KR102420352B1 - Method for manufacturing non-combustible adhesive for building using ceramic binder - Google Patents

Abstract

The present invention relates to a manufacturing method of nonflammable adhesive for building materials using ceramic binder, which comprises the steps of: stirring 1) methyltrimethoxysilane and 2) isopropyl alcohol first at the same weight ratio in a stirrer, followed by stirring 3) tetraethoxysilane and 4) acetic acid at a ratio of 1.5 to 2 : 1 to obtain a stirred material A; stirring 5) colloidal silica and 6) distilled water in a separate stirrer to obtain a stirred material B; adding 1/n of the stirred material B to the stirred material A to stir the same primarily, adding 1/n of the stirred material B, which is a part of the remaining stirred material B, sequentially and repeatedly every time the transparency recognition degree is 80 to 90 %, and when the final recognition degree is recognized at 60 ℃, at 80 to 90 %, only performing stirring, and stopping to obtain a stirred material C when the temperature is from 60 to 80 ℃; ceramic binder manufacturing of adding and stirring 7) hydroxypropyl cellulose, 8) butoxyethanol part, and 9) glycidoxypropyltrimethoxysilane sequentially to age the same with the stirred material C to obtain a stirred material D, which is a silicon binder; and inorganic powder mixing of preparing an incombustible adhesive E by mixing an inorganic substance with the stirred material D to perform a homogenization process for heat resistance and water resistance.

Description

Method for manufacturing non-combustible adhesive for building using ceramic binder

The present invention relates to a method for manufacturing a non-combustible adhesive for building materials using a ceramic binder.

A binder refers to a material that combines materials of different materials to provide required properties such as adhesion, coating film properties, or chemical resistance in the end use. Binders can be largely divided into organic binders and inorganic binders. Organic binders form a bond between materials by carbon bonding or ether bonding, and inorganic binders bind materials by Si-O bonding or Al-O bonding. The binder may be used for the manufacture of various materials such as paints, waterproofing agents, fibers or rubbers. On the other hand, ceramic is an inorganic non-metal that is hardened by firing and mainly refers to a non-metal solid combined with oxygen.

A problem with organic binders widely used in various industrial fields is that they may generate volatile organic compounds (VOCs). Since volatile organic compounds can have a serious impact on the environment, regulations are being gradually tightened. As an alternative to such organic binders, water-based binders or inorganic binders have been proposed.

As a prior art related to a method for manufacturing an inorganic binder, there is Patent Publication No. 2001-0027894 "Silica-based binder and manufacturing method thereof". The prior art relates to a silica (SiO2)-based coating material having excellent adhesion to form a thin film by being coated on the surface of glass, single crystal silicon, and metal, and a method for manufacturing the same, and Si(OC ₂ H ₅ ) ₄ or ethyl silicate Silica sol prepared by hydrolysis in aqueous solution and polysiloxane or R ₂ Si(OR') ₂ (R is CH ₃ and R' is any one selected from H, CH ₃ and CH ₂ CH ₃ ) Disclosed is a silica sol binder having a low viscosity and excellent adhesion by having a Si-CH ₃ group prepared by reaction. As another prior art related to a method for manufacturing an inorganic binder, there is Patent Registration No. 0758286 “Method for Manufacturing Inorganic Polymer Binder”. In the prior art, 27 to 30 repeating units (n) of monosiloxane based on a bonding unit of -Si-O- and disiloxane having a -Si-O-Si- bonding unit as a basic unit ( disiloxane) is disclosed for an inorganic binder having 15 to 18 repeating units.

In general, in the field of materials that require heat resistance, such as kitchen appliances and food products, a method of preparing a coating agent by reacting silica sol and silane using a sol-gel reaction is widely used.

As such a method, two methods have been proposed in the prior art.

1). There is a method of composing a coating agent by mixing and stirring silica sol, silane, alcohol, a base catalyst or an acid catalyst (hereinafter referred to as 'conventional method 1').

2). Add a part of the catalyst to the silica sol to make 1 solution, mix the two with silane first, stir and react, and after aging for a certain period of time, add alcohol as 3 solution, stir again, and mature to make a coating agent There is a method of making (hereinafter referred to as 'conventional method 2').

And in the case of manufacturing a colored coating agent, a coating agent is prepared by adding a pigment in the last process.

However, in the case of the conventional method 1, after 48 hours at room temperature, the coating agent gels due to a condensation reaction and can no longer work, so it is difficult to store the coating agent for a long time or transport it over a long distance .

In addition, in the case of the conventional method 2, since the catalyst is added to the silica sol, it is difficult to store one liquid for a long time, and there is a problem that the working time, which is the use time after the coating agent is formed, does not exceed 48 hours. Therefore, it has become a big obstacle in overseas exports that require long-term storage and transportation.

On the other hand, the coating agent produced by the conventional methods 1 and 2, both require preheating of the corresponding material before coating the coating agent, and there is also a problem that a high temperature drying process of 200° C. or more is required during the coating process.

To this end, a method for manufacturing an inorganic non-combustible ceramic binder capable of long-term preservation, which is a coating composition that extends the working time of the coating material and has non-flammability by overcoming the limitations of working conditions such as preheating and high temperature drying, is disclosed in Korean Patent Application Laid-Open No. 10-2019-0005924 As a result, 25 to 35% by weight of isopropyl alcohol (IPA) was added to 35 to 38% by weight of methoxysilane, and 1.5 to 5% by weight of tetraethoxysilane (TEOS) was gradually added with primary stirring for 5 to 10 minutes. Step 1-1 to prepare a 1-1 solution while dispersing by input;

The first 1-2 step of preparing a 1-2 solution by adding 1.5 to 2.5 wt% of an acid catalyst to the 1-1 solution and stirring for 20 to 30 minutes;

A second step of mixing and stirring 8-15 wt% of distilled water to 10-15 wt% of colloidal silica (silica sol) to prepare a second solution;

Repeatedly drop the 2 liquids little by little into the 1-2 liquids, but when it turns white at the time of initial drop, stir until it becomes transparent, and when it turns transparent, drop some 2 liquids again until it becomes transparent for a total of 20~ A third step of reacting for 30 minutes;

Then, 0.5 to 1.5% by weight of epoxy silane is gradually added to perform the fourth step of improving adhesion. However, although this has the effect of prolonging the storage period, the amount of isopropyl alcohol added is small and the dispersibility is lowered, so the stirring time is increased, so it takes a lot of time to prepare. Since the dispersibility is low, there is a problem that the desired function is not uniformly implemented when the functional inorganic powder is added.

On the other hand, adhesives have been manufactured in the form of using volatile organic compounds as solvents or using formaldehyde or isocyanate as curing agents. has been pointed out

To solve this problem, an emulsion-type water-soluble polymer adhesive that uses water as a solvent instead of a volatile organic compound and does not use a curing agent has been developed, but it does not have flame retardancy and is a cause of suffocation by releasing a large amount of various poisonous gases while burning in a fire. .

On the other hand, sodium silicate is called sodium metasillica, sesqui-silicate, ortho-sillicate, etc. depending on the bonding ratio of Na ₂ O and SiO ₂ More than one type of sodium silicate has been commercialized and marketed. In particular, liquid sodium silicate called water glass is a transparent solution showing viscous alkalinity. This liquid sodium silicate has inherent flame retardancy and adhesive strength, so it is used as an adhesive for various materials.

However, when sodium silicate is used alone as an adhesive, when exposed to moisture or water in the atmosphere, it has a disadvantage in water resistance such as a marked decrease in adhesive strength. It has a property of being easily broken when bent, which is a big problem in terms of flexibility.

In relation to the above problems, Japanese Patent Application Laid-Open No. 61-252395 and Japanese Patent Application Laid-Open No. Hei 5-32931 include mixing sodium silicate with an adhesive organic compound such as water-soluble polyvinyl alcohol to produce an intellectual strength enhancer or coating agent. The technology is introduced, and Korean Patent Publication No. 1999-0070515 and Korean Patent Publication No. 1999-0070516 disclose a technology for manufacturing by mixing ethylene vinyl acetate, acrylic resin, etc. with sodium silicate, but the above technology Adhesives produced by the company have a problem in that their storage stability is remarkably low, which causes problems in the distribution process, resulting in a decrease in value as a product.

The present invention is to solve this problem, and an object of the present invention is to increase the viscosity of the ceramic binder used in the present invention by stirring methoxysilane and isopropyl alcohol in a 1:1 ratio to improve the dispersibility of tetraethoxysilane. An object of the present invention is to provide a method for manufacturing a non-combustible adhesive for building materials using a ceramic binder that facilitates the addition of particles.

Another object of the present invention is to repeat the constant divided amount of the stirred material B when the ceramic binder used in the present invention is stirred with acetic acid by diluting silane and stirring the stirring material B with colloidal silica diluted. A ceramic binder that allows accurate stirring even for beginners is obtained by repeating stirring to add the same amount of the remaining stirring material whenever it changes from opaque to transparent due to temperature rise during stirring. An object of the present invention is to provide a method for manufacturing a non-combustible adhesive for building materials.

Another object of the present invention is that the ceramic binder used in the present invention is added to the stirred material A in which silane is diluted and acetic acid is stirred, and the stirred material C in which colloidal silica is diluted and stirred is added to achieve a heating state. An object of the present invention is to provide a method for manufacturing a non-combustible adhesive for building materials using a ceramic binder that allows the storage period to be maintained for 6 months to 1 year because the dispersing agent dissolves well to provide a ceramic binder of agitated material D that maintains dispersibility.

Another object of the present invention is to provide a method for manufacturing a non-combustible adhesive for building materials using a ceramic binder that can realize the functions of heat resistance, corrosion resistance and water resistance even when inorganic particles are added because the stirring material D, which is the ceramic binder used in the present invention, has improved dispersibility. it is intended to provide

For this purpose, the present invention stirs the following 1), 2), 3), 4) on the stirrer 1,

1) 330 to 370 parts by weight of methyltrimethoxysilane;

2) Stirring 330 to 370 parts by weight of isopropyl alcohol in a 1:1 ratio, here

3) 30-40 parts by weight of tetraethoxysilane;

4) Stirring 20 parts by weight of catalyst acetic acid in a ratio of 1.5 to 2; 1 to obtain a stirred product A.

To the stirrer 2, 5) colloidal silica 258-300 parts by weight;

6) 60 parts by weight of water (H2O) is stirred in a ratio of 4.3 to 5:1 to obtain a stirred product B.

Divide the stirred material B n times (n is the number of equal divisions), and add 1/n of the stirring material B to the stirrer 1 containing the stirring material A. At the time of the first stirring, C at the bottom of the stirrer 1 A confirmation plate with a shape border band is installed, and a camera capable of photographing the inside is installed on the cover of the stirrer 1 so that a separate control unit recognizes the camera picture taken with the confirmation plate and the temperature through the internal temperature sensor, and shoots while stirring. Transparency is checked in the control unit to see if the thumb line between both ends and both ends of the C-shaped border strip is visible in a picture of a confirmation plate, and the distance between the ends of the border strip and the sum line of the confirmation plate is 80 When it is recognized as ~90%, the control unit performs a mixing process that determines that the stirred material is transparent, and when it is confirmed as transparent, the 1/n amount, which is a part of the remaining stirring material B, is repeatedly mixed, but the start of each mixing process is a confirmation plate. It is judged whether the gap between the ends of the border strip and the sum line is recognized as 80~90% of the normal distance forming the ends of the border strip, and after adding the last remaining stirring material B, the temperature reaches 60 ° C, and the check plate border strip ends and the sum line When the interval is recognized as 80 to 90% of the normal interval forming both ends of the rim, only stirring is continued and the stirring is stopped when the temperature of the stirring material rises from 60°C to 80°C to obtain the stirring material C.

7) 7-13 parts by weight of hydroxypropyl cellulose,

8) 10-12 parts by weight of butoxyethanol;

9) 3-7 parts by weight of glycidoxy propyl trimethoxy silane is stirred, but in a sealed state, an exothermic reaction is performed for the initial 2 to 6 hours by hydrolysis with silane, and an additional 6 hours after the exothermic reaction is brought to room temperature A ceramic binder manufacturing process of cooling and aging to maintain a dispersed state of silane to obtain agitated material D, which is a ceramic binder; and

Put the stirring material D into a homomixer, 10) 180-240 parts by weight of kaolin, 11) 60-120 parts by weight of talc, 12) 60-120 parts by weight of titanium oxide inorganic powders are sequentially added. Mix at 500 rpm in one step at medium speed to increase the adhesion between the stirred substance D and kaolin, and then mix at 600 to 700 rpm for 2 to 4 hours at high speed in two steps to increase the viscosity of kaolin and titanium dioxide, and then for 30 to 60 minutes By sequentially performing a low-speed mixing process in three steps of 100 to 150 rpm, inorganic powders of 10) kaolin, 11) talc, and 12) titanium oxide are added to the stirring water D, but aged to maintain adhesion to provide storage and non-combustibility. An object of the present invention is to provide a method for manufacturing a non-combustible adhesive for building materials using a ceramic binder for performing an adhesive manufacturing process for manufacturing non-combustible adhesive E.

As described above, the present invention provides various effects as follows.

Effect 1. In the manufacturing process of the ceramic binder in the present invention, 5) colloidal silica and 4) acetic acid are separated and stirred separately. )---Prevents the promotion of the initial self-hydrolysis reaction.

Effect 2. In the process of obtaining hydrolysis pyrogen C during the ceramic binder manufacturing process in the present invention, additional stirring is performed based on the recognition state and temperature change of the transparency recognition confirmation plate, so the stirring time is shortened and there is no manufacturing error, so that even unskilled people can manufacture it becomes possible

Effect 3. During the ceramic binder manufacturing process in the present invention, since the hydrolysis exothermic stirring material C is self-heated to 60-80°C, 7) hydroxypropyl cellulose, 8) butoxyethanol, and 9) glycidoxy propyl methoxysilane are sequentially added and stirred. The viscosity of the stirring material D is increased to increase the viscosity, so the performance as a binder is improved, and the stirrer cover is sealed during the stirring material D process during ceramic binder production to prevent evaporation of alcohol components and maintain the viscosity state.

Effect 4. In the preparation of the ceramic binder in the present invention, the hydrolysis reaction of the binder is completed as an exothermic process for the first 1-6 hours in the process of preparing agitated material D, and the following 2 to 6 hours are cooled and aged from the exothermic temperature to room temperature and then silane Since the component maintains a uniformly dispersed state, the preservation of the binder itself is possible from 6 months to 1 year. It has good adhesion and functions as a non-combustible adhesive.

Effect 5; An adhesive of inorganic stirrer E is prepared by stirring kaolin, which increases adhesion to stirring material D, talc, which increases storage, and titanium oxide, which increases viscosity. It is non-combustible and has viscosity to provide shape retention of building materials to prevent fire propagation by providing non-combustibility in case of fire, and provides stability from moisture in case of fire.

1 is a process diagram of the present invention;
2 is a block diagram of the stirrer of the present invention;
3 is a waveform diagram showing the time of addition of the stirred material to obtain the stirred material C of the present invention;
Figure 4 is a control configuration diagram of Figure 2;
5 is an enlarged view of the confirmation plate and main parts of the present invention;
6 is a control flow diagram of the present invention;
7 is a view of the confirmation plate transparency recognition principle of the present invention,
8 is a test report cover of the present invention,
9 is a non-flammability test and gas hazard test report of the present invention,
10 is a size condition for each specimen for the non-combustibility test of the test report of the present invention;
11 is a test report showing a non-combustibility test for each specimen of FIG. 10 .

Hereinafter, the present invention will be described in detail.

Glossary of terms

＋2

◎Silane compound--

+2

(--R, R'가 알킬기[

－]이고, n=1~3이면 알킬알콕시실란(alkylalkoxysilane))◎Alkoxysilane (organoalkoxysilane)--

(--R, R' is an alkyl group [

-], and if n = 1 to 3, alkylalkoxysilane

=RO-, 메톡시(

), 에톡시(

)◎Alkoxy group

=RO-, methoxy (

), ethoxy (

)

－로 표시되며 약호는 R이다. 메테인(methane)의 수소 1개를 제외한 CH3-는 메틸(methyl), 에틸 C2H5-, 프로필 CH3CH2CH2-, 부틸 CH3CH2CH2CH2－이 있다.◎alkyl group It is the remaining atomic group except for one hydrogen in chain-shaped saturated hydrocarbons. general meal

It is marked with - and the abbreviation is R. Except for one hydrogen in methane, CH3- is methyl, ethyl C2H5-, propyl CH3CH2CH2-, butyl CH3CH2CH2CH2-.

◎TEOS

It is a compound of the formula Si (OC ₂ H ₅ ) ₄ , which is tetraethylorthosilicate, officially tetraethoxy silane, abbreviated as TEOS. TEOS is a colorless liquid that decomposes in water. TEOS is the ethyl ester of orthosilicic acid, Si(OH) ₄ . It is the most common alkoxide of silicon.

TEOS is a tetrahedral molecule, prepared by alcoholysis of silicon tetrachloride.

SiCl ₄ + 4 EtOH → Si (OEt) ₄ + 4 HCl

Here, Et is an ethyl group, C ₂ H ₅ , so EtOH is ethanol.

TEOS is used in the production of airgels. These applications exploit the reactivity of Si-OR bonds.

◎Glycidoxy propyl trimethoxysilane-OFS-6040

XIAMETER™ OFS-6040 Silane is a bifunctional silane containing a glycidoxy reactive organic group and a trimethoxysilyl inorganic group. Represented by γ-glycidoxy propyl trimethoxy silane. This glycidoxy functional silane is reactive with many different types of organic polymers.

OFS-6040 silane can be applied to inorganic surfaces as a diluted aqueous solution (0.1-0.5% silane concentration). It is recommended that the aqueous solution of OFS-6040 silane be used within 24 hours of preparation. The old solution will start to become cloudy. In the case of mineral fillers, minerals can be treated by mixing with silanes at very low shear for several minutes without additional solvents. Silanes can be diluted with water or solvents.

Summary of ingredients and addition amount

1) 300 to 370 parts by weight of methyltrimethoxysilane

]-[OFS-6070](다우실리콘 코퍼레이션 사 제품)(분산제)[

]-[OFS-6070] (Dow Silicon Corporation) (Dispersant)

(silane compound → alkoxysilane → methyltrimethoxysilane)

2) 300-370 parts by weight of isopropyl alcohol

,

]--용해 용[

,

]--For dissolving

[1):2) = agitation in a 1:1 ratio]

3) 30-40 parts by weight of tetraethoxysilane

]-[OFS-6697](다우실리콘 코퍼레이션 사 제품)(분산제)[TEOS; Tetraethoxysilane; Si

]-[OFS-6697] (Dow Silicon Corporation) (Dispersant)

1) Methyltrimethoxysilane + 2) isopropyl alcohol mixed with 3) tetraethoxysilane mixed and stirred to 1) improve dispersibility of methyltrimethoxysilane to provide caking properties.

COOH 촉매) 20중량부4) Acetic Acid (C)

COOH catalyst) 20 parts by weight

1) methyltrimethoxysilane, 2) isopropyl alcohol, 3) tetraethoxysilane, 4) agitation of acetic acid It can be stored because there is no reaction, and 4) the catalyst promotes the reaction only with a stirred product of 5) colloidal silica and 6) water.

5) 258-300 parts by weight of colloidal silica

Colloidal SiO ₂ particles, usually called silica, vary in size from several tens of nm to several μm, and colloidal silica is a material in which silica particles are dispersed in a dispersed phase of water or ethanol. -Japanese Catalyst Cataloid SN]

6) 60 parts by weight of water (H ₂ O)---[5):6) = 4.3-5:1 stirring-stirred material B]

Agitated substance B is evenly divided (the number of division is represented by n) and repeatedly added to stirred substance A, but when it becomes transparent (control means for transparency recognition will be described later), repeatedly add stirring, and when it becomes transparent after the last addition, 80 Agitation C is obtained by only stirring without addition until it reaches ℃.

7-15중량부,To stir C, 7) hydroxypropylcellulose

7-15 parts by weight,

[HPC; hydroxypropyl cellulose; Cellulose 2-hydroxypropyl ether]-ceramic thickener

8) 10-12 parts by weight of butoxyethanol;

]--바인더 건조지연, 증점제를 잘 녹여준다[Butoxyethanol;

]--Binder drying delay, thickening agent dissolves well

9) 3-7 parts by weight of glycidoxy propyl trimethoxy silane;

[Glycidoxy propyl tri methoxy silane] (XIAMETER ™ OFS-6040 Silane)

--Add various thermosetting resins and glass or mineral coupling agents, binders--.

That is, 7) hydroxypropyl cellulose, 8) butoxyethanol, and 9) glycidoxy propyl trimethoxy silane are sequentially added to the stirred material C while stirring to obtain a stirred material D, which is a ceramic binder. Stirring D is followed by an exothermic (radical hydrolysis) reaction for 2-6 hours, and then the heat is stopped for the following 6 hours, and aging at room temperature is added.

To the aged stirred mixture D, 10) 180-240 parts by weight of kaolin,

[Kaolinite-Al ₂ O ₃ 2SiO ₂ 2H ₂ 0 is the main component, and when moisture is added, it has plasticity (可塑性), and when dried, it shows rigidity (剛性), so it is used to increase the adhesion of the ceramic binder. The melting degree (熔融度) is 1,770 ~ 1,790 ℃ has fire resistance. If the content of kaolin added to the stirring material D is less than 180 parts by weight, the adhesive strength is lowered and the adhesive function cannot be performed.

11) 60-120 parts by weight of talc,

[Talc powdered, component composition is 3MgO ₄ SiOH ₂ O, used as a filler, and has the same acidity as agitated material D, a ceramic binder. It is uneconomical because there is no change in storability.]

12) 60-120 parts by weight of titanium oxide,

[titanium dioxide, TiO ₂ , melting point--1843℃, to maintain the viscosity in neutral, if it is less than 60 parts by weight, the viscosity is lowered, and if it exceeds 120 parts by weight, the viscosity is not maintained and thus the commercial property is lowered.] do.

That is, 10) kaolin, 11) talc, and 12) titanium oxide are sequentially added to the stirring material D and mixed to obtain an inorganic flame retardant E.

[Specifically, the stirring material D is put in a homomixer, 10) 180-280 parts by weight of kaolin, 11) 60-120 parts by weight of talc, 12) 60-120 parts by weight of titanium oxide inorganic powder is sequentially added to the first 50-70 Mix at 400-500 rpm for one minute at medium speed to increase the adhesion between the stirring material D and kaolin, and then high-speed mixing in two steps at 600-700 rpm for 2 to 4 hours to increase the viscosity of kaolin and titanium oxide, followed by Inorganic powder mixing process is performed to produce non-combustible adhesive E by mixing at low speed in 3 steps of 100 to 150 rpm for 30 to 60 minutes and aging to maintain storability between talc and ceramic binder, stirring material D.]

Manufacture process

I. Ceramic binder manufacturing process (agitator) --250~300rpm

The stirrer 1 shown in FIG. 2 is provided with a sensor 2 for detecting the internal temperature on the side wall, and the sensed value of the sensor 2 is converted into a digital value by a built-in analog-to-digital converter, so that the controller 3 can recognize it. Supplied as available. The control unit 3 displays the recognized temperature value in the form of characters such as seven segments on the display 4 so that a third party can check it from the outside. The output terminal O1 of the control unit 3 commands the rotation of the motor unit 5 (of course, the motor driving unit 5-1 shown in Fig. 4 is used for controlling the motor M rotation), and, if necessary, a feeder ( The raw material supplied in 6) is controlled to be supplied by opening and closing the additive supply valve (V1) through the output terminal (O2) of the control unit (3). The opening and closing of the valve V1 may be exemplified by, for example, opening and closing a supply path of a raw material by driving a built-in solenoid to perform an opening and closing function to perform a valve function in a forward or reverse rotation, but is not limited thereto. (7) is a stirring blade, (8) is a camera that is installed on the cover and photographed the confirmation plate 9 installed on the bottom of the stirrer, and sends the photographed picture to the control unit 30 in the form of a picture file. After stirring and addition, the stirrer 1 of FIG. 2 is used, and the related symbols are not described one by one.

4 is an exemplary view showing the control configuration of FIG. 2 as a block diagram, the sensor for internal temperature recognition 2 is a sensor unit 2-1 for detecting the temperature by recognizing the ultraviolet rays emitted by the temperature change in the stirred material; It consists of an analog-to-digital converter 2-2 that converts the recognized value of the sensor unit 2-1 into a digital value and provides it to the input terminal I2 of the control unit 3 . The motor unit 5 includes a motor driving unit 5-1 connected to the output terminal O1 of the control unit 3 and a motor M rotating in association with the motor driving unit 5-1.

)분말[OFS-6070](다우실리콘 코퍼레이션 사 제품) 330-370중량부에,During stirring, the following materials 1), 2), 3), and 4) are supplied by sequentially opening the valve V1 through the feeder 6 provided with a feeder for supplying the additives to the stirrer 1, so as to be stirred. That is, 1) methyltrimethoxysilane (

) powder [OFS-6070] (manufactured by Dow Silicon Corporation) 330-370 parts by weight,

2) 330-370 parts by weight of isopropyl alcohol- 1) for dissolving methyltrimethoxysilane in a 1:1 ratio, so that the viscosity by alcohol is lowered, the control unit 3 controls the motor unit ( 5) After stirring for 10-20 minutes by rotating the stirring blade (7) linked to the operation of the motor (M),

3) 30-40 parts by weight of tetraethoxysilane ([TEOS; Tetraethoxysilane]-[OFS-6697] (product of Dow Silicon Corporation) (dispersant)) is further supplied from the feeder 6, stirred for 10 to 15 minutes, 1 ), TEOS works to improve dispersibility and impart uniform caking properties in a state where the viscosity is lowered.

4) Then, in the feeder (6), 15-20 parts by weight of Acetic Acid [3); 4) 1.5-2; 1 ratio] , 1) methyltrimethoxysilane + 2) isopropyl alcohol + 3) Tetraethoxysilane is added dropwise to 690-780 parts by weight of a stirred substance to disperse acetic acid together to obtain 710-800 parts by weight of a stirred substance A.

In a separate stirrer (which has the same control configuration of FIGS. 2 and 4),

5) 260-300 parts by weight of colloidal silica (Cataloid SN of Illhi Catalyst Hwaseong, Japan),

6) 60 parts by weight of water (H2O) are stirred and mixed to obtain 320-360 parts by weight of agitated water B.

Then, the stirring water B (320-360 parts by weight) is divided several times (n times if the number is set to n) in the same amount and slowly dropped and stirred into the stirring material A (710-800 parts by weight), but the temperature rises after the initial stirring reaction When it changes from opaque to transparent, the stirring for each process of repeating the additional stirring process is stirred in the same manner as in FIG. 6 .

Specifically, 1) the amount (for example, 80 parts by weight) divided by the same number of times (n times) (for example, n times is 4 times) of the stirring material B is dropped into the stirrer 1 containing the stirring material A, colloidal When silica and alkoxysilane (methyltrimethoxysilane, tetraethoxysilane) generate bubbles due to hydrolysis reaction, they change to opaque state when heat starts, and then turns from opaque to transparent after 3 to 5 minutes of stirring. It coincides with the time of rising from 20°C to 30°C, but it is difficult to confirm the exact time due to the time of temperature rise and the delay time for recognizing it, so in the present invention, the confirmation plate 9 shown in FIGS. ) is installed on the inner floor of the stirrer 1, and to confirm the completion of the reaction, the photograph taken after photographing the confirmation plate 9 through the camera 8 is the transparency recognition mixing process of whether the line can be identified as shown in FIG. to determine transparency as shown in FIG. 6 [Step 1 (S1)].

The transparency recognition process uses the confirmation plate 9 as shown in FIG. 5 . The confirmation plate 9 is a circular, elliptical, or polygonal bottom plate 9-1, and an open edge band 9-2 having a C-shaped open loop shape added to the edge of the bottom plate 9-1 as a constant band. ), the sum line 9-3 placed in the open portions of both ends of the frame band 9-2, and a short interval 1 (9-) between the frame band 9-2 and the thumb line 9-3. 4) and interval 1 (9-4) longer than interval 2 (9-5) are configured to form. When the confirmation plate 9 is repeatedly photographed with the camera 8 at a certain period, the control unit 3 recognizes the change from the opaque state to the transparent state, for example, from (a) to (d) of FIG. When the level of 1 (9-4) and the interval 2 (9-5) is recognized as 80 to 90% of the normal interval, the control unit 3 recognizes it as transparent. This is in consideration of the vibration of the inner surface of the stirrer 1 and the normal time to become transparent is 3 to 5 minutes.

The transparency check process is the interval 1 (9-4) and interval 2 (9-5) between the border strip (9-2) and the thumb line (9-3) of the confirmation plate (9) photographed by the camera (8) for each period. The control unit 3 distinguishes and recognizes, but as an example of a recognition method that the control unit 3 can recognize, the dark colored border band 9-2 and the thumb line 9-3 are at a high level, and a light interval is set at a high level. 1 (9-4) and Gingyek 2 (9-5) are recognized as low level, and recognized as binary number 110110011 in which high level and low level are repeated (binary numbers are illustrative and not limited thereto. ) to determine whether it is transparent, but when the low-level interval reaches 80~90% of the normal interval, it is judged as transparent. This is to prevent the inner surface from being recognized as opaque due to the wave-like vibration, although it is actually transparent due to the wave vibration of the agitated material during stirring. Therefore, if it is less than 80~90%, it is opaque, and if it is within 80~90%, it is recognized as transparent. When the control unit 3 determines that it is transparent in this way, it is output to the display 4 and notified [Step 1 (S1)]. In general, in this case, the temperature coincides with the time point T1 when the temperature rises from room temperature to 30° C. as shown in FIG. 3 .

2) Following step 1 (S1), a part (80 parts by weight) of the remaining stirring material B is dropped again, bubbles are generated due to hydrolysis, an exothermic reaction occurs, and after 3-5 minutes of stirring, the reaction becomes opaque according to the reaction It is checked whether the transparent state is completed by taking a picture of the confirmation plate 9 through the camera 8 . That is, as shown in FIG. 7 (d), the control unit 3 repeats the process 2 (S2), which determines whether it is within 80 to 90% of the normal transparent interval, several times [process 4 (S3, in which the agitated material B is exhausted) S4)], stirring conditions are 250 to 350 rpm, when less than 250 rpm, the stirring time increases, and when it exceeds 350 rpm, the viscosity becomes too high due to gelation.

In process 1 (S1), if the initial (starting at 20 ° C.) exothermic temperature is 30 ° C, process 2 (S2) is 40 ° C, process 3 (S3) is 50 ° C, and process 4 (S4) has a transparency of 80~ When it reaches 90%, it is considered that the temperature rises to 60° C., but the present invention prioritizes whether it is transparent and functions to accurately determine the transparent time point without error.

3) Add and stir the last remaining stirring material B in the stirrer and when the stirring material transparency reaches 80 to 90%, only additional stirring is performed. When the temperature reaches from 60°C to 80°C, stirring is stopped, is obtained (step S5). Specifically, when the transparency reaches 80 to 90% and the temperature reaches 60° C., only stirring is performed thereafter, and when the temperature rises from 60° C. to 80° C., the stirring is terminated. In the present invention, accurate and rapid stirring is possible by determining based on temperature and transparency, prioritizing transparency, and further confirming the temperature only at the time of last addition to perform quick judgment and stirring.

Then, 7) 7-15 parts by weight of hydroxypropyl cellulose powder (thickener) was gradually added to the stirring water C, and the viscosity was increased by adding a thickener, 8) butoxyethanol 10-12 parts by weight is dropped, delaying drying of the stirring material C, and inducing uniform dispersion by dissolving the thickener (HPC) well, 9) Glycidoxy propyl trimethoxy silane (XIAMETER ™ OFS-6040 Silane) It maintains the dispersed state by adding 3 to 7 parts by weight.

In a sealed state, an exothermic reaction occurs when the first is stirred for 2 to 6 hours, and secondly, when stirred for 2 to 6 hours, aging (stop exothermicity, temperature is cooled to room temperature) is performed to obtain stirred material D, a ceramic binder.

In the above process (S5), if the stirring material B is viscous and the amount of the mixture added to the stirring material A is not constant as shown in Table 1 below, the temperature at which it is judged to be transparent is measured to give 1 of the stirring material B It functions to manufacture precise and uniform stirring material C by double checking the transparency and temperature rise temperature to contribute to the improvement of the precision of the added amount by measuring whether the amount is excessive or insufficient than the /n amount by temperature change.

Stirring A Stirring B
Dividing amount = (stir B)1/n
(n is the number of additions by dividing, for example, when n = 4, when not equally divided) temperature change transparency 650 to 800 parts by weight 80 parts by weight from 20℃ to 30℃ ○ 85 parts by weight (excess amount) From 30℃ to 42℃ ○ 75 parts by weight (not enough) from 42°C to 51°C ○ 80 parts by weight from 51°C to 61°C ○ Stir to 80℃

II. Non-combustible adhesive manufacturing process by mixing inorganic powder (Homo Mixer)

Put the stirred material D into the homomixer at 800~900rpm and rotate the mixer rotor

10) 180-280 parts by weight of kaolin (heat-resistant adhesive, melting point 1760° C.), 11) 60-120 parts by weight of talc (improved storage property with the same acid as agitator D), 12) 60-120 parts by weight of titanium oxide (neutral) Maintain storage properties and provide non-combustibility), but in one step at medium speed mixing at 400 to 500 rpm for the first 50 to 70 minutes to increase the adhesion between the stirred substance D and kaolin, and then to 2 at 600 to 700 rpm for 2 to 4 hours The viscosity of kaolin and titanium dioxide is increased by high-speed mixing step by step, and then the low-speed mixing process is sequentially performed in three steps of 100-150 rpm for 30 to 60 minutes, to the stirred material D, 10) kaolin, 11) talc, 12 ) A non-combustible adhesive manufacturing process is performed to produce non-combustible adhesive E that maintains storage properties by adding inorganic powder of titanium oxide and aging it to have adhesiveness.

Hereinafter, Examples and Comparative Examples of the present invention will be described.

<Comparative Example 1>

1. 1) Dow Silicon Corporation, which is methyltrimethoxysilane, is mixed with 420 grams of OFS-6070, 2) 300 grams of isopropyl alcohol is mixed for 15 minutes, and then stirred for 15 minutes, 3) tetraethoxysilane, brand name of Dow Silicon Corporation, OFS-6697 20 More grams were mixed and stirred for 15 minutes, and 20 grams of acid catalyst 4) acetic acid was mixed to make a stirred product (1 solution),

2. 5) Mix 140 grams of Cataloid SN, a trade name of Japan Ilhwi Catalyst, which is a silica sol, 6) in 120 ml of water to make a stirred mixture 2 (2 liquids),

3. A coating composition is prepared by mixing and stirring the two liquids with one liquid to function as a separate coagulant.

4. In 1100 g of the coating composition, 180 g of kaolin, 60 g of talc, and 60 g of titanium oxide were mixed and stirred and used as a building adhesive for steel plates and building plates.

At the time of painting, after preheating and painting on a sand blast-treated iron plate, it was combined with a building plate and dried at a temperature between 130 and 150° C. to complete it.

The adhesion of the finished building plate and the steel plate was good because the building plate did not separate from the steel plate base, the storage stability was one year, and the port life of the coating agent was 168 hours. The heat resistance temperature was 900°C.

<Comparative Example 2>

In Comparative Example 2, 300 grams of isopropyl alcohol (IPA) was added to 380 grams of Dow Corning's trade name OFS-6060, which is methoxysilane, and stirred at 300 rpm for 7 minutes, while tetraethoxysilane (TEOS), a trade name of Dow Corning's trade name OFS, was added. -Step 1-1 of preparing a 1-1 solution while slowly adding and dispersing 20 grams of -6697;

A first 1-2 step of preparing a 1-2 solution by dropping 20 grams of acetic acid as an acid catalyst to the 1-1 solution and stirring at 300 rpm for 20 to 30 minutes;

A second step of mixing and stirring 120 g of distilled water to 140 g of colloidal silica (silica sol) at 300 rpm to prepare a second solution;

The 2 liquids are repeatedly dropped into the 1-2 liquids little by little, but when the initial drop turns white, the mixture is stirred at 300 rpm and stirred until it becomes transparent. a third step of reacting for a total of 30 minutes in a manner of stirring;

Then, 10 grams of Dow Corning's OFS-6040, which is ethoxysilane, is slowly added to perform the fourth step of improving adhesion to prepare a coating composition,

To 1100 g of the coating composition, 200 g of kaolin, 80 g of talc, and 80 g of titanium oxide were mixed and stirred and coated.

At the time of painting, the sand blasted iron plate was preheated and painted, combined with the building plate, and then dried at a temperature between 60 and 100° C. to complete it.

The adhesion between the finished building plate and the steel plate was good because the steel plate and the building plate were not separated, the storage stability was one year, and the port life of the coating agent was 168 hours. The heat resistance temperature was 900°C.

Example 1

I. Ceramic binder manufacturing process (agitator)

Agitated material A manufacturing process

In agitator 1,

1) Methyltrimethoxysilane [OFS-6070] (manufactured by Dow Silicon Corporation) powder in 330g

2) After stirring 330 g of isopropyl alcohol------------ with a stirrer for 10 to 20 minutes,

3) Add 30 g of tetraethoxysilane ([OFS-6697] (manufactured by Dow Silicon Corporation)) and stir for 10 to 15 minutes,

4) 20 parts by weight of acetic acid was added dropwise to obtain 710 g of a stirred substance A.

Stirred material B manufacturing process

In stirrer 2,

5) To 260g of colloidal silica (Cataloid SN, Cataloid SN, Inc., Ihwi Catalyst, Japan)

6) 60 g of water (H ₂ O) was stirred and mixed to obtain 320 g of a stirred product B.

Stirred material C manufacturing process

Stirred water B (320g) is divided into 4 times, for example (1/4), and 80g of stirred water B is slowly dropped and stirred in stirred water A (710g). It is added by judging by the recognition of the plate (9). The addition process can be exemplified in the state of FIG. 3 .

1) 80 g of a part (1/4) of the stirred material B is dropped into the stirrer 1 of the stirring material A, and when stirred in the stirrer 1, colloidal silica forming the stirred material B and alkoxysilane (methyltrimethoxysilane, Tetraethoxysilane) becomes an opaque state as it begins to exotherm as bubbles are generated by the hydrolysis reaction. Stirring is 3-5 minutes, and the time from opaque to transparent from starting to exotherm at room temperature (20°C) coincides with the time (T1) when the temperature rises by 10°C, and the camera shown in FIG. 2 ( When the confirmation plate 9 photographed through 8) is transparent, it has the same shape as in FIG. 5 , and the photographed picture passes through the input/output interface 10 in the memory shown in FIG. 4 through the control unit 3 input terminal I1 In order to recognize through and determine whether the recognized photo has the desired transparency, as shown in FIG. 5 , the dark colored border band 9-2 and the thumb line 9-3 are at a high level, and the light color interval 1 ( 9-4) and interval 2 (9-5) are recognized as low level, which makes it difficult to identify the confirmation plate 9 as shown in FIG. does not appear, becomes partially identified as shown in (b), becomes clearer as shown in (c), and then reaches 80 to 90% of the normal interval as shown in (d), the control unit 3 adjusts the level at regular intervals. In subdivision, for example, binary number 110110011 (in Fig. 7(d), when the low-level interval is small, it is defined as “0” and when the interval is wide, it is defined as “00”. Similarly, the high-level is defined as 11 when the interval is wide. defined) as the normal transparency value. When the control unit 3 recognizes that it is transparent, the control unit 3 stops the output to the output terminal O1, and at this time, it is the time T1 in FIG .

2) While the control unit 3 stops the output to the output terminal O1, a high level is applied to the output terminal O2 to open the valve V1 (valve driving a high level signal to the valve V1 built-in driving means) (apply for the set time for which the stirring material B can be dropped to open the valve) Then, 80 g of the stirring material B is dropped again, and again, through the picture of the confirmation plate 9 taken through the camera 8, FIG. 7 ( When the transparent state reaches 80 to 90% of the normal interval as in d), the control unit 3 stops stirring by considering the time T2 of FIG. 3 raised to 40° C. by hydrolysis ( process 2), and then Until time [T3 (transparency 80-90%), T4 (transparency 80-90%) in FIG. Repeat (up to process 4 when the agitated material B is exhausted). Stirring conditions are 250-350 rpm, when less than 250 rpm, the stirring time increases, and when it exceeds 350 rpm, the viscosity becomes too high due to gelation.

3) Process 4 stops when it is transparent corresponding to the time point when the temperature becomes 60 ° C [time T4 (transparency is 80-90%) in FIG. 3], and additional stirring for 10-20 minutes after process 4 (60 during additional stirring) When the temperature rises from ℃ to 80℃, stirring is stopped) to obtain a stirred substance C in a sol state. Of course, the temperature measurement is to recognize the recognition value through the sensor (2) in the control unit (3).

Stirred material D manufacturing process

in the agitation c,

7) Slowly drop 7 g of hydroxypropyl cellulose powder (thickener) and stir for 3 to 5 minutes

8) 10 g of butoxyethanol is added dropwise,

9) After adding 7 g of glycidoxy propyl trimethoxy silane (XIAMETER ™ OFS-6040 Silane), seal and exothermic reaction during the first 6 hours of stirring, and aging (cooling to room temperature) during the second 6 hours of stirring, resulting in a ceramic binder, stirring material D get

II. Non-combustible adhesive manufacturing process by mixing inorganic powder (Homo Mixer)

Put the stirred material D into the homomixer at 800~900rpm and rotate the mixer rotor

10) 200 g of kaolin, 11) 100 g of talc, and 12) 100 g of titanium oxide are sequentially added and mixed in one step at medium speed at 400 to 500 rpm for the first 50 to 70 minutes to increase the adhesion between the stirred substance D and kaolin, followed by 2 The viscosity of kaolin and titanium dioxide is increased by high-speed mixing in two steps at 600-700 rpm for ~4 hours, and then the low-speed mixing process is sequentially performed in three steps of 100-150 rpm for 30 minutes to 60 minutes. 10) kaolin, 11) talc, 12) inorganic powder of titanium oxide is added, but the non-combustible adhesive manufacturing process is performed to produce non-combustible adhesive E that maintains storability by aging to have adhesiveness. It was bonded to the plate at room temperature.

As a result, the adhered building plate and metal plate did not peel and had good adhesion, the storage stability of the non-combustible adhesive of the present invention was 1 year, the port life of the non-combustible adhesive of the present invention was 240 hours, and the heat-resistant temperature was 1100 ℃ and maintained incombustibility at 700 ℃ for 20 minutes.

Example 2

The same preparation as in Example 1 except that 1) methyltrimethoxysilane 340 g, 2) isopropyl alcohol 340 g, 10) kaolin 220 g, 11) talc 100 g, 12) titanium oxide 100 g was added and applied to a metal plate. It was mutually bonded to the building board at room temperature.

As a result, the adhered building plate and metal plate did not peel off and had good adhesion. The incombustibility was maintained for a minute.

Example 3

Same as Example 1 except that 1) methyltrimethoxysilane 350g, 2) isopropyl alcohol 350g, 3) tetraethoxysilane 40g, 10) kaolin 280g, 11) talc 120g, 12) titanium oxide 120g It was prepared in the same way and applied to a metal plate and adhered to a building plate material.

As a result, the adhered building plate and metal plate did not peel and had good adhesion, storage stability was 1 year, port life of the non-combustible adhesive of the present invention was 240 hours, and the heat resistance temperature was 1150 ° C., 700 Incombustibility was maintained at ℃ for 20 minutes.

In Examples 1 to 3, compared to Comparative Examples 1 and 2, the use time of the adhesive was extended, and the heat resistance temperature was increased. This is kaolin, which increases the dispersibility of the silane by controlling the content ratio, and improves the heat resistance temperature while improving the adhesion to the ceramic binder in a homogenized state, which is thickened by adding HPC, butoxyethanol and glycidoxypropyltrimethoxysilane. The storage and use time of the non-combustible adhesive of the present invention are improved, because talc with improved storage properties is added, titanium oxide is added to improve the viscosity, and the rotation speed and time of 3 steps are combined to increase the adhesion. It is judged that the heat resistance temperature is increased and the adhesiveness is improved.

The non-combustible adhesive of the present invention was also coated on a galvanized steel sheet and tested for non-combustibility and gas toxicity in the Korean Construction Living Environment Test Research Institute under the name of non-combustible coating agent (HJN-750), and received a test report as shown in FIG. Haejinnuri is a company represented by the applicant), and as a result of testing the specimen as shown in Fig. 10, it can be confirmed that it has non-combustibility as shown in Figs. It can be confirmed that the state is maintained), and it was confirmed that there was no abnormality in the gas toxicity test as shown in FIG. 9 .

1; Agitator 2; Sensor 2-1; Sensor 2-2; Analog-to-digital converter 3; Control unit 4; Display 5; Motor unit M; Motor 5-1; Motor drive unit 6; Feeder 7; Stirring blade 8; Camera 9; Confirmation plate 9-1; Bottom plate 9-2; Border strip 9-3; Thumb line 9-4; Interval 1 9-5; Interval 2 10; Input/output interface V1; Supply valve

Claims (3)

In the stirrer 1, the following 1), 2), 3), and 4) are mixed,
1) 300-370 parts by weight of methyltrimethoxysilane,
2) 300-370 parts by weight of isopropyl alcohol,
was first stirred at the same weight ratio (1:1),
Then, 3) 30-40 parts by weight of tetraethoxysilane in the first stirring,
4) the process of obtaining a stirred product A by second stirring 20 parts by weight of acetic acid in a ratio of 1.5 to 2:1;
5) 260-300 parts by weight of colloidal silica,
6) stirring 60 parts by weight of distilled water to obtain a stirred product B;
Divide the stirred material B equally by 1/n (n is the number of divisions), and add 1/n of the stirring material B to the stirrer 1 containing the stirring material A. A confirmation plate with a C-shaped rim band and a camera capable of photographing the inside of the stirrer 1 cover are installed so that a separate control unit recognizes the camera picture taken with the confirmation plate. Transparency is checked by the control unit as the sum line between both ends of the band is visible so that the thumb line can be distinguished from each other. After performing the mixing process, 1/n amount, which is a part of the remaining stirring material B, is further mixed, but each mixing process is judged by whether or not the check plate border and thumbline spacing is recognized as 80~90% of the normal interval, After adding the last remaining stirring material B, the interval between the border band and the thumbline of the confirmation plate is recognized as 80~90% of normal, and if the temperature is 60℃, only stirring is continued. When the temperature rises from 60℃ to 80℃, stirring is stopped the process of obtaining a stirred material C;
7) 7-13 parts by weight of hydroxypropyl cellulose,
8) 10-12 parts by weight of butoxyethanol;
9) 3-7 parts by weight of glycidoxypropyltrimethoxysilane
Stirred in turn, but in a sealed state, an exothermic reaction due to hydrolysis by silane is performed for the initial 2 to 6 hours, and after the exothermic reaction, the mixture is aged to maintain the dispersion state of silane at room temperature for an additional 6 hours. Ceramic binder manufacturing process to obtain; and
Put the stirred material D into a homomixer, 10) 180-240 parts by weight of kaolin, 11) 60-120 parts by weight of talc, and 12) 60-120 parts by weight of titanium oxide inorganic powders are sequentially added to change the stirring speed step-by-step to increase the adhesion. A method for manufacturing a non-combustible adhesive for a building using a ceramic binder, characterized in that a non-combustible adhesive manufacturing process is performed to produce a non-combustible adhesive E which has a viscosity and maintains storability by increasing the viscosity.
The method of claim 1, wherein in the manufacturing process of non-combustible adhesive E, 10) 180-240 parts by weight of kaolin, 11) 60-120 parts by weight of talc, and 12) 60-120 parts by weight of titanium oxide are sequentially added to the stirring material D and stirred. The stirring speed is high-speed mixing in one step at 400-500 rpm for the first 50-70 minutes to increase the adhesion between the stirred material D and kaolin, and then high-speed mixing in two steps at 600-700 rpm for 2 to 4 hours to mix kaolin and titanium dioxide A method for manufacturing a non-combustible adhesive for buildings using a ceramic binder, characterized in that by increasing the viscosity of the and then sequentially performing a low-speed mixing process in three steps of 100 to 150 rpm for 30 to 60 minutes.
According to claim 1, wherein the confirmation plate is formed in the form of a bottom plate installed on the inner bottom of the stirrer 1, a C-shaped edge strip added to the edge of the bottom plate, and a gap 1 and a gap 2 between the both ends of the edge strip are positioned Interval 2 is twice the distance of interval 1, dark colored border strips and thumb lines are recognized as high level, and light colored interval 1 and interval 2 are recognized as low level, so whether the distance ratio of light color matches Performs a confirmation process that the control unit confirms as a camera picture,
The verification process recognizes the binary number 11011001 based on the dark and light color arrangement of the border strip, gap 2, island line, gap 1, and border strip part of the photographed picture, and the distance of 0 in the recognized binary number is 80~90 normal. %, it is judged to be transparent, and a method for manufacturing a non-combustible adhesive for buildings using a ceramic binder, characterized in that it is carried out including the process of proceeding with additional addition.

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