-06-19 1999-01-19 Matsushita Electric Ind Co Ltd Production of water-repellent glass coating
KR20060118906A (en) * 2005-05-17 2006-11-24 엘지전자 주식회사 Warer-repellent coating composition containing surface-modified nano particles and method for forming a coating layer with a contrilled transparency and contact angle using the composition
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