Glass fiber mat laminate, composition for producing polyurethane foam containing same, method for producing same, polyurethane foam, and heat insulating material containing same

Abstract

The present specification provides a composition for producing a polyurethane foam, including a glass fiber mat laminate and a polyurethane composition, the glass fiber mat laminate including first and second glass fiber mats alternately laminated one or more times, the first and second glass fiber mats containing different surfactant contents, a method for producing the composition, a polyurethane foam, and a thermal insulating material including the composition.The thermal insulating material including the polyurethane foam according to the present invention has excellent mechanical properties and excellent thermal insulating properties, and is therefore widely applicable in fields such as automobiles, construction, and LNG ships.

Description

[Technical Field]

[0001] The present specification relates to a glass fiber mat laminate, a composition for producing a polyurethane foam containing the same, a method for producing the same, a polyurethane foam, and a thermal insulation material containing the same. [Background technology]

[0002] Generally, polyurethane foams are obtained by adding a blowing agent, a catalyst, and other additives to polyol and isocyanate components. Polyurethane foams are broadly divided into two types: flexible polyurethane foams and rigid polyurethane foams. Flexible polyurethane foams are primarily used as cushioning materials for mattresses, while rigid polyurethane foams are used as insulation materials due to their excellent physical properties and insulating performance. However, to be used as ultra-low temperature insulation materials for LNG ships and storage tanks, existing rigid polyurethane foams are damaged by shrinkage, cracks, and impacts at ultra-low temperatures.

[0003] Therefore, to compensate for this, a continuous glass fiber strand mat is included inside the rigid polyurethane foam to compensate for the problems that occur at ultra-low temperatures.

[0004] Conventional continuous glass fiber strand mats are supplied in a stacked state, but problems arise related to the stacking of the mats, the presence of air spaces within the mats themselves, and the dispersibility of the mats. The air spaces are removed when the polyurethane concentrate is sprayed onto and impregnated into the mats, but the air spaces that are not released remain inside the polyurethane foam, reducing the insulation performance and physical properties.

[0005] To solve this problem, Korean Patent No. 10-0938120 attempted to install a pressure device to remove the air gap inside the laminated glass fiber strand mat, which resulted in improved physical properties compared to existing methods. However, the glass fiber mat was not uniformly distributed inside the foam, but was concentrated in certain areas, which still left a problem of weak points. Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention relates to a glass fiber mat laminate, a composition for producing a polyurethane foam containing the same, a method for producing the same, a polyurethane foam, and a heat insulating material containing the same. [Means for solving the problem]

[0007] One embodiment of the present invention provides a glass fiber mat laminate including a first glass fiber mat and a second glass fiber mat that are alternately stacked one or more times, wherein the first glass fiber mat and the second glass fiber mat have different unit weights.

[0008] One embodiment of the present invention provides a composition for producing polyurethane foam, comprising the above-described glass fiber mat laminate and a polyurethane composition.

[0009] One embodiment of the present invention provides a method for producing a polyurethane foam, comprising the steps of: preparing the polyurethane foam-producing composition described above; and curing the polyurethane foam-producing composition.

[0010] One embodiment of the present invention provides a polyurethane foam comprising a polyurethane foam-making composition.

[0011] One embodiment of the present invention provides an insulating material comprising the polyurethane foam described above. [Effects of the Invention]

[0012] The present invention relates to a fiberglass mat laminate that can provide improved strength and thermal insulation performance. BEST MODE FOR CARRYING OUT THE INVENTION

[0013] The present specification will be explained in more detail below.

[0014] In one embodiment of the present invention, the term "glass fiber mat laminate" refers to a laminate of one or more glass fiber mats.

[0015] Conventional polyurethane foams are produced by spraying a polyurethane composition onto a glass fiber mat and curing it. During this process, air gaps remaining in the glass fiber mat can degrade the physical properties and insulating performance of the polyurethane foam, and the glass fiber mat can be inconsistently dispersed. To address this issue, attempts have been made to remove the air gaps using a separate pressurizing device. While removing the air gaps improved the physical properties of the polyurethane foam, this left the glass fiber mat with weak spots due to the lack of dispersibility.

[0016] The inventors aim to prevent air spaces from remaining in the glass fiber mat laminate without the need for a separate pressurizing device by modifying the properties of the glass fiber mat laminate, and to prevent the occurrence of weak spots by uniformly dispersing the glass fiber mats inside the polyurethane foam, thereby improving the physical properties and heat insulating performance of the produced polyurethane foam.

[0017] One embodiment of the present specification provides a glass fiber mat laminate including a first glass fiber mat and a second glass fiber mat that are alternately stacked one or more times, wherein the first glass fiber mat and the second glass fiber mat have different unit weights.

[0018] The glass fiber mat laminate can improve its strength and flexibility during the polyurethane foam manufacturing process by adjusting the unit weights of the first and second glass fiber mats to be different from each other. That is, by adjusting both strength and flexibility, which are difficult to achieve at the same time, a polyurethane foam with excellent physical properties can be manufactured.

[0019] In one embodiment of the present invention, the glass fiber mat laminate includes a first glass fiber mat and a second glass fiber mat that are alternately stacked one or more times. The term "alternately stacked" may refer to a structure in which the first glass fiber mat and the second glass fiber mat are alternately stacked one or more times. Here, the term "alternately stacked" may refer to a structure in which the first glass fiber mat and the second glass fiber mat are in direct contact with each other, as well as a structure in which a third glass fiber mat is provided between the first and second glass fiber mats. For example, the term "...first glass fiber mat / second glass fiber mat..." may be used in addition to the structure "...first glass fiber mat / second glass fiber mat...", or "...first glass fiber mat / second glass fiber mat / first glass fiber mat / second glass fiber mat...", or "...first glass fiber mat / third glass fiber mat / second glass fiber mat...".

[0020] In one embodiment of the present invention, the glass fiber mat laminate may be formed by repeating one or more times a configuration in which a first glass fiber mat and a second glass fiber mat are stacked one upon another, with an additional first glass fiber mat being stacked on the other side of the second glass fiber mat that is opposite the side of the glass fiber mat laminate. Alternatively, the glass fiber mat laminate may be formed by repeating one or more times a configuration in which a first glass fiber mat and a second glass fiber mat are stacked one upon another, with an additional second glass fiber mat being stacked on the other side of the first glass fiber mat that is opposite the side of the glass fiber mat laminate.

[0021] In one embodiment of the present invention, the glass fiber mat laminate may be formed by repeatedly stacking a first glass fiber mat and a second glass fiber mat one or more times, and the number of repetitions may be 1 to 100. Preferably, the number of repetitions may be 1 to 20 or 1 to 10. When the above numerical range is satisfied, air spaces remain in the glass fiber mat laminate, and the glass fiber mats are uniformly dispersed inside the polyurethane foam, preventing the occurrence of weak parts inside the polyurethane foam.

[0022] In one embodiment of the present invention, the difference in unit weight between the first glass fiber mat and the second glass fiber mat is 100 g / m 2 More than 1,000g / m 2 Preferably, it is 150 g / m 2 More than 800g / m 2 or less than 200g / m 2 More than 500g / m 2 Within the above range of values, the strength of the glass fiber mat laminate can be improved, and flexibility during the polyurethane foam production process can be improved.

[0023] In one embodiment of the present invention, the difference in unit weight between the first glass fiber mat and the second glass fiber mat is 50 g / m 2 More than 800g / m 2 Preferably, it is 100 g / m 2 More than 300g / m 2 or less than 120g / m 2 More than 250g / m 2 Within the above range of values, the strength of the glass fiber mat laminate can be improved, and flexibility during the polyurethane foam production process can be improved.

[0024] In one embodiment of the present invention, the unit weight of the first glass fiber mat may be greater than the unit weight of the second glass fiber mat, and the content of the second glass fiber mat may be 50 to 800 parts by weight based on 100 parts by weight of the first glass fiber mat. Preferably, the content of the second glass fiber mat may be 80 to 600 parts by weight, 100 to 500 parts by weight, or 150 to 300 parts by weight. The above numerical ranges can improve the strength of the glass fiber mat laminate and the flexibility during the polyurethane foam manufacturing process.

[0025] In one embodiment of the present invention, the number of the first glass fiber mat and the second glass fiber mat may be the same or different, and may include 1 to 20 glass fiber mat units. Specifically, the number of glass fiber mat units may be 2 to 18 or 2 to 10. By adjusting the number of glass fiber mat units, air spaces remain in the glass fiber mat laminate, and the glass fiber mats are uniformly dispersed inside the polyurethane foam, preventing the occurrence of weak parts inside the polyurethane foam.

[0026] In one embodiment of the present invention, the difference in number between the glass fiber mat units contained in the first glass fiber mat and the glass fiber mat units contained in the second glass fiber mat may be from 1 to 10. Preferably, it may be from 1 to 8 or from 1 to 5. When the difference is within the above numerical range, it is possible to prevent air spaces from remaining in the glass fiber mat laminate and the occurrence of weak portions in the polyurethane foam.

[0027] In one embodiment of the present invention, the glass fiber mat laminate may be a continuous strand glass fiber mat (CSM).

[0028] In one embodiment of the present invention, each of the first glass fiber mat and the second glass fiber mat can contain glass fiber filaments having an average diameter of 1 μm to 50 μm. Preferably, the first glass fiber mat and the second glass fiber mat can contain glass fiber filaments having an average diameter of 5 μm to 40 μm or 10 μm to 25 μm. When the above numerical ranges are satisfied, the glass fiber mat laminate can maintain the mat shape and prevent the formation of air layers inside the mats.

[0029] In one embodiment of the present invention, the first and second glass fiber mats may each contain a surfactant. The surfactant can control the surface properties of the glass fiber mats, thereby changing the rate and amount of impregnation of the polyurethane composition into the glass fiber mats. A higher surfactant content increases the impregnation rate into the glass fiber mat laminate, but a larger amount of polyurethane composition is impregnated, resulting in less polyurethane composition remaining in the upper part of the laminate, or the glass fiber mats being less uniformly dispersed within the polyurethane foam. Furthermore, surfactants used in glass fiber mats in polyurethane foams themselves can act as impurities, and excessive use can impair the physical properties of the polyurethane foam. Therefore, by using an appropriate amount of surfactant to facilitate impregnation into the glass fiber mat laminate, efficient air gap removal and uniform dispersion can be achieved. However, adjusting the surface properties of the first and second glass fiber mats to be different from each other can further enhance the above-mentioned prevention effect. An example of a method for adjusting the surfactant contents of the first and second glass fiber mats to be different from each other is to treat each glass fiber mat with a surfactant composition having a different surfactant content.

[0030] In one embodiment of the present invention, the surfactant may include a silane-based compound.

[0031] In an embodiment of the present invention, the silane-based compound may include an epoxy-based silane compound.

[0032] In one embodiment of the present invention, the epoxy-based silane compound may be vinyl methoxysilane, vinyl trimethoxysilane, vinyl epoxy silane, vinyl triepoxy silane, 3-aminopropyl triethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, 3-metaglyoxypropyl trimethoxysilane, γ-glycidoxypropyl triethoxysilane, or a combination thereof. Preferably, 3-glycidoxypropyl triethoxysilane may be used.

[0033] In one embodiment of the present invention, the difference in surfactant content between the first glass fiber mat and the second glass fiber mat may be 0.1 wt% to 10 wt%, preferably 0.1 wt% to 8 wt%, or 0.1 wt% to 5 wt%. When the difference is within the above range, the degree of dispersion between the mats can be adjusted when the polyurethane composition is impregnated into the glass fiber mat laminate, thereby preventing the formation of residual air spaces in the glass fiber mat laminate and effectively preventing the formation of brittle portions.

[0034] One embodiment of the present invention provides a composition for producing polyurethane foam, comprising the glass fiber mat laminate described above and a polyurethane composition, which can be used to produce polyurethane foam.

[0035] In one embodiment of the present invention, the "polyurethane foam-making composition" can be used to make polyurethane foam.

[0036] In one embodiment of the present invention, the composition for producing a polyurethane foam includes a glass fiber mat laminate and a polyurethane composition, wherein the polyurethane composition may be impregnated into the glass fiber mat laminate, or the glass fiber mat laminate and the polyurethane composition may simply be mixed together.

[0037] In one embodiment of the present invention, the polyurethane composition may include a polyol compound and an isocyanate-based compound.

[0038] In one embodiment of the present invention, the type of the polyol compound is not particularly limited, and examples thereof include polyether polyol, polyester polyol, etc. When the polyester polyol is used, a polycondensation product of an aromatic and / or aliphatic dicarboxylic acid with an alkanediol and / or alkanetriol or ether diol can be used.

[0039] In one embodiment of the present invention, the polyether polyol may be a polyol obtained by adding an alkylene oxide (e.g., ethylene oxide, propylene oxide, butylene oxide, or a mixture thereof) to a polyfunctional alcohol such as glycerin, trimethanolpropane, pentaerythritol, dipentaerythritol, α-methylglucoside, xylitol, sorbitol, or sucrose, and / or a polyfunctional amine such as ortho-toluenediamine, ethylenediamine, or triethanolamine, as a starting material.

[0040] In one embodiment of the present invention, the polyester polyol generally uses a polycondensate of an aromatic and / or aliphatic dicarboxylic acid with an alkanediol and / or alkanetriol or etherdiol.

[0041] In one embodiment of the present invention, the aromatic polyester polyol is advantageous in the production of rigid polyurethane foams due to its low cost, high compressive strength and heat resistance, especially excellent thermal conductivity. One widely used class of aromatic polyester polyols is a polyol produced by esterifying phthalic acid or phthalic anhydride with an aliphatic polyhydric alcohol.

[0042] In one embodiment of the present invention, the type of the isocyanate-based compound is not particularly limited, and the isocyanate-based compound may contain two or more isocyanate groups.

[0043] In one embodiment of the present invention, the isocyanate-based compound is selected from the group consisting of 1,12-dodecane diisocyanate, 2-ethyltetramethylene 1,4-diisocyanate, 2-methylpentamethylene 1,5-diisocyanate, tetramethylene 1,4-diisocyanate, hexamethylene 1,6-diisocyanate, cyclohexane 1,3-diisocyanate, cyclohexane 1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 2,4- Hexahydrotolylene diisocyanate, 2,6-hexahydrotolylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,2'-dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, polyphenylpoly Methylene polyisocyanate, 1,5-naphthylene diisocyanate (NDI), 3,3'-dimethylbiphenyl diisocyanate, 1,2-diphenylethane diisocyanate, p-phenylene diisocyanate (PPDI), trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, 2-methylpentamethylene 1,5-diisocyanate, 2-ethylene Examples include, but are not limited to, butylene 1,4-diisocyanate, pentamethylene 1,5-diisocyanate, butylene 1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate, IPDI), 1,4-bis(isocyanatomethyl)cyclohexane, 1,3-bis(isocyanatomethyl)cyclohexane (HXDI), 1,4-cyclohexane diisocyanate, isomers thereof, or mixtures thereof.

[0044] In one embodiment of the present invention, the polyurethane composition may include one or more additives selected from the group consisting of a foaming agent, a chain extender, a crosslinking agent, a foam stabilizer, a tackifier, a plasticizer, an antioxidant, an ultraviolet absorber, a light stabilizer, a catalyst, a cocatalyst, a filler, a colorant, a pigment, a water scavenger, a surfactant, a solvent, a diluent, a flame retardant, an antislip agent, an antistatic agent, a preservative, and a biocide.

[0045] In one embodiment of the present invention, the blowing agent may be, but is not limited to, water, carboxylic acid, fluorocarbon blowing agent, carbon dioxide, hydrocarbon blowing agent such as straight or branched chain alkane hydrocarbon.

[0046] In one embodiment of the present invention, the flame retardant may be a commonly used flame retardant, such as a brominated ester, brominated ether, or brominated alcohol, such as dibromoneopentyl alcohol, tribromoneopentyl alcohol, and PHT-4-diol, and / or a chlorinated phosphate, such as tris(2-chloroethyl)phosphate, tris(2-chloropropyl)phosphate (TCPP), tris(1,3-dichloropropyl)phosphate, tricresylphosphate, tris(2,3-dibromopropyl)phosphate, tetrakis(2-chloroethyl)ethylenediphosphate, dimethylmethanephosphonate, diethyldiethanolaminomethylphosphonate, and commercially available halogenated flame retardant polyols. Additional phosphates or phosphonates may also be used as liquid flame retardants, such as, but not limited to, diethylethanephosphonate (DEEP), triethylphosphate (TEP), dimethylpropylphosphonate (DMPP), or diphenylcresylphosphate (DPK).

[0047] In one embodiment of the present invention, the foam stabilizer may be a silicone foam stabilizer, a nonionic foam stabilizer, a non-silicone foam stabilizer, or the like, specifically, dinonylphenol, methyl glucoside, methyl propanediol, vinyl ether maleic acid, Si copolymer series foam stabilizer, or the like, but is not limited thereto.

[0048] In one embodiment of the present invention, the catalyst may be a commonly used catalyst, for example, triethylamine, tributylamine, dimethylbenzylamine, dicyclohexylmethylamine, dimethylcyclohexylamine, N,N,N',N'-tetramethyldiaminodiethyl ether, bis(dimethylaminopropyl)urea, N-methylmorpholine, N-ethylmorpholine, N-cyclohexylmorpholine, N,N,N',N'-tetramethylethylenediamine, N,N,N,N-tetramethylbutanediamine, N,N,N,N-tetramethylhexane-1,6-diamine, pentamethyldiethylenetriamine, bis(2-dimethylaminoethyl)ether, dimethylpiperazine, N-dimethylaminoethylpiperidine, 1,2-dimethylimidazole, 1-azabicyclo[2.2.0]octane, 1,4-diazabicyclo[2.2.2]octane (Dabco), triethanolamine, triisopropanolamine, N-methyldiethanolamine amine, N-ethyldiethanolamine, dimethylaminoethanol, 2-(N,N-dimethylaminoethoxy)ethanol, N,N',N"-tris(dialkylaminoalkyl)hexahydrotriazine, N,N',N"-tris(dimethylaminopropyl)-s-hexahydrotriazine, triethylenediamine, iron(II) chloride, zinc chloride, lead octoate, tin dioctoate, tin diethylhexoate, dibutyltin dilaurate, tetraisopropyl titanate, butylstannoic acid, butylchlorotin dihydroxide, tetrabutyl titanate, and mixtures thereof.

[0049] One embodiment of the present invention provides a method for producing the above-mentioned composition for producing a polyurethane foam, the method including the steps of: preparing the first glass fiber mat and the second glass fiber mat; adjusting the surfactant contents of the first glass fiber mat and the second glass fiber mat to be different from each other; alternately repeating the first glass fiber mat and the second glass fiber mat at least once to produce a glass fiber mat laminate; and mixing the glass fiber mat laminate with a polyurethane composition.

[0050] In one embodiment of the present invention, the step of adjusting the surfactant contents contained in the first glass fiber mat and the second glass fiber mat to be different from each other includes the step of adding a first surfactant composition to the surface of the first glass fiber mat and the step of adding a second surfactant composition to the surface of the second glass fiber mat, and the surfactant contents contained in the first surfactant composition and the second surfactant composition may be different from each other.

[0051] In one embodiment of the present invention, the step of mixing the glass fiber mat laminate and the polyurethane composition may include the steps of applying the polyurethane composition to the glass fiber mat laminate, specifically, the steps of continuously supplying the glass fiber mat laminate and applying the polyurethane composition to the continuously supplied glass fiber mat laminate.

[0052] In one embodiment of the present invention, the step of mixing the glass fiber mat laminate with the polyurethane composition may include a step of pressing the glass fiber mat laminate to remove air spaces that may be present in the glass fiber mat laminate. The pressing means is not particularly limited, and a known pressure roller may be used.

[0053] One embodiment of the present invention provides a method for producing a polyurethane foam, comprising the steps of: preparing the polyurethane foam-producing composition described above; and curing the polyurethane foam-producing composition.

[0054] In one embodiment of the present invention, the step of curing the composition for preparing a polyurethane foam may be carried out at room temperature (23°C) for 1 to 30 days, preferably 5 to 25 days or 7 to 20 days. Within the above ranges, a strong polyurethane foam structure can be formed.

[0055] One embodiment of the present invention provides a polyurethane foam comprising the above-described polyurethane foam-making composition.

[0056] In one embodiment of the present invention, the compressive strength of the polyurethane foam at room temperature (23°C) may be 1.28 MPa or more, preferably 1.3 MPa or more or 1.35 MPa or more. The upper limit is not particularly limited, but may be 10 MPa or less or 8 MPa or less. When the above numerical range is satisfied, the strength of the polyurethane foam can be improved.

[0057] In one embodiment of the present invention, the compressive strength of the polyurethane foam at ultra-low temperature (-170°C) may be 2.58 MPa or more, preferably 2.6 MPa or 2.65 MPa or more. The upper limit is not particularly limited, but may be 10 MPa or less or 8 MPa or less. When the above numerical range is satisfied, the strength of the polyurethane foam can be improved.

[0058] In one embodiment of the present invention, the thermal conductivity of the polyurethane foam at room temperature (23°C) may be 0.021 W / mK or less, preferably 0.0208 W / mK or less or 0.02 W / mK or less. The lower limit is not particularly limited, but may be 0.001 W / mK or more or 0.01 W / mK or more. When the above numerical range is satisfied, the insulating performance of the polyurethane foam can be improved.

[0059] In one embodiment of the present invention, the room temperature tensile strength in the horizontal direction at room temperature (23°C) may be 3.0 MPa or more, preferably 3.1 MPa or more or 3.5 MPa or more. There is no particular upper limit, but it may be 10 MPa or less or 8 MPa or less. When the above numerical range is satisfied, the strength of the polyurethane foam can be improved.

[0060] In one embodiment of the present invention, the room temperature tensile strength in the vertical direction at room temperature (23°C) may be 1.25 MPa or more. Preferably, it may be 1.25 MPa or more or 1.32 MPa or more. The upper limit is not particularly limited, but may be 10 MPa or less or 8 MPa or less. When the above numerical range is satisfied, the strength of the polyurethane foam can be improved.

[0061] In one embodiment of the present invention, the horizontal tensile strength at ultra-low temperatures (-170°C) may be 3.0 MPa or more, preferably 3.1 MPa or 3.5 MPa or more. The upper limit is not particularly limited, but may be 10 MPa or less or 8 MPa or less. When the above numerical range is satisfied, the strength of the polyurethane foam can be improved.

[0062] In one embodiment of the present invention, the tensile strength in the vertical direction at an ultra-low temperature (-170°C) may be 1.5 MPa or more. Preferably, it may be 1.5 MPa or 1.7 MPa or more. The upper limit is not particularly limited, but may be 10 MPa or less or 8 MPa or less. When the above numerical range is satisfied, the strength of the polyurethane foam can be improved.

[0063] One embodiment of the present invention provides an insulating material comprising the polyurethane foam described above.

[0064] In one embodiment of the present invention, the insulating material may be an insulating material for an LNG carrier. The insulating material has excellent mechanical strength and excellent insulating performance, and therefore can be applied to an LNG carrier. Generally, a ship transporting LNG is equipped with a number of cargo holds in the form of tanks capable of storing LNG, and stores and transports liquid LNG in the cargo holds. Due to the characteristics of LNG, the LNG cargo holds installed on such LNG carriers must be capable of storing cryogenic fluids, and at the same time, must have sufficient strength to withstand sloshing loads of the fluid generated by environmental loads such as ocean currents, waves, and wind. Furthermore, while LNGCs (Liquefied Natural Gas Carriers) can be dry docked for repairs, FLNGs (Floating Liquefied Natural Gas) must be able to operate for more than 20 years at their installation site, and therefore may require even greater strength than existing cargo holds depending on the environmental conditions of the installation area. [Example]

[0065] The present invention will now be described with reference to examples.

[0066] <Production Example 1: Production of Glass Fiber Unit A> A mat-shaped glass fiber unit was prepared by adding a polyester adhesive to glass fiber filaments having an average diameter of 5 to 40 μm and bonding them together. At this time, the unit weight of the glass fiber unit was 300 g / m 2 , 450g / m 2 , 500g / m 2 , 600g / m 2 , 700g / m 2 , 900g / m 2 and 1,000 g / m 2 It was.

[0067] <Production Example 2: Production of Glass Fiber Unit B> A glass fiber unit body B was prepared in the same manner as in Production Example 1, except that the weight of the glass fiber filament was changed. At this time, the unit weight of the glass fiber unit body was 100 g / m 2 , 200g / m 2 , 250g / m 2 , 300g / m 2 , 380g / m 2 , 440g / m 2 and 500g / m 2 It was.

[0068] <Production Example 3: Preparation of polyurethane composition> A polyurethane composition containing a polyol compound (a polyether polyol and a polyester polyol), an isocyanate compound (Polymeric MDI: PMDI), and a blowing agent was prepared.

[0069] The polyol compound was prepared by mixing 100 parts by weight of a polyol composition containing 40% by weight of ether polyol (KPX Chemical Co., Ltd. HF-490LR) and 60% by weight of ester polyol (KPX Chemical Co., Ltd. SL-4100), 2.0 parts by weight of a foam stabilizer (Momentive Niax silicone L-6124), 0.5 parts by weight of a flame retardant (Kumyoung Chemical (Triethyl Phosphate) TEP), 0.05 parts by weight of a catalyst (Momentive Niax Catalyst C-8), and 8.65 parts by weight of a blowing agent (Honeywell Solstice® LBA (trans-1-Chloro-3,3,3-trifluoropropene)). An equal amount of methylene diphenyl diisocyanate (MDI, Kumho Mitsui Chemical Co., Ltd. M-200) was added to the polyol composition containing the foam stabilizer, flame retardant, catalyst, and blowing agent to prepare a polyurethane composition as a mixed liquid.

[0070] <Examples and Comparative Examples: Preparation of Glass Fiber Mat Laminate> Example 1 Glass fiber unit A manufactured in Manufacturing Example 1 (unit weight: 450 g / m 2) and glass fiber unit B (unit weight: 300 g / m) manufactured in Manufacturing Example 2 2 ) were laminated to prepare a glass fiber mat laminate. At this time, the content of the glass fiber unit B was 262 parts by weight based on 100 parts by weight of the glass fiber unit A.

[0071] <Example 2> Glass fiber unit A manufactured in Manufacturing Example 1 (unit weight: 450 g / m 2 ) and glass fiber unit B (unit weight: 300 g / m) manufactured in Manufacturing Example 2 2 ) were laminated to prepare a glass fiber mat laminate. At this time, the content of the glass fiber unit B was 115 parts by weight based on 100 parts by weight of the glass fiber unit A.

[0072] Example 3 Glass fiber unit A manufactured in Manufacturing Example 1 (unit weight: 450 g / m 2 ) and glass fiber unit B (unit weight: 300 g / m) manufactured in Manufacturing Example 2 2 ) were laminated to prepare a glass fiber mat laminate. At this time, the content of the glass fiber unit B was 500 parts by weight based on 100 parts by weight of the glass fiber unit A.

[0073] Example 4 Glass fiber unit A manufactured in Manufacturing Example 1 (unit weight: 500 g / m 2 ) and glass fiber unit B (unit weight: 250 g / m) manufactured in Manufacturing Example 2 2 ) were laminated to prepare a glass fiber mat laminate. At this time, the content of the glass fiber unit B was 80 parts by weight based on 100 parts by weight of the glass fiber unit A.

[0074] <Example 5> Glass fiber unit A manufactured in Manufacturing Example 1 (unit weight: 450 g / m 2 ) and glass fiber unit B (unit weight: 380 g / m) manufactured in Manufacturing Example 2 2) were laminated to prepare a glass fiber mat laminate. At this time, the content of the glass fiber unit B was 400 parts by weight based on 100 parts by weight of the glass fiber unit A.

[0075] Example 6 Glass fiber unit A manufactured in Manufacturing Example 1 (unit weight: 900 g / m 2 ) and glass fiber unit B (unit weight: 200 g / m) manufactured in Manufacturing Example 2 2 ) were laminated to prepare a glass fiber mat laminate. At this time, the content of the glass fiber unit B was 700 parts by weight based on 100 parts by weight of the glass fiber unit A.

[0076] <Comparative Example 1> Glass fiber unit A manufactured in Manufacturing Example 1 (unit weight: 450 g / m 2 ) but not containing glass fiber unit B was prepared.

[0077] <Comparative Example 2> Glass fiber unit B manufactured in Manufacturing Example 2 (unit weight: 300 g / m 2 ) but not containing the glass fiber unit A was prepared.

[0078] <Comparative Example 3> Glass fiber unit A manufactured in Manufacturing Example 1 (unit weight: 300 g / m 2 ) and glass fiber unit B (unit weight: 500 g / m) manufactured in Manufacturing Example 2 2 ) were laminated to prepare a glass fiber mat laminate. At this time, the content of the glass fiber unit B was 300 parts by weight based on 100 parts by weight of the glass fiber unit A.

[0079] <Comparative Example 4> Glass fiber unit A manufactured in Manufacturing Example 1 (unit weight: 600 g / m 2 ) and glass fiber unit B (unit weight: 200 g / m) manufactured in Manufacturing Example 2 2) were laminated to prepare a glass fiber mat laminate. At this time, the content of the glass fiber unit B was 40 parts by weight based on 100 parts by weight of the glass fiber unit A.

[0080] <Comparative Example 5> Glass fiber unit A manufactured in Manufacturing Example 1 (unit weight: 700 g / m 2 ) and glass fiber unit B (unit weight: 300 g / m) manufactured in Manufacturing Example 2 2 ) were laminated to prepare a glass fiber mat laminate. At this time, the content of the glass fiber unit B was 850 parts by weight based on 100 parts by weight of the glass fiber unit A.

[0081] <Comparative Example 6> Glass fiber unit A manufactured in Manufacturing Example 1 (unit weight: 450 g / m 2 ) and glass fiber unit B (unit weight: 440 g / m) manufactured in Manufacturing Example 2 2 ) were laminated to prepare a glass fiber mat laminate. At this time, the content of the glass fiber unit B was 300 parts by weight based on 100 parts by weight of the glass fiber unit A.

[0082] <Comparative Example 7> Glass fiber unit A manufactured in Manufacturing Example 1 (unit weight: 1,000 g / m 2 ) and glass fiber unit B (unit weight: 100 g / m) manufactured in Manufacturing Example 2 2 ) were laminated to prepare a glass fiber mat laminate. At this time, the content of the glass fiber unit B was 400 parts by weight based on 100 parts by weight of the glass fiber unit A.

[0083] <Production of polyurethane foam> The polyurethane composition prepared in Preparation Example 3 was sprayed onto the glass fiber mat laminate prepared in the Examples and Comparative Examples, and cured at room temperature for 2 weeks to prepare a glass fiber reinforced polyurethane foam.

[0084] <Experimental Example 1: Density Measurement> Samples of glass fiber reinforced polyurethane foam measuring 50 x 50 x 50 (mm) were taken at five different height positions, and the width, length, and height of three samples each were measured using Vernier Calipers (MITUTOYO, CD-P30S) to determine the volume (mm 3 The weight of the sample was measured using a balance (OHAUS, PAG4102), and the density was measured by weight / volume to obtain the average value.

[0085] <Experimental Example 2: Measurement of room temperature compressive strength> To measure the compressive strength in the vertical direction, the manufactured polyurethane foam was cut into a sample measuring 50 x 50 x 50 (width x length x height, mm) and a load was applied at a rate of 5 mm / min using a Universal Test Machine (UTM, hardness tester, KSU-10M). The compressive strength was measured as a function of compressive load / cross-sectional area and the average value was calculated. The measurement temperature was room temperature (23°C).

[0086] <Experimental Example 3: Measurement of ultra-low temperature compressive strength> The ultra-low temperature compressive strength was measured in the same manner as in Experimental Example 2, except that the measurement temperature was changed to an ultra-low temperature (-170°C).

[0087] <Experimental Example 4: Measurement of room temperature tensile strength> (Measurement of horizontal tensile strength) Three samples of dog-bone-shaped polyurethane foam were prepared at five different height sections and pulled at a speed of 5 mm / min using a universal material testing machine (hardness testing machine, KSU-10M). The tensile strength was measured as a function of tensile load / cross-sectional area and the average value was calculated.

[0088] (Measurement of vertical tensile strength) Three samples of polyurethane foam measuring 50 x 50 x 50 (width x length x height, mm) were prepared and pulled at a rate of 5 mm / min using a universal material testing machine (hardness tester, KSU-10M). The vertical tensile strength was measured as a function of tensile load / cross-sectional area and the average value was calculated. The measurement temperature was room temperature (23°C).

[0089] <Experimental Example 5: Measurement of ultra-low temperature tensile strength> The ultra-low temperature tensile strength was measured in the same manner as in Experimental Example 4, except that the measurement temperature was changed to an ultra-low temperature (-170°C).

[0090] <Experimental Example 6: Measurement of room temperature thermal conductivity> The manufactured polyurethane was cut into a size of 200mm x 200mm x 25mm (width x length x height) to prepare a sample corresponding to the LM section. Using a thermal conductivity measuring device (TA Instrument, FOX200), the upper plate was set at 10°C and the lower plate at 37°C, and the heat flow meter method was used to measure the thermal conductivity. The measurement temperature was room temperature (23°C).

[0091] [Table 1]

[0092] From Table 1, it can be seen that the polyurethane foams prepared in the examples have excellent compressive strength at room temperature and at cryogenic temperatures, tensile strength at room temperature and at cryogenic temperatures, and thermal conductivity.

[0093] [Table 2]

[0094] From Table 2, it can be seen that in Comparative Examples 1 and 2, which used only a single glass fiber unit, the compressive strength at ultra-low temperature and the thermal conductivity at room temperature were reduced.

[0095] In Comparative Example 3, in which the weight of the second glass fiber mat was greater than that of the first glass fiber mat, and Comparative Examples 4 and 5, in which the content of the second glass fiber mat was small or large, the glass fiber distribution was uneven, and the room temperature and ultra-low temperature compressive strength and the room temperature tensile strength in the vertical direction were reduced.

[0096] In Comparative Examples 6 and 7, in which the weight difference between the first glass fiber mat and the second glass fiber mat was outside the range, the glass fiber distribution was uneven, resulting in reduced room temperature and cryogenic temperature compressive strength, vertical room temperature tensile strength, and horizontal cryogenic tensile strength.

[0097] From the above results, it was confirmed that the polyurethane foams produced in the comparative examples had poor durability and insulation performance overall, or that even if one of the performances was good, the other performance was poor. In contrast, it was confirmed that the polyurethane foams produced in the examples had excellent durability and insulation performance.

[0098] This is believed to be the result of ensuring uniformity in density by ensuring uniform distribution of glass fibers within the polyurethane foam, and reinforcing weak mechanical strength areas. [Industrial Applicability]

[0099] The heat insulating material containing the polyurethane foam of the present invention not only has excellent mechanical properties but also has excellent heat insulating effect, and therefore can be widely used in the fields of automobiles, construction, LNG ships, etc.

Claims

1. A glass fiber mat laminate comprising a first glass fiber mat and a second glass fiber mat that are alternately laminated one or more times, the first glass fiber mat and the second glass fiber mat having different unit weights.

2. The unit weight of the first glass fiber mat and the second glass fiber mat is 100 g / m ２ 1,000g / m or more ２ 2. The glass fiber mat laminate of claim 1, wherein:

3. The difference in unit weight between the first glass fiber mat and the second glass fiber mat is 50 g / m ２ 800g / m or more ２ 2. The glass fiber mat laminate of claim 1, wherein:

4. 2. The glass fiber mat laminate according to claim 1, wherein the unit weight of the first glass fiber mat is greater than the unit weight of the second glass fiber mat, and the content of the second glass fiber mat is 50 parts by weight or more and 800 parts by weight or less based on 100 parts by weight of the first glass fiber mat.

5. 2. The glass fiber mat laminate according to claim 1, wherein the number of the first glass fiber mat and the number of the second glass fiber mat are the same or different, and the number of glass fiber mat units is 1 to 20.

6. 10. The glass fiber mat laminate of claim 1, wherein the glass fiber mat laminate is a continuous fiber glass strand mat (CSM).

7. 2. The glass fiber mat laminate of claim 1, wherein each of the first glass fiber mat and the second glass fiber mat comprises glass fiber filaments having an average diameter of 1 μm to 50 μm.

8. A composition for producing a polyurethane foam, comprising the glass fiber mat laminate according to any one of claims 1 to 7 and a polyurethane composition.

9. The polyurethane composition according to claim 8, wherein the polyurethane composition comprises a polyol compound and an isocyanate compound.

10. 9. The composition for producing a polyurethane foam according to claim 8, wherein the polyurethane composition further comprises one or more additives selected from the group consisting of blowing agents, chain extenders, crosslinking agents, foam stabilizers, tackifiers, plasticizers, antioxidants, ultraviolet absorbers, light stabilizers, catalysts, cocatalysts, fillers, colorants, pigments, water scavengers, surfactants, solvents, diluents, flame retardants, antislip agents, antistatic agents, preservatives, and biocides.

11. providing a polyurethane foam-making composition according to claim 8; and curing the polyurethane foam-producing composition.

12. A polyurethane foam comprising the polyurethane foam-producing composition of claim 8.

13. The polyurethane foam has a compressive strength of 1.28 MPa or more at room temperature (23°C), a compressive strength of 2.58 MPa or more at ultra-low temperature (-170°C), and a thermal conductivity of 0.021 W / mK or less at room temperature (23°C).

14. An insulating material comprising the polyurethane foam of claim 12.

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