WO2019066504A2 - Thermosetting foam and manufacturing method therefor - Google Patents

Abstract

Provided are a thermosetting foam and a manufacturing method therefor, the thermosetting foam being obtained by foaming and curing of a foamable composition containing: a phenolic resin; a foaming agent comprising a hydrofluoroolefin (HFO)-based compound and a hydrocarbon-based compound; and a non-ionic surfactant having a hydrophile-lipophile balance (HLB) of 12-17.

Description

Thermosetting foams and methods for their preparation

Thermosetting foams and processes for their preparation.

BACKGROUND ART [0002] Thermosetting foams are foamed or foamed foams formed by foaming and thermosetting a foamed composition, and are widely used as heat insulation materials because of their excellent properties such as heat insulation and sound absorption properties.

Such thermosetting foams may vary in physical properties depending on the kinds of main resins, foaming agents, surfactants, and other additives contained in the foam composition, and their respective contents. For example, polyurethane foams, polyisocyanurate foams, Phenol-based foams and the like.

As the foaming agent used in the production of the thermosetting foams, the freon series has been mainly used. However, in recent years, hydrofluoroolefin foams or hydrocarbon series foams having a low ozone layer destruction index and warming coefficient are important.

In one embodiment of the present invention, there is provided a thermosetting foam that has a sufficient and uniform thickness, yet exhibits excellent heat insulation and excellent environmental friendliness.

In another embodiment of the present invention, there is provided a process for producing a thermosetting foam which has a sufficient and uniform thickness, yet exhibits excellent heat insulation and good environment friendliness.

However, the technical problem to be solved by the present invention is not limited to the above-mentioned problems, and other matters not mentioned can be clearly understood by those skilled in the art from the following description.

The present invention provides, in one embodiment, a composition comprising a phenolic resin; A foaming agent comprising a hydrofluoroolefin (HFO) -based compound and a hydrocarbon-based compound; And a nonionic surfactant having a Hydrophile-Lipophile Balance (HLB) of 12 to 17. The thermosetting foam is a foamed cured product of the foamable composition.

In another embodiment of the present invention, a phenolic resin; A hydrofluoroolefin (HFO) -based compound and a hydrocarbon-based compound as a blowing agent; And a nonionic surfactant having a Hydrophile-Lipophile Balance (HLB) of 12 to 17, to prepare a foamable composition; And foaming and curing the foamable composition to produce a thermosetting foam; Wherein the thermosetting foam comprises a thermosetting foam.

The thermosetting foam and the method for producing the same are capable of realizing excellent heat insulation and excellent environment friendliness while having a sufficient and uniform thickness.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram showing a method for measuring the thickness deviation of the thermosetting foam of the present invention.

In the present specification, it is to be understood that when certain embodiments and / or certain components included therein are referred to as " comprising ", it is understood that they do not exclude other components, It can mean that it can include more.

In this specification, the formation or positioning of an arbitrary structure on the top (or bottom) of the substrate or on the top (or bottom) of the substrate means that any configuration is formed or located in contact with the top surface But is not limited to not including other configurations between the substrate and any structure formed on (or under) the substrate.

As used herein, the term " step " or " step " does not mean " step for.

As used herein, the terms "about", "substantially", and the like are used herein to refer to the manufacturing and material tolerances inherent in the meaning referred to, Accurate or absolute numbers may be used to help prevent unauthorized exploitation by unauthorized intruders of the referenced disclosure.

Hereinafter, exemplary embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. It should be understood, however, that the present invention may be embodied in many different forms and should not be construed as limited to the exemplary embodiments set forth herein.

In one embodiment of the present invention, a phenolic resin; A foaming agent comprising a hydrofluoroolefin (HFO) -based compound and a hydrocarbon-based compound; And a nonionic surfactant having a Hydrophile-Lipophile Balance (HLB) of 12 to 17. The thermosetting foam is a foamed cured product of the foamable composition.

In general, the foaming agent used in the production of thermosetting foams is predominantly freon-based, but in recent years, hydrofluoroolefin foams or hydrocarbon-based foams having a low ozone layer destruction index and a low warming coefficient .

However, when a hydrofluoroolefin-based blowing agent is used alone, its volatility is so high that the foaming agent is low at the initial stage of foaming due to the loss of the foaming agent, so that the foaming composition containing the foaming agent is sufficiently foamed There is a problem that is difficult to be done.

Accordingly, in one embodiment, the foamable composition forming the thermosetting foam simultaneously contains a hydrofluoroolefin compound and a hydrocarbon compound as a foaming agent, and the content of the hydrofluoroolefin compound and the hydrocarbon compound is controlled so that the thermosetting foam is formed to a sufficient and uniform thickness There is an advantage to be able to.

At the same time, excellent thermal conductivity and excellent environment friendliness can be realized.

The foamable composition comprises a phenolic resin.

The phenolic resin can be obtained, for example, by reacting phenol and formaldehyde, and can also be, for example, a resol-based phenolic resin.

The phenolic resin may comprise from about 30% to about 90% by weight.

By including it in the content within the above range, excellent foam resistance can be realized while stably forming the foamed cell. Specifically, when the content is less than about 30% by weight, it is difficult to form an independent cell and the flame retardancy is deteriorated. When the content exceeds about 90% by weight, the ratio of other additives is inevitably lowered, have.

The phenolic resin can be, for example, from about 1,000 cps to about 30,000 cps, and more specifically from about 3,000 cps to about 5,000 cps, at a temperature of 40 ° C. The viscosity can be measured using, for example, a Brookfield viscometer.

By having the viscosity within the above range, the foaming power is appropriately controlled to form a closed cell at a good level, and the thickness of the thermosetting foam can be formed sufficiently and uniformly. Specifically, if the viscosity is too low or the viscosity is too low, the loss of the foaming gas may occur at the initial stage of foaming and the thermal conductivity may be lowered after the completion of production. When the viscosity is too high, the foaming rate is slower than the curing rate The thickness of the foam can not be formed to a sufficient level.

In addition, the phenolic resin may have a moisture content of about 5% by weight or more, specifically about 5% by weight to about 20% by weight. More specifically from about 6% to about 15% by weight. The water content can be measured by the Karl Fischer titration method. By having a water content in the above range, excellent workability and excellent heat insulating property can be realized. Specifically, if the moisture content is out of the above-mentioned moisture content range and the moisture content is too low, it is difficult to smoothly mix with other components of the foamable composition and is difficult to control in the process. If the moisture content is too high, the adhesiveness of the foam decreases, , It may be difficult to adhere firmly by, for example, a surface material or the like by a lamination method.

In addition, the phenolic resin may not contain a urea bond. Accordingly, moisture generated by the urea-formaldehyde reaction may not be generated in the polymerization process of the phenolic resin, so that the viscosity and moisture of the foamable composition can be easily controlled.

Further, the foamable composition includes two kinds of blowing agents, specifically, a hydrofluoroolefin (HFO) -based compound and a hydrocarbon-based compound as a blowing agent.

As described above, the thermosetting foam can be formed to have a sufficient and uniform thickness by simultaneously containing the hydrofluoroolefin-based compound and the hydrocarbon-based compound and adjusting the content thereof.

The hydrofluoroolefin-based compound may include, for example, a chlorinated hydrofluoroolefin-based compound, a non-chlorinated hydrofluoroolefin-based compound, or both of them.

The hydrofluoroolefin compound may be selected from the group consisting of trans CF3CH = CClH (1233zdE), cis CF3CH = CClH (1233zdZ), trans CHF2CF = CClH CHF2CF = CClH (1233ydZ), trans CHF2CH = CClF (1233zbE), cis CHF2CH = CClF 1233zbZ, trans CHF2CCl = CHF 1233xeE, cis CHF2CCl = CHF 1233xeZ, CH2FCCl = CF2 1233xc, trans CHFClCF = CFH (1233yeE), cis CHFClCF = CFH (1233yeZ), CH2ClCF = CF2 (1233yc), CF2ClCF = CH2 (1233xf); Trifluoropropenes such as CHF ₂ CF = CH ₂ , CH ₃ CF═CF ₂ , CH ₂ FCF = CF ₂ , CH ₂ FCH = CF ₂ , CHF ₂ CH = CHF; 1,2,3,3-tetrafluoro-1-propene, 2,3,3,3-tetrafluoro-1-propene, 1,3,3,3-tetrafluoro-1-propene , 1,1,2,3-tetrafluoro-1-propene, 1,1,3,3-tetrafluoro-1-propene, 1,2,3,3-tetrafluoro-1- Tetrafluoropropene such as pen; 1,2,3,3,3-pentafluoro-1-propene, 1,1,3,3,3-pentafluoro-1-propene, 1,1,2,3,3-pentafluoro Pentafluoropropene such as 1-propene; Hexafluoro-1-butene, 1,1,1,4,4,4-hexafluoro-2-butene, 1,3,3,4,4,4- Hexafluoro-1-butene, 1,2,3,4,4,4-hexafluoro-1-butene, 1,2,3,3,4,4-hexafluoro-1-butene 1 , 1,2,3,4,4-hexafluoro-2-butene, 1,1,1,2,3,4-hexafluoro-2-butene, 1,1,1,2,3,3 -Hexafluoro-2-butene, 1,1,1,3,4,4-hexafluoro-2-butene, 1,1,2,3,3,4-hexafluoro-1-butene, etc. Hexafluorobutene, hexafluorobutene, hexafluorobutene, and combinations thereof.

In addition, the hydrocarbon-based compound may include one to five hydrocarbons, and may include, for example, a chlorinated hydrocarbon compound, a non-chlorinated hydrocarbon compound, or both.

The hydrocarbon-based compound may be at least one selected from the group consisting of dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride, n-butane, isobutane, n-pentane, isopentane, cyclopentane, But it is not limited thereto.

Specifically, the foaming agent may be a mixture of trifluoropropene and a hydrocarbon-based compound or hexafluorobutene and a hydrocarbon-based compound. For example, the blowing agent may be a hydrofluoroolefin compound such as HFO-1233zdE, 1,1,1,4,4,4-hexafluoro-2-butene (1,1,1,4,4,4- hexafluoro-2-butene), and combinations thereof. Hydrocarbon compounds such as n-pentane, cyclopentane, isopentane, and combinations thereof may be used in combination. The thermosetting foam comprising the blowing agent may exhibit a sufficient and uniform thickness.

The foamable composition may include about 5 to about 15 parts by weight of the blowing agent based on about 100 parts by weight of the phenolic resin.

By limiting the total content of the foaming agent to the above range, the foaming power can be controlled so that the thermosetting foam can have a stable cell structure while realizing its excellent strength.

The foaming agent may contain the hydrofluoroolefin compound and the hydrocarbon compound in an equivalent amount or may contain the hydrofluoroolefin compound in a larger amount. For example, the hydrofluoroolefin compound The weight ratio of the hydrocarbon compound may be about 1: 0.01 to about 1: 1, and more specifically about 1: 0.1 to about 1: 0.7.

The thickness of the thermosetting foam can be sufficiently and uniformly included by the weight ratio within the above range. Specifically, when the amount of the hydrofluoroolefin compound is too much or the hydrocarbon compound is too small, the loss of the foaming agent at the early stage of foaming is large and the foaming power is low and the thickness of the thermosetting foam is thin And there is a problem that the thickness deviation may be large. When the hydrofluoroolefin compound contains too little or too much hydrocarbon compound, the cell structure of the thermosetting foam is unstable There is a problem that thermal conductivity and strength may be lowered.

The foamable composition includes a nonionic surfactant having a Hydrophile-Lipophile Balance (HLB) of 12 to 17, and preferably the HLB of the nonionic surfactant may be 13 to 16.

The HLB is a numerical value indicating the degree of affinity of the surfactant for water and oil, which is a concept proposed by Wallace Griffin of Atlas Powder Company. It is from 0 to 20, and the closer to 0 the lipophilicity is, Big.

By having the HLB value within the above range, it is possible to stably and uniformly form the foamed cells, while achieving excellent strength and excellent thermal conductivity. The interface can be stabilized in the process of growing the foamed cell to stably and uniformly form it, and the strength and thermal conductivity can be formed at a good level. Specifically, when the HLB is less than 12, there is a problem that the interface can not be stabilized so that the foamed cells can not be blown or uniformly grown. When the HLB is more than 17, it is present in a high viscosity or solid state at room temperature, so that it is difficult to apply in the process and the hydrophilic property rapidly increases, so that the hydrophobic blowing agent can not be dispersed in the phenol resin.

Examples of the nonionic surfactant include glyceryl trinitolate ethylene oxide adduct to which an alkylene oxide is added to castor oil, that is, a castor oil ethylene oxide adduct, polyoxyalkylene sorbitan alkyl ester polyoxyalkylene sorbitan alkyl ester A polyoxyalkylene alkyl ester, a polyalkylsiloxane-based silicone surfactant, a polydimethylsiloxane-polyoxyalkylene copolymer, and a combination of these.

 The nonionic surfactant may have different HLB values depending on the molecular structure of the hydrophobic part, the length and the distribution of the repeating structure of the hydrophilic part. Specifically, the nonionic surfactant includes a castor oil ethylene oxide adduct having an HLB of 12 to 17, and has a sufficient and uniform thickness, and can exhibit excellent heat insulation, compressive strength, and excellent environmental friendliness. More specifically, the nonionic surfactant may not include, for example, block copolymers of ethylene oxide-propylene oxide and polyoxyethylene dodecylphenyl ether. The block copolymer of ethylene oxide-propylene oxide and the polyoxyethylene dodecylphenyl ether are difficult to form a stable interface between the phenol resin and the foaming agent, so that the foaming cells are bonded to each other or burst when they are foamed, and the thermal conductivity of the final foam is deteriorated And shrinkage of the foam.

The surfactant may be included in an amount of about 1 part by weight to about 20 parts by weight based on 100 parts by weight of the phenolic resin.

By including it as a weight portion within the above range, the components in the foamable composition can be easily dispersed, and the foam structure of the thermosetting foam can be sufficiently and stably formed to realize excellent thermal conductivity and excellent physical strength.

The foamable composition may further include at least one selected from the group consisting of a flame retardant, a plasticizer, a neutralizing agent, and a combination thereof as a curing agent, a solvent, and other additives.

The curing agent may include, but is not limited to, at least one member selected from the group including, for example, acid anhydride compounds, inorganic acid compounds or organic acid compounds, isocyanate compounds, and combinations thereof.

And about 5 parts by weight to about 30 parts by weight of the curing agent relative to about 100 parts by weight of the phenolic resin.

The foamable composition can be foamed and cured to obtain the thermosetting foam.

The average thickness of the thermosetting foam can be from about 70 mm to about 300 mm.

The thermosetting foam has an average thickness within the above range, so that a sufficient level of heat insulation can be realized without excessively increasing the total thickness of the building insulation including it.

Specifically, when the average thickness is less than about 70 mm, there is a problem that the pressure is excessively generated at the time of foaming and the thickness deviation can not be adjusted. To lower the foaming agent content, a thermal conductivity of 0.0184 W / mK can not be secured , And when it is more than about 300 mm, the growth rate of the foamed cells varies between the upper end, the lower end, and the lower end in the growth process of the foamed material, thereby causing cracks.

Also, the thickness variation according to the following equation 1 of the thermosetting foam may be less than about 5%, and specifically about 0.1% to about 5%:

[Equation 1]

Thickness deviation (T _d ,%) = (T _max - T _min ) / T _avg X 100

In Equation 1, T _max means the maximum thickness measured for the foam to be measured, T _min means the minimum thickness measured for the foam, T _avg means the minimum thickness measured for the foam Means an average thickness.

By having the thickness deviation within the above range, the thermosetting foam can be formed with a more uniform thickness, and the long-term heat insulation property can be improved more effectively, and the product can be further improved in workability and workability when applied to a predetermined product.

As described above, the thermosetting foam can be prepared by suitably controlling the viscosity of the phenolic resin, the kind and content of the foaming agent, or the HLB of the nonionic surfactant to thereby make the thermosetting foam sufficiently thick and uniform Workability and workability can be improved while realizing heat insulation.

Also, the thermosetting foam may have a thermal conductivity of 0.0184 W / mK or less measured at a temperature of about 20 캜 and a thickness of about 50 mm, and specifically about 0.0165 W / mK to about 0.0184 W / mK .

There is a possibility that the thermal conductivity measured in the thickness direction generally decreases as the thickness of the foam increases.

As described above, the thermosetting foam has an advantage of being able to maintain excellent heat insulation because it has a sufficiently thick thickness and does not lower its thermal conductivity.

In addition, the thermosetting foam may have a density of from about 20 kg / m ³ to about 50 kg / m ³ . By having a density within the above range, the thermosetting foam can realize excellent strength and excellent heat insulating property.

The thermosetting foam can be applied, for example, to the use of a thermal insulation material for construction, thereby satisfying both the thermal conductivity and the thermal insulation required for a building thermal insulation material, while achieving excellent environmental friendliness.

For example, the building insulation may further include a surface material on one or both surfaces of the thermosetting foam, and the surface material may be of a kind known in the art, for example, an organic or inorganic- , Non-woven fabric, cloth, metal foil such as aluminum, paper, and the like.

In another embodiment of the present invention, a phenolic resin; A hydrofluoroolefin (HFO) -based compound and a hydrocarbon-based compound as a blowing agent; And a nonionic surfactant having a Hydrophile-Lipophile Balance (HLB) of 12 to 17, to prepare a foamable composition; And foaming and curing the foamable composition to form a thermosetting foam. The present invention also provides a method for producing a thermosetting foam. The thermosetting foams described above in one embodiment can be prepared by the above process.

In the above production process, a phenolic resin; A hydrofluoroolefin (HFO) -based compound and a hydrocarbon-based compound as a blowing agent; And a nonionic surfactant having a Hydrophile-Lipophile Balance (HLB) of 12 to 17 may be mixed to prepare a foamable composition, as described above in an embodiment.

In the step of preparing the foamable composition, the phenolic resin may be mixed in the foamable composition in an amount of about 30% by weight to about 90% by weight.

Also, a phenolic resin having a viscosity of about 1,000 cps to about 30,000 cps under a temperature condition of 40 can be mixed.

By mixing a phenolic resin having a viscosity within the above range, the foaming power is appropriately controlled, and excellent processability is realized, so that the thickness of the thermosetting foam can be formed to a sufficient and uniform level. Specifically, if the viscosity is too low or the viscosity is too low, the loss of the foaming gas may occur at the initial stage of foaming and the thermal conductivity may be lowered after the completion of production. When the viscosity is too high, the foaming rate is slower than the curing rate The thickness of the foam can not be formed to a sufficient level.

In the preparation of the foamable composition, the total amount of the foaming agent may be about 5 parts by weight to about 15 parts by weight based on about 100 parts by weight of the phenolic resin.

By adjusting the foaming power by mixing the total amount of the foaming agent to the above range, the thermosetting foam can have a stable cell structure while realizing its excellent strength.

As the foaming agent, the weight ratio of the hydrofluoroolefin compound to the hydrocarbon compound may be in the range of about 1: 0.01 to about 1: 1, and specifically about 1: 0.1 to 1: They can be mixed so as to have a weight ratio of about 1: 0.7.

By mixing at a weight ratio within the above range, the thickness of the thermosetting foam can be realized to a sufficient and uniform level. Specifically, when the amount of the hydrofluoroolefin compound is too much or the hydrocarbon compound is too small, the loss of the foaming agent at the early stage of foaming is large and the foaming power is low and the thickness of the thermosetting foam is thin If the hydrofluoroolefin compound contains too little or too much of the hydrocarbon compound, the cell structure of the thermosetting foam may become unstable and the strength may be lowered there is a problem.

In the preparation of the foamable composition, the surfactant may be mixed in an amount of about 1 part by weight to about 20 parts by weight based on 100 parts by weight of the phenolic resin.

The components in the foamable composition can be easily dispersed by mixing the surfactant in a weight portion within the range, and the foam structure of the thermosetting foam can be sufficiently and stably formed.

Specifically, a nonionic surfactant having an HLB of about 13 to about 15 can be mixed. Further, the foamable composition may be prepared by further mixing at least one selected from the group consisting of a flame retardant, a plasticizer, a neutralizer and a combination thereof as a curing agent, a solvent and other additives.

In the above production method, the foamable composition can be foamed and cured to produce a thermosetting foam.

The foamable composition is simultaneously foamed and cured, and either the foamed or the cured foam may be initiated at the same time, or they may be simultaneously initiated.

The foaming and curing may be performed, for example, at a temperature of from about 50 to about 90 ° C.

In addition, the foaming and curing may be performed for a time of about 2 minutes to about 20 minutes, but it is not limited thereto, and may be suitably varied according to the purpose and use of the invention.

The foamable composition may be foamed and cured, for example, but not limited to, foamed and cured in a predetermined mold or foamed and cured while being injected or discharged between, for example, both surfaces.

In the step of preparing the thermosetting foam, the thermosetting foam may have an average thickness of 70 mm to 300 mm.

The thermosetting foam is formed with an average thickness within the above range, so that a sufficient level of heat insulation can be realized without excessively increasing the total thickness of the building insulation material containing the foam. Specifically, when the average thickness is less than about 70 mm, there is a problem that the pressure is excessively generated at the time of foaming and the thickness deviation can not be adjusted. To lower the foaming agent content, a thermal conductivity of 0.0184 W / mK can not be secured , And when it is more than about 300 mm, the growth rate of the foamed cells varies between the upper end, the lower end, and the lower end in the growth process of the foamed material, thereby causing cracks. In addition, the thickness variation of the thermosetting foam according to the following equation 1 can be formed to less than about 5%, and specifically about 0.1% to about 5%:

[Equation 1]

Thickness deviation (Td,%) = (T _max - T _min ) / T _avg X 100

In Equation 1, T _max means the maximum thickness measured for the foam to be measured, T _min means the minimum thickness measured for the foam, T _avg means the minimum thickness measured for the foam Means an average thickness.

The thermosetting foam can be formed to have a more uniform thickness by being formed with the thickness deviation within the above range, and the long-term heat insulation property can be improved more effectively thereby, and workability and workability can be further improved when applied to a predetermined product.

As described above, the thermosetting foam can be prepared by suitably controlling the viscosity of the phenolic resin, the kind and content of the foaming agent, or the HLB of the nonionic surfactant to thereby make the thermosetting foam sufficiently thick and uniform The workability and workability can be improved while realizing heat insulation.

In addition, the thermosetting foam may be manufactured such that the thermal conductivity measured in the direction of thickness under the conditions of a temperature of 20 캜 and a thickness of 50 mm is 0.0184 W / mK or less, specifically about 0.0165 W / mK to about 0.0184 W / mK .

As described above, the thermosetting foam is formed to have a sufficiently thick thickness and its thermal conductivity is not lowered, so that there is an advantage that excellent heat insulation can be maintained.

In addition, the thermosetting foam may have a density of from about 20 kg / m ³ to about 50 kg / m ³ . The thermosetting foam can be produced with a density within the above range to realize excellent strength and excellent heat insulation property.

The thermoset foam may also have a compressive strength of from about 110 kPa to about 200 kPa. Or a compressive strength of from about 120 kPa to about 200 kPa or from about 130 kPa to about 200 kPa. By having a compressive strength within the above range, excellent long term durability can be exhibited.

Hereinafter, specific embodiments of the present invention will be described. However, the embodiments described below are only intended to illustrate or explain the present invention, and the present invention should not be limited thereto.

Example

Example  One

A phenol resin having a viscosity of 3,900 cps at a temperature of 40 ° C was prepared at a temperature of 20 ° C. Then, hydrofluoroolefin-based compound HFO-1233zdE and hydrocarbons-based compound n-pentane were added to 100 parts by weight of the phenolic resin : 0.25, and 5 parts by weight of a glyceryl trilinolate ethylene oxide adduct, which is a nonionic surfactant having an HLB (Hydrophile-Lipophile Balance) of 15, were mixed to prepare a foamable composition .

Subsequently, the foamable composition was mixed with 22 parts by weight of a 70% aqueous solution of para-toluenesulfonic acid (PTSA) serving as a curing catalyst at 2000 rpm to form a foam foam, which was then flowed under the caterpillar to produce a thermoset foam foam .

At this time, the caterpillar as the forming mold was set so that the thickness of the thermosetting foamed foam was 90 mm at a line speed of 7 m / min and a temperature of 70 degrees.

Example  2

A thermosetting foamed foam was prepared in the same manner as in Example 1 except that a caterpillar was set so that the thickness of the thermosetting foamed foam was 130 mm and a phenol resin having a viscosity of 3700 cps was used.

Example  3

A thermosetting foamed foam was prepared in the same manner as in Example 1 except that a caterpillar was set so that the thickness of the thermosetting foamed foam was 200 mm and a phenol resin having a viscosity of 3300 cps was used.

Example  4

A thermosetting foamed foam was prepared in the same manner as in Example 3 except that a phenol resin having a viscosity of 5000 cps was used.

Example  5

A thermosetting foamed foam was prepared in the same manner as in Example 1, except that glyceryl trinitolate ethylene oxide adduct, which is a nonionic surfactant having an HLB (Hydrophile-Lipophile Balance) of 12, was used.

Example  6

A thermosetting foamed foam was prepared in the same manner as in Example 1, except that glyceryl trinitolate ethylene oxide adduct, which is a nonionic surfactant having an HLB (Hydrophile-Lipophile Balance) of 17, was used.

Example  7

A thermosetting foamed foam was prepared in the same manner as in Example 1, except that a foaming agent in which a hydrofluoroolefin-based compound, HFO-1233zdE, and a hydrocarbon compound, n-pentane, were mixed in a weight ratio of 1: 0.7.

Example  8

A thermosetting foamed foam was prepared in the same manner as in Example 1, except that a polydimethylsiloxane-polyoxyalkylene copolymer, which is a nonionic surfactant having an HLB (Hydrophile-Lipophile Balance) of 15, was used.

Example  9

A thermosetting foamed foam was prepared in the same manner as in Example 1 except that glyceryl trinitolate ethylene oxide adduct, which is a nonionic surfactant of HLB (Hydrophile-Lipophile Balance) 13, was used.

Example  10

A thermosetting foamed foam was prepared in the same manner as in Example 1, except that glyceryl trirricolate ethylene oxide adduct, which is a nonionic surfactant of HLB (Hydrophile-Lipophile Balance) 16, was used.

Example  11

1,1,1,4,4,4-hexafluoro-2-butene, which is a hydrofluoroolefin compound, and a hydrocarbon compound, A thermosetting foamed foam was prepared in the same manner as in Example 1, except that a blowing agent in which cyclopentane was mixed at a weight ratio of 1: 0.2 was used.

Comparative Example  One

A thermosetting foamed foam was prepared in the same manner as in Example 1 except that the foaming agent containing hydrofluoroolefin-based compound HFO-1233zdE alone was used instead of the hydrocarbon-based compound n-pentane.

Comparative Example  2

A thermosetting foamed foam was prepared in the same manner as in Example 1 except that glyceryl trinitolate ethylene oxide adduct, which is a nonionic surfactant having an HLB (Hydrophile-Lipophile Balance) of 10, was used.

Comparative Example  3

A thermosetting foamed foam was prepared in the same manner as in Example 1 except that glyceryl trinitolate ethylene oxide adduct, which is a nonionic surfactant having an HLB (Hydrophile-Lipophile Balance) of 18, was used.

Comparative Example  4

Except that a surfactant having an HLB (Hydrophile-Lipophile Balance) of 11 (nonionic) was used by mixing a block copolymer of ethylene oxide-propylene oxide and polyoxyethylene dodecylphenyl ether at a ratio of 1: 1. 1, a thermosetting foamed foam was prepared.

The foamable compositions and the thermosetting foamed foam production conditions of the above Examples and Comparative Examples are shown in Table 1 below.

	Caterpillar setting thickness	Surfactant HLB value	Resin viscosity	Foaming agent mixing weight ratio
	(mm)		(cps, 40 < 0 > C)	(HFO: hydrocarbon)
Example 1	90	15	3900	1: 0.25
Example 2	130	15	3700	1: 0.25
Example 3	200	15	3300	1: 0.25
Example 4	200	15	5000	1: 0.25
Example 5	90	12	3900	1: 0.25
Example 6	90	17	3900	1: 0.25
Example 7	90	15	4000	1: 0.7
Example 8	90	15	3900	1: 0.25
Example 9	90	13	3900	1: 0.25
Example 10	90	16	3900	1: 0.25
Example 11	90	15	3900	1: 0.2
Comparative Example 1	90	15	3800	1: 0
Comparative Example 2	90	10	3900	1: 0.25
Comparative Example 3	90	18	3900	1: 0.25
Comparative Example 4	90	11	3900	1: 0.25

Experimental Example

Various properties of the thermosetting foams according to the above Examples and Comparative Examples were evaluated and are shown in Table 2 below.

Assessment Methods

Experimental Example  1: Average thickness and thickness variation

Measuring method: The thermosetting foams of Examples and Comparative Examples were each prepared with a specimen having a size of 600 mm X 600 mm and a thickness corresponding thereto. Then, using a sliding caliper apparatus having a precision of 0.1 mm, the specimen was measured at intervals of 100 mm The thickness of five points was measured. That is, the thicknesses at 20 points on all four sides of the specimen were measured to set T _{avg ,} T _max , T _min , and the thickness deviation was measured according to the following equation (1).

[Equation 1]

Thickness deviation (T _d ,%) = (T _max - T _min ) / T _avg X 100

In Equation 1, T _max denotes a maximum thickness measured on a foam sheet, T _min denotes a measured minimum thickness, and T _avg denotes an average thickness measured.

Experimental Example  2: Thermal conductivity

Measuring method: The thermosetting foams of the examples and comparative examples were cut into a size of 300 mm × 300 mm and a thickness of 50 mm from the top, respectively, and the samples were pre-treated by drying at 70 ° C. for 12 hours. Each of the above specimens was measured using an HC-074-300 (EKO) thermal conductivity instrument at an average temperature of 20 ° C according to the measurement conditions of KS L 9016 (Flat Plate Heater Measurement Method).

Experimental Example  3: Density

Measuring method: The thermosetting foams of Examples and Comparative Examples were each prepared with a specimen having a size of 300 mm x 300 mm and a corresponding thickness, and the mass and volume were measured for each of the specimens, and the density was measured by the method of KS M ISO 845 standard.

Experimental Example  4: Compressive strength

Measuring method: Prepare the thermosetting foams of Examples and Comparative Examples in a size of 100 mm × 100 mm and a corresponding thickness, respectively, and set the specimen between the compression tester plates at a rate of 10% / min of the thickness of the specimen in the UTM equipment. Begin the compressive strength test to record the maximum load reached during the thickness reduction. The compressive strength was measured basically by the method of KS M ISO 845 standard.

	Average thickness	Thickness deviation	Thermal conductivity	density	Compressive strength
	(mm)	(%)	(W / mK)	(kg / m 3 )	(kPa)
Example 1	90.4	1.4	0.0173	37	142
Example 2	130.8	2.3	0.0175	37	135
Example 3	200.2	2.7	0.0179	36	158
Example 4	197.4	3.3	0.0182	39	173
Example 5	90.8	4.4	0.0182	37	118
Example 6	90	4.3	0.0182	37	127
Example 7	90.3	1.7	0.0183	37	136
Example 8	90.7	2.1	0.0177	37	154
Example 9	90.6	2.4	0.0179	37	147
Example 10	90.2	2.9	0.0181	37	143
Example 11	90.4	2.3	0.0181	36	146
Comparative Example 1	88.7	6.9	0.0167	38	124
Comparative Example 2	90.6	2.7	0.0201	37	98
Comparative Example 3	89.7	6.3	0.0189	37	100
Comparative Example 4	88.7	7.1	0.0227	38	100

As shown in Table 2, it can be seen that the embodiment has a thickness variation of less than 5%, has a uniform thickness, has excellent thermal conductivity and compressive strength, while the comparative example has considerably large thickness deviation.

Claims (19)

1. Phenolic resin; A foaming agent comprising a hydrofluoroolefin (HFO) -based compound and a hydrocarbon-based compound; And a nonionic surfactant having a Hydrophile-Lipophile Balance (HLB) of 12 to 17, which is a foamed composition of a foamable composition

   Thermosetting foam.
2. The method according to claim 1,

   Wherein the thermosetting foam has an average thickness of 70 mm to 300 mm

   Thermosetting foam.
3. The method according to claim 1,

   The thermosetting foam has a thickness deviation according to the following equation 1 of less than 5%

   Thermosetting foams:

   [Equation 1]

   Thickness deviation (T _d ,%) = (T _max - T _min ) / T _avg X 100

   In Equation 1, T _max means the maximum thickness measured for the foam to be measured, T _min means the minimum thickness measured for the foam, T _avg means the minimum thickness measured for the foam Means an average thickness.
4. The method according to claim 1,

   The nonionic surfactant has an HLB of 13 to 16

   Thermosetting foam.
5. The method according to claim 1,

   The phenolic resin has a viscosity of from 1,000 cps to 30,000 cps

   Thermosetting foam.
6. The method according to claim 1,

   The phenolic resin preferably contains no urea bond

   Thermosetting foam.
7. The method according to claim 1,

   The phenolic resin has a water content of 5 wt%

   Thermosetting foam.
8. The method according to claim 1,

   Wherein the foaming agent comprises the hydrofluoroolefin compound and the hydrocarbon compound in a weight ratio of 1: 0.01 to 1: 1

   Thermosetting foam.
9. The method according to claim 1,

   Wherein the total amount of the foaming agent is 5 parts by weight to 15 parts by weight relative to 100 parts by weight of the phenolic resin

   Thermosetting foam.
10. The method according to claim 1,

    Wherein the surfactant is contained in an amount of 1 to 20 parts by weight based on 100 parts by weight of the phenolic resin

    Thermosetting foam.
11. The method according to claim 1,

    A thermal conductivity measured in the thickness direction under a condition of a temperature of 20 DEG C and a thickness of 50 mm is 0.0184 W / mK or less

    Thermosetting foam.
12. The method according to claim 1,

    Having a density of 20 kg / m ³ to 50 kg / m ³

    Thermosetting foam.
13. Phenolic resin; A hydrofluoroolefin (HFO) -based compound and a hydrocarbon-based compound as a blowing agent; And a nonionic surfactant having a Hydrophile-Lipophile Balance (HLB) of 12 to 17, to prepare a foamable composition; And

    Foaming and curing the foamable composition to produce a thermosetting foam;

    ≪ / RTI >
14. 14. The method of claim 13,

    In the step of producing the thermosetting foam, the thermosetting foam has an average thickness of 70 to 300 mm

    A method of making a thermosetting foam.
15. 14. The method of claim 13,

    In the step of producing the thermosetting foam, the thickness deviation of the thermosetting foam according to the following equation 1 is formed to be less than 5%

    Method of preparing thermosetting foams:

    [Equation 1]

    Thickness deviation (T _d ,%) = (T _max - T _min ) / T _avg X 100

    In Equation 1, T _max means the maximum thickness measured for the foam to be measured, T _min means the minimum thickness measured for the foam, T _avg means the minimum thickness measured for the foam Means an average thickness.
16. 14. The method of claim 13,

    In the step of preparing the foamable composition, a nonionic surfactant having an HLB of 12 to 17 is mixed

    A method of making a thermosetting foam.
17. 14. The method of claim 13,

    In the step of preparing the foamable composition, a phenolic resin having a viscosity of 1,000 cps to 30,000 cps under a temperature condition of 40 캜 is mixed

    A method of making a thermosetting foam.
18. 14. The method of claim 13,

    In the step of preparing the foamable composition, the weight ratio of the hydrofluoroolefin compound to the hydrocarbon compound is 1: 0.1 to 1: 1,

    A method of making a thermosetting foam.
19. 14. The method of claim 13,

    The thermosetting foam is prepared so that the thermal conductivity measured in the direction of thickness under a condition of a temperature of 20 캜 and a thickness of 50 mm is 0.0184 W / mK or less

    A method of making a thermosetting foam.

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