KR102630659B1 - Sealant Composition - Google Patents

Abstract

The present invention relates to a sealant composition comprising a high-viscosity hydroxyl group-containing polyorganosiloxane, a low-viscosity hydroxyl group-containing polyorganosiloxane, an inorganic filler, and a silane curing agent.

Description

Sealant Composition {Sealant Composition}

The present invention relates to sealant compositions.

Sealant refers to a material that can be filled into joints or joints between various members of a building to provide waterproofing and airtightness to the joint, while also fixing glass, etc. When this joint is left unattended, it causes water leakage, heat loss, mixing of various foreign substances, and corrosion of internal materials. The form or composition is determined depending on the purpose or area of use of the sealant.

These sealants must have excellent adhesion and bonding power even in harsh climates, must be compatible with various building materials, and must also have excellent weather resistance and stability such as cold resistance, heat resistance, UV resistance, and flame resistance. In addition, to be usable in actual industry, it must have excellent workability and excellent storage stability.

Among them, alkoxy sealant is an elastic adhesive that hardens by reacting with moisture in the air, and has less odor problems than products of other curing types (acetic acid/oxime), so its demand is increasing recently. These alkoxy sealants have excellent film properties and adhesion, are not corrosive to metals, and have been widely used in structural (SSG) buildings due to the excellent elasticity and durability of silicon, but despite the above advantages, they are difficult to store. The downside is that it lacks stability.

To improve this, Japanese Patent Publication No. 2010-100667 discloses dimethylpolysiloxane in which both ends are blocked with hydroxyl or alkoxy groups, but layer separation may occur within a short period of time.

Accordingly, in order to apply it to architectural sealants, much research is being conducted to develop sealant compositions that have excellent coating film properties and improved storage stability and workability.

Japanese Patent Publication No. 2010-100667

The present invention was developed to solve the above problems, and is intended to provide a sealant composition that has excellent physical properties (modulus, elongation, etc.) of the cured product while improving storage stability and workability.

In order to solve the above problems, the present invention uses two types of hydroxy group-containing polyorganosiloxanes with different viscosities as the main polymer and improves workability by adjusting the content of inorganic filler. Furthermore, a sealant composition with improved storage stability is provided by additionally adding a hydroxy group-containing monomer to the above sealant composition.

The sealant composition of the present invention has excellent workability, excellent coating film properties (modulus, elongation), and can form a cured product with improved discharge properties. In particular, it is suitable for application to architectural sealants due to its fast drying time to touch and excellent storage stability, and is especially useful for silicone structural glazing. In addition, dimensional deformation of the cured product is minimized in response to external factors (temperature, wind, etc.) of continuous construction, and it has excellent weather resistance without discoloration or cracking even when exposed to ultraviolet rays for a long time.

Hereinafter, the present invention will be described in detail.

The present invention provides a sealant composition.

The sealant composition of the present invention includes a high-viscosity hydroxyl group-containing polyorganosiloxane, a low-viscosity hydroxyl group-containing polyorganosiloxane, an inorganic filler, and a silane curing agent.

<Polyorganosiloxane containing hydroxyl group>

The hydroxy group-containing polyorganosiloxane used in the present invention constitutes the main framework (main material) of the sealant composition. In particular, the present invention provides a high-viscosity hydroxy group-containing polyorganosiloxane and a low-viscosity hide with different viscosities. By using polyorganosiloxane containing a hydroxyl group, the sealant composition has excellent workability and a cured product with excellent physical properties can be formed.

Both the high-viscosity hydroxy group-containing polyorganosiloxane and the low-viscosity hydroxy group-containing polyorganosiloxane may be in the form of containing hydroxy groups at both ends, at one end, or at the side chain.

The high-viscosity hydroxyl group-containing polydimethylsiloxane may be represented by the following formula (1).

[Formula 1]

(Here, n is the number of repeating units in parentheses, and is an integer from 1,000 to 1,000,000,

R ¹ to R ⁸ are the same as or different from each other and are each independently an alkyl group with 1 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, an aryl group with 6 to 15 carbon atoms, or a hydroxyl group,

However, at least one of R ¹ to R ³ or at least one of R ⁴ to R ⁶ is a hydroxyl group.)

R ¹ to R ⁸ may be the same as or different from each other, and may each independently be an alkyl group with 1 to 6 carbon atoms, an alkenyl group with 2 to 6 carbon atoms, an aryl group with 6 to 10 carbon atoms, or a hydroxyl group.

The high viscosity hydroxy group-containing polyorganosiloxane may have a viscosity of 10,000 cPs or more and 100,000 cPs or less at 25°C, and more preferably 45,000 cPs or more and 55,000 cPs or less. By controlling the viscosity of the high-viscosity hydroxy group-containing polyorganosiloxane within the above range, the processability of the sealant composition and the hardness characteristics of the cured product can be excellently maintained. Specifically, if the viscosity of the high-viscosity hydroxy group-containing polyorganosiloxane is less than 10,000 cPs, the physical properties such as tensile strength of the sealant composition may be poor, and if the viscosity is more than 100,000 cPs, the workability or storage of the sealant composition may be poor. Stability may become poor.

The weight average molecular weight of the high viscosity hydroxyl group-containing polyorganosiloxane may be 40,000 to 150,000 g/mol.

The hydroxyl group content of the high viscosity hydroxyl group-containing polyorganosiloxane may be 0.01 to 0.1 wt%.

If the hydroxyl group content of the high-viscosity hydroxyl group-containing polyorganosiloxane is less than 0.01 wt%, the workability or storage stability of the sealant composition may be poor, and if it is more than 0.1 wt%, the physical properties such as tensile strength of the sealant composition may be poor. You can.

The low-viscosity hydroxyl group-containing polydimethylsiloxane may be represented by the following formula (2).

[Formula 2]

(Here, m is the number of repeating units in parentheses, and is an integer from 100 to 1,000,

R ⁹ to R ¹⁶ are the same or different from each other and are each independently an alkyl group with 1 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, an aryl group with 6 to 15 carbon atoms, or a hydroxyl group,

However, at least one of R ⁹ to R ¹¹ or at least one of R ¹² to R ¹⁴ is a hydroxyl group.)

R ⁹ to R ¹⁶ may be the same as or different from each other, and may each independently be an alkyl group with 1 to 6 carbon atoms, an alkenyl group with 2 to 6 carbon atoms, an aryl group with 6 to 10 carbon atoms, or a hydroxyl group.

The low-viscosity hydroxyl group-containing polyorganosiloxane may have a viscosity of 1,000 cPs or more and less than 10,000 cPs at 25°C, and more preferably 4,500 cPs or more and 5,500 cPs or less. By controlling the viscosity of the low-viscosity hydroxyl group-containing polyorganosiloxane within the above range, the processability of the sealant composition and the hardness characteristics of the cured product can be excellently maintained. Specifically, if the viscosity of the low-viscosity hydroxyl group-containing polyorganosiloxane is less than 1,000 cPs, the hardness of the cured sealant composition may be poor, and if the viscosity is more than 10,000 cPs, the hardness or tensile strength of the cured sealant composition may be poor. It can happen.

The weight average molecular weight of the low viscosity hydroxyl group-containing polyorganosiloxane may be 15,000 to 80,000 g/mol.

The hydroxyl group content of the low-viscosity hydroxyl group-containing polyorganosiloxane may be 0.01 to 0.5 wt%.

If the hydroxyl group content of the low-viscosity hydroxyl group-containing polyorganosiloxane is less than 0.01 wt%, the hardness or tensile strength of the sealant composition may be poor, and if it is more than 0.5 wt%, the hardness of the cured product of the sealant composition may be poor. .

As above, when the high viscosity hydroxyl group-containing polyorganosiloxane and the low viscosity hydroxyl group-containing polyorganosiloxane are simultaneously included, the high viscosity hydroxyl group-containing polyorganosiloxane and the low viscosity hydroxyl group The polyorganosiloxane contained may be included in a weight ratio of 1:1 to 3:1, and more preferably, may be included in a weight ratio of more than 1:1 and less than or equal to 3:1.

That is, the content of the high-viscosity hydroxyl group-containing polyorganosiloxane may be greater than the content of the low-viscosity hydroxyl group-containing polyorganosiloxane, or may be included in the same amount.

If the weight ratio of the high-viscosity hydroxyl group-containing polyorganosiloxane and the low-viscosity hydroxyl group-containing polyorganosiloxane is less than 1:1, the discharge amount is very large and workability is reduced, and if the weight ratio is greater than 3:1 As the viscosity increases, the discharge performance deteriorates.

The high viscosity hydroxyl group-containing polyorganosiloxane may be included in an amount of 20 to 30 parts by weight, more preferably 25 to 30 parts by weight.

When the content of the high-viscosity hydroxyl group-containing polyorganosiloxane satisfies the above range, the sealant composition has excellent workability and can form a cured product with excellent physical properties. Specifically, if the content of the high viscosity hydroxyl group-containing polyorganosiloxane is less than 20 parts by weight, the workability and storage stability of the sealant composition prepared using it may be poor, and if it is more than 30 parts by weight, the curing of the sealant composition may be impaired. Physical properties such as water hardness and elongation may become poor.

The low viscosity hydroxyl group-containing polyorganosiloxane may be included in an amount of 10 to 20 parts by weight, and more preferably in an amount of 15 to 20 parts by weight.

When the content of the low-viscosity hydroxyl group-containing polyorganosiloxane satisfies the above range, the sealant composition has excellent workability and can form a cured product with excellent physical properties. Specifically, if the content of the low-viscosity hydroxyl group-containing polyorganosiloxane is less than 10 parts by weight, the adhesion and physical properties of the sealant composition manufactured using it may be poor, and if it is more than 20 parts by weight, the sealant composition may have poor quality. Physical properties such as hardness, tensile strength, and elongation of the cured product may become poor.

<Inorganic filler>

The inorganic filler used in the present invention can enhance the physical properties (modulus/elongation, etc.) of the cured product and can be used to impart hardness to the cured product.

The inorganic fillers include, for example, powdered silica, calcium carbonate, calcium sulfate, barium sulfate, barium carbonate, strontium carbonate, magnesium carbonate, strontianite, iron oxide, aluminum oxide, magnesium hydroxide, aluminum trihydroxide, diatomaceous earth, and talc. , wollastonite, locustite, gypsum, clay, kaolin, barite, bicarbonate, or silicate, but among these, calcium carbonate is preferable in order to ensure excellent film properties and economic efficiency of the cured product.

The inorganic filler may be included in an amount of 40 to 60 parts by weight. If the content of the inorganic filler is less than 40 parts by weight, there may be problems with a decrease in the flow of the sealant composition and the hardness of the cured product, and if it exceeds 60 parts by weight, there may be problems with a decrease in the workability of the sealant composition and the elasticity of the cured product.

<Silane curing agent>

The silane curing agent used in the present invention is used for curing the sealant composition, and examples of the silane curing agent include oxime-based silanes such as methyltris(methylethylketoxime)silane and tetra(methylethylketoxime)silane. hardener; Alternatively, it may be an alkoxy-based silane curing agent such as methyltrimethoxysilane or vinyltrimethoxysilane. When using the oxime-based silane curing agent and the alkoxy-based silane curing agent in combination, the oxime-based silane curing agent and the alkoxy-based silane curing agent may be combined at a weight ratio of 1:0.1 to 1:10, but are not limited thereto.

The silane curing agent may be included in an amount of 1 to 10 parts by weight, and more preferably in an amount of 1 to 5 parts by weight.

When the content of the silane curing agent satisfies the above range, it can react with the hydroxyl group-containing polyorganosiloxane to ensure excellent curing properties. Specifically, if the content of the silane curing agent is less than 1 part by weight, the physical properties of the coating film, such as hardness and elongation, may be poor due to uncuring, and if it is more than 10 parts by weight, problems with storage stability and curing delay of the sealant composition may occur.

<Non-silicone monomer containing hydroxyl group>

The sealant composition of the present invention may further include a non-silicone monomer containing a hydroxyl group. The hydroxyl group-containing non-silicone monomer partially reacts with the silane curing agent, thereby improving the storage stability of the sealant composition.

The hydroxyl group-containing non-silicone monomer may be a monomer containing one or more hydroxyl groups, for example, ethylene glycol, propylene glycol, butylene glycol, ethoxylated bisphenol A (Ethoxylated BPA), 2- Hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 1,3-butanediol di(meth) ) Acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, 4-hydroxybutyl(meth)acrylate, 6 -Hydroxyhexyl (meth)acrylate, 2-hydroxyethylene glycol (meth)acrylate, 2-hydroxypropylene glycol (meth)acrylate, Cardura acrylate, Cardura methacrylate, caprolactone acrylate, caprolactone It may be methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, or 4-hydroxymethylcyclohexylmethyl acrylate.

The hydroxy group-containing non-silicone monomer may be included in an amount of 0.1 to 5 parts by weight. When the content of the hydroxy group-containing non-silicone monomer satisfies the above range, the storage stability of the sealant composition may be improved. Specifically, if the content of the hydroxy group-containing non-silicone monomer is less than 0.1 parts by weight, the storage stability of the sealant composition may be poor, and if it is more than 5 parts by weight, the hardness, tensile strength, and Physical properties such as elongation may become poor.

<Additives>

The sealant composition of the present invention may further include reinforcing fillers, silicone oil, a curing catalyst, an adhesion agent, a coloring agent, etc.

reinforcing filler

The reinforcing filler reinforces the film properties of the sealant composition, and in particular, can shorten the contact time of the sealant composition and improve storage stability.

The reinforcing filler may be silica, and silica surface-treated or untreated with siloxane, silazane, etc. may be used alone or in combination, and fused silica, fumed silica, etc. may be used. It is not limited to this.

Additionally, when the silica is surface treated, for example, dimethyldichlorosilane, hexamethylsiloxane, polydimethylsiloxane, hexamethyldisilazane, octamethylcyclotetrasilazane, methacrylsilane, hexadecylsilane, octylsilane, divinyltetra. It may be surface treated using a silane compound for surface treatment such as methyldisilazane.

The silica may have a particle size of 1 nm to 100 nm. The silica may have a specific surface area of 100 to 300 m ² /g, more preferably 130 to 170 m ² /g. If the specific surface area of the silica is less than 100 m ² /g, the sealant composition may not obtain sufficient strength after curing, and if it is more than 300 m ² /g, the viscosity of the sealant composition may increase, resulting in poor discharge amount.

The reinforcing filler may be included in an amount of 1 to 5 parts by weight. If the content of the reinforcing filler is less than 1 part by weight, it is difficult to expect reinforcement of mechanical properties such as hardness and elongation of the cured sealant composition, and if it exceeds 5 parts by weight, dispersion of the reinforcing filler becomes difficult and hardness increases, resulting in low storage stability. There is a problem with losing.

silicone oil

The silicone oil can control (lower the viscosity) the viscosity of the sealant composition, reinforcing the physical properties (modulus, etc.) of the coating film and improving storage stability.

The silicone oil includes, for example, polydimethyl silicone oil, polymethylphenyl silicone oil, polymethylhydrogen silicone oil, amino-modified silicone oil, and epoxy-modified silicone oil. However, the storage stability of the sealant composition and the film properties of the cured product are important. Considering this, polydimethyl silicone oil is preferable.

The viscosity of the silicone oil may be 50 to 3,000 cPs at 25°C, specifically 50 to 150 cPs, and the acid value may be up to 0.01 mgKOH/g.

The silicone oil may be included in an amount of 0.1 to 30 parts by weight. If the content of the silicone oil is less than 0.1 parts by weight, it is impossible to control the viscosity of the sealant composition, and the storage stability of the sealant composition may be reduced. If the content of the silicone oil is more than 30 parts by weight, mechanical properties such as hardness and elongation of the cured product may be poor. There may be a problem with silicone oil bleeding.

curing catalyst

The curing catalyst serves to promote curing of the hydroxyl group-containing polyorganosiloxane and the silane curing agent.

The curing catalyst may be a metal chelate compound, for example, a titanium chelate compound, a zinc chelate compound, an aluminum chelate compound, a zirconium chelate compound, a vanadium chelate compound, a molybdenum chelate compound, etc.

The curing catalyst is bis(ethyl acetoacetato-O1',O3) bis(2-methylpropan-1-oleto) titanium (bis(ethyl acetoacetato-O1',O3) bis(2-methylpropan-1-olato) titanium).

The curing catalyst may be included in an amount of 0.1 to 3 parts by weight. If the content of the curing catalyst is less than 0.1 parts by weight, curing of the sealant composition may not be promoted and the physical properties of the cured product may deteriorate, and if the content of the curing catalyst is more than 3 parts by weight, the storage stability of the sealant composition may be poor.

Adhesion agent

The adhesion imparting agent serves to improve the adhesion between the cured sealant composition and the material.

The adhesion imparting agent may be a silane-based adhesion imparting agent, for example, epoxy silane, ethoxy silane, methacryloxy silane, imidazole silane, isocyanate silane, etc.

The adhesion imparting agent is preferably methoxy silane to ensure excellent adhesion to metal, and specifically, N-2-(aminoethyl)3-aminopropyltrimethoxysilane (N-2-(aminoethyl) -3-aminopropyltrimethoxysilane).

The adhesion imparting agent may be included in an amount of 0.01 to 5 parts by weight. If the content of the adhesion agent is less than 0.01 parts by weight, there may be a problem of poor adhesion, and if it is more than 5 parts by weight, the storability may be poor, there may be a problem of curing delay, and the adhesion agent may bleed into the coating film after curing. Otherwise, water resistance may decrease and costs may rise.

colorant

The coloring agent can be used without limitation as long as it is intended to impart color to the cured product to exhibit excellent external physical properties. For example, carbon black, titanium oxide, zinc oxide, zinc sulfide, iron oxide, chromium oxide, iron sulfur oxide, zinc It may be chromate, etc., but is not limited thereto as long as it is colorable.

The colorant may be included in an amount of 0.01 to 5 parts by weight.

Other additives

In addition to those listed above, the sealant composition of the present invention may further include additives such as antifoaming agents, thickeners, weathering additives, ultraviolet absorbers, and light stabilizers.

In this case, the additive may be included in an amount of 0.01 to 3 parts by weight.

Hereinafter, the present invention will be described in more detail through examples. However, these examples are only intended to aid understanding of the present invention, and the scope of the present invention is not limited to these examples in any way.

<Examples 1 to 11>

A sealant composition was prepared by mixing the compositions shown in Tables 1 and 2 below.

division Example One 2 3 4 5 main polymer A1 28.276 28.776 26.776 25.276 29.776 A2 16.902 16.902 16.902 16.902 16.902 A3 A4 Thinning and viscosity modifiers B 1.414 1.414 1.414 1.414 1.414 inorganic filler C 41.5 41.5 43 45 42 reinforcing filler D 2 1.5 2 1.5 Non-silicone monomer containing hydroxyl group E 0.177 0.177 0.177 0.177 0.177 curing catalyst F 1.2 1.2 1.2 1.2 1.2 hardener G 4 4 4 4 4 Adhesion agent H 0.131 0.131 0.131 0.131 0.131 colorant I 4.4 4.4 4.4 4.4 4.4 Sum 100 100 100 100 100

division Example 6 7 8 9 10 11 main polymer A1 19.908 29.776 21.822 29.776 25.526 29.776 A2 19.908 10.853 19.856 16.902 19.478 10.853 A3 A4 Thinning and viscosity modifiers B 1.414 1.414 1.414 1.414 1.414 1.414 inorganic filler C 46.862 46.049 45 40 41.674 46.049 reinforcing filler D 2 2 2 2 2 2 Non-silicone monomer containing hydroxyl group E 0.177 0.177 0.177 0.177 0.177 0.177 curing catalyst F 1.2 1.2 1.2 1.2 1.2 1.2 hardener G 4 4 4 4 4 4 Adhesion agent H 0.131 0.131 0.131 0.131 0.131 0.131 colorant I 4.4 4.4 4.4 4.4 4.4 4.4 Sum 100 100 100 100 100 100

<Comparative Examples 1 to 11>

A sealant composition was prepared by mixing the compositions shown in Tables 3 and 4 below.

division Comparative example One 2 3 4 5 6 7 main polymer A1 27.678 23 16 27.678 27.678 29.776 A2 6.902 A3 38.772 19 19 19 10 A4 9.32 23.678 27.678 Thinning and viscosity modifiers B 1.414 1.414 1.414 1.414 1.414 1.414 inorganic filler C 43 43 43 46 43 41.5 41.5 reinforcing filler D 1.5 1.5 Non-silicone monomer containing hydroxyl group E 0.177 0.177 0.177 0.177 0.177 0.177 0.177 curing catalyst F 1.2 1.2 1.2 1.2 1.2 1.2 1.2 hardener G 3 3 3 3 3 3 3 Adhesion agent H 0.131 0.131 0.131 0.131 0.131 0.131 0.131 colorant I 4.4 4.4 4.4 4.4 4.4 4.4 4.4 Sum 100 100 100 100 100 100 100

division Comparative example 8 9 10 11 main polymer A1 42.178 15.924 38.475 A2 43.678 29.254 6.703 A3 A4 Thinning and viscosity modifiers B 1.414 1.414 1.414 1.414 inorganic filler C 45 43 41.5 41.5 reinforcing filler D 1.5 2 2 2 Non-silicone monomer containing hydroxyl group E 0.177 0.177 0.177 0.177 curing catalyst F 1.2 1.2 1.2 1.2 hardener G 4 4 4 4 Adhesion agent H 0.131 0.131 0.131 0.131 colorant I 4.4 4.4 4.4 4.4 Sum 100 100 100 100

The raw materials used in the above examples and comparative examples are as follows.

A1: OH-terminated silicone polymer (viscosity: 50,000 cPs, hydroxyl group content: 0.02 wt%, weight average molecular weight 110,000 g/mol)

A2: OH-terminated silicone polymer (viscosity: 5,000 cPs, hydroxyl group content: 0.1 wt%, weight average molecular weight 49,000 g/mol)

A3: Alkoxy terminated silicone polymer (viscosity 10,000 cPs)

A4: Alkoxy terminated silicone polymer (viscosity 150,000 cPs)

B: Silicone oil (methyl terminated polydimethylsiloxane (PDMS), viscosity 100 cPs)

C: Calcium carbonate (specific surface area: 26 m ² /g)

D: Fumed silica (specific surface area: 150 m ² /g)

E: Propylene glycol (specific gravity: 1.038, refractive index: 1.431)

F: Bis(ethylacetoacetato-O1',O3) bis(2-methylpropane-1-oleto) titanium (purity: 98% or more)

G: Methyltrimethoxysilane (purity: 100%)

H: N-2-(aminoethyl)3-aminopropyltrimethoxysilane (purity: 100%)

I: Colorant (MEP-1K (78%), carbon black (22%)

<Experimental example>

The sealant compositions of Examples 1 to 11 prepared by mixing the compositions of Tables 1 and 2 and Comparative Examples 1 to 11 prepared by mixing the compositions of Tables 3 and 4 were placed at 23°C and 50% RH (relative humidity). Under constant temperature and humidity conditions, each sealant composition was filled into a 2 mm Teflon mold, and the cured properties (adhesion, hardness, tensile strength, elongation, storage stability, discharge amount, etc.) were measured after being stored for 7 days under the same conditions. are shown in Tables 5 to 8 below.

Assessment Methods

1) Adhesion: This indicates the degree of adhesion between the cured material, glass, and fluorine-coated board. After producing an adhesion specimen under the conditions of 23°C and 50% RH, adhesion is evaluated after storing for 3 days under the same conditions.

2) Hardness: This indicates the hardness of the cured product. In the case of general silicone cured products, it ranges from a low hardness of at least 15-20 degrees to a maximum hardness of 90 degrees. The measuring instrument uses a SHORE A TYPE hardness meter, and the thickness of the measurement specimen must be measured by overlapping a 6 mm thick specimen or three 2 mm thick specimens and measuring at least 1/2 inch from the edge. Make sure the needle is in contact with the specimen. The value is read within 1 second, measured repeatedly more than 5 times, and the average value is displayed as the hardness value.

3) Tensile strength: This is a quantification of the maximum stress force per unit area of the silicone cured specimen. The degree to which it can withstand force is expressed as tensile strength, expressed in MPa units. The measuring device uses the Universal Testing Machine and measures silicone rubber specimens made according to the ASTM D412 standard by pulling them from the measuring machine at a speed of 500 mm/min, and the average value of the four specimens is expressed.

4) Elongation: This indicates how many times the original length is increased. The increase in length of the final stretched specimen when the specimen breaks is expressed as a percentage of the original length of the specimen. The measuring device can be measured together when measuring tensile strength using the Universal Testing Machine, and is measured based on the specimen length of 2 cm.

5) Storage stability: After storing in an oven at 80℃, tack freedom is measured (23℃, 50% relative humidity (RH)), and the drying time to touch is measured and displayed after storage for 28 days from immediately after manufacture.

6) Discharge amount: Discharge amount is a test method related to the workability of the sealant that measures the amount of sealant that flows out when the sealant is ejected for a certain time under the conditions of a certain pressure and a certain nozzle. A small discharge amount means that the viscosity is high, which means that a lot of force is required to work.

The test method is,

① After leaving the sealant for a certain period of time (24 hours) under constant temperature and humidity conditions (23℃, relative humidity 50%), connect the sealant air gun to the air line.

② Connect the nozzle to the sealant, and set the nozzle diameter to 5 mm (marked on the nozzle).

③ Fill the sealant into the sealant air gun connected to the nitrogen cylinder.

④ Place an empty paper cup on the scale and take the ‘zero point’.

⑤ After setting the air pressure to 2 kgf, spray sealant (RTV-1) into the paper cup for 10 seconds.

⑥ Measure the weight of the discharged sealant (RTV-1) using a scale.

division Example One 2 3 4 5 Adhesion
(must be good) fluorine, glass
100% CF fluorine, glass
100% CF fluorine, glass
100% CF fluorine, glass
100% CF fluorine, glass
100% CF Hardness (Min. 35) 43 42 44 45 39 Tensile strength (Min. 2 MPa) 3.23 MPa 2.53 MPa 3.03 MPa 2.84 MPa 3.21 MPa Elongation (Min. 300) 316% 366% 372% 348% 398% storage stability
(Tack free measurement after storage in oven at 80℃ (23℃, 50 % RH) Immediately after manufacturing 9 min 15min 8 min 14min 15min After storing for 1 day 9 min 16min 8 min 14min 15min After storing for 2 days 9 min 16min 8 min 14min 19 min After storing for 3 days 9 min 16min 8 min 14min 19 min After storing for 7 days 9 min 20min 8 min 16min 22min After storing for 10 days 18min 25min 15min 16min 22min After storing for 14 days 22min 28min 19 min 25min 42min After saving for 28 days 35min 40min 35min 40min 60min Discharge amount Discharged weight (g) under conditions of 2kgf, 5mm, 10sec 57 56 54 52 48

division Example 6 7 8 9 10 11 Adhesion
(must be good) fluorine, glass
100% CF fluorine, glass
100% CF fluorine, glass
100% CF fluorine, glass
100% CF fluorine, glass
100% CF fluorine, glass
100% CF Hardness (Min. 35) 40 38 45 43 45 38 Tensile strength (Min. 2 MPa) 2.94 MPa 3.02 MPa 3.36 MPa 3.14 MPa 2.84 MPa 3.02 MPa Elongation (Min. 300) 371% 312% 245% 418% 338% 312% storage stability
(Tack free measurement after storage in oven at 80℃ (23℃, 50 % RH) Immediately after manufacturing 15min 15min 14min 14min 14min 15min After storing for 1 day 15min 15min 14min 14min 14min 15min After storing for 2 days 16min 15min 15min 15min 14min 15min After storing for 3 days 16min 16min 15min 15min 14min 16min After storing for 7 days 16min 18min 18min 16min 16min 18min After storing for 10 days 18min 21 min 22min 16min 19 min 21 min After storing for 14 days 29 min 35min 35min 28min 25min 35min After saving for 28 days 51 min 48min 50min 45min 43min 48min Discharge amount Discharged weight (g) under conditions of 2kgf, 5mm, 10sec 60 43 49 45 50 43

division Comparative example One 2 3 4 5 6 7 Adhesion
(must be good) glass
75% CF fluorine, glass
100% CF fluorine, glass
100% CF fluorine, glass
100% CF fluorine, glass
100% CF fluorine, glass
100% CF fluorine, glass
100% CF Hardness (Min. 35) 46 42 35 39 35 44 42 Tensile strength (Min. 2 MPa) 2.90 MPa 3.27 MPa 2.82 MPa 2.70 MPa 3.03 MPa 3.23 MPa 2.94 MPa Elongation (Min. 300) 222% 327% 459% 365% 518% 412% 398% storage stability
(Tack free measurement after storage in oven at 80℃ (23℃, 50 % RH) Immediately after manufacturing 20min 25min 16min 14min 17min 8 min 14min After storing for 1 day 18min 19 min 16min 12min 17min 8 min 14min After storing for 2 days 12min 15min 16min 13min 17min 8 min 14min After storing for 3 days 10min 15min 16min 14min 17min 8 min 14min After storing for 7 days 13min 19 min 16min 13min 17min 8 min 16min After storing for 10 days 15min 19 min 16min 13min 35min 14min 16min After storing for 14 days 21 min 41 min 17min 14min 67min 16min 18min After saving for 28 days 25min 60min 33min 31min 72min 25min 33min Discharge amount Discharged weight (g) under conditions of 2kgf, 5mm, 10sec 10 17 19 18 12 12 14

division Comparative example 8 9 10 11 Adhesion
(must be good) Good Good Good Good Hardness (Min. 35) 41 50 45 42 Tensile strength (Min. 2 MPa) 3.40 MPa 3.30 MPa 3.20 MPa 3.10 MPa Elongation (Min. 300) 450% 272% 336% 351% storage stability
(Tack free measurement after storage in oven at 80℃ (23℃, 50 % RH) Immediately after manufacturing 15min 10min 14min 14min After storing for 1 day 15min 10min 14min 14min After storing for 2 days 15min 10min 14min 14min After storing for 3 days 17min 10min 15min 14min After storing for 7 days 17min 11 min 15min 15min After storing for 10 days 17min 12min 16min 15min After storing for 14 days 25min 29 min 33min 38min After saving for 28 days 45min 40min 44min 53min Discharge amount Discharged weight (g) under conditions of 2kgf, 5mm, 10sec 18 78 67 21

According to Tables 5 to 8, in the case of Examples 1 to 11 containing a high viscosity hydroxy group-containing polyorganosiloxane and a low viscosity hydroxy group-containing polyorganosiloxane, the adhesion, hardness, tensile strength, and elongation were Although it is excellent, it can be confirmed that the storage stability is improved because the drying time to touch is short even after long-term storage, and the workability is improved due to the excellent discharge amount.

On the other hand, in the case of Comparative Example 8, in which only high-viscosity polyorganosiloxane containing hydroxy groups was used, the discharge amount was very low, and the sealant became thick, resulting in poor workability, and in the case of Comparative Example 9, in which only low-viscosity hydroxy group-containing polyorganosiloxane was used, The elongation is low and the discharge amount is very high, so there is a risk of slump due to the sealant becoming too diluted.

Even in Comparative Example 10, where the weight ratio of the high-viscosity hydroxyl group-containing polyorganosiloxane and the low-viscosity hydroxyl group-containing polyorganosiloxane is less than 1:1, the discharge amount becomes very large and slump occurs, and in the Comparative Example where the weight ratio is more than 3:1 In case 11, the discharge amount is small, so the workability of the sealant deteriorates and long-term storage stability becomes poor.

In particular, in the case of Comparative Example 1 in which only alkoxy silicone polymer was used instead of hydroxyl group-containing polyorganosiloxane, and Comparative Examples 2 to 7 in which hydroxyl group-containing polyorganosiloxane and alkoxy silicone polymer were used in combination, tensile strength, elongation, or hardness It can be confirmed that the physical properties of the cured sealant such as these are deteriorated, the storage stability is poor due to the initial touch drying time, or the sealant workability is poor due to the very small discharge amount.

In the above, the present invention has been described in detail only with respect to the described embodiments, but it is clear to those skilled in the art that various changes and modifications are possible within the technical scope of the present invention, and it is natural that such changes and modifications fall within the scope of the appended patent claims.

Claims (6)

25 to 30 parts by weight of high viscosity hydroxy group-containing polyorganosiloxane;
15 to 20 parts by weight of low-viscosity hydroxyl group-containing polyorganosiloxane;
40 to 60 parts by weight of inorganic filler;
1 to 5 parts by weight of reinforcing filler; and
1 to 5 parts by weight of silane curing agent;
A sealant composition comprising:
The high viscosity hydroxy group-containing polyorganosiloxane has a viscosity of 10,000 cPs to 100,000 cPs at 25°C, a weight average molecular weight of 40,000 to 150,000 g/mol, and a hydroxyl group content of 0.01 to 0.1 wt%,
The low-viscosity hydroxyl group-containing polyorganosiloxane has a viscosity of 1,000 cPs or more and less than 10,000 cPs at 25°C, a weight average molecular weight of 15,000 to 80,000 g/mol, and a hydroxyl group content of 0.01 to 0.5 wt%. A sealant composition. In claim 1,
A sealant composition wherein the high-viscosity hydroxy group-containing polyorganosiloxane and the low-viscosity hydroxy group-containing polyorganosiloxane are included in a weight ratio of 1:1 to 3:1. In claim 1,
A sealant composition further comprising a hydroxy group-containing non-silicone monomer. In claim 3,
The hydroxy group-containing non-silicone monomers include ethylene glycol, propylene glycol, butylene glycol, ethoxylated bisphenol A (Ethoxylated BPA), 2-hydroxymethyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylic. Rate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1, 6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, 4-hydroxybutyl(meth)acrylate, 6-hydroxyhexyl(meth)acrylate, 2-hydroxyethylene glycol (meth)acrylate ) Acrylate, 2-hydroxypropylene glycol (meth)acrylate, cardura acrylate, cardura methacrylate, caprolactone acrylate, caprolactone methacrylate, 2,3-dihydroxypropyl acrylate, 2,3 - A sealant composition comprising at least one member selected from the group consisting of dihydroxypropyl methacrylate and 4-hydroxymethylcyclohexylmethyl acrylate. delete In claim 3,
A sealant composition wherein the hydroxy group-containing non-silicone monomer is included in an amount of 0.1 to 5 parts by weight.