KR20190126575A - Silicone-based water repellent for thermal insulator and thermal insulator using the same - Google Patents

Abstract

The present invention relates to a silicone-based water repellent for a thermal insulation and a thermal insulation using the same, wherein the silicone-based water repellent for the thermal insulation comprises: a first silicone oil; an emulsifier or a solution thereof; and water, wherein the first silicone oil is formed of a composition comprising an epoxy group-containing alkoxysilane, a C_6 to C_20 alkyl group-containing trialkoxysilane, and a tetraalkoxysilane.

Description

Silicone-based water repellent for heat insulating material and heat insulating material using the same {SILICONE-BASED WATER REPELLENT FOR THERMAL INSULATOR AND THERMAL INSULATOR USING THE SAME}

The present invention relates to a silicone-based water repellent for heat insulating material and heat insulating material using the same.

Glass fiber (glass fiber) is a kind of inorganic fiber, has excellent incombustibility, heat resistance, high tensile strength, insulation, etc., and is widely used as a thermal insulation material in various industries such as automobiles, construction, and electronic products. However, due to the water absorption of the glass fiber, the heat insulating insulation made of glass fiber is lowered the heat insulating insulation when exposed to moisture. In order to solve this, the thermal insulation material made of glass fibers is water repellent treated with a water repellent.

As a water repellent agent for glass fibers, C8 type fluorine-based water repellents using a fluorine compound containing a perfluoroalkyl (Rf) group are frequently used. The C8 fluorine-based water repellent is widely used as a surface treatment agent for imparting various functions such as water repellency, oil repellency, water resistance, oil resistance, and antifouling property to the surface of various substrates such as fibers and paper.

However, recently, toxicity and environmental problems of some fluorine compounds having a specific chemical structure, such as perfluorooctanoic acid (C ₇ F ₁₅ COOH) and perfluorooctantanesulfonic acid (C ₈ F ₁₇ SO ₃ H), have been reported. Accordingly, there is a movement to regulate the use of C8 type fluorine-based water repellent agent in Asia as well as major developed countries such as Europe and the United States.

In order to avoid such usage restrictions, instead of the C8 type fluorine-based water repellent, a C4 type fluorine-based water repellent or a C6 type fluorine-based water repellent was developed and used. However, C4 and C6 type fluorine compounds not only form perfluorobutane sulfonic acid (PFBS) and perfluorohexanoic acid (PFHxA) upon decomposition, but also accumulate in the body.

Accordingly, research on new water repellent materials that are harmless to the environment and human body and excellent in water repellency are continuously required.

SUMMARY OF THE INVENTION An object of the present invention is to provide a non-fluorine silicone water repellent which is harmless to the environment and human body and can exhibit excellent water repellency, high temperature water repellency sustainability, and laundry durability.

Moreover, an object of this invention is to provide the heat insulation heat insulating material excellent in heat insulation and heat insulation using the above-mentioned silicone type water repellent agent.

In order to achieve the above object, the present invention provides a silicone-based water repellent for thermal insulation.

According to one embodiment of the present invention, the silicone-based water repellent for thermal insulation is first silicone oil (silicone oil); Emulsifiers or solutions thereof; And water, wherein the first silicone oil is formed of a composition comprising an epoxy group-containing alkoxysilane, a C ₆ -C ₂₀ alkyl group-containing trialkoxysilane, and a tetraalkoxysilane.

According to another example of the present invention, the silicone-based water repellent for thermal insulation is a first silicone oil (silicone oil); A second silicone oil different from the first silicone oil; Emulsifiers or solutions thereof; And water, wherein the first silicone oil is formed of a composition comprising an epoxy group-containing alkoxysilane, a C ₆ -C ₂₀ alkyl group-containing trialkoxysilane, and a tetraalkoxysilane.

Moreover, this invention is a base material; And a water repellent coating layer formed of the above-described silicone-based water repellent agent on the substrate.

Here, it is preferable that the said base material is a member containing glass fiber.

Silicone-based water repellent agent according to the present invention is not only excellent in environmental friendliness, but also excellent in water repellency, washing durability, heat resistance and high temperature water repellency durability is composed of a material harmless to humans and the environment. Therefore, when the heat insulating material is water-repellent treatment using the silicon-based water repellent of the present invention, it is possible to maximize the heat insulating performance of the heat insulating material.

1 is a cross-sectional view schematically showing an insulating heat insulating material according to an example of the present invention.
Figure 2 is a schematic cross-sectional view of the thermal insulation insulating material according to another example of the present invention.
Figure 3 is a graph showing the particle size distribution of the emulsion particles in the silicone-based water repellent of the emulsion type prepared in Example 1-2.
4 is a graph showing gel permeation chromatography of the silicone oil prepared in Example 1-1.
5 is a photograph showing the wicking state of the insulation of Example 1 and Comparative Examples 1 and 2 in the wicking test according to Experimental Example 2.

Hereinafter, the present invention will be described in detail.

<Silicone-based water repellent>

The present invention is an emulsion-type silicone-based water-repellent agent used in thermal insulation, the first silicone oil (silicone oil); Emulsifiers or solutions thereof; And water, wherein the first silicone oil is formed of a composition comprising an epoxy group-containing alkoxysilane, a C ₆ -C ₂₀ alkyl group-containing trialkoxysilane, and a tetraalkoxysilane. In addition, if necessary, the silicone water repellent agent of the present invention may further include a second silicone oil.

Since the silicone-based water repellent agent of the present invention uses a non-fluorine-based silicone component, it is harmless to a human body or the environment and can completely prevent environmental damage due to water repellent processing. In addition, the silicone component is composed of emulsion particles (emulsified particles) of several micrometers (μm). The micro particles of the emulsion not only remain on the surface of the substrate but also penetrate deeply into the substrate to bond with the substrate. Therefore, it is excellent in initial stage water repellency and water repellency sustainability. In addition, since the silicone water-repellent agent of the present invention penetrates to the surface and the inside of the substrate and hardens to bond firmly to the substrate, durability is very high.

Hereinafter, each component and composition of the silicone-based water repellent agent according to the present invention will be described.

(a) first silicone oil

In the silicone water-repellent agent of the present invention, the first silicone oil is formed of a first silicone oil-forming composition comprising an epoxy group-containing alkoxysilane, a C ₆ -C ₂₀ alkyl group-containing trialkoxysilane, and a tetraalkoxysilane. A fluorine-type silicone polymer can impart water repellency, water resistance, and laundry durability to a substrate.

Specifically, the first silicone oil of the present invention formed of the composition for forming the first silicone oil may be any one or two of epoxy group-containing alkoxysilanes, C ₆ to C ₂₀ alkyl group-containing trialkoxysilanes, and tetraalkoxysilanes. Unlike silicone oils formed from species, they have hydrophobicity and have a three-dimensional network structure. In particular, since the first silicone oil has hydrophobicity due to the long alkyl group in the molecule, the water repellency can be maximized. In addition, the first silicone oil has a three-dimensional network structure because of the tetraalkoxysilane. In addition, the first silicone oil can enhance the adhesion of the water repellent because of the side chain epoxy group. The silicone water repellent agent of the present invention containing such a first silicone oil is not only excellent in heat resistance and water repellency, but also maintains water repellency even at a high temperature of 200 ° C or higher. For this reason, the heat insulating heat insulating material treated with the silicone-based water repellent agent of the present invention can stably maintain water repellency even when exposed to high temperature, and thus can be processed at a high temperature of about 200 ° C or higher. In addition, the first silicone oil is a non-fluorine-based silicone polymer. Therefore, the silicone-based water repellent agent of the present invention including the first silicone oil, which is a non-fluorine-based silicone polymer, does not release a fluorine-containing substance upon decomposition, and is also a wax-based water repellent or fluorine-free acrylic resin. Unlike water repellents, since they decompose into CO ₂ , SiO ₂ , H ₂ O by high temperature heat, no toxic gas is generated during high temperature processing.

In the composition for forming the first silicone oil, the use ratio (mixing ratio) of the epoxy group-containing alkoxysilane, the C ₆ to C ₂₀ alkyl group-containing trialkoxysilane and the tetraalkoxysilane is not particularly limited. 2: It may be 0.5 to 2 weight ratio. If the use ratio of the epoxy group-containing alkoxysilane, the C ₆ to C ₂₀ alkyl group-containing trialkoxysilane and the tetraalkoxysilane is in the above-mentioned range, the water-repellent agent of the first silicone oil may be Excellent water repellency, heat resistance, adhesion and high temperature water repellency durability.

The epoxy group-containing alkoxysilane is a monomer for imparting an epoxy group to the side chain of the first silicone oil, and an intramolecular epoxy group is ring-opened and converted into a hydroxyl group (-OH) when the heat insulating material is subjected to a water repellent treatment at a high temperature with the water repellent agent of the present invention. For this reason, the water repellent of the present invention can form a water repellent coating layer with improved adhesion to the thermal insulation.

As such an epoxy group-containing alkoxysilane, any alkoxysilane containing an epoxy group at the terminal can be used without limitation. For example, a compound in which at least one (specifically, 1 to 2) epoxy group and at least one alkoxy group having 1 to 12 carbon atoms is directly bonded to the silicon atom may be used.

Specifically, examples of the epoxy group-containing alkoxysilanes include epoxy alkylalkoxysilanes [preferably epoxy group-containing- (C ₁ -C ₆ ) alkyl (C ₁ -C ₆ ) alkoxysilanes, etc.], glycidoxyalkylalkoxysilanes [preferably Glycidoxy (C ₁ -C ₆ ) alkyl (C ₁ -C ₆ ) alkoxysilane and the like].

More specifically, examples of the epoxy group-containing alkoxysilane include 3-glycidoxypropyl trimethoxysilane, glycidoxymethyl trimethoxysilane, glycidoxymethyl triethoxysilane ( glycidoxymethyltriethoxysilane, glycidoxymethyltripropoxysilane, glycidoxymethyl tributoxysilane, glycidoxyethyl trimethoxysilane, glycidoxyethyltriethoxysilane (glycidoxyoxyoxyethoxy ), Glycidoxyethyltripropoxysilane, glycidoxyethyl tributoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropyltripropoxysilane, Glycidoxypropyl tributoxysilane oxysilane), but is not limited thereto. These may be used alone or in combination of two or more thereof.

The C ₆ to C ₂₀ alkyl group-containing trialkoxysilane is a compound in which at least one alkyl group having 6 to 20 carbon atoms and at least one alkoxy group having 1 to 2 carbon atoms are directly bonded to a silicon atom, By giving hydrophobicity can maximize the water repellency. In one example, the C ₆ to C ₂₀ alkyl group-containing trialkoxysilane is a compound in which at least one alkyl group having 6 to 12 carbon atoms and at least one alkoxy group having 1 to 2 carbon atoms are bonded directly to the silicon atom.

Non-limiting examples of such alkyl group-containing trialkoxysilanes are hexyltrimethoxysilane, hexyltriethoxysilane, heptyltrimethoxy silane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, nonyl Trimethoxysilane, Nonyltriethoxysilane, Decyltrimethoxysilane, Decyltriethoxysilane, Undecyltrimethoxysilane, Undecyltriethoxysilane, Dodecyltrimethoxysilane, Dodecyltriethoxysilane Etc. These may be used alone or in combination of two or more thereof.

The tetraalkoxysilane is a compound in which four alkoxy groups having 1 to 10 carbon atoms are directly bonded to a silicon atom. By hydrolysis and condensation reaction with other alkoxysilanes, the first silicone oil may have a three-dimensional network structure. As a result, the silicone-based water repellent of the present invention not only has excellent water repellency and heat resistance, but also has excellent water repellency durability at high temperatures.

Examples of such tetraalkoxysilanes include C, such as tetraethoxysilane, tetramethoxysilane, tetrakis [2- (2-methoxyethoxy) ethoxy] silane, tetrakis (methoxyethoxy) silane, and the like. Tetraalkoxysilane of ₁ to C ₁₀ , etc., but is not limited thereto. These may be used alone or in combination of two or more thereof.

Examples of the first silicone oil formed by the reaction of the aforementioned epoxy group-containing alkoxysilane, C ₆ to C ₂₀ alkyl group-containing trialkoxysilane, and tetraalkoxysilane include a silicone oil represented by the following Chemical Formula 1, and the like. It is not limited.

In Chemical Formula 1,

이고, a 및 b는 각각 1 내지 5의 정수이고;R ₁ is

And a and b are each an integer of 1 to 5;

R ₂ is selected from the group consisting of C ₆ ˜ C ₂₀ alkyl groups;

R ₃ and R ₄ are the same as or different from each other, and are each independently hydrogen or a methyl group;

n is an integer of 3 to 10.

Examples of the silicone oil represented by Chemical Formula 1 include a silicone oil represented by Chemical Formula 2, but are not limited thereto.

In Chemical Formula 2,

R ₃ and R ₄ are the same as or different from each other, and are each independently hydrogen or a methyl group;

n is an integer of 3 to 10.

The first silicone oil may have a weight average molecular weight of about 270 to 1500 g / mol, a polydispersity index (PDI) of 1.0024 to 1.1589, and a viscosity of 1.5 to 1.8 cPs.

In the silicone-based water repellent of the present invention, the content of the first silicone oil is not particularly limited, and may be, for example, about 30 to 70% by weight based on the total amount of the silicone-based water repellent. If the content of the first silicone oil is less than the above-mentioned range, it is difficult to exhibit a sufficient water repellent effect, the permeability of the water repellent active ingredient is reduced. On the other hand, when the content of the silicone oil exceeds the above-mentioned range, the size of the emulsified particles in the water repellent can not be optimized, thereby reducing the stability of the water repellent.

The first silicone oil of the present invention comprising the aforementioned components can be prepared according to conventional methods known in the art.

For example, the above-mentioned epoxy group-containing alkoxysilane, C ₆ -C ₂₀ alkyl group-containing trialkoxysilane, tetraalkoxysilane, organic solvent, a composition for forming a silicone oil comprising an organic solvent, an acid component and water is subjected to hydrolysis and condensation reaction. A first silicone oil can be obtained.

Specifically, an epoxy group-containing alkoxysilane, a C ₆ to C ₂₀ alkyl group-containing trialkoxysilane, a tetraalkoxysilane and an organic solvent are introduced into a reactor, and the reactor is cooled to a temperature of about 7 to 13 ° C. to about 7 Acid components such as hydrochloric acid and water at a temperature of ˜13 ° C. were added and stirred for 6-10 hours to be replaced with hydroxysilanes, followed by hydrolysis and condensation reactions. In order to proceed to increase the internal temperature to about 30 ~ 60 ℃ by stirring under reflux for 14 to 18 hours and proceeding under reduced pressure to obtain a colorless first silicone oil (silicone polymer).

In the silicone oil-forming composition, the organic solvent may be used a conventional organic solvent known in the art. For example, N-methyl pyrrolidinone, dimethylformamide; Alcohols such as methanol, ethanol, iso-propanol (IPA), N-butanol, iso-butanol, 2-butanol, 1-pentanol and the like.

In addition, water is not particularly limited, and distilled water, purified water or pure water (D / I water) may be used.

The composition of the silicone oil-forming composition is not particularly limited. For example, the silicone oil-forming composition may contain 5-25 wt% of an epoxy group-containing alkoxysilane and an alkyl group of C ₆ -C ₂₀ based on the total amount of the silicone oil-forming composition. 5-25 wt% of trialkoxysilane-containing, 10-40 wt% of tetraalkoxysilane, 1-10 wt% of organic solvent, 0.1-1 wt% of acid component, and the remaining amount of water to make the composition 100 wt% It may include.

(b) emulsifiers or solutions thereof

In the silicone-based water repellent of the present invention, the emulsifier can use any conventional emulsifier component known in the art without limitation.

The emulsifier may be selected from anionic emulsifiers, nonionic emulsifiers, cationic emulsifiers or zwitterionic emulsifiers alone or in combination. According to an example, the emulsifier may be a poly vinyl alcohol (PVA) -based emulsifier. In this case, compared with the case where other emulsifiers are used, emulsification safety can be improved.

In the silicone water repellent of the present invention, the content of the emulsifier is not particularly limited, but may be, for example, about 5 to 35% by weight based on the total amount of the silicone water repellent. At this time, when the content of the emulsifier is smaller than the above-mentioned range, it is difficult to obtain an emulsion in a stable state, and when it exceeds the above-mentioned range, the water-repellent active ingredient is relatively low and sufficient water absorption prevention performance is achieved by the hydrophilic group of the emulsifier (surfactant). Since it is difficult to obtain, the water repellency is reduced.

In the silicone water-repellent agent of the present invention, when the emulsifier is in a solid phase, the emulsifier may be used in an emulsifier solution state obtained by dissolving in a solvent such as water or an organic solvent. At this time, the content (concentration) of the emulsifier in the emulsifier solution may be about 6 to 17% by weight, preferably about 9 to 12% by weight, based on the total amount of the emulsifier solution. Here, examples of the organic solvent include N-methyl pyrrolidinone and dimethylformamide; Alcohols such as methanol, ethanol, iso-propanol (IPA), N-butanol, iso-butanol, 2-butanol, 1-pentanol and the like. In view of the fact that the silicone water-repellent agent of the present invention is in an oil-in-water (O / W type) emulsion state, dissolving and using a water-soluble emulsifier in water is preferable because it can improve the dispersibility of the emulsifier in the water-repellent agent. For example, when the emulsifier is a poly vinyl alcohol (PVA) -based emulsifier, a solvent usable may be water.

(c) water

The silicone water repellent agent of the present invention contains water in a continuous phase (continuous medium). As a result, the silicone-based water repellent agent is in an oil-in-water (O / W type) emulsion state in which silicone oil is dispersed in water in the form of emulsion particles.

Water is not particularly limited, and for example, distilled water, purified water, pure water (D / I water), tap water, and the like.

In the silicone-based water repellent of the present invention, water may be a residual amount that satisfies the water repellent to be 100% by weight.

(d) second silicone oil

Optionally, the silicone-based water repellent of the present invention may further include a second silicone oil in addition to the above-mentioned components.

The second silicone oil is a silicone oil different from the first silicone oil, and can increase the viscosity of the silicone-based water repellent.

The second silicone oil may be used without limitation as long as it is a silicone oil generally known in the art. However, it is preferable that a 2nd silicone oil is also a non-fluorine type like 1st silicone oil. Examples include polydimethylsiloxane (PDMS), methylphenylsiloxane, amino modified silicone oil, higher fatty acid modified silicone oil, alkyl modified silicone oil, alkylaralkyl modified silicone oil, epoxy modified silicone oil, and the like, but are not limited thereto. Do not. These may be used alone or in combination of two or more thereof.

The second silicone oil may have a weight average molecular weight of about 40,000 to 270,000 g / mol and a kinematic viscosity of about 100 to 200 cs.

The content of the second silicone oil is not particularly limited and may be appropriately adjusted according to the required viscosity of the silicone-based water repellent or the content of the first silicone oil. For example, the use ratio of the first silicone oil and the second silicone oil may be 1: 0.3 to 0.7 weight ratio. The total content of the first silicone oil and the second silicone oil is not particularly limited, and may be, for example, about 30 to 70 wt% based on the total amount of the silicone-based water repellent. If the total content of the first silicone oil and the second silicone oil mixed at the above-mentioned usage ratio is in the above-described range, the silicone-based water repellent of the present invention has a viscosity of about 2.5 to 5.5 cPs.

(e) additives

Silicone-based water repellent agent according to the present invention is a conventional additive known in the art, such as emulsion protective colloids, heat stabilizers, pH adjusting agents, preservatives, antiseptics and antifoaming agent selected from the group consisting of one or two or more additives It may be optionally included within a range that does not adversely affect the dispersibility and water repellent performance.

The emulsion protective colloidal agent includes fumed silica (Fumed Silica) for improving the thickening and viscoelasticity of the emulsion in the silicone-based water repellent. In this case, the emulsion protective colloid may be used in consideration of the storage stability, particle diameter, viscosity, viscoelasticity, etc. of the silicone-based water repellent, or does not require long-term storage stability, and according to the needs of the user.

The heat stabilizer is to give heat resistance to the silicone-based water repellent to have a storage stability for long-term storage at a high temperature of more than room temperature (20 ℃ or more), for example urea (urea) may be used.

The pH adjusting agent is added to prevent the hydrolysis of the epoxy group-containing alkoxysilane, the alkyl group-containing trialkoxysilane and the tetraalkoxysilane by adjusting the pH of the silicone-based water repellent. Such pH adjusting agents may be selected from alkaline compounds, including organic bases and inorganic bases and salts thereof, or buffers such as aqueous sodium acetate solution.

The preservative is selected from conventional preservatives that prevent the silicone-based water repellent from being altered. For example, 1.2-benzoisothiazoline-3 and the like.

The antimicrobial agent is selected from conventional antimicrobial agents having the effect of antibacterial, antifungal and the like. For example, 2-n-octyl-4-isothiazoline-3 and the like.

The antifoaming agent may use a conventional antifoaming agent that suppresses the bubble generation of the silicone-based water repellent.

In the present invention, in addition to the above-described emulsion protective colloid, heat stabilizer, pH adjusting agent, preservative, antiseptic agent, antifoaming agent may further include other additives. Such additives are not particularly limited, but examples thereof include pigments, flame retardants, surface conditioners, curing accelerators, leveling agents, UV absorbers, skinning inhibitors, and dispersants. At this time, the addition amount of the additive is not particularly limited, and may be added within a range in which the water repellent performance of the silicone-based water repellent does not decrease.

Silicone-based water repellent according to the present invention comprises a first silicone oil formed of a composition comprising an epoxy group-containing alkoxysilane, an alkyl group-containing trialkoxysilane and a tetraalkoxysilane; Emulsifiers; And water and, optionally, a second silicone oil, followed by stirring to emulsify. Here, when emulsification is carried out using an emulsifier (for example, PVA 10), a silicone-based water repellent in a white emulsion state can be obtained, in which case the average particle diameter of the emulsion (emulsified particles) is about 1 to 2.0 μm.

The emulsifying method may use a conventional emulsifier known in the art, for example, a homomixer or a high speed stirrer may be used.

Silicone-based water repellent of the present invention is an oil-in-water type (O / W type) emulsion, may include emulsified particles (oil particles) in the emulsion, preferably the first silicone oil is 1.0 ~ 2.0 ㎛ It may be an O / W type emulsion granulated in the state of droplets having an average particle diameter in the range.

When the size of the emulsified particles in the silicone-based water repellent agent has an average particle diameter of about 1.0 to 2.0 μm, the silicone polymer, which is a water-repellent active ingredient, hardly hydrolyzes with water, so that the emulsified particles are stably dispersed, and even if time passes. The emulsified particles can be kept stable in a uniformly dispersed state. Therefore, the size of the emulsified particles in the silicone-based water repellent agent of the present invention is preferably adjusted to have a uniform diameter of about 1.0 to 2.0 μm, specifically about 1.4 to 1.8 μm.

In the present invention, the size of the emulsified particles may be appropriately adjusted according to the emulsification conditions such as the type and content of the silicone-based polymer, the rotational speed of the emulsifier or the time of emulsification.

The silicone-based water repellent prepared as described above may be used as it is or diluted with a certain concentration in an aqueous solvent or water. At this time, the dilution concentration may be appropriately adjusted according to the needs of the user, for example, may be about 1 to 15%, specifically about 3 to 7%.

Silicone-based water repellent agent of the present invention can be used in the thermal insulation insulating material in the interior of the industry, automobile, construction, etc. can impart excellent water repellency. In particular, the silicone-based water repellent agent can not only impart excellent water repellency, water repellency sustainability, washing durability to the heat insulating material containing glass fibers, and can stably maintain water repellency at high temperatures. In addition, the silicone-based water repellent of the present invention may form a water repellent coating layer on the surface of the glass fiber to impart water repellency to the glass fiber itself. In addition, the silicone water repellent agent of the present invention has a thermal decomposition temperature of about 280 to 600 ℃, preferably about 300 to 400 ℃. According to one example, the silicone-based water repellent of the present invention has a pyrolysis temperature of about 320 ° C. in a thermogravimetric analysis (TGA) test. As described above, the silicone water-repellent agent of the present invention is excellent in heat resistance. For this reason, when water-retaining heat insulation heat insulating material, especially the heat insulation heat insulating material of glass fiber using the water repellent agent of this invention, it can thermoset at high temperature 200 degreeC or more. According to one example, when the water repellent of the present invention is a water-repellent treatment of the thermal insulating material made of E-glass, it may be thermally cured at about 280 ℃ or more, preferably about 280 to 320 ℃ to form a water repellent coating layer.

<Thermal insulation material>

On the other hand, the present invention provides a heat insulating material using the above-described silicone-based water repellent.

1 and 2 are each a schematic view showing a cross-section of the thermal insulation in accordance with the present invention, the thermal insulation 10 includes a substrate 11, and a water-repellent coating layer 12 formed on the surface of the substrate.

In the insulating heat insulating material 10 of the present invention, the substrate 11 is not particularly limited as long as it is used as a base member of the insulating heat insulating material in the art, for example, may be a member containing glass fibers. According to one example, the substrate may be a fabric containing glass fibers.

Specifically, the substrate may be a woven fabric containing glass fibers, a non-woven fabric containing glass fibers, a mat containing glass fibers (eg, chopped strand mats, continuous filaments). Continuous filament mat, surfacing mat, etc., but is not limited thereto. According to an example, the substrate may be glass wool.

Examples of the glass fiber can be used without limitation as long as it is known in the art, such as E-glass, C-glass, D-glass, S-glass, NE-glass, T-glass, Q-glass, etc. It is not limited.

In the heat insulating material 10 of the present invention, the water repellent coating layer 12 is a coating layer formed of the above-described silicone-based water repellent, is formed on one side or both sides of the substrate. At this time, as shown in Figures 1 and 2, the silicone-based water repellent may be formed to penetrate into the substrate.

The above thermal insulation can be produced by a variety of methods known in the art. For example, it may be formed by applying a silicone-based water repellent to the surface of the substrate using a coating method such as a dipping method, a roll coating method, a die coating method, a gravure coating method, a spray coating method, and the like and then curing the applied silicone water repellent agent.

According to an example, the thermal insulation material (S100) after the substrate is immersed in the aforementioned silicone-based water repellent; And (S200) it may be formed by a method comprising the step of curing the padding is completed. However, if necessary, the steps of each process may be modified or optionally mixed.

Hereinafter, each step of manufacturing the above-described heat insulating material will be described.

Step S100: The substrate is immersed in a silicone water repellent and padded.

Here, the silicone-based water repellent may be used as it is or diluted with a certain concentration in an aqueous solvent or water. At this time, the dilution concentration of the silicone-based water repellent may be appropriately adjusted according to the needs of the user, for example, may be about 1 to 15%, specifically about 3 to 7%.

When using such a silicone-based water repellent, it is possible to adjust the amount of impregnation or to adjust the degree of curing by adjusting the solids content of the silicone-based water repellent according to the required physical properties of the final product. For example, it is preferable to adjust the solids content of the silicone-based water repellent to about 15 to 45% by weight in view of the ease of impregnation and the degree of curing of the substrate. If the solid content of the silicone-based water repellent is less than 15% by weight, the water content is too high to be impregnated, and may be insufficient to cure even when dried. On the other hand, when the solid content of the silicone water repellent is more than 45% by weight, a viscosity increase is caused and water dispersibility is inferior.

The padding process adjusts the padding pressure and speed, and the number of process repetitions according to the type of substrate or the concentration of the silicone-based water repellent. For example, a fabric (e.g., non-woven) made of fiberglass is impregnated in 7% silicone-based water repellent for about 1-5 minutes (preferably, about 1-2 minutes) and then at about 0.5-1.0 MPa under a pressure of about 0.5-1.0 MPa. Padding at a speed of 2 rpm. At this time, the process may be repeated one or more times.

After the padding process, the pick-up ratio of the padded substrate is not particularly limited and may be appropriately adjusted according to the material of the substrate. For example, when the substrate is a member containing glass fibers, specifically a fabric containing glass fibers, the average pickup rate of the silicone-based water repellent may be 70 to 100%, specifically about 98% to 100%. As described above, since the silicone-based water repellent has excellent permeability to the member containing the glass fiber, the silicone-based water repellent penetrates into the inside of the member containing the glass fiber, thereby providing excellent water repellency, and thus, the thermal insulation insulating performance of the thermal insulating material can be improved.

(S200) step: the substrate is padded and dried and cured.

In this step, the silicone-based water repellent, which is present on the surface of the padded substrate or penetrates into the internal pore structure of the substrate, is cured to form a water-repellent coating layer firmly bonded to the substrate. Thereby, the heat insulation insulating material which is excellent in water repellency and washing durability, and can maintain water repellency stably at high temperature can be obtained.

The said hardening conditions are not specifically limited. According to one example, the substrate padding is completed in step (S100) is heat-cured at about 170 ℃ or more, specifically about 190 to 300 ℃ for about 40 to 80 minutes to heat-repellent coating layer on all surfaces and inside of the substrate 11 (12) can be formed.

In the thermal insulation of the present invention manufactured as described above, the water-repellent coating layer 12 is excellent in water repellency and wash durability, even when exposed to high temperatures can maintain a stable water repellency. According to one example, the thermal insulation of the present invention is the maximum wicking resistance test according to AATCC Test Method 197-2013: Vertical wicking of Textiles, the start time of water absorption after 50 minutes, wherein the water absorption height is 0.2 Mm. The thermal insulation of the present invention can be used in various industrial fields, such as interior materials of automobiles, as well as building interior materials.

Hereinafter, the present invention will be described in detail by way of Examples, but the following Examples and Experimental Examples are merely illustrative of one embodiment of the present invention, and the scope of the present invention is not limited to the following Examples and Experimental Examples. .

[Preparation Example]

Among the materials used in Example 1, 3-glycidoxypropyltrimethoxysilane (SG007), triethoxyoctylsilane (SM008) and tetraethoxysilane (TEOS), which are raw materials used in the preparation of silicone oil, were purchased from Aldrich, respectively, Polydimethylsiloxane (PDMS) [PDMS-200X (100 cs)], a raw material used in the manufacture, was purchased from Saehan Silychem.

In addition, methanol (methanol, MeOH) and 35% of HCl used during the reaction were purchased from large purified gold, respectively, and the purchased reagents were used directly without further treatment. Pure water (Deionization water, D / I water) was used for the reaction. The emulsifier used in the emulsification was prepared by mixing PVA 205 MB (Kuraray) with pure water (D / I water) (weight ratio of PVA 205 MB: D / I water = 1: 9) and then heating at 80 ° C. Material (PVA 10) was used.

Example 1

1-1. Manufacture of silicone oil

200.75 g of SG007, 196.86 g of SM008, 201.76 g of TEOS and 56 g of MeOH were added to a 2 L double jacket reactor, and the reactor was cooled to 10 ° C. When the internal temperature of the reactor reached 10 ° C, 1 g of HCl and 343.63 g of D / I water were added to the reactor, followed by stirring for about 8 hours. After 8 hours had elapsed, the temperature was raised so that the reactor internal temperature was 45 ° C, and when the internal temperature reached 45 ° C, the mixture was stirred under reflux for about 16 hours. After the reflux agitation was completed, purification was performed under reduced pressure using a rotary evaporator to prepare 400 g of a colorless silicone oil.

1-2. Preparation of Silicone Water Repellent

400 g of the silicone oil prepared in Example 1-1, 250 g of emulsifier (PVA 10), 180 g of PDMS, and 170 g of D / I water were mixed using a homomixer, and the average particle diameter was about 1.0 to Emulsification was stopped when 2.0 μm to prepare 1000 g of a silicone-based water repellent (solid content: 32 ± 2 wt%) in the form of a white emulsion.

Figure 3 is a graph showing the average particle diameter of the emulsified particles in the water repellent prepared in Example 1-2. As shown in FIG. 3, the particle size of the emulsified particles in the water repellent of Example 1-2 maintained the shape of a Gaussian distribution, wherein the average particle diameter of the emulsified particles was about 1.7 μm. Specifically, the emulsified particles in the water repellent had a particle size distribution having a particle size d90 of about 2.65 μm, a particle size d50 of about 1.64 μm, and a particle size d10 of about 0.86 μm.

1-3. Manufacture of thermal insulation

Glass fiber fabric (Seunti S Co., Ltd.) was prepared by cutting to a size of 25mm X 150mm. After diluting 1000 g of water in 70 g of the silicone-based water repellent prepared in Example 1-2, and then immersing the fabric prepared therein for 2 minutes, a padding machine at a speed of 1 rpm at a pressure of 0.6 MPa The fabric was padded through a padder. The above-described process was repeated three times to fix the water repellent to the fabric. Subsequently, the padded fabric was cured in an oven at 190 ° C. for 60 minutes to prepare an insulating heat insulating material having a water repellent layer.

Comparative Example 1

Except for using the water repellent NR-7080 (Nicca, JP) in place of the water repellent of Example 1-2 used in Example 1-3, the same as in Example 1-3, the heat insulating layer formed water repellent layer Was prepared.

Comparative Example 2

Except for using the water repellent RHP-700 (Huntsman, US) instead of the water repellent of Example 1-2 used in Example 1-3, the same as in Example 1-3, the heat insulating layer formed water repellent layer Was prepared.

Experimental Example 1 Measurement of Average Molecular Weight and Molecular Weight Distribution of Silicone Oil

Gel permeation chromatography (GPC) was performed on the silicone oil prepared in Example 1-1, and the results are shown in Table 1 and FIG. 4.

Gel permeation chromatography was performed on the silicone oil obtained in Example 1-1 using a gel permeation chromatography analysis system [YL9100 HPLC, Detector: YL9170 RI detector of Younglin Instruments]. At this time, HPLC grade THF was used as a moving solvent of the silicone oil, and the converted molecular weight was shown in Table 1 using Shodex standard polystyrene as a standard polymer.

Max. RT Start RT End RT Flow rate correction Mn Mw PD Height [mV] Height [%] Area [mV.s] Area [%] 23.34 20.63 25.13 1.000 1213 1406 1.1589 1.85 2.37 269.57 15.94 25.59 25.13 26.17 1.000 548 555 1.0124 1.60 2.05 73.69 4.36 26.49 26.17 26.82 1.000 373 374 1.0032 4.09 5.23 79.85 4.72 27.23 26.82 27.73 1.000 277 278 1.0024 48.40 61.91 814.02 48.14 28.28 27.82 28.74 1.000 178 178 1.0021 15.55 19.89 258.34 15.28 30.38 29.95 31.02 1.000 72 72 1.0052 2.18 2.79 43.76 2.59 31.92 31.46 32.94 1.000 36 37 1.0093 4.50 5.76 151.81 8.98

As can be seen from Table 1 and Figure 4, the silicone oil prepared in Example 1-1 has a molecular weight distribution of 1213 ~ 1406 [15.94%], and 277 ~ 278 [48.14%].

[ Experimental Example  2: Pickup rate (pick-up ratio) evaluation]

Pickup rates for the silicone water repellent of Example 1 and the water repellents of Comparative Examples 1 and 2 were evaluated as follows.

After diluting with 1000 g of water in each water repellent, the glass fiber fabric (Seunti S Co., 25 mm X 150 mm) was immersed for 2 minutes and then padded at a speed of 1 rpm at a pressure of 0.6 MPa. The fabric was padded through a padder of a padding machine. After repeating the above-described process three times, their average pickup rate was calculated according to Equation 1 shown in Table 2.

[Equation 1]

(Equation 1,

W ₁ is the weight of the initial fabric,

W ₂ is the weight of the fabric soaked in water repellent)

Example 1 Comparative Example 1 Comparative Example 2 Pickup rate (%) 98 92 94

As shown in Table 2, the water repellent of Example 1 showed an average pickup rate of about 98%. This was found to be similar to the average pickup rate of the water repellents of Comparative Examples 1 and 2.

Experimental Example 3: Evaluation of Wicking Resistance

About the heat insulating material obtained by coating the glass fiber fabric using the water repellents prepared in Example 1 and Comparative Examples 1 and 2, the wicking resistance was evaluated as follows. Evaluation results are shown in Table 3 and FIG. 5.

Specifically, after adjusting the water repellent concentration of Example 1 and Comparative Examples 1 and 2 to about 7%, after immersing the glass fiber fabric (Seunti s, Inc., size: 25mm X 150 mm) prepared for each water repellent for 2 minutes, The fabric was padded through the padder of the padding machine at a speed of 1 rpm at a pressure of 0.6 MPa. After repeating the above-described process three times, the padded fabric was cured in an oven at 190 ° C. for 60 minutes to prepare a heat insulating layer having a water repellent layer. Subsequently, for water repellency evaluation, referring to AATCC test method 197-2013: Vertical wicking of Textiles, each thermal insulation was immersed in a glass flask containing water for 10 minutes, and then wicking occurred and the absorption height when wicking occurred. It measured until the time point which arises. In the following Table 3 'x' means that no wicking occurs.

Wicking test according to immersion time of thermal insulation 10 minutes elapsed (mm) 20 minutes elapsed (mm) 30 minutes elapsed (mm) 40 minutes elapsed (mm) 50 minutes elapsed (mm) Example 1 × × × × 0.2 mm Comparative Example 1 0.6 mm - - - - Comparative Example 2 0.8 mm - - - -

1) As shown in Table 3, as a result of performing a wicking test for 10 minutes, the thermal insulation insulating material of Example 1 did not generate wicking. That is, after 10 minutes passed, the heat insulating material of Example 1 had a water absorption height of 0 mm and did not absorb water at all. On the other hand, after 10 minutes of the wicking test, the heat insulating material of Comparative Example 1 absorbed water by 0.6 mm, and the heat insulating material of Comparative Example 2 absorbed water by 0.8 mm.

2) For the thermal insulation of Example 1, to determine the wicking resistance for 10 minutes to determine the maximum wicking resistance was measured for 50 minutes, after 50 minutes, water was absorbed by 0.2 mm (see Table 3). This was about five times better than the water repellent of Comparative Examples 1 and 2.

5, the heat insulating material of Example 1 after 50 minutes passed was lower than the heat insulating material of Comparative Examples 1 and 2 after 10 minutes of water absorption heights.

As described above, when the insulating heat insulating material (glass fiber fabric) is coated by using the water repellent agent according to the present invention, it was confirmed that exhibiting excellent wicking resistance compared with the case of using the conventional water repellent agent.

10: thermal insulation, 11: base material,
12: water repellent coating layer

Claims (13)

First silicone oil; Emulsifiers or solutions thereof; And silicone-based water repellent agent for the thermal insulation of the emulsion form containing water,
The first silicone oil is formed of a composition comprising an epoxy group-containing alkoxysilane, a C ₆ ~ C ₂₀ alkyl group-containing trialkoxysilane, and tetraalkoxysilane, silicone-based water repellent for thermal insulation. The method of claim 1,
The epoxy group-containing alkoxysilane, C ₆ ~ C ₂₀ alkyl group-containing trialkoxysilane and tetraalkoxysilane mixture ratio of 1: 0.5-2: 0.5-2 by weight ratio of, a silicon-based water repellent agent for insulating insulation. The method of claim 1,
Wherein the first silicone oil is a silicone oil represented by the formula (1), silicone-based water repellent for thermal insulation:
[Formula 1]

(In Formula 1,
R ₁ is

And a and b are each an integer of 1 to 5;
R ₂ is selected from the group consisting of C ₆ ˜ C ₂₀ alkyl groups;
R ₃ and R ₄ are the same as or different from each other, and are each independently hydrogen or a methyl group;
n is an integer from 3 to 10). The method of claim 3,
The silicone oil represented by Formula 1 is a silicone oil represented by Formula 2 below, a silicone-based water repellent for thermal insulation:
[Formula 2]

(In Formula 2,
R ₃ and R ₄ are the same as or different from each other, and are each independently hydrogen or a methyl group;
n is an integer from 3 to 10). The method of claim 1,
Silicone-based water repellent agent for insulating insulation further comprising a second silicone oil different from the first silicone oil. The method of claim 5,
The use ratio of the first silicone oil and the second silicone oil is a silicone-based water-repellent agent for heat insulating material is 1: 0.3 ~ 0.7 weight ratio. The method of claim 5,
The total content of the first silicone oil and the second silicone oil is 30 to 70% by weight relative to the total amount of the water repellent for the heat insulating material silicone-based water repellent. The method of claim 1,
The amount of the emulsifier in the emulsifier solution is 6 to 17% by weight based on the total amount of the emulsifier solution silicone-based water repellent for thermal insulation. The method of claim 1,
The water-repellent agent is a silicone-based water-repellent agent for heat insulating material is an oil-in-water (O / W type) emulsion in which the first silicone oil is granulated to an average particle diameter in the range of 1 to 2 ㎛. The method of claim 1,
Silicone-based water repellent for insulating insulation having an average pick-up ratio of 70 to 100%. materials; And
The water-repellent coating layer formed on the said base material with the silicone type water repellent as described in any one of Claims 1-10.
Thermal insulation comprising a. The method of claim 11,
The said base material is a heat insulation insulating material which is a member containing glass fiber. The method of claim 11,
AATCC Test Method 197-2013: Insulating insulation with maximum wicking resistance test according to Vertical wicking of Textiles, water absorption start time is after 50 minutes and water absorption height is 0.2 mm.

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