KR102404686B1 - Two liquid type polyurethane composition for Semi-nonflammable urethane composite material and Semi-nonflammable urethane composite material using the same - Google Patents

Abstract

The present invention relates to a two-component rigid polyurethane composition, a semi-non-combustible urethane composite material using the same, which minimizes toxic and harmful gases, the biggest cause of suffocation in the event of a fire in a building, and relates to a technology that exhibits the insulation effect of existing polyurethane with low thermal conductivity.

Description

Two liquid type polyurethane composition for Semi-nonflammable urethane composite material and Semi-nonflammable urethane composite material using the same}

The present invention is a two-component rigid polyurethane composition, a semi-non-combustible urethane composite material manufactured using the same, and minimizes toxic and harmful gases, the biggest cause of suffocation in the event of a fire in a building, and has a thermal conductivity of 0.026 (W/m·K) or less It relates to a semi-non-combustible composite material that has a low thermal conductivity of the bar and has excellent thermal insulation properties and is suitable for use as interior and exterior wall interior materials and/or insulation materials of buildings.

The main cause of casualties due to fire is smoke generated including harmful/toxic gas. It accounts for about 80%.

Moreover, when a fire occurs, the movement speed of harmful/toxic gas is much faster than the speed at which the fire spreads, so when smoke containing harmful/toxic gas is generated, it is difficult to quickly evacuate because visibility is not secured, especially the elderly and the weak. Children have a problem in that the risk of worse situations increases rapidly. In addition, since the flame spreads rapidly, the damage of the fire is large, and a large amount of smoke including toxic/noxious gas is generated, so that as a secondary damage, there is an extreme problem in human casualties.

Recently, several large-scale fires such as the Uijeongbu Urban Housing Fire (January 2015), the Jecheon Sports Center Fire (December 2017), the Icheon Logistics Warehouse Fire (April 2020), and the Ulsan Residential Complex Fire (October 2020) Accidents have occurred, and composite finishing materials for exterior walls such as sandwich panels and dry-bit method or combustible aluminum composite panels have been pointed out as the main factors affecting the spread of fire. In addition, the Grenfell Tower fire in North Kensignton, London, England, caused many casualties and damage to buildings, and this fire incident can also be viewed as a case of serious damage to life and property due to the spread of fire from combustible exterior materials.

The domestic building law stipulates that the finishing materials for buildings are divided into interior and exterior. The finishing materials used for the exterior walls of buildings are to be made of materials that do not interfere with fire prevention by Presidential Decree according to the purpose and height of the buildings. It is stipulated that non-combustible materials should be used as finishing materials (including coating materials such as insulation and painting, and all other materials constituting finishing materials). However, in the case of non-combustible or semi-non-combustible materials considering the entire material constituting the exterior wall finishing material, the insulating material among the finishing materials can be used as a flame-retardant material.

In other words, when the exterior wall finishing material installed outside the main structural part of the building is viewed as a single system, the entire system should be used as a non-combustible or semi-non-combustible material, and only the insulation inside the system was relaxed to be used more than the flame-retardant material.

The performance standards for flame-retardant, semi-incombustible, and non-combustible materials stipulated in the current building law are evaluated by measuring heat release and gas hazard with a small test piece (100Х100 mm) size. In order to evaluate the fire safety of the entire external finishing material system, a new test method will be introduced to conduct a "real-scale performance test" to evaluate structural deformation, collapse, and fire combustion/spreading performance.

Recently, research on a bead-based flame-retardant insulation material composed only of a core material manufactured by coating a flame-retardant material on polystyrene or an intermediate foamed with polystyrene, or by polymerizing and impregnating a flame-retardant material inside, and a coated flame-retardant insulation material coated with a flame-retardant material on the flame-retardant insulation material In the case of these flame-retardant insulation materials, it is difficult to pass a heat release test or a gas hazard test, and there are many problems to be used as semi-non-combustible insulation materials for construction, such as there is a limit in securing quality stability due to a large quality deviation in the manufacturing process. have.

Accordingly, there is an urgent need for a new polyurethane material applicable to the manufacture of semi-non-combustible composite materials as interior and exterior materials for buildings that can significantly reduce human casualties while ensuring sufficient mechanical properties while having excellent thermal insulation properties while reducing the generation of toxic/toxic gases to be.

Republic of Korea Patent Publication No. 10-2019-0117397 (published on October 16, 2019)

The present invention is a material suitable for applying materials such as insulation and finishing materials for interior and exterior materials for construction, and provides a semi-non-combustible urethane composite material having excellent mechanical properties and low thermal conductivity and low gas emission during combustion, and a composition used for manufacturing the same. do.

The present invention for solving the above problems is a two-component rigid polyurethane composition, an organic flame retardant, an inorganic flame retardant, a foam stabilizer, a blowing catalyst, a gelling catalyst, a trimerization catalyst, a blowing agent and subject comprising polyols; and a curing agent including MDI (Methylene diphenyl diisocyanat).

In addition, the present invention includes a semi-non-combustible urethane composite material produced by using the composition as a semi-non-combustible urethane composite material, which is a foam obtained by mixing and foaming the main and curing agent of the two-component rigid polyurethane composition.

The semi-incombustible urethane composite material prepared with the two-component rigid polyurethane composition of the present invention has high compressive strength and low thermal conductivity, and has excellent flame retardancy of low total heat release and low gas release during combustion. It is suitable for use as a material for insulation and finishing materials.

Hereinafter, the present invention will be described in more detail.

The rigid polyurethane composition of the present invention is a composition used for manufacturing a semi-non-flammable urethane composite material, and is a two-component composition including a main agent and a curing agent.

The subject includes polyols, organic flame retardants, inorganic flame retardants, foam stabilizers, blowing catalysts, gelling catalysts, trimerization catalysts, blowing agents.

Among the main components, the polyol contains polyester polyol and polyether polyol in a weight ratio of 1: 0.1 to 0.5, preferably, in a weight ratio of 1: 0.2 to 0.4. It may not be possible to secure mechanical properties such as sufficient compressive strength, and if the polyether polyol mixing amount exceeds 0.5 weight ratio, the mechanical properties of the urethane foam are excellent, but there may be a problem in the flame retardant performance equivalent to that of the semi-non-combustible, rather than the foam Since the pore size does not become relatively dense, there may be a problem in that the thermal conductivity of the composite material, which is a urethane foam, may increase, so it is preferable to use it within the above range.

The polyester polyol has a functional group (fuctionality) of 1.8 to 2.2, a weight average molecular weight of 300 to 1800, and an OH-V (value) of 180 to 380 mg KOH/g, preferably a functional group of 1.9 to 2.2, a weight average molecular weight of 300 to 1500 and OH-V (value) of 220 to 350 mg KOH/g, more preferably functional group 2.0 to 2.2, weight average molecular weight of 300 to 1000, and OH-V (value) of 240 to 330 mg KOH/g. have. And, in the present invention, the polyester polyol contains 2 to 10% by weight of diethylene glycol and the remaining amount of diethylene glycol-phthalic anhydrad polymer, preferably 3 to 8% by weight of diethylene glycol and the remaining amount of diethylene glycol-phthalic anhydrad polymer may be used.

The polyether polyol serves to increase hydrophobicity and improve mechanical strength, and has a functional group of 3.8 to 5.2, a weight average molecular weight of 280 to 1500 and an OH-V (value) of 280 to 500 mg KOH/g, preferably a functional group 4.0 ~ 5.0, weight average molecular weight 400 ~ 1300 and OH-V 320 ~ 450 mg KOH / g, more preferably a functional group 4.0 ~ 4.6, weight average molecular weight 500 ~ 1200 and OH-V 320 ~ 400 mg KOH / g can And, as the polyether polyol in the present invention, a sucrose-based polyether polyol prepared by polymerizing a mixture of sucrose and glycerin derivatives condensed with an alkylene oxide such as ethylene oxide and/or propylene oxide may be used.

The content of the polyol in the main component of the composition of the present invention is the remaining amount excluding the organic flame retardant, inorganic flame retardant, foam stabilizer, foam catalyst, gelling catalyst, trimerization catalyst and foaming agent in 100% by weight of the main agent.

Next, the organic flame retardant of the main component serves to impart flame retardancy of the urethane foam together with the inorganic flame retardant, and may include at least one selected from general phosphorus-based flame retardants and melamine-based flame retardants used in the art, preferably It may include a phosphorus-based flame retardant comprising at least one selected from among TCPP (Tris-choroisopropyl phosphate), TEP (Triethyl phosphate) and TCPE (Tris carboxyethyl phosphate), wherein the phosphorus (P) content is 5 ~ 30% by weight is preferred.

And, it is appropriate that the amount of the organic flame retardant used is 3.0 to 15% by weight, preferably 4.0 to 13% by weight, and more preferably 5.0 to 11.5% by weight of the total weight% of the main ingredient, and at this time, the organic flame retardant content is 3% by weight If it is less than, the flame retardancy of the urethane foam may be low, and if the flame retardant content exceeds 15% by weight, it is preferable to use it within the above range because it can lower the mechanical strength of the urethane foam without further increasing the flame retardancy due to excessive use.

Next, the inorganic flame retardant among the main ingredients serves to increase the flame retardancy of the urethane foam composite material together with the organic flame retardant, delay and/or suppress the release of harmful gases during combustion, and expand graphite and fiber glass chopped strands ) in a weight ratio of 1: 0.2 to 0.7, preferably 1: 0.4 to 0.6 by weight.

The expanded graphite has an expansion rate of 350% to 450%, a particle size of 80 μm to 200 μm, and a sulfur (S) content of 2,500 ppm or less in terms of compatibility with other compositions, dispersibility and smoke trapping power.

And, the cut glass fiber is produced by cutting glass fiber having a ZrO ₂ content of 12 to 18 wt%, and the cut glass fiber has an average diameter of 10 to 13 μm and a length of 10 to 18 mm in terms of miscibility and dispersibility. , It is preferable to use an average diameter of 10 to 13㎛, and a length of 10 to 12 mm.

And, the amount of the inorganic flame retardant in the main agent is 20.0 to 40.0 wt%, preferably 21.0 to 35.0 wt%, more preferably 23.5 to 34.0 wt%, based on the total weight of the main agent. At this time, if the content of the inorganic flame retardant is less than 20.0% by weight, the amount used is small, and the effect of delaying the release of harmful gases during combustion may be insignificant. Since there may be problems such as deterioration of physical properties and reduction of moldability due to increase in viscosity, it is recommended to use within the above range.

Next, the foam stabilizer serves to maintain cell uniformity and shape of the foamed urethane foam, and a general foam stabilizer used in the art may be used, preferably silicone, silicone glycol copolymer ( It is preferable to use a silicone-based foam stabilizer such as silicon glycol copolymer or polysiloxane ether, and more preferably, a silicone glycol copolymer represented by the following formula (1).

[Formula 1]

In Formula 1, each of R ¹ , R ² and R ³ is independently a hydrogen atom or a linear alkyl group having 1 to 3 carbon atoms, preferably R ¹ , R ² and R ³ are each independently a straight chain alkyl group having 1 to 3 carbon atoms. It is a chain-type alkyl group. And, R ⁴ in Formula 1 is a straight-chain alkylene group having 1 to 5 carbon atoms, preferably a straight-chain alkylene group having 2 to 4 carbon atoms. In addition, each of R ⁵ and R ⁶ in Formula 1 is independently a linear alkylene group having 1 to 3 carbon atoms, and preferably, each of R ⁵ and R ⁶ is independently a linear alkylene group having 1 to 2 carbon atoms. Further, each of R ⁷ is a hydrogen atom, a linear alkyl group having 1 to 3 carbon atoms, or a pulverized alkyl group having 3 to 5 carbon atoms, preferably a hydrogen atom or a straight chain alkyl group having 1 to 3 carbon atoms. And, in Formula 1, A is H or a t-butyl group, x and y are molar ratios, x is an integer from 1 to 20, y is an integer from 1 to 5, x is an integer from 1 to 10, y is an integer from 1 to 3. And, each of m and n is independently a natural number of 1 to 3, preferably 1 or 2.

And, the amount of the foam stabilizer used in the main agent is 0.5 to 4.0 wt%, preferably 0.8 to 3.5 wt%, more preferably 1.0 to 3.2 wt%, based on the total weight of the main agent, and in this case, the amount of the foam stabilizer used is less than 0.5 wt% On the other hand, the cells in the urethane foam may be formed non-uniformly, so there may be a problem that the mechanical properties are not uniform, and when the amount of urethane foam used exceeds 4.0 wt%, compatibility with other compositions is lowered, so that the mechanical properties of the urethane foam and / or Since there may be a problem that the flame retardancy is rather deteriorated, it is better to use it within the above range.

Next, the subject matter in the composition of the present invention includes three catalysts to shorten the reaction time during foam formation and appropriately control the flowability of the foam in relation to the swelling, that is, rising of the foam, specifically, the foam catalyst (blowing catalyst), gelling catalyst (gelling catalyst), trimerization catalyst (Trimerization catalyst).

The foam catalyst facilitates the reaction between water, which is a foaming agent, and MDI in the curing agent, supplies heat required for foaming, and serves to accelerate the resinization reaction between polyol and MDI. PMDETA (pentamethyl diethylene triamine) and BDMEE (di -(N,N-dimethyl aminoethyl)ether) may include at least one selected from the group consisting of, and preferably, PMDETA and BDMEE may be mixed in a 1:1 to 2 weight ratio. Preferred commercially available examples of the PMDETA include PC-5, TC-DT, KAO-3, and the like. Further, commercially available preferred examples of BDMEE include trade names DABCO BL-11, TC-ET, NIAX A-1, and the like.

And, the amount of the foam catalyst used in the main agent is 0.20 to 1.20% by weight, preferably 0.40 to 1.15% by weight, more preferably 0.42 to 1.10% by weight of the total weight of the main agent. At this time, if the amount of the foam catalyst used is less than 0.20% by weight, the amount is small and there may be no effect of accelerating the reaction between the polyol and MDI due to its use, and if it is used in excess of 1.20% by weight, the mechanical properties of the urethane foam are rather reduced due to excessive use However, since there may be problems with dimensional stability and internal temperature control after foaming, it is recommended to use within the above range.

Among the catalysts, the gelation catalyst serves to make a polyurethane resin by reacting MDI (Methylene diphenyl diisocyanat) activated as a foam catalyst with a polyol, DMCHA (dimethylcyclohexyl amine), TMHDA (N,N,N',N'- Tetramethyl-1,6-hexanediamine) and may include one or more selected from TEDA (triethylenediamine), and preferably may include one or more selected from DMCHA and TMHDA. Preferred commercially available examples of DMCHA include trade names PC-8, PC-33, TC-DMCH, KAO-10, and the like. In addition, commercially available preferred examples of the TMHDA include trade names PC-6, TC-MR, KAO-1, and the like. In addition, commercially available preferred examples of TEDA include trade names DABCO33LV, NIAXA-33, TC TEA-L33, and the like.

And, the amount of the gelling catalyst used in the main agent is 0.01 to 0.20 wt%, preferably 0.03 to 0.18 wt%, more preferably 0.03 to 0.16 wt%, based on the total weight of the main agent. At this time, if the content of the gelation catalyst is less than 0.01% by weight, the amount used is too small, and the matrix formation in the polyurethane resin due to the use thereof may be poor, and the mechanical properties may be poor. Cell formation in the foam does not work well, so the thermal conductivity of the urethane foam may increase, and there may be problems in foam shrinkage and foam molding, so it is better to use it within the above range.

Among the catalysts, the trimerization catalyst serves to increase the reactivity between the main agent and the curing agent and to increase the bonding between the curing agent and the curing agent to increase the mechanical and flame retardancy. Metal salts of organic carboxylic acids, tertiary amine compounds And it is preferable to use a trimerization catalyst comprising a quaternary ammonium salt, preferably commercially available under the trade names DABCO K-15, DABCO T-45, DABCO TMR-30 and/or POLYCAT-46 (Air Product Co.) may be used alone or as a mixture of two or more. And, the amount of the trimerization catalyst used in the main agent is 0.50 to 2.50 wt%, preferably 0.65 to 2.30 wt%, more preferably 0.74 to 2.15 wt%, based on the total weight of the main agent. At this time, if the amount of the trimerization catalyst used is less than 0.50 wt%, the formation rate of the trimerization structure in the urethane foam is low, and there may be a problem in the semi-incombustible performance, and if it exceeds 2.50 wt%, the trimerization structure is formed in the urethane foam Although the ratio is excellent, it is better to use it within the above range because there are problems in dimensional stability and formability.

Next, among the main components, the blowing agent may be used by mixing a chemical blowing agent and a physical blowing agent, water is used as the chemical blowing agent, and cyclopentane, 1,1-dichloro-1-fluoroethane ( 1,1-Dichloro-1-fluoroethane) and 1,1,1,3,3-pentafluoropropane (1,1,1,3,3-Pentafluoropropane).

And, the foaming agent may include the chemical foaming agent water and the physical foaming agent in a weight ratio of 1: 5 to 30, preferably in a weight ratio of 1: 8 to 25, more preferably in a weight ratio of 1: 12 to 18. This is advantageous in terms of foamability at an appropriate rate of the foam and proper cell formation in the urethane foam.

And, the content of the foaming agent in the main agent is 6.0 to 20.0 wt%, preferably 7.5 to 18.0 wt%, more preferably 8.5 to 16.0 wt%, based on the total weight of the main agent. At this time, if the amount of the foaming agent used is less than 6.0% by weight, there may be a problem that the foaming property is too insufficient. It is recommended to use within the above range because there may be a problem that it cannot be used as an interior or exterior material for construction due to its low mechanical properties.

In addition, in the composition of the present invention, the subject may further include a polymer represented by the following formula (2) as a dispersant in order to increase dispersibility in the main and foam of the organic flame retardant and/or inorganic flame retardant.

[Formula 2]

In Formula 2, R ¹ is a linear alkyl group having 1 to 5 carbon atoms, a pulverized alkyl group having 4 to 8 carbon atoms, or -C(=O)CH ₃ , and preferably a pulverized alkyl group having 4 to 8 carbon atoms or -C( =O)CH ₃ , and more preferably a pulverized alkyl group having 4 to 8 carbon atoms. In addition, R ² of Formula 2 is —CH ₂ C(=O)R ³ or —CH ₂ SO ₃ R ⁴ , preferably —CH ₂ SO ₃ R ⁴ . And, R ³ is a hydrogen atom or a straight-chain alkyl group having 1 to 3 carbon atoms. And, R ⁴ is a hydrogen atom, Na ⁺ or K ⁺ , preferably a hydrogen atom. In addition, in Formula 2, m is a natural number of 2 to 5, preferably m is a natural number of 3 to 4.

And, the amount of the dispersant used is 0.1 to 0.5% by weight, preferably 0.15 to 0.40% by weight, more preferably 0.15 to 0.35% by weight, based on the total weight of the main agent, and in this case, if the dispersant content is less than 0.1% by weight of the total weight of the main body Since the amount used is small, the effect of ensuring uniform flame retardancy of the foam due to the improvement of the dispersibility of the flame retardant component due to its use may be insufficient, and if it is used in excess of 0.5 wt %, the flame retardancy and / or mechanical properties of the foam may be reduced. Therefore, it is recommended to use it within the above range.

The curing agent in the two-component rigid polyurethane composition of the present invention may include MDI (Methylene diphenyl diisocyanat) having an NCO content of 29 to 34 wt%, and preferably MDI having an NCO content of 30 to 33 wt%.

The semi-nonflammable urethane composite material of the present invention is prepared from the two-component rigid polyurethane composition described above, and includes a foam prepared by mixing the main agent and the curing agent in a weight ratio of 1:1.2 to 1:2.0 and foaming.

At this time, a high-pressure foaming machine may be used for foaming, and the foaming may be performed by adjusting the foaming temperature to 18 to 25° C. based on the storage tank, and the pressure of the high-pressure pump to 110 to 140 bar.

The semi-non-flammable urethane composite material (urethane foam) of the present invention manufactured by foaming as described above has a thermal conductivity of 0.026 W/m·K or less, preferably 0.025 W/m·K or less, when measured in accordance with KS M 3809. More preferably, it may be 0.018 W/m·K to 0.024 W/m·K.

In addition, the semi-nonflammable urethane composite material (urethane foam) of the present invention has a compressive strength of 25.0 N/cm 2 or more, preferably 25.0 N/cm 2 ~ 35.0 N/cm 2 , more preferably 25.0 measured in accordance with KS M 3809 It may be N/cm 2 ~ 30.0 N/cm 2 .

In addition, the semi-incombustible urethane composite material (urethane foam) of the present invention may have a total heat release amount of less than 8 MJ/m2 measured in accordance with KS F ISO 5660-1, preferably 7.9 MJ/m2 to 6.0 MJ/m2 , 7.8 MJ/m2 to 6.5 MJ/m2 may be satisfied.

In addition, the semi-nonflammable urethane composite material (urethane foam) of the present invention satisfies 9 minutes or more when measuring gas toxicity measured in accordance with KS F 2271, and preferably 10 minutes to 15 minutes or more.

Hereinafter, the present invention will be described in more detail through examples, but the following examples are not intended to limit the scope of the present invention, which should be construed to aid understanding of the present invention.

[Example]

Example 1: Preparation of two-component rigid polyurethane composition and semi-non-combustible urethane composite material

(1) Preparation of two-component rigid polyurethane composition

Average A polyester polyol having a functional group of 2.0, a weight average molecular weight of 300 to 600 and an OH-V of 180 to 280 mg KOH/g was prepared. In this case, the polyester polyol contains 4.8 wt% of diethylene glycol and the remaining amount of diethylene glycol-phthalic anhydrad polymer.

A polyether polyol (specific gravity 1.085) having an average functional group of 4.5, a weight average molecular weight of 700 to 900 and an OH-V of 350 to 370 mg KOH/g was prepared. In this case, the polyether polyol is a sucrose-based polyether polyol prepared by polymerizing a mixture of sucrose condensed with ethylene oxide and a glycerin derivative.

The polyester polyol and the polyether polyol were mixed in a weight ratio of 1: 0.253 to prepare a polyol.

As an organic flame retardant, a liquid phosphorus-based flame retardant (phosphorus content of 20 to 25% by weight) containing Tris-choroisopropyl phosphate (TCP) and Triethyl phosphate (TEP) in a weight ratio of 1: 0.8 was prepared.

As an inorganic flame retardant, expanded graphite and fiber glass chopped strands were prepared by mixing them in a weight ratio of 1:0.5. At this time, the expanded graphite had an expansion rate of 350 to 450%, a particle size of 80 μm to 200 μm, and a sulfur (S) content of 2,500 ppm or less was used, and the cut glass fiber was a glass fiber having a Zro ₂ content of 14 to 15% by weight. After cutting, those having an average diameter of about 11 to 12 μm and a length of 10 to 12 mm were used.

As a foam stabilizer, a silicone glycol copolymer (viscosity 800 to 950 mPas, pH 6.0 to 7.0 in water, density 1.04 to 1.06) represented by the following Chemical Formula 1-1 was prepared.

[Formula 1-1]

In Formula 1-1, R ¹ , R ² and R ³ are a methyl group, R ⁴ is an ethylene group, R ⁵ and R ⁶ are a methylene group, R ⁷ is a methyl group, A is a t-butyl group, x is 5, y is 2, and m and n are 2 each.

As a foam catalyst, PMDETA (pentamethyl diethylene triamine) and BDMEE (di-(N,N-dimethyl aminoethyl)ether) were prepared by mixing in a weight ratio of 1:1.2.

DMCHA (dimethylcyclohexyl amine) was prepared as a gelation catalyst.

As a trimerization catalyst, POLYCAT-46 (Air Product Co.) was prepared.

As a foaming agent, water and 1,1,1,3,3-pentafluoropropane (1,1,1,3,3-Pentafluoropropane) were mixed in a weight ratio of 1: 15.2 to prepare.

And, 9.5% by weight of the organic flame retardant, 25.3% by weight of the inorganic flame retardant, 2.0% by weight of the foam stabilizer, 0.78% by weight of the foam catalyst, 0.12% by weight of the gelation catalyst, 1.60% by weight of the trimerization catalyst, 16.2% by weight of the blowing agent, and the remainder of the polyol was mixed to prepare the subject.

In addition, as an isocyanate as a curing agent, MDI Methylene diphenyl diisocyanat) having an NCO content of 31 to 32% by weight) was prepared.

(2) Manufacture of semi-non-flammable urethane composite material (urethane foam)

A semi-non-combustible urethane composite material was prepared by mixing and foaming the above-prepared base material and curing agent in a weight ratio of 1: 1.5 to form a foamed urethane foam.

At this time, a high-pressure foaming machine was used for foaming, and the foaming was performed by adjusting the foaming temperature to 20°C based on the storage tank and the high-pressure pump pressure of the high-pressure foaming machine to 120 ~ 125 bar.

Example 2

A semi-non-flammable urethane composite material was prepared by forming a urethane foam in the same manner as in Example 1, but the dispersing agent represented by the following Chemical Formula 2-1 was further mixed with 0.35% by weight of the total weight of the main material. did

[Formula 2-1]

In Formula 2-1, R ¹ is a t-butyl group, R ² is -CH ₂ SO ₃ R ⁴ , R ⁴ is a hydrogen atom, and m is 3.

Examples 3 to 11 and Comparative Examples 1 to 10

After preparing the main and curing agent of the two-component rigid polyurethane composition with the same composition as in Example 1 or Example 2, using this, a urethane foam was formed in the same manner to prepare a semi-non-combustible urethane composite material, respectively, Examples 2 ~ 10 and Comparative Examples 1 to 10 were performed, respectively. However, as shown in Tables 1 to 4 below, it was carried out by varying the content of the composition in the main subject.

Comparative Example 11

After preparing the main and curing agent of the two-component rigid polyurethane composition with the same composition as in Example 1, urethane foam was formed in the same manner using this to prepare semi-nonflammable urethane composite materials, respectively. However, as a polyol among the main components, the polyester polyol and the polyether polyol were mixed in a weight ratio of 1:0.050 to prepare a polyol.

Comparative Example 12

After preparing the main and curing agent of the two-component rigid polyurethane composition with the same composition as in Example 1, urethane foam was formed in the same manner using this to prepare semi-nonflammable urethane composite materials, respectively. However, as a polyol among the main components, the polyester polyol and the polyether polyol were mixed in a weight ratio of 1:0.610 to prepare a polyol.

Comparative Example 13

A semi-non-flammable urethane composite material was prepared by forming a urethane foam in the same manner as in Example 1, but the dispersing agent represented by the following Chemical Formula 2-1 was further mixed with 0.55 wt% of the total weight of the main material. did

[Formula 2-1]

In Formula 2-1, R ¹ is a t-butyl group, R ² is -CH ₂ SO ₃ R ⁴ , R ⁴ is a hydrogen atom, and m is 3.

topic
Composition (wt%) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 abandonment
flame retardant TCP/TEP 9.5 9.5 14.5 9.5 9.5 9.5 9.5 weapon
flame retardant expanded graphite 13.8 13.8 13.8 11.5 17.5 13.8 13.8 cut
fiberglass 9.5 9.5 9.5 9.7 14.5 9.5 9.5 antifoaming agent silicone glycol copolymer 2.0 2.0 2.0 2.0 2.0 1.0 3.5 catalyst foam catalyst 0.78 0.78 0.78 0.78 0.78 0.78 0.78 gelation catalyst 0.12 0.12 0.12 0.12 0.12 0.12 0.12 trimerization catalyst 1.6 1.6 1.6 1.6 1.6 1.6 1.6 blowing agent water 1.0 1.0 1.0 1.0 1.0 1.0 1.0 physical blowing agent 15.2 15.2 15.2 15.2 15.2 15.2 15.2 dispersant Formula 2-1 - 0.35 - - - - - polyol polyester polyols and polyether polyols Remainder
100% by weight remaining

topic
Composition (wt%) Example 8 Example 9 Example 10 Example 11 abandonment
flame retardant TCPP and
TEP 9.5 9.5 9.5 9.5 weapon
flame retardant expanded graphite 13.8 13.8 13.8 13.8 cutting fiberglass 9.5 9.5 9.5 9.5 antifoaming agent silicone glycol copolymer 2.0 2.0 2.0 2.0 catalyst foam catalyst 1.20 0.78 0.78 0.78 gelation catalyst 0.12 0.12 0.12 0.12 trimerization catalyst 1.6 0.8 2.5 1.6 blowing agent water 1.0 1.0 1.0 2.9 physical blowing agent 15.2 15.2 15.2 15.2 dispersant Formula 2-1 - - - - polyol polyester polyols and polyether polyols Remainder
100% by weight remaining

topic
Composition (wt%) Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 abandonment
flame retardant TCP/TEP 4.7 16.2 9.5 9.5 9.5 9.5 9.5 weapon
flame retardant expanded graphite 13.8 13.8 10.5 22.5 13.8 13.8 13.8 cut
fiberglass 9.5 9.5 7.2 19.4 9.5 9.5 9.5 antifoaming agent silicone glycol copolymer 2.0 2.0 2.0 2.0 0.3 4.5 2.0 catalyst foam catalyst 0.78 0.78 0.78 0.78 0.78 0.78 1.60 gelation catalyst 0.12 0.12 0.12 0.12 0.12 0.12 0.15 trimerization catalyst 1.6 1.6 1.6 1.6 1.6 1.6 1.7 blowing agent water 1.0 1.0 1.0 1.0 1.0 1.0 1.0 physical blowing agent 15.2 15.2 15.2 15.2 15.2 15.2 15.2 polyol polyester polyols and polyether polyols Remainder
100% by weight remaining

topic
Composition (wt%) Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Comparative Example 13 abandonment
flame retardant TCP/TEP 9.5 9.5 9.5 9.5 9.5 9.5 weapon
flame retardant expanded graphite 13.8 13.8 13.8 13.8 13.8 13.8 cut
fiberglass 9.5 9.5 9.5 9.5 9.5 9.5 antifoaming agent silicone glycol copolymer 2.0 2.0 2.0 2.0 2.0 2.0 catalyst foam catalyst 0.78 0.78 0.78 0.78 0.78 0.78 gelation catalyst 0.12 0.12 0.12 0.12 0.12 0.12 trimerization catalyst 0.4 3.5 1.6 1.6 1.6 1.6 blowing agent water 1.0 1.0 5.0 1.0 1.0 1.0 physical blowing agent 15.2 15.2 13.5 15.2 15.2 15.2 dispersant Formula 2-1 - - - - - 0.55 polyol polyester polyols and polyether polyols Remainder
100% by weight remaining

Experimental Example 1: Measurement of physical properties of semi-nonflammable urethane composite material

The thermal conductivity, compressive strength, total heat release, and gas hazard of the semi-incombustible urethane composite material, which is the urethane foam prepared in Examples and Comparative Examples, was measured as follows, and the results are shown in Table 5 below.

(1) Method of measuring thermal conductivity

The thermal conductivity (W/m·K) of the semi-incombustible polyurethane composite materials prepared in Examples and Comparative Examples according to the present invention was measured in accordance with KS M 3809. As a method of measuring the amount of entrained heat and calculating the conductivity from this, it was automatically measured with a thermal conductivity meter (TCA-8).

(2) Compressive strength measurement method

The semi-incombustible polyurethane composite material prepared in Examples and Comparative Examples was compressed by 10% of the height of the foam vertically or horizontally with respect to the foaming direction in accordance with KS M 3809 to measure the extrusion strength (kg/cm2). .

(3) Method of measuring total heat release

The total amount of heat released (MJ/m2) of the semi-incombustible polyurethane composite materials prepared in Examples and Comparative Examples was measured in accordance with KS F ISO 5660-1. Specifically, 50 kW/m2 of radiation was irradiated to a 100 mm × 100 mm (width × length) specimen, and the amount of heat generated from the specimen was accumulated and measured for 5 minutes.

(4) Gas toxicity measurement method

Gas toxicity was measured in accordance with KS F 2271 of the semi-incombustible polyurethane composite materials prepared in Examples and Comparative Examples.

division thermal conductivity
(W/m K) compressive strength
(kg/cm2) total heat release
(MJ/㎡) gas toxicity
(minutes:seconds) Example 1 0.020 25.2 7.5 14:35 Example 2 0.019 27.8 7.0 15:12 Example 3 0.021 25.6 7.6 14:42 Example 4 0.020 25.0 7.4 13:23 Example 5 0.028 25.3 7.7 14:58 Example 6 0.020 25.3 7.5 14:22 Example 7 0.020 25.5 7.8 14:39 Example 8 0.020 25.8 7.9 14:30 Example 9 0.021 26.7 7.5 14:20 Example 10 0.020 25.4 7.7 14:16 Example 11 0.020 25.6 7.8 14:05 Comparative Example 1 0.065 24.4 12.2 08:26 Comparative Example 2 0.024 14.4 10.0 10:01 Comparative Example 3 0.022 25.6 11.5 07:12 Comparative Example 4 0.036 15.8 7.7 11:22 Comparative Example 5 0.024 15.2 8.5 12:09 Comparative Example 6 0.031 18.8 7.7 11:36 Comparative Example 7 0.052 25.7 7.8 12:34 Comparative Example 8 0.046 22.8 8.8 11:50 Comparative Example 9 0.023 23.9 7.9 12:20 Comparative Example 10 0.021 14.5 8.0 12:35 Comparative Example 11 0.020 13.6 7.2 12:40 Comparative Example 12 0.069 26.5 8.8 9:13 Comparative Example 13 0.032 15.8 7.7 13:01

Looking at the experimental results in Table 5, Examples 1 to 11 showed excellent results in overall low thermal conductivity, high compressive strength, low total heat release and gas harm reduction. In particular, Example 2 using a dispersant showed relatively superior mechanical properties, flame retardancy and gas hazard reduction measurement results than Examples 1 and 3 to 11.

On the other hand, in the case of Comparative Example 1 using less than 5% by weight of the organic flame retardant, compared with Example 1, there was no significant effect on the compressive strength, but the thermal conductivity was greatly increased, and there was a problem that the total heat release amount was greatly increased. .

In addition, in the case of Comparative Example 2 in which the organic flame retardant was used in excess of 15% by weight, compared with Examples 1 and 3, the thermal conductivity was low and the total heat emission was small, so the flame retardancy was excellent, but the compressive strength was less than 15 kg/cm 2 There was a problem of significantly lowering.

In the case of Comparative Example 3 using less than 20.0 wt% of the inorganic flame retardant, there was a problem in that the gas toxicity measurement time was significantly shortened as compared to Example 4, In the case of Comparative Example 4 using the inorganic flame retardant in excess of 40.0 wt%, practice Compared with Example 5, the gas-harm inhibitory property is excellent, but mechanical properties and flame retardancy were rather deteriorated, because the foamability of the foam was poor, and the mechanical properties were lowered because uniform cell formation was not achieved.

In addition, in the case of Comparative Example 5 using less than 0.5% by weight of the foam stabilizer, when compared with Example 6, the mechanical properties were significantly lowered, which is because the cell homogeneity in the urethane foam was poor. In addition, in the case of Comparative Example 6 in which the foaming agent was used in excess of 4.0% by weight, compared with Example 7, the results were rather decreased in mechanical properties and flame retardancy, which had poor compatibility with other compositions, resulting in a flame retardant effect and / Or because it interfered with the cell formation in the urethane foam.

In the case of Comparative Example 7 using more than 1.20 wt% of the foam catalyst, there was a problem in that the thermal conductivity of the foam was greatly increased due to insufficient foamability of the urethane foam when compared with Example 8.

In addition, Comparative Example 8, in which the trimerization catalyst was used in less than 0.5% by weight, had a low cell formation rate in the urethane foam, compared with Example 9, and the cell was formed too small, resulting in significantly low overall physical properties, In the case of Comparative Example 9, in which the catalyst was used in excess of 2.50 wt%, the compressive strength was rather lowered compared to that of Example 10.

In addition, in the case of Comparative Example 10, in which the chemical foaming agent and the physical foaming agent in the foaming agent were used in a weight ratio of less than 1:3 and the foaming agent was used in excess of 17.5% by weight, the foaming property was very good, but rather large cells were formed unnecessarily, and some cells were It was rather crushed, so the defect rate was high, and compared with Example 11, the physical properties were low.

In Comparative Example 11, in which polyester polyol and polyether polyol among the main components were used in a weight ratio of less than 1: 0.1, there was a problem in that the compressive strength was low compared to Example 1, and polyester polyol and polyether polyol were used as 1 of the main components. : In the case of Comparative Example 12 used in excess of 0.5 weight ratio, there was a problem in that the thermal conductivity of the urethane foam was greatly increased.

And, in the case of Comparative Example 13 using 0.55% by weight, which exceeds 0.50% by weight of the dispersing agent in the main ingredient, compared with Example 2 using 0.35% by weight of the dispersant, the overall physical properties were significantly lowered, rather, the dispersant was not used Example 1, there was a problem in that the thermal conductivity increased and the compressive strength was lowered.

Through the above Examples and Experimental Examples, it was confirmed that the semi-non-flammable urethane composite material, which is a urethane foam prepared using the two-component rigid polyurethane composition of the present invention, has excellent flame retardancy and low thermal conductivity, and has excellent mechanical properties. Through this, it was confirmed that the composite material of the present invention is suitable for application as an interior and/or insulation material for interior and exterior walls of buildings.

Claims (3)

Organic flame retardant 5.0 to 15.0 wt%, inorganic flame retardant 21.0 to 35.0 wt%, foam stabilizer 0.8 to 3.5 wt%, blowing catalyst 0.40 to 1.20 wt%, gelling catalyst 0.03 to 0.18 wt%, trimerization a main agent comprising 0.65 to 2.50% by weight of a Trimerizationcatalyst, 7.5 to 18.0% by weight of a blowing agent and the balance of a polyol; and a curing agent comprising MDI (Methylene diphenyl diisocyanate) having an NCO content of 29 to 34 wt%;
The main agent and the curing agent are included in a weight ratio of 1: 1.2 to 2.0,
The polyol comprises a polyester polyol and a polyether polyol in a weight ratio of 1: 0.2 to 0.4,
The polyester polyol has a functional group (functionality) of 1.8 to 2.2, a weight average molecular weight of 300 to 1,800, and an OH-V (value) of 180 to 380 mg KOH/g,
The polyether polyol has a functional group of 4.0 to 4.5, a weight average molecular weight of 500 to 1200, and OH-V 320 to 400 mg KOH/g,
The organic flame retardant comprises a phosphorus-based flame retardant comprising at least one selected from Tris-choroisopropyl phosphate (TCP), Triethyl phosphate (TEP), and Tris carboxyethyl phosphate (TCPE),
The inorganic flame retardant comprises expanded graphite and cut glass fibers having an average diameter of 10 to 13 μm and a length of 10 to 18 mm in a weight ratio of 1: 0.2 to 0.7,
The expanded graphite has an expansion rate of 350% to 450%, a particle size of 80 μm to 200 μm, and a sulfur (S) content of 2,500 ppm or less,
The cut glass fiber is a cut glass fiber having a ZrO ₂ content of 12 to 18% by weight,
The foam stabilizer includes a silicone-based foam stabilizer including a silicone glycol copolymer represented by the following Chemical Formula 1,
The foam catalyst includes at least one selected from pentamethyl diethylene triamine (PMDETA) and di-(N,N-dimethyl aminoethyl)ether (BDMEE),
The gelation catalyst includes at least one selected from dimethylcyclohexyl amine (DMCHA), N,N,N',N'-Tetramethyl-1,6-hexanediamine (TEDA), and triethylenediamine (TEDA),
The trimerization catalyst is a catalyst comprising an organic carboxylic acid metal salt, a tertiary amine compound, and a quaternary ammonium salt,
The foaming agent contains water and a physical foaming agent in a weight ratio of 1: 8 to 25,
The physical blowing agent is cyclopentane, 1,1-dichloro-1-fluoroethane and 1,1,1,3,3-pentafluoropropane (1,1,1). ,3,3-Pentafluoropropane) a two-component rigid polyurethane composition for a semi-non-flammable urethane composite material comprising at least one selected from the group consisting of.
[Formula 1]

In Formula 1, each of R ¹ , R ² and R ³ is independently a hydrogen atom or a straight-chain alkyl group having 1 to 3 carbon atoms, R ⁴ is a straight-chain alkylene group having 1 to 5 carbon atoms, and R ⁵ and R ⁶ are each independently a linear alkylene group having 1 to 3 carbon atoms, R ⁷ is a hydrogen atom, a linear alkyl group having 1 to 3 carbon atoms, or a pulverized alkyl group having 3 to 5 carbon atoms, A is H or a t-butyl group, x, y, m, and n are molar ratios, where x is an integer from 1 to 20, y is an integer from 1 to 5, and each of m and n is independently a natural number from 1 to 3.
delete It includes a urethane foam formed by mixing and foaming the subject and curing agent of claim 1, wherein the urethane foam,
When measured in accordance with KS M 3809, the thermal conductivity is 0.026 W/m·K or less,
Compressive strength measured in accordance with KS M 3809 is 25.0 N/㎠ or more,
The total heat release measured according to KS F ISO 5660-1 is less than 8 MJ/m2,
Semi-nonflammable urethane composite material, characterized in that it satisfies 9 minutes or more when measuring gas toxicity measured in accordance with KS F 2271.