KR20210130350A - Foaming Agent Composition for Polyurethane and Method of Preparing Polyurethane Foam Using the Same - Google Patents

Abstract

A polyurethane foaming agent composition according to the present invention comprises dichloroethylene and chloroalkane. A polyurethane foam manufactured using the same has a very low global warming index and ozone destruction index, and at the same time has the effect of having improved thermal conductivity, absorption amount, flexural strength, and compressive strength at a level satisfying a rigid urethane foam insulation standard.

Description

Polyurethane foaming agent composition and method of manufacturing a polyurethane foam using the same

The present invention relates to a polyurethane foaming agent composition and a polyurethane foam using the same, and more particularly, it has a very low global warming potential and ozone depletion potential, including dichloroethylene and chloroalkane in the polyurethane foaming agent composition, and a rigid urethane It relates to a polyurethane foaming agent composition having physical properties of improved thermal conductivity, absorption amount, flexural strength and compressive strength at a level that meets the foam insulation standards, and a polyurethane foam using the same.

Low-density rigid polyurethane foams are used in various fields such as bedding such as mattresses and pillows, cushioning materials such as home chairs and automobile seats, roof systems, and insulation materials of buildings such as building panels. An important factor in the large-scale commercial use of rigid polyurethane foams is the ability to provide good balance properties. Rigid polyurethane foams are known to provide excellent structural properties with excellent thermal insulation, good heat resistance and a significant low density. The foam industry has used liquid fluorocarbon blowing agents because of the ease of processing conditions.

Fluorine-containing olefin compounds that are blowing agents in the art, such as HFO-1234ze (1,3,3,3-tetrafluoropropene), HCFO-1233zd (1-chloro-3,3,3-trifluoropropene) Pen), HFC-245fa (pentafluoropropane), HCFC-141b (1,1-dichloro-1-fluoroethane), etc. have properties such as low thermal conductivity and high dimensional stability. It was widely used because of its excellence. However, the fluorine-containing olefin compounds have a high global warming potential (GWP) as well as a high cost of the blowing agent, and their use has been reduced in recent years when environmental issues are becoming more important.

In order to compensate for the disadvantages of these fluorine-containing olefin compounds, hydrocarbon blowing agents such as iso-pentane, normal-pentane and cyclopentane may be used. The hydrocarbon blowing agent has an ozone depletion potential (ODP) of zero and is an eco-friendly blowing agent showing a very low global warming potential. However, foams prepared from these foaming agents have a disadvantage in that the thermal insulation efficiency is lower than that of foams prepared by using a fluorine-containing olefin compound as a foaming agent. In addition, the hydrocarbon foaming agent is uneconomical because the process and equipment are complicated due to insufficient miscibility with the materials and additives essential for the production of polyurethane foams such as polyols, and additives are additionally added to the composition to improve various properties of the polyurethane foam There is a disadvantage in that the mechanical properties of the polyurethane foam finally produced when included in the lowered. Moreover, in the case of cyclopentane, due to its flammability, it is difficult to handle when used in an actual process.

이므로, 실온에서 액체인 무독성 물질이다. 오존층을 파괴하지 않으며 대기 수명이 매우 짧기 때문에 오존 파괴 지수가 매우 낮다. 미국특허 제7,144,926호는 trans-1,2-디클로로에틸렌 및 하이드로플루오로카본 화합물을 포함하는 조성물을 개시하고 있고, 한국등록특허 제10-1532221호는 trans-1,2-디클로로에틸렌 등을 포함하는 하이드로할로올레핀 발포제, 폴리올, 비-실리콘 계면활성제이면서 실질적으로 실리콘 계면활성제가 없는 계면활성 성분, 및 3차 아민 촉매의 혼합물을 포함하는 폴리올 프리믹스 조성물을 개시하고 있다. 그러나 상기 특허들은 GWP가 높은 하이드로플루오로 카본(hydrofluoro carbon, HFC)를 포함한다는 점과 환경적인 문제는 적으나 가격이 매우 비싸 경제적 접근이 어려운 하이드로할로올레핀(hydrofluoro olefin, HFO)를 포함하는 문제점이 있다.In addition, trans-1,2-dichloroethylene, another compound that can compensate for the shortcomings of fluorine-containing olefin compounds, has a boiling point of 48

Therefore, it is a non-toxic substance that is liquid at room temperature. The ozone depletion potential is very low because it does not destroy the ozone layer and has a very short atmospheric life. U.S. Patent No. 7,144,926 discloses a composition containing trans-1,2-dichloroethylene and a hydrofluorocarbon compound, and Korean Patent No. 10-1532221 discloses a composition containing trans-1,2-dichloroethylene and the like. Disclosed is a polyol premix composition comprising a mixture of a hydrohaloolefin blowing agent, a polyol, a non-silicone surfactant and substantially free of silicone surfactant, and a tertiary amine catalyst. However, the above patents contain hydrofluoro carbon (HFC) having a high GWP and a problem including hydrofluoro olefin (HFO), which is difficult to access economically because it has few environmental problems but is very expensive There is this.

On the other hand, methyl formate can also be used as a foaming agent, and Patent Publication No. 2016-0023050 discloses a composition for forming a rigid polyurethane foam including a polyester polyol and/or a polyether polyol, and a methyl formate foaming agent. have. When a polyurethane foam is produced using methyl formate, the foam has severe shrinkage and poor dimensional stability, and miscibility and storage stability with materials essential for the production of polyurethane foam, such as polyol, are also unstable.

Therefore, there is a need for a novel foaming agent having excellent physical properties of a polyurethane foam produced using the same while minimizing the disadvantages of a foaming agent used in the production of a polyurethane foam used in the past and a composition for producing a polyurethane foam including the same. the current situation.

Accordingly, the present inventors have made diligent efforts to solve the above problems, and as a result, when a polyurethane foam is manufactured using a polyurethane foaming agent composition containing a certain ratio of dichloroethylene and chloroalkane, thermal conductivity, absorption amount, flexural strength and compressive strength, etc. It was confirmed that the physical properties of the polyurethane foam are very suitable for the rigid urethane foam insulation standard and at the same time the global warming potential and ozone depletion potential are very low, so that an eco-friendly polyurethane foam can be manufactured, and the present invention has been completed.

An object of the present invention is a polyurethane foaming agent composition having a very low global warming potential and ozone depletion potential, and having improved performance such as thermal conductivity, absorption amount, flexural strength and compressive strength to meet the rigid urethane foam insulation standard, and polyurethane foam using the same To provide a manufacturing method of

In order to achieve the above object, the present invention provides a polyurethane foaming agent composition comprising dichloroethylene and chloroalkane.

The present invention also comprises the steps of (a) preparing a first liquid comprising a polyol, a reaction catalyst, a silicone-based surfactant, trichloropropyl phosphate and the polyurethane foaming agent composition; (b) mixing a second liquid containing polyisocyanate in the same weight as the first liquid; and (c) reacting a mixture of the first liquid and the second liquid to prepare a polyurethane foam.

The polyurethane foam manufactured using the polyurethane foaming agent composition according to the present invention has a very low global warming potential and ozone depletion potential, and at the same time, improved thermal conductivity, absorption amount, flexural strength and compressive strength to a level that meets the rigid urethane foam insulation standard It has the effect of having the physical properties of

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is those well known and commonly used in the art.

In the present invention, when a polyurethane foaming agent composition containing a certain ratio of dichloroethylene and chloroalkane is used in the process for producing a polyurethane foam, physical properties such as thermal conductivity, absorption amount, flexural strength and compressive strength meet the rigid urethane foam insulation standards. It was confirmed that environmentally friendly polyurethane foam can be manufactured as the global warming potential and ozone depletion potential are very low at the same time as the level is improved.

Accordingly, the present invention, in one aspect, relates to a polyurethane foaming agent composition comprising dichloroethylene and chloroalkane.

In another aspect, the present invention comprises the steps of: (a) preparing a first solution comprising a polyol, a reaction catalyst, a silicone-based surfactant, trichloropropyl phosphate, and the polyurethane foaming agent composition; (b) mixing a second liquid containing polyisocyanate in the same weight as the first liquid; and (c) reacting a mixture of the first liquid and the second liquid to prepare a polyurethane foam.

Hereinafter, a polyurethane foaming agent composition according to the present invention and a method for producing a polyurethane foam using the same will be described in detail.

The present invention is first to provide a blowing agent composition that simultaneously satisfies the criteria of a very low global warming potential and ozone depletion potential.

Herein, "GWP" is a 100-year period relative to carbon dioxide, as defined in "The Scientific Assessment of Ozone Depletion, 2002, a report of the World Meteorological Association's Global Ozone Research and Monitoring Project," which is incorporated herein by reference. is measured for

The blowing agent composition according to the present invention has a global warming potential of 150 or less, more preferably 100 or less, and most preferably 75 or less. Further, it has an ozone depletion index of 0.05 or less, more preferably 0.02 or less, and most preferably about 0 or so.

In the polyurethane foaming agent composition of the present invention, dichloroethylene may be trans-1,2-dichloroethylene or cis-1,2-dichloroethylene. Preferably, trans-1,2-dichloroethylene is used.

In the polyurethane foaming agent composition of the present invention, the chloroalkane is C _x H _y Cl _z (where x = 2 or 3, y = an integer of 4 to 7, z = 1 or 2, provided that x = 2 when y+z=6, and when x=3, y+z=8).

In the present invention, the chloroalkane is chloroethane, 1-chloropropane, 2-chloropropane, 1,1-dichloroethane, 1 ,2-dichloroethane (1,2-dichloroethane), 1,1-dichloropropane (1,1-dichloropropane), 1,2-dichloropropane (1,2-dichloropropane) and 1,3-dichloropropane (1, 3-dichloropropane) may be at least one selected from the group consisting of.

In the polyurethane foaming agent composition of the present invention, it may contain 30 to 90% by weight of dichloroethylene and 10 to 70% by weight of 1-chloropropane.

When the content of dichloroethylene in the polyurethane foaming agent composition according to the present invention is less than 30% by weight or the content of 1-chloropropane exceeds 70% by weight, there is a problem that the thermal conductivity does not meet the specifications of the rigid urethane foam insulation, When the content of dichloroethylene exceeds 90% by weight or the content of 1-chloropropane is less than 10% by weight, there is a problem in that absorption and compressive strength are lowered.

In addition, the polyurethane foaming agent composition of the present invention can be prepared by adding 30 to 90% by weight of dichloroethylene and 10 to 70% by weight of 1-chloropropane.

The thermal conductivity of the polyurethane foam prepared using the polyurethane foaming agent composition of the present invention is 0.023 W/m·K or less, the absorption is 3.0 g/100cm ² or less, the flexural breaking load is 25 N or more, and the compressive strength is 10 N/ cm ^{2 or} larger.

Thermal conductivity, one of the most important physical properties, of 0.023 or less, is required in the rigid urethane foam insulation standard (according to KS M 3809) of type 2 No. 2 (density 35 or higher) of insulation, and the polyurethane foaming agent composition according to the present invention satisfies this. It works.

The method for producing a polyurethane foam according to the present invention comprises (a) a first solution comprising a polyol, a reaction catalyst, a silicone-based surfactant, trichloropropyl phosphate, and the polyurethane foaming agent composition of any one of claims 1 to 3; manufacturing; (b) mixing a second liquid containing polyisocyanate in the same weight as the first liquid; and (c) reacting a mixture of the first liquid and the second liquid to prepare a polyurethane foam.

In the present invention, the polyol may be a mixture of one or more polyol components, any polyol component comprising at least two reactive groups, preferably OH groups, in particular polyether alcohols having a hydroxyl value in the range of 200 to 600 mg KOH/g and/or polyester alcohol. Specific examples include 25% to 35% by weight of a polyol having a hydroxyl value of 450 to 500 mg KOH/g obtained by adding glycerin and propylene glycol to sucrose, and 360 to 400 mg KOH/g of a hydroxyl value by adding glycerin and propylene glycol to sucrose 15% to 25% by weight of phosphorus sucrose polyol, 15% to 25% by weight of sorbitol polyol having a hydroxyl value of 460 to 520 mg KOH/g obtained by adding propylene glycol to sorbitol, and ethylene oxide and propylene oxide to glycerin substituted with a bromine group It is a polyol mixture obtained by adding 25 wt% to 35 wt% of a polyether polyol having a hydroxyl value of 300 to 350 mg KOH/g. Alternatively, 30% by weight of a polyol having a hydroxyl value of 450 to 500 mg KOH/g obtained by adding glycerin and propylene glycol to sucrose, 20 weight percent of a sucrose polyol having a hydroxyl value of 360 to 400 mg KOH/g by adding glycerin and propylene glycol to sucrose %, 20 wt% of a sorbitol polyol having a hydroxyl value of 460 to 520 mg KOH/g obtained by adding propylene glycol to sorbitol and ethylene oxide and propylene oxide obtained by adding ethylene oxide and propylene oxide to glycerin substituted with a bromine group has a hydroxyl value of 300 to 350 mg KOH/g It may be a polyol mixture in which 30 wt% of phosphorus polyether polyol is mixed.

In the present invention, the reaction catalyst promotes the reaction between the isocyanate group in the polyisocyanate and the active hydrogen-containing group in the polyol. As such a reaction catalyst, amines such as dimethylcyclohexylamine and salts such as potassium octoate are used together. The compounding quantity of these reaction catalysts is made into the quantity normally used for the said reaction acceleration|stimulation. In addition, the catalysts may be used alone or in any desired mixture as needed. A specific example is the use of equal weight of dimethylcyclohexylamine and potassium octoate. Preferably, the amine catalyst and potassium octoate are included in an amount of 0.5 to 2 parts by weight based on 100 parts by weight of the polyol. When included in less than 0.5 parts by weight, the reaction promoting effect is insufficient, and when included in excess of 2 parts by weight, there is a disadvantage that catalyst efficiency is lowered.

In the present invention, a specific example of including the silicone-based surfactant is L-6900. Commercially available products can be used for this. The silicone-based surfactant is preferably included in an amount of 1 to 5 parts by weight based on 100 parts by weight of the polyol. When the amount of the silicone-based surfactant is less than 1 part by weight, the surfactant effect is insignificant, and when it exceeds 5 parts by weight, only raw materials are wasted without an additional surfactant effect.

Hereinafter, the present invention will be described in more detail through examples. These examples are only for illustrating the present invention, and it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples.

[Example]

Preparation Example 1: Preparation of polyurethane foaming agent composition

100% by weight of trans-1,2-dichloroethylene was added to prepare a polyurethane foaming agent composition.

Preparation Example 2: Preparation of polyurethane foaming agent composition

A polyurethane foaming agent composition was prepared in the same manner as in Preparation Example 1 except that 90% by weight of trans-1,2-dichloroethylene and 10% by weight of 1-chloropropane were added in Preparation Example 1.

Preparation Example 3: Preparation of polyurethane foaming agent composition

A polyurethane foaming agent composition was prepared in the same manner as in Preparation Example 1, except that 80% by weight of trans-1,2-dichloroethylene and 20% by weight of 1-chloropropane were added in Preparation Example 1.

Preparation Example 4: Preparation of polyurethane foaming agent composition

A polyurethane foaming agent composition was prepared in the same manner as in Preparation Example 1, except that 70% by weight of trans-1,2-dichloroethylene and 30% by weight of 1-chloropropane were added in Preparation Example 1.

Preparation Example 5: Preparation of polyurethane foaming agent composition

A polyurethane foaming agent composition was prepared in the same manner as in Preparation Example 1 except that 60% by weight of trans-1,2-dichloroethylene and 40% by weight of 1-chloropropane were added in Preparation Example 1.

Preparation Example 6: Preparation of polyurethane foaming agent composition

A polyurethane foaming agent composition was prepared in the same manner as in Preparation Example 1 except that 50% by weight of trans-1,2-dichloroethylene and 50% by weight of 1-chloropropane were added in Preparation Example 1.

Preparation Example 7: Preparation of polyurethane foaming agent composition

A polyurethane foaming agent composition was prepared in the same manner as in Preparation Example 1, except that 40% by weight of trans-1,2-dichloroethylene and 60% by weight of 1-chloropropane were added in Preparation Example 1.

Preparation Example 8: Preparation of polyurethane foaming agent composition

A polyurethane foaming agent composition was prepared in the same manner as in Preparation Example 1, except that 30% by weight of trans-1,2-dichloroethylene and 70% by weight of 1-chloropropane were added in Preparation Example 1.

Preparation Example 9: Preparation of polyurethane foaming agent composition

A polyurethane foaming agent composition was prepared in the same manner as in Preparation Example 1 except that 20% by weight of trans-1,2-dichloroethylene and 80% by weight of 1-chloropropane were added in Preparation Example 1.

Preparation 10: Preparation of polyurethane foaming agent composition

A polyurethane foaming agent composition was prepared in the same manner as in Preparation Example 1 except that 10% by weight of trans-1,2-dichloroethylene and 90% by weight of 1-chloropropane were added in Preparation Example 1.

Preparation Example 11: Preparation of polyurethane foaming agent composition

A polyurethane foaming agent composition was prepared in the same manner as in Preparation Example 1, except that 100% by weight of 1-chloropropane was added in Preparation Example 1.

Example 1: Preparation of polyurethane foam

Example 1-1

A polyurethane foam was prepared using the polyurethane foaming agent composition prepared in Preparation Example 1.

30 wt% of a polyol having a hydroxyl value of 450 to 500 mg KOH/g obtained by adding glycerin and propylene glycol to sucrose as a polyol, 20 wt.% of a sucrose polyol having a hydroxyl value of 360 to 400 mg KOH/g by adding glycerin and propylene glycol to sucrose %, 20 wt% of a sorbitol polyol having a hydroxyl value of 460 to 520 mg KOH/g obtained by adding propylene glycol to sorbitol and ethylene oxide and propylene oxide obtained by adding ethylene oxide and propylene oxide to glycerin substituted with a bromine group has a hydroxyl value of 300 to 350 mg KOH/g 30 wt% of phosphorus polyether polyol was mixed to prepare a polyol (a mixture, hereinafter used in the same sense as “polyol”).

1 part by weight of each of dimethylcyclohexylamine (manufactured by HUNTSMAN) and K-15 (potassium octoate in diethylene glycol (manufactured by Air Product) in 100 parts by weight of the polyol, 2 parts by weight of silicone surfactant L-6900, triclo 25 parts by weight of lopropyl phosphate and 15 parts by weight of trans-1,2-dichloroethylene as a foaming agent were mixed and used.

144 parts by weight of polymethylenediphenyl isocyanate (manufactured by BASF, 31% NCO content) having a functional group number of 2.6 to 3.0 as the second solution was mixed with the first solution based on 100 parts by weight of the polyol (weight ratio of 1 solution/2 solution) is 1/1). The mixture of the first liquid and the second liquid was applied to an injection system for cryogenic cold storage (GUSMER H20.35, GRACO (USA)) to prepare a polyurethane foam by a one-shot foaming method.

Example 1-2

A polyurethane foam was prepared in the same manner as in Example 1-1, except that 15 parts by weight of a foaming agent mixed with trans-1,2-dichloroethylene and 1-chloropropane in a ratio of 9:1 was used as a foaming agent.

Examples 1-3

A polyurethane foam was prepared in the same manner as in Example 1-1, except that 15 parts by weight of a foaming agent mixed with trans-1,2-dichloroethylene and 1-chloropropane in a ratio of 8:2 was used as a foaming agent.

Examples 1-4

A polyurethane foam was prepared in the same manner as in Example 1-1, except that 15 parts by weight of a foaming agent mixed with trans-1,2-dichloroethylene and 1-chloropropane in a ratio of 7:3 as a foaming agent was used.

Examples 1-5

A polyurethane foam was prepared in the same manner as in Example 1-1, except that 15 parts by weight of a foaming agent mixed with trans-1,2-dichloroethylene and 1-chloropropane in a ratio of 6:4 was used as a foaming agent.

Examples 1-6

A polyurethane foam was prepared in the same manner as in Example 1-1, except that 15 parts by weight of a foaming agent mixed with trans-1,2-dichloroethylene and 1-chloropropane in a ratio of 5:5 was used as a foaming agent.

Examples 1-7

A polyurethane foam was prepared in the same manner as in Example 1-1, except that 15 parts by weight of a foaming agent mixed with trans-1,2-dichloroethylene and 1-chloropropane in a ratio of 4:6 was used as a foaming agent.

Examples 1-8

A polyurethane foam was prepared in the same manner as in Example 1-1, except that 15 parts by weight of a foaming agent mixed with trans-1,2-dichloroethylene and 1-chloropropane in a ratio of 3:7 was used as a foaming agent.

Examples 1-9

A polyurethane foam was prepared in the same manner as in Example 1-1, except that 15 parts by weight of a foaming agent obtained by mixing trans-1,2-dichloroethylene and 1-chloropropane in a ratio of 2:8 as a foaming agent was used.

Examples 1-10

A polyurethane foam was prepared in the same manner as in Example 1-1, except that 15 parts by weight of a foaming agent mixed with trans-1,2-dichloroethylene and 1-chloropropane in a ratio of 1:9 was used as a foaming agent.

Examples 1-11

A polyurethane foam was prepared in the same manner as in Example 1-1, except that 15 parts by weight of a foaming agent mixed with trans-1,2-dichloroethylene and 1-chloropropane in a ratio of 0:10 was used as a foaming agent.

Comparative Example 1

Comparative Example 1-1

A polyurethane foam was prepared in the same manner as in Example 1-1, except that 15 parts by weight of a foaming agent mixed with trans-1,2-dichloroethylene and HFC-365mfc in a ratio of 4:6 was used as a foaming agent.

Comparative Example 1-2

A polyurethane foam was prepared in the same manner as in Example 1-1, except that 15 parts by weight of a foaming agent mixed with trans-1,2-dichloroethylene and HFC-365mfc in a ratio of 5:5 as a foaming agent was used.

Comparative Example 1-3

A polyurethane foam was prepared in the same manner as in Example 1-1, except that 15 parts by weight of a foaming agent mixed with trans-1,2-dichloroethylene and HFC-365mfc in a ratio of 6:4 was used as a foaming agent.

Comparative Example 2

Comparative Example 2-1

A polyurethane foam was prepared in the same manner as in Example 1-1, except that 15 parts by weight of a foaming agent mixed with trans-1,2-dichloroethylene and methyl formate in a ratio of 5:5 as a foaming agent was used. did.

Comparative Example 2-2

A polyurethane foam was prepared in the same manner as in Example 1-1, except that 15 parts by weight of a foaming agent mixed with trans-1,2-dichloroethylene and methyl formate in a ratio of 6:4 was used as a foaming agent. did.

Example 2: Measurement of Apparent Density of Rigid Polyurethane Foam

The measurement of the apparent density measurement is in accordance with KS M ISO 845 and the following. The thickness of the insulation plate is the same as the sample, and three specimens of about 100 mm * 100 mm are cut out from the sample.

Density (kg/m ³ ) = m/V

Example 3: Measurement of water absorption of rigid polyurethane foam

1) Remove the epidermis from the sample and measure the dimensions by making three 100mm*100mm*25mm test pieces.

2) Immerse the test piece 50 mm below the water surface of a container filled with clear water at about 25°C. After 10 seconds, take out the test piece, leave it for 30 seconds, measure the weight, and use this as the reference weight (C). Then, immerse it in clear water again and let it absorb for 24 hours, and then measure the weight (B). The amount of absorption is calculated according to the following equation.

Absorption (g/100cm ² ) = (BC)/surface area * 100

Example 4: Measurement of Compressive Strength of Rigid Polyurethane Foam

Compressive strength was measured according to KS M ISO 844 using a universal tester for the polyurethane foam prepared in the above Example.

Example 5: Measurement of flexural fracture load of rigid polyurethane foam

Compressive strength was measured according to KS M ISO 1209-1, -2 using a universal tester for the polyurethane foam prepared in the above Example.

Example 6: Measurement of Thermal Conductivity of Rigid Polyurethane Foam

For the polyurethane foams prepared in Examples and Comparative Examples, the thermal conductivity was measured according to KS L 9016 using a thermal conductivity meter (model number: MA01906) of Laser Comp.

The physical properties of the rigid polyurethane foams of Examples 1-1 to 1-11 measured in Examples 2 to 6 are shown in Table 1, and the physical properties of the rigid polyurethane foams of Comparative Examples 1 to 2 are Table 1 shown in

manufacturing example One 2 3 4 5 6 7 8 9 10 11 Example 1-1 1-2 1-3 1-4 1-5 1-6 1-7 1-8 1-9 1-10 1-11 tDCE/1-CP ^{Note 1)} Ratio (weight) 10:0 9:1 8:2 7:3 6:4 5:5 4:6 3:7 2:8 1:9 0:10 Apparent density (kg/m ³ ) 36 37 36 36 37 37 37 37 37 39 39 Absorption (g/100cm ² ) 3.2 1.8 1.3 1.5 1.5 1.4 1.5 1.5 2.5 3.2 3.0 Compressive strength (N/cm ² ) 9 11 15 17 18 17 17 15 19 20 20 Flexural fracture load (N) 25 39 40 38 75 77 86 89 80 85 88 Thermal conductivity (20℃, W/(m.K)) 0.023 0.023 0.023 0.022 0.022 0.022 0.022 0.023 0.025 0.035 0.043

Note) tDCE: trans-1,2-dichlorethylene

1-CP: 1-chloropropane

chloroalkane (Carbon number = 2-3, Cl number = 1-2)

manufacturing example 12 13 14 15 16 comparative example 1-1 1-2 1-3 2-1 2-2 tDCE/365mfc ^{Note 2)} Ratio (weight) 4:6 5:5 6:4 - - tDCE/MF ^{Note 2)} Ratio (weight) - - - 5:5 6:4 Apparent density (kg/m ³ ) 36 37 36 36 37 Absorption (g/100cm ² ) 1.2 1.1 1.2 1.1 1.1 Compressive strength (N/cm ² ) 6 12 8 8 6 Flexural strength (N/cm ² ) 12 13 11 12 12 Thermal conductivity (20℃ , W/(mK)) 0.031 0.033 0.033 0.033 0.035

Note 2) HFC-365mfc: 1,1,1,3,3-pentafluorobutane

MF: methyl formate

The polyurethane foam produced using the polyurethane foaming agent composition according to the present invention has a thermal conductivity of 0.023 W/m·K or less, an absorption of 3.0 g/100cm ² or less, a flexural breaking load of 25 N or more, and a compressive strength of 10 N/ cm ² or more, has the effect of meeting the rigid urethane foam insulation standard (KS M 3809).

As described above in detail a specific part of the content of the present invention, for those of ordinary skill in the art, it is clear that this specific description is only a preferred embodiment, and the scope of the present invention is not limited thereby. will be. Accordingly, it is intended that the substantial scope of the invention be defined by the claims and their equivalents.

Claims (7)

A polyurethane foaming agent composition comprising dichloroethylene and chloroalkane.
The polyurethane foaming agent composition according to claim 1, wherein the dichloroethylene is trans-1,2-dichloroethylene.
The method according to claim 1, wherein the chloroalkane is C _x H _y Cl _z (wherein x=2 or 3, y=an integer of 4 to 7, z=1 or 2, provided that when x=2, y+z= 6, and when x = 3, y + z = 8) Polyurethane foaming agent composition, characterized in that represented by the formula.
4. The method of claim 3, wherein the chloroalkane is chloroethane, 1-chloropropane, 2-chloropropane, 1,1-dichloroethane, 1,2-dichloroethane, 1,1-dichloropropane, 1,2-dichloropropane and 1,3-dichloropropane (1 ,3-dichloropropane) polyurethane foaming agent composition, characterized in that at least one selected from the group consisting of.
The polyurethane foaming agent composition according to claim 1, comprising 30 to 90% by weight of dichloroethylene and 10 to 70% by weight of chloroalkane.
A method for producing a polyurethane foam comprising the steps of:
(a) preparing a first liquid comprising a polyol, a reaction catalyst, a silicone-based surfactant, trichloropropyl phosphate, and the polyurethane foaming agent composition of any one of claims 1 to 5;
(b) mixing a second liquid containing polyisocyanate in the same weight as the first liquid; and
(c) reacting a mixture of the first liquid and the second liquid to prepare a polyurethane foam.
The method according to claim 6, wherein the polyurethane foam has a thermal conductivity of more than 0.018 and 0.023 W/m·K or less, an absorption of more than 0 and 3.0 g/100cm ² or less, a flexural failure load of more than 25 N and 100 N or less, and a compressive strength of more than 10. 20 N/cm ² Method for producing a polyurethane foam, characterized in that less than.