Glass fiber mat laminate, composition for manufacturing polyurethane foam comprising same, preparation method therefor, polyurethane foam, and thermal insulation material comprising same

Abstract

The present specification relates to a composition for manufacturing polyurethane foam, a preparation method therefor, a polyurethane foam, and a thermal insulation material including same, wherein the composition comprises: a glass fiber mat laminate; and a polyurethane composition, the glass fiber mat laminate including a first glass fiber mat and a second glass fiber mat alternately laminated at least once, the first glass fiber mat and the second glass fiber mat being difference from each other in terms of the content of surfactant therein. The thermal insulation material comprising the polyurethane foam according to the present invention exhibits excellent mechanical properties and thermal insulation performance, and thus can be widely used in the fields of automobiles, construction, LNG, ships, and the like.

Description

Glass fiber mat laminate, composition for producing polyurethane foam including the same, method for producing the same, polyurethane foam and insulating material including the same

[0001] The present specification relates to a glass fiber mat laminate, a composition for producing a polyurethane foam comprising the same, a method for producing the same, a polyurethane foam, and an insulating material comprising the same.

[0002] Polyurethane foam is typically obtained by adding a blowing agent, catalyst, and other additives to polyol and isocyanate components. Polyurethane foam can be divided into two types: flexible and rigid. Flexible polyurethane foam is primarily used as cushioning material for mattresses, while rigid polyurethane foam is used as insulation due to its excellent physical properties and insulating performance. However, conventional rigid polyurethane foam is not suitable for use as ultra-low-temperature insulation for LNG vessels and storage tanks due to shrinkage, cracking, and damage from impact 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 configuration. This creates problems with the mat's dispersibility due to the presence of air pockets within the mat itself and the mat's lamination process. These air pockets are removed when the polyurethane solution is sprayed onto the mat and impregnated. However, any air pockets that remain within the polyurethane foam degrade its insulation performance and physical properties.

[0005] To address the above issue, Korean Patent No. 10-0938120 attempted to remove air layers within laminated glass fiber strand mats by installing a pressurizing device. This resulted in improved physical properties compared to existing methods. However, the glass fiber mats still remain vulnerable, as they are not uniformly distributed within the foam and are concentrated in specific areas, creating weak points.

[0006]

[0007] The present invention relates to a glass fiber mat laminate, a composition for producing a polyurethane foam comprising the same, a method for producing the same, a polyurethane foam, and an insulating material comprising the same.

[0008] One embodiment of the present invention provides a glass fiber mat laminate comprising a first glass fiber mat and a second glass fiber mat alternately laminated one or more times, wherein the unit weights of the first glass fiber mat and the second glass fiber mat are different from each other.

[0009] One embodiment of the present invention provides a composition for producing a polyurethane foam comprising the above-described glass fiber mat laminate and a polyurethane composition.

[0010] One embodiment of the present invention provides a method for producing a polyurethane foam, comprising the steps of preparing a composition for producing a polyurethane foam as described above; and the step of curing the composition for producing a polyurethane foam.

[0011] One embodiment of the present invention provides a polyurethane foam comprising a composition for producing a polyurethane foam.

[0012] One embodiment of the present invention includes an insulating material comprising the polyurethane foam described above.

[0013] The present invention relates to a glass fiber mat laminate capable of improving strength and insulation performance.

[0014]

[0015] Hereinafter, the present specification will be described in more detail.

[0016] In one embodiment of the present invention, 'glass fiber mat laminate' means a form in which one or more glass fiber mats are laminated.

[0017] Conventional polyurethane foam can be manufactured by spraying a polyurethane composition onto a glass fiber mat and curing it. However, the remaining air layer in the glass fiber mat reduces the physical properties and insulation performance of the polyurethane foam, and there is a problem with the glass fiber mat not being uniformly distributed. To solve the problem of residual air layer, attempts were made to remove the air layer using a separate pressurized device. While the removal of the air layer improved the physical properties of the polyurethane foam, the remaining dispersibility of the glass fiber mat caused a problem of vulnerability.

[0018] The present inventors, by changing the characteristics of a glass fiber mat laminate, aim to prevent an air layer from remaining in the glass fiber mat laminate without introducing a separate pressurizing device, prevent the occurrence of weak points while uniformly dispersing the glass fiber mat inside the polyurethane foam, and improve the physical properties and insulating performance of the manufactured polyurethane foam.

[0019] One embodiment of the present specification provides a glass fiber mat laminate comprising a first glass fiber mat and a second glass fiber mat alternately laminated one or more times, wherein the unit weights of the first glass fiber mat and the second glass fiber mat are different from each other.

[0020] The above glass fiber mat laminate can improve the strength of the glass fiber mat laminate and enhance flexibility during the polyurethane foam manufacturing process by differently controlling the unit weights of the first and second glass fiber mats. In other words, by controlling both strength and flexibility, which are difficult to achieve together, a polyurethane foam with excellent physical properties can be manufactured.

[0021] 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 and repeatedly laminated one or more times. The meaning of the above 'alternatively and repeatedly' may mean a form in which 'a form in which a first glass fiber mat and a second glass fiber mat are laminated to each other' are repeatedly laminated one or more times. At this time, it may include not only a form in which the first glass fiber mat and the second glass fiber mat are in direct contact, but also a form in which a third glass fiber mat is provided between the first glass fiber mat and the second glass fiber mat. For example, in addition to the form of '... first glass fiber mat / second glass fiber mat... ', it may also include a form of '... first glass fiber mat / second glass fiber mat / first glass fiber mat... ', '... 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... '.

[0022] 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 an additional first glass fiber mat may be laminated on the other side of the glass fiber mat laminate of the second glass fiber mat. Alternatively, 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 an additional second glass fiber mat may be laminated on the other side of the glass fiber mat laminate of the first glass fiber mat.

[0023] In one embodiment of the present invention, the glass fiber mat laminate may be a laminate in which a first glass fiber mat and a second glass fiber mat are laminated to each other and repeatedly arranged at least once, and the number of repetitions may be 1 to 100 times. Preferably, the number of repetitions may be 1 to 20 times or 1 to 10 times. When the above numerical range is satisfied, the remaining air layer in the glass fiber mat laminate and the glass fiber mats are uniformly dispersed inside the polyurethane foam, thereby preventing the occurrence of weak points inside the polyurethane foam.

[0024] In one embodiment of the present invention, the unit weights of the first glass fiber mat and the second glass fiber mat are each 100 g / m 2 More than 1,000g / m 2 It may be less than 150g / m. Preferably, 150g / m 2 More than 800g / m 2 Less than or equal to 200g / m 2 More than 500g / m 2 It may be as follows. In the above numerical range, the strength of the glass fiber mat laminate can be improved and flexibility can be improved during the polyurethane foam manufacturing process.

[0025] In one embodiment of the present invention, the difference in unit weight of the first glass fiber mat and the second glass fiber mat is 50 g / m 2 More than 800g / m 2 It may be less than 100g / m. Preferably, 100g / m 2 More than 300g / m 2 Less than or equal to 120g / m 2 More than 250g / m 2 It may be as follows. In the above numerical range, the strength of the glass fiber mat laminate can be improved and flexibility can be improved during the polyurethane foam manufacturing process.

[0026] In one embodiment of the present invention, 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 may be 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. Preferably, it may be 80 parts by weight or more and 600 parts by weight or less, 100 parts by weight or more and 500 parts by weight or less, or 150 parts by weight or more and 300 parts by weight or less. In the above numerical range, the strength of the glass fiber mat laminate can be improved and flexibility can be improved during the polyurethane foam manufacturing process.

[0027] 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 the number of glass fiber mat units may be 1 to 20. Specifically, the number of glass fiber mat units may be 2 to 18, or 2 to 10. By controlling the number of glass fiber mat units, the remaining air layer in the glass fiber mat laminate and the occurrence of weak points within the polyurethane foam can be prevented while the glass fiber mats are uniformly dispersed within the polyurethane foam.

[0028] In one embodiment of the present invention, the difference in the number of glass fiber mat units included in the first glass fiber mat and the number of glass fiber mat units included in the second glass fiber mat may be 1 to 10. Preferably, the difference may be 1 to 8 or 1 to 5. When the above numerical range is satisfied, the residual air layer in the glass fiber mat laminate and the occurrence of a weak polyurethane foam portion can be prevented.

[0029] In one embodiment of the present invention, the glass fiber mat laminate may be a continuous strand mat (CSM).

[0030] In one embodiment of the present invention, each of the first glass fiber mat and the second glass fiber mat may include glass fiber filaments having an average diameter of 1 um to 50 um. Preferably, the glass fiber filaments may include an average diameter of 5 um to 40 um or an average diameter of 10 um to 25 um. When the above numerical ranges are satisfied, the glass fiber mat laminate can maintain the mat shape and prevent an air layer from forming inside the mat.

[0031] In one embodiment of the present invention, the first glass fiber mat and the second glass fiber mat may each include a surfactant. The surfactant can control the surface properties of the glass fiber mats, thereby changing the speed and amount of impregnation of the polyurethane composition into the glass fiber mats. The higher the content of the surfactant, the faster the speed of impregnation into the glass fiber mat laminate. However, as a large content of the polyurethane composition is impregnated, no polyurethane composition remains on the upper portion of the laminate, so that the polyurethane foam is not included on the upper portion of the glass fiber mat laminate or the glass fiber mat is not uniformly dispersed within the polyurethane foam. In addition, the surfactant used in the glass fiber mat may act as an impurity in the polyurethane foam itself, and if used in large amounts, it may impair the physical properties of the polyurethane foam. Therefore, by applying an appropriate content of the surfactant to facilitate impregnation into the glass fiber mat laminate, efficient air layer removal and uniform dispersibility can be achieved. However, when the surface properties of the first glass fiber mat and the second glass fiber mat are adjusted differently, the aforementioned preventive effect can be further enhanced. Methods for adjusting the surfactant content in the first glass fiber mat and the second glass fiber mat differently include methods for treating each glass fiber mat with a surfactant composition having a different surfactant content.

[0032] In one embodiment of the present invention, the surfactant may include a silane compound.

[0033] In one embodiment of the present invention, the silane compound may include an epoxy silane compound.

[0034] In one embodiment of the present invention, the epoxy-based silane compound may be vinylmethoxy silane, vinyltrimethoxy silane, vinylepoxy silane, vinyltriepoxy silane, 3-aminopropyltriethoxy silane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, 3-metaglycyxpropyltrimethoxy silane, γ-glycidoxypropyltriethoxy silane, or a combination thereof. Preferably, 3-glycidoxypropyl triethoxysilane may be used.

[0035] In one embodiment of the present invention, the difference in the surfactant content contained in the first glass fiber mat and the second glass fiber mat may be 0.1 wt% or more and 10 wt% or less. Preferably, it may be 0.1 wt% or more and 8 wt% or less, or 0.1 wt% or more and 5 wt% or less. When the above numerical range is satisfied, when the composition for producing polyurethane foam is impregnated into the glass fiber mat laminate, the degree of dispersion between the mats is controlled, thereby preventing the occurrence of air layer residues in the glass mat fiber laminate and effectively preventing the occurrence of weak points.

[0036] 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. The composition for producing polyurethane foam can be used for producing polyurethane foam.

[0037] In one embodiment of the present invention, the 'composition for producing polyurethane foam' can be used for the purpose of producing polyurethane foam.

[0038] In one embodiment of the present invention, the composition for producing polyurethane foam comprises a glass fiber mat laminate and a polyurethane composition. In this case, the polyurethane composition may be impregnated into the glass fiber mat laminate, or the glass fiber mat laminate and the polyurethane composition may be simply mixed.

[0039] In one embodiment of the present invention, the polyurethane composition may include a polyol compound and an isocyanate compound.

[0040] In one embodiment of the present invention, the type of the polyol compound is not particularly limited, and polyether polyol, polyester polyol, etc. can be used. When using the polyester polyol, a polycondensate of an aromatic and / or aliphatic dicarboxylic acid and an alkanediol and / or alkanetriol or ether diol can be used.

[0041] In one embodiment of the present invention, the polyether polyol may be a polyol starting from a polyfunctional alcohol such as glycerin, trimethanolpropane, pentaerythritol, dipentaerythritol, α-methylglucoside, xylitol, sorbitol, and sucrose; and / or a polyfunctional amine such as o-toluene diamine, ethylene diamine, and triethanol amine, to which an alkylene oxide (e.g., ethylene oxide, propylene oxide, butylene oxide, or a mixture thereof) is added.

[0042] In one embodiment of the present invention, the polyester polyol is generally a polycondensate of an aromatic and / or aliphatic dicarboxylic acid and an alkanediol and / or alkanetriol or ether diol.

[0043] In one embodiment of the present invention, the aromatic polyester polyol tends to be inexpensive and is advantageous in the production of rigid polyurethane foam due to its high compressive strength and heat resistance, and particularly excellent thermal conductivity. One class of widely used aromatic polyester polyols is a polyol produced by esterifying phthalic acid or phthalic anhydride with an aliphatic polyhydric alcohol.

[0044] In one embodiment of the present invention, the type of the isocyanate compound is not particularly limited, and the isocyanate compound may include two or more isocyanate groups.

[0045] In one embodiment of the present invention, the isocyanate compound is 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, polyphenylpolymethylene Polyisocyanates, 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-ethylbutylene 1,4-diisocyanate, pentamethylene 1,5-diisocyanate, butylene 1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate, IPDI), Examples thereof include, but are not limited to, 1,4-bis(isocyanatomethyl)cyclohexane, 1,3-bis(isocyanatomethyl)cyclohexane (HXDI), 1,4-cyclohexane diisocyanate, isomers thereof, or mixtures thereof.

[0046] In one embodiment of the present invention, the polyurethane composition may include at least one additive selected from the group consisting of a foaming agent, a chain extender, a crosslinking agent, a foaming agent, a tackifier, a plasticizer, an antioxidant, an ultraviolet absorber, a light stabilizer, a catalyst, a cocatalyst, a filler, a colorant, a pigment, a water-binding agent, a surfactant, a solvent, a diluent, a flame retardant, an anti-slip agent, an antistatic agent, a preservative, and a biocide.

[0047] In one embodiment of the present invention, the foaming agent includes, but is not limited to, water, carboxylic acid, fluorocarbon foaming agent, carbon dioxide, hydrocarbon foaming agent such as linear or branched alkane hydrocarbon, etc.

[0048] In one embodiment of the present invention, the flame retardant may be a generally used flame retardant, and includes, for example, a brominated ester, a brominated ether or a brominated alcohol, such as dibromoneopentyl alcohol, tribromoneopentyl alcohol and PHT-4-diol, and also a chlorinated phosphate, such as tris(2-chloroethyl) phosphate, tris(2-chloropropyl) phosphate (TCPP), tris(1,3-dichloropropyl) phosphate, tricresyl phosphate, tris(2,3-dibromopropyl) phosphate, tetrakis(2-chloroethyl) ethylenediphosphate, dimethyl methanephosphonate, diethyl diethanolaminomethylphosphonate and also a commercially available halogenated flame retardant polyol. Additional phosphates or phosphonates include, but are not limited to, liquid flame retardants such as diethyl ethanephosphonate (DEEP), triethyl phosphate (TEP), dimethyl propylphosphonate (DMPP), or diphenyl cresyl phosphate (DPK).

[0049] In one embodiment of the present invention, the foaming agent is a silicone foaming agent, a non-ionic foaming agent, a non-silicone foaming agent, and specifically, a foaming agent such as dinonyl phenol, methyl glucoside, methylpropanediol, vinyl ether maleic acid, Si-copolymer series, etc., but is not limited thereto.

[0050] 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, 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, butylcrotin dihydroxide, tetrabutyl titanate, and mixtures thereof, but are not limited thereto.

[0051] One embodiment of the present invention provides a method for producing a composition for producing the above-described polyurethane foam, comprising the steps of: preparing the first glass fiber mat and the second glass fiber mat; adjusting the surfactant content contained in the first glass fiber mat and the second glass fiber mat to be different from each other; producing a glass fiber mat laminate by alternately repeating the first glass fiber mat and the second glass fiber mat at least once; and mixing the glass fiber mat laminate and the polyurethane composition.

[0052] 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, in one embodiment of the present invention, the step of applying a first surfactant composition to the surface of the first glass fiber mat; and the step of applying a second surfactant composition to the surface of the second glass fiber mat, and the contents of the surfactants contained in the first surfactant composition and the second surfactant composition may be different from each other.

[0053] In one embodiment of the present invention, the step of mixing the glass fiber mat laminate and the polyurethane composition may include a step of applying the polyurethane composition to the glass fiber mat laminate. Specifically, the step may include a step of continuously supplying the glass fiber mat laminate; and a step of applying the polyurethane composition to the continuously supplied glass fiber mat laminate.

[0054] In one embodiment of the present invention, the step of mixing the glass fiber mat laminate and the polyurethane composition may include a step of pressurizing the glass fiber mat laminate. This is to remove air layers that may be included in the glass fiber mat laminate. The pressurizing means is not particularly limited, and a known pressure roller may be used.

[0055] One embodiment of the present invention provides a method for producing a polyurethane foam, comprising the steps of preparing a composition for producing a polyurethane foam as described above; and the step of curing the composition for producing a polyurethane foam.

[0056] In one embodiment of the present invention, the step of curing the composition for producing polyurethane foam may be performed at room temperature (23°C) for 1 to 30 days. Preferably, the step may be performed for 5 to 25 days or 7 to 20 days. Within the above numerical range, the polyurethane foam structure can be firmly formed.

[0057] One embodiment of the present invention provides a polyurethane foam comprising the composition for producing the above-described polyurethane foam.

[0058] 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, it may be 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 may be improved.

[0059] In one embodiment of the present invention, the compressive strength of the polyurethane foam at ultra-low temperatures (-170°C) may be 2.58 MPa or more. Preferably, it may be 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 may be improved.

[0060] 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, it may be 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 insulation performance of the polyurethane foam may be improved.

[0061] In one embodiment of the present invention, the horizontal room temperature tensile strength at room temperature (23°C) may be 3.0 Mpa or more. Preferably, it may be 3.1 Mpa or more 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 may be improved.

[0062] In one embodiment of the present invention, the vertical room temperature tensile strength 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 may be improved.

[0063] In one embodiment of the present invention, the horizontal tensile strength at ultra-low temperature (-170°C) may be 3.0 MPa or more. Preferably, it may be 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 may be improved.

[0064] In one embodiment of the present invention, the vertical tensile strength at 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 may be improved.

[0065] One embodiment of the present invention provides an insulating material comprising the above-described polyurethane foam.

[0066] In one embodiment of the present invention, the insulation may be an LNG carrier insulation material. The above-described insulation material has excellent mechanical strength and excellent insulation performance, and thus can be applied to LNG carriers. Typically, ships transporting LNG are equipped with multiple tank-shaped cargo holds capable of storing LNG, thereby storing and transporting liquid LNG in the cargo holds. The LNG cargo hold installed on such an LNG carrier must be capable of storing the cryogenic fluid due to the nature of LNG, and at the same time, must have the strength to withstand the sloshing load of the fluid generated by environmental loads such as current, waves, and wind. In addition, while an LNGC (Liquefied Natural Gas Carrier) can be dry docked for repairs, an FLNG (Floating Liquefied Natural Gas) must be capable of operating at the installed location for more than 20 years, and therefore, depending on the environmental conditions of the installation area, a higher strength than existing cargo holds may be required.

[0067] Hereinafter, the present invention will be described through examples.

[0068]

[0069] <Manufacturing Example 1: Manufacturing of Glass Fiber Unit A>

[0070] A mat-shaped glass fiber unit was prepared by bonding glass fiber filaments with an average diameter of 5 to 40 μm with polyester adhesive. 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 1,000g / m 2 It was.

[0071]

[0072] <Manufacturing Example 2: Manufacturing of Glass Fiber Unit B>

[0073] Glass fiber unit B was prepared in the same manner as in Manufacturing Example 1, except that the weight of the glass fiber filament was changed. At this time, the unit weight of the glass fiber unit 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.

[0074]

[0075] <Manufacturing Example 3: Preparation of polyurethane composition>

[0076] A polyurethane composition containing a polyol compound (polyether polyol and polyester polyol), an isocyanate compound (polymeric MDI: PMDI) and a blowing agent was prepared.

[0077] The polyol compound was mixed with 100 parts by weight of a polyol composition containing 40 wt% of ether polyol (HF-490LR, KPX Chemical Co., Ltd.) and 60 wt% of ester polyol (SL-4100, KPX Chemical Co., Ltd.), 2.0 parts by weight of a foaming agent (Momentive Niax silicone L-6124), 0.5 parts by weight of a flame retardant (Triethyl Phosphate TEP, Kumho Mitsui Chemical Co., Ltd.), 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)). The polyol composition containing the foaming agent, flame retardant, catalyst, and blowing agent was mixed with the same amount of methylenediphenyl diisocyanate (MDI, Kumho Mitsui Chemical Co., Ltd. M-200) to obtain a polyurethane mixture. A composition was prepared.

[0078]

[0079] <Examples and Comparative Examples: Preparation of Glass Fiber Mat Laminates>

[0080] <Example 1>

[0081] Glass fiber unit A (unit weight: 450 g / m) manufactured in Manufacturing Example 1 2 ) and glass fiber unit B manufactured in Manufacturing Example 2 (unit weight: 300 g / m 2 ) was 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.

[0082] <Example 2>

[0083] Glass fiber unit A (unit weight: 450 g / m) manufactured in Manufacturing Example 1 2 ) and glass fiber unit B manufactured in Manufacturing Example 2 (unit weight: 300 g / m 2) was 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.

[0084] <Example 3>

[0085] Glass fiber unit A (unit weight: 450 g / m) manufactured in Manufacturing Example 1 2 ) and glass fiber unit B manufactured in Manufacturing Example 2 (unit weight: 300 g / m 2 ) was 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.

[0086] <Example 4>

[0087] Glass fiber unit A (unit weight: 500 g / m) manufactured in Manufacturing Example 1 2 ) and glass fiber unit B manufactured in Manufacturing Example 2 (unit weight: 250 g / m 2 ) was 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.

[0088] <Example 5>

[0089] Glass fiber unit A (unit weight: 450 g / m) manufactured in Manufacturing Example 1 2 ) and glass fiber unit B manufactured in Manufacturing Example 2 (unit weight: 380 g / m 2 ) was 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.

[0090] <Example 6>

[0091] Glass fiber unit A (unit weight: 900 g / m) manufactured in Manufacturing Example 1 2 ) and glass fiber unit B manufactured in Manufacturing Example 2 (unit weight: 200 g / m 2) was 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.

[0092]

[0093] <Comparative Example 1>

[0094] Glass fiber unit A (unit weight: 450 g / m) manufactured in Manufacturing Example 1 2 ) but did not include glass fiber unit B, was prepared.

[0095]

[0096] Comparative Example 2

[0097] Glass fiber unit B manufactured in Manufacturing Example 2 (unit weight: 300 g / m) 2 ) but did not include glass fiber unit A, was prepared.

[0098]

[0099] <Comparative Example 3>

[0100] Glass fiber unit A (unit weight: 300 g / m) manufactured in Manufacturing Example 1 2 ) and glass fiber unit B manufactured in Manufacturing Example 2 (unit weight: 500 g / m 2 ) was 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.

[0101]

[0102] <Comparative Example 4>

[0103] Glass fiber unit A (unit weight: 600 g / m) manufactured in Manufacturing Example 1 2 ) and glass fiber unit B manufactured in Manufacturing Example 2 (unit weight: 200 g / m 2 ) was 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.

[0104]

[0105] Comparative Example 5

[0106] Glass fiber unit A (unit weight: 700 g / m) manufactured in Manufacturing Example 1 2 ) and glass fiber unit B manufactured in Manufacturing Example 2 (unit weight: 300 g / m 2 ) was 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.

[0107]

[0108] <Comparative Example 6>

[0109] Glass fiber unit A (unit weight: 450 g / m) manufactured in Manufacturing Example 1 2 ) and glass fiber unit B manufactured in Manufacturing Example 2 (unit weight: 440 g / m 2 ) was 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.

[0110]

[0111] Comparative Example 7

[0112] Glass fiber unit A (unit weight: 1,000 g / m) manufactured in Manufacturing Example 1 2 ) and glass fiber unit B manufactured in Manufacturing Example 2 (unit weight: 100 g / m 2 ) was 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.

[0113]

[0114] <Manufacturing of polyurethane foam>

[0115] A glass fiber reinforced polyurethane foam was manufactured by spraying the polyurethane composition manufactured in Manufacturing Example 3 onto the glass fiber mat laminate manufactured in the examples and comparative examples and curing it at room temperature for two weeks.

[0116]

[0117] <Experimental Example 1: Density Measurement>

[0118] The width, length, and height of 5 sections of 50x50x50(mm) glass fiber reinforced polyurethane foam samples at each height location were measured using a vernier caliper (MITUTOYO, CD-P30S) to obtain the volume (㎣). The weight of the sample was measured using a scale (OHAUS, PAG4102), and the density was measured as weight / volume to obtain the average value.

[0119]

[0120] <Experimental Example 2: Measurement of room temperature compressive strength>

[0121] To measure the compressive strength in the vertical direction, the manufactured polyurethane foam was taken as a sample of 50x50x50 (width x length x height, mm) and a load was applied at a speed of 5 mm / min using a universal test machine (Universal Test Machine, UTM, hardness tester, KSU-10M). The compressive strength was measured as compressive load / cross-sectional area and the average value was obtained. At this time, the measurement temperature was room temperature (23℃).

[0122]

[0123] <Experimental Example 3: Measurement of ultra-low temperature compressive strength>

[0124] The ultra-low temperature compressive strength was measured using the same method as Experimental Example 2, except that the measurement temperature was changed to ultra-low temperature (-170℃).

[0125]

[0126] <Experimental Example 4: Measurement of tensile strength at room temperature>

[0127] (Measurement of horizontal tensile strength) Three samples of dog bone-shaped polyurethane foam were prepared at each of five 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 tensile load / cross-sectional area, and the average value was obtained.

[0128] (Measurement of vertical tensile strength) Three samples of polyurethane foam measuring 50x50x50 (widthxlengthxheight, mm) were prepared and pulled at a speed of 5 mm / min using a universal material testing machine (hardness testing machine, KSU-10M). The vertical tensile strength was measured by tensile load / cross-sectional area, and the average value was obtained. At this time, the measurement temperature was room temperature (23℃).

[0129]

[0130] <Experimental Example 5: Measurement of Ultra-Low Temperature Tensile Strength>

[0131] The ultra-low temperature compressive strength was measured using the same method as Experimental Example 4, except that the measurement temperature was changed to ultra-low temperature (-170℃).

[0132]

[0133] <Experimental Example 6: Measurement of thermal conductivity at room temperature>

[0134] The manufactured polyurethane was cut to a size of 200mm x 200mm x 25mm (width x length x height), and a sample corresponding to the LM section was prepared. A thermal conductivity meter (TA Instrument, FOX 200) was used, and the upper plate was set to 10℃ and the lower plate to 37℃, and the measurement was performed using the heat flow meter method. At this time, the measurement temperature was room temperature (23℃).

[0135] Classification Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Experimental Example 1 Density (g / m 2)121122122126122126Experimental example 2Compressive strength at room temperature (Mpa)1.381.281.291.371.281.31Experimental example 3Ultra-low temperature compressive strength (Mpa)2.682.592.632.842.682.59Experimental example 4Horizontal direction tensile strength at room temperature (Mpa)3.373.213.233.373.123.43Vertical direction tensile strength at room temperature (Mpa)1.321.251.271.301.291.30Experimental example 5Horizontal direction ultra-low temperature tensile strength (Mpa)3.213.003.023.223.013.09Vertical direction ultra-low temperature Tensile strength (Mpa) 1.66 1.64 1.65 1.73 1.76 1.76 Experimental example 6 Room temperature thermal conductivity Unit: W / mk 0.01987 0.0203 20.02028 0.0204 20.02034 0.02047

[0136] From Table 1, it was confirmed that the polyurethane foam manufactured in the examples exhibited excellent overall room temperature and ultra-low temperature compressive strength, room temperature and ultra-low temperature tensile strength, and thermal conductivity.

[0137] Comparison Example 1 Comparison Example 2 Comparison Example 3 Comparison Example 4 Comparison Example 5 Comparison Example 6 Comparison Example 7 Experimental Example 1 Density (g / m 2 )123126123124123117124Experimental example 2 Room temperature compressive strength (Mpa)1.291.321.251.231.241.221.21Experimental example 3 Ultra-low temperature compressive strength (Mpa)2.462.532.292.372.422.412.54Experimental example 4 Horizontal direction Room temperature tensile strength (Mpa)3.024.403.623.413.103.123.05 Vertical direction Room temperature tensile strength (Mpa)1.211.301.191.191.281.231.22Experimental example 5 Horizontal direction Ultra-low temperature tensile strength (Mpa)2.904.493.143.092.802.802.94Vertical direction Cryogenic tensile strength (Mpa) 1.47 1.65 1.59 1.33 1.69 1.50 1.53 Experimental example 6 Room temperature thermal conductivity Unit: W / mk 0.02 10 20.02 10 40.02 0 5 9 0.02 0 9 40.02 0 7 9 0.02 0 4 5 0.02 10 1

[0138] From Table 2, it was found that Comparative Examples 1 and 2, which used only a single glass fiber unit, had lower ultra-low temperature compressive strength and room temperature thermal conductivity.

[0139] 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 less or greater, had uneven distribution of glass fibers, resulting in a decrease in the room temperature and ultra-low temperature compressive strength and the vertical room temperature tensile strength.

[0140] Comparative examples 6 and 7, in which the weight difference between the first glass fiber mat and the second glass fiber mat was out of the range, also showed that the glass fiber distribution became uneven, resulting in a decrease in the room temperature and cryogenic compressive strength, the vertical room temperature tensile strength, and the horizontal cryogenic tensile strength.

[0141]

[0142] From the above results, it was confirmed that the polyurethane foam manufactured in the comparative example had poor durability and insulation performance overall, or that even if one performance was good, the other performance was degraded. In contrast, the polyurethane foam manufactured in the examples was confirmed to have excellent durability and insulation performance.

[0143] This is believed to be the result of securing uniformity of density by ensuring uniform distribution of glass fibers within the polyurethane foam and reinforcing areas with weak mechanical strength.

[0144]

[0145] The insulating material comprising the polyurethane foam according to the present invention not only has excellent mechanical properties but also has excellent insulating effects, and therefore can be widely used in fields such as automobiles, construction, and LNG ships.

Claims

1. A glass fiber mat laminate comprising first glass fiber mats and second glass fiber mats alternately laminated one or more times, wherein the unit weights of the first glass fiber mats and the second glass fiber mats are different from each other.

2. In the first paragraph, the unit weights of the first glass fiber mat and the second glass fiber mat are each 100 g / m 2 More than 1,000 g / m 2 A glass fiber mat laminate having the following properties:

3. In the first paragraph, the difference in the unit weight of the first glass fiber mat and the second glass fiber mat is 50 g / m. 2 More than 800g / m 2 A glass fiber mat laminate having the following properties:

4. A glass fiber mat laminate in the first paragraph, 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. A glass fiber mat laminate in the first paragraph, wherein the number of the first glass fiber mat and the second glass fiber mat are the same or different, and the glass fiber mat unit is comprised of 1 or more and 20 or less.

6. A glass fiber mat laminate according to claim 1, wherein the glass fiber mat laminate is a continuous strand mat (CSM).

7. A glass fiber mat laminate according to claim 1, wherein each of the first glass fiber mat and the second glass fiber mat includes glass fiber filaments having an average diameter of 1 um to 50 um.

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

9. A composition for producing polyurethane foam according to claim 8, wherein the polyurethane composition comprises a polyol compound and an isocyanate compound.

10. A composition for producing a polyurethane foam, wherein the polyurethane composition of claim 8 comprises at least one additive selected from the group consisting of a blowing agent, a chain extender, a crosslinking agent, a foaming agent, a tackifier, a plasticizer, an antioxidant, an ultraviolet absorber, a light stabilizer, a catalyst, a cocatalyst, a filler, a colorant, a pigment, a water-binding agent, a surfactant, a solvent, a diluent, a flame retardant, an anti-slip agent, an antistatic agent, a preservative, and a biocide.

11. A step of preparing a composition for manufacturing polyurethane foam according to Article 8; and A method for producing polyurethane foam, comprising the step of curing the composition for producing the above polyurethane foam.

12. A polyurethane foam comprising a composition for producing a polyurethane foam according to Article 8.

13. In the 12th paragraph, 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. Insulating material comprising polyurethane foam according to Article 12.