KR102834348B1 - Organic semi-non-flammable pir spray foam insulation, manufactureing method thereof - Google Patents

Abstract

The present invention relates to an organic semi-fireproof polyisocyanurate (PIR) spray foam insulation and a method for producing the same. Specifically, the present invention relates to a semi-fireproof PIR spray foam insulation made entirely of organic materials without containing inorganic substances and a method for producing the same.

Description

Organic semi-non-flammable PIR spray foam insulation and its manufacturing method {ORGANIC SEMI-NON-FLAMMABLE PIR SPRAY FOAM INSULATION, MANUFACTUREING METHOD THEREOF}

The present invention relates to an organic semi-fireproof polyisocyanurate (PIR) spray foam insulation and a method for producing the same. Specifically, the present invention relates to a semi-fireproof PIR spray foam insulation made entirely of organic materials without containing inorganic substances and a method for producing the same.

Polyurethane spray foam has excellent properties such as insulation (low thermal conductivity), compressive strength, and absorbency (low moisture absorption), and is easy to construct, so it is widely used as insulation material for exterior or interior walls of shipyards and construction sites, and is known as a material for insulation of building panels, panels for cold storage warehouses, and tanks such as LNG and LPG.

Despite these advantages, conventionally used polyurethane spray foam has the problem of being vulnerable to fire due to the flammability, toxic gases emitted in the event of a fire, and continuous combustion caused by flame propagation. Therefore, active research is being conducted to improve the flame retardancy of polyurethane spray foam.

To solve this problem, inorganic mineral perlite is laminated on the upper surface of the polyurethane spray foam, or a polymer coating process with highly flame retardant urea is performed. However, this does not fundamentally provide semi-fire retardant performance to the polyurethane spray foam itself, so the flame retardant effect is limited when a strong flame occurs, and since the construction thickness must be thick, there is a problem that material and work costs increase due to double work.

In addition, inorganic phosphorus compounds such as expanded graphite, aluminum hydroxide, potassium hydroxide, and phosphorus are used to provide semi-flame retardant performance to the polyurethane spray foam core itself. However, when these flame retardant materials in solid powder form are used, it is difficult to uniformly disperse them in the liquid polyol system, so that undispersed solid powder accumulates in the high-pressure spray equipment, causing frequent breakdowns. In addition, there is a problem that the residual amount of the polyol system is large, which increases the cost of waste disposal.

There are also attempts to provide semi-fireproof performance by using bromine-containing polyols, but bromine is harmful to the human body and is prohibited for use in Korea.

Therefore, research is needed to stably secure the semi-fireproof performance of a polyol composition made entirely of organic materials that does not contain inorganic materials such as expanded graphite, aluminum hydroxide, potassium hydroxide, and red chromium, and does not contain bromine, and a polyurethane spray foam core using the same.

Korean Patent Publication No. 10-2022-0118623 A (2022.08.26)

One object of the present invention is to provide a polyurethane organic PIR spray foam that satisfies quasi-fireproof performance with the polyurethane core itself while maintaining the advantages of conventional polyurethane spray foam, such as insulation, compressive strength, absorbency, and easy construction. That is, rather than evaluating quasi-fireproof performance in a state where the foam is formed on a metal plate, etc., the present invention provides a polyurethane organic PIR spray foam that can satisfy quasi-fireproof performance according to the criteria of the cone calorimeter method according to KS F ISO 5660-1.

In addition, the present invention provides a spray foam composition that satisfies semi-fireproof performance despite being made entirely of organic materials and does not contain inorganic materials such as expanded graphite, aluminum hydroxide, potassium hydroxide, or red chromium, and does not contain bromine, and a polyurethane organic PIR spray foam using the same.

In addition, the present invention provides a spray foam composition that satisfies quasi-fireproof performance and exhibits almost no shrinkage even after a quasi-fireproof performance test, and a polyurethane organic PIR spray foam using the same. More specifically, the present invention provides a spray foam composition that prevents flame or heat applied from the upper part of the foam from reaching the lower part of the foam and causing shrinkage in the lower part during a quasi-fireproof performance test according to a cone calorimeter test, and a polyurethane organic PIR spray foam using the same.

Typically, polyurethane foam is manufactured by mixing a polyol composition and an isocyanate compound in a weight ratio of 1:1 using a spray gun. However, this mixing ratio does not satisfy the semi-flammability characteristics according to KS F ISO 5660-1.

Accordingly, in the prior art, there have been attempts to satisfy the semi-fireproof characteristics by using brominated compounds or adding inorganic particles. However, when inorganic particles are included, the particles settle within the composition, making it difficult to disperse them uniformly. Accordingly, there is a problem in that it is difficult to express the semi-fireproof characteristics uniformly over the entire area of the foam. Above all, there is a problem in that when foaming using a spray gun, the particles accumulate within the high-pressure spray equipment, causing a clogging phenomenon.

The present inventors conducted research to develop a combination of a polyol composition and an isocyanate compound that is composed entirely of organic materials without using brominated compounds or inorganic particles, yet is capable of foaming using a spray gun and satisfies semi-non-flammable properties.

To this end, a method was conducted to form a polyisocyanurate (PIR) structure by using a larger amount of isocyanate compound compared to the polyol composition. That is, a study was conducted to provide a spray foaming composition in which an isocyanate compound can be mixed in an amount of 130 to 180 parts by weight, 140 to 170 parts by weight, or 150 to 160 parts by weight with respect to 100 parts by weight of the polyol composition.

As a result, a novel aromatic polyester polyol was developed, and by specifying the mixing ratio of the isocyanate compound and the polyol composition, it was found that the semi-fireproof properties could be satisfied by the cone calorimeter method according to KS F ISO 5660-1 without including inorganic substances, and that no shrinkage occurred in the foam even after performing the semi-fireproof test, thereby completing the present invention.

Specifically, a novel aromatic polyester polyol containing structures derived from phthalic anhydride, terephthalic acid, benzoic acid, trimellitic acid, and adipic acid as polyol components was developed, and by controlling the hydroxyl value (OH value) of these to 100 to 300 mgKOH/g, the content of isocyanate compounds can be further increased for use, thereby forming a polyisocyanurate (PIR) structure. At the same time, it was confirmed that the flame retardancy is excellent despite not containing inorganic substances, and that almost no shrinkage occurs in the foam even after performing a semi-fireproof test.

In addition, the present invention was completed by confirming that when the aromatic polyester polyol is mixed with an organic phosphorus flame retardant of a specific component, even more excellent semi-flame retardant properties can be satisfied.

One aspect of the present invention is a foam foam prepared by foaming a spray foam composition in which 130 to 180 parts by weight of an isocyanate compound is mixed with 100 parts by weight of a polyol composition comprising an organic substance including an aromatic polyester polyol, a blowing agent, an organic flame retardant, a catalyst, and a foam stabilizer,

The above aromatic polyester polyol comprises a structure derived from phthalic anhydride, terephthalic acid, benzoic acid, trimellitic acid and adipic acid, and has a hydroxyl value (OH value) of 100 to 300 mgKOH/g.

The above polyol composition provides an organic semi-combustible PIR spray foam insulation having a viscosity measured at 20° C. of 100 to 600 cps.

In one embodiment, the organic semi-combustible PIR spray foam insulation satisfies the semi-combustible characteristics according to the cone calorimeter method according to KS F ISO 5660-1, and satisfies the shrinkage ratio of the foam of 20% or less after the semi-combustible evaluation according to KS F ISO 5660-1.

In one aspect, the aromatic polyester polyol

A first polyol produced by reacting phthalic anhydride, terephthalic acid and benzoic acid as acid components and diethylene glycol and triethylene glycol as glycol components;

A second polyol in which phthalic anhydride and adipic acid are reacted as acid components and diethylene glycol is reacted as a glycol component; and

A third polyol produced by reacting phthalic anhydride, terephthalic acid and trimellitic acid as acid components and trimethylolpropane and diethylene glycol as glycol components;

It may be a mixture of .

In one embodiment, the first polyol has an acid value of 1.0 or less, a hydroxyl value of 130 mgKOH/g or less, and a viscosity measured at 25°C of 25,000 to 35,000 cps,

The above second polyol has an acid value of 2.0 or less, a hydroxyl value of 95 mgKOH/g or less, and a viscosity measured at 25°C of 5,000 to 7,000 cps.

The above third polyol may have an acid value of 1.0 or less, a hydroxyl value of 300 mgKOH/g or less, and a viscosity measured at 25°C of 9,000 to 12,000 cps, but is not limited thereto.

In one embodiment, the mixing ratio of the first polyol: the second polyol: the third polyol may be 30 to 40:25 to 35:30 to 40 by weight.

In one embodiment, the aromatic polyester polyol may have a hydroxyl value (OH value) of 100 to 300 mgKOH/g and a viscosity measured at 25°C of 10,000 to 20,000 cps, in a state where the first polyol, the second polyol, and the third polyol are mixed, but is not limited thereto.

In one embodiment, the polyol composition may include, but is not limited to, 45 to 60 wt% of an aromatic polyester polyol, 15 to 25 wt% of a blowing agent, 15 to 30 wt% of an organic flame retardant, 5 to 15 wt% of a catalyst, and 0.2 to 1 wt% of a foaming agent.

In one embodiment, the organic flame retardant may include one selected from dimethyl methylphosphonate and triethyl phosphate (TEP) or a mixture thereof.

In one embodiment, the organic flame retardant is a mixture of dimethyl methyl phosphonate (DMMP) and tris(1-chloro-2-propyl) phosphate (TCPP), or a mixture of dimethyl methyl phosphonate (DMMP), triethyl phosphate (TEP), and tris(1-chloro-2-propyl) phosphate (TCPP), and the content of dimethyl methyl phosphonate (DMMP) may be 50 wt% or more of the total content of the organic flame retardant.

In one embodiment, the isocyanate compound may include 4,4'-MDI, 2,4'-MDI and 2,2'-MDI, and may have an NCO content of 25 to 35%, an average number of functional groups of 2 to 3, and a viscosity measured at 25° C. of 100 to 400 cps.

In one embodiment, the blowing agent may be any one or a mixture of two or more selected from a chemical blowing agent selected from water, azodicarbonamide, azobisisobutyronitrile, diazoaminoazobenzene, N,N'-dinitro-sopentamethylenetetramine p-toluenesulfonylhydrazide, and p,p'-oxybis(benzenesulfonylhydrazide) p-toluene-sulfonylsemicarba, and sodium dicarbonate; and a physical blowing agent selected from a hydrocarbon blowing agent, a hydrochlorofluorocarbon (HCFCs) blowing agent, a hydrofluorocarbon (HFC) blowing agent, and a hydrofluoroolefin (HFO) blowing agent, but is not limited thereto.

In one embodiment, the surfactant may be a silicone-based surfactant.

Another aspect of the present invention comprises the steps of preparing a polyol composition comprising an aromatic polyester polyol having a structure derived from phthalic anhydride, terephthalic acid, benzoic acid, trimellitic acid and adipic acid and having an OH value of 100 to 300 mgKOH/g, a blowing agent, an organic flame retardant, a catalyst and a foaming agent, and comprising an organic substance and having a viscosity measured at 20°C of 100 to 600 cps;

A step of foaming by mixing 130 to 180 parts by weight of an isocyanate compound with respect to 100 parts by weight of the above polyol composition;

A method for manufacturing an organic semi-combustible PIR spray foam insulation material including:

In one embodiment, the organic semi-combustible PIR spray foam insulation satisfies the semi-combustible characteristics according to the cone calorimeter method according to KS F ISO 5660-1, and the shrinkage ratio of the foam may be 20% or less after the semi-combustible evaluation according to KS F ISO 5660-1.

In one embodiment, the polyol composition may include, but is not limited to, 45 to 60 wt% of an aromatic polyester polyol, 15 to 25 wt% of a blowing agent, 15 to 30 wt% of an organic flame retardant, 5 to 15 wt% of a catalyst, and 0.2 to 1 wt% of a foaming agent.

In one embodiment, the organic flame retardant may include, but is not limited to, one selected from dimethyl methylphosphonate and triethyl phosphate (TEP) or a mixture thereof.

In one embodiment, the organic flame retardant is a mixture of dimethylmethylphosphonate (DMMP) and tris(1-chloro-2-propyl)phosphate (TCPP), or a mixture of dimethylmethylphosphonate (DMMP), triethylphosphate (TEP), and tris(1-chloro-2-propyl)phosphate (TCPP).

The content of dimethyl methyl phosphonate (DMMP) among the total content of organic flame retardants may be 50 wt% or more.

In one embodiment, the isocyanate compound may include 4,4'-MDI, 2,4'-MDI and 2,2'-MDI, and may have an NCO content of 25 to 35%, an average number of functional groups of 2 to 3, and a viscosity measured at 25° C. of 100 to 400 cps.

In one embodiment, the mixing and foaming step may be performed using spray equipment.

Another aspect of the present invention comprises a polyol composition comprising an aromatic polyester polyol having a structure derived from phthalic anhydride, terephthalic acid, benzoic acid, trimellitic acid and adipic acid, having an OH value of 100 to 300 mgKOH/g, an organic substance including a blowing agent, an organic flame retardant, a catalyst and a foaming agent, and having a viscosity measured at 20° C. of 100 to 600 cps; and an isocyanate compound,

A spray foaming composition is provided, wherein 130 to 180 parts by weight of an isocyanate compound is mixed with 100 parts by weight of the above polyol composition.

In one aspect, the aromatic polyester polyol

A first polyol produced by reacting phthalic anhydride, terephthalic acid and benzoic acid as acid components and diethylene glycol and triethylene glycol as glycol components;

A second polyol in which phthalic anhydride and adipic acid are reacted as acid components and diethylene glycol is reacted as a glycol component; and

A third polyol produced by reacting phthalic anhydride, terephthalic acid and trimellitic acid as acid components and trimethylolpropane and diethylene glycol as glycol components;

It may be a mixture of .

In one embodiment, the first polyol has an acid value of 1.0 or less, a hydroxyl value of 130 mgKOH/g or less, and a viscosity measured at 25°C of 25,000 to 35,000 cps,

The above second polyol has an acid value of 2.0 or less, a hydroxyl value of 95 mgKOH/g or less, and a viscosity measured at 25°C of 5,000 to 7,000 cps.

The above third polyol may have an acid value of 1.0 or less, a hydroxyl value of 300 mgKOH/g or less, and a viscosity measured at 25°C of 9,000 to 12,000 cps.

In one embodiment, the mixing ratio of the first polyol: the second polyol: the third polyol may be 30 to 40:25 to 35:30 to 40 by weight.

In one embodiment, the aromatic polyester polyol may have a hydroxyl value (OH value) of 100 to 300 mgKOH/g and a viscosity measured at 25°C of 10,000 to 20,000 cps, in a state where the first polyol, the second polyol, and the third polyol are mixed, but is not limited thereto.

In one embodiment, the polyol composition may include, but is not limited to, 45 to 60 wt% of an aromatic polyester polyol, 15 to 25 wt% of a blowing agent, 15 to 30 wt% of an organic flame retardant, 5 to 15 wt% of a catalyst, and 0.2 to 1 wt% of a foaming agent.

In one embodiment, the organic flame retardant may include, but is not limited to, one selected from dimethyl methylphosphonate and tris(1-chloro-2-propyl)phosphate (TCPP) or triethylphosphate (TEP), or a mixture thereof.

In one embodiment, the organic flame retardant is a mixture of dimethyl methyl phosphonate (DMMP) and tris(1-chloro-2-propyl) phosphate (TCPP), or a mixture of dimethyl methyl phosphonate (DMMP), triethyl phosphate (TEP), and tris(1-chloro-2-propyl) phosphate (TCPP), and the content of dimethyl methyl phosphonate (DMMP) may be 50 wt% or more of the total content of the organic flame retardant.

In one embodiment, the isocyanate compound may include 4,4'-MDI, 2,4'-MDI and 2,2'-MDI, and may have an NCO content of 25 to 35%, an average number of functional groups of 2 to 3, and a viscosity measured at 25° C. of 100 to 400 cps.

In one embodiment, the surfactant may be a silicone-based surfactant.

An organic semi-fireproof PIR spray foam manufactured using a spray foaming composition according to one embodiment of the present invention maintains excellent properties such as conventional insulation, compressive strength, and absorbency, while having semi-fireproof performance as the core material itself, and can secure improved workability by using an organic material rather than an inorganic material.

In addition, the organic semi-combustible PIR spray foam according to one embodiment of the present invention satisfies the KS M 3809 Type 1 No. 2 standard.

In addition, even after evaluating the semi-fireproof characteristics by the cone calorimeter method according to KS F ISO 5660-1, it can provide an excellent effect with a shrinkage rate of 20% or less, 10% or less, 5% or less, or virtually no shrinkage.

In addition, the polyurethane spray foam manufactured according to the present invention can provide excellent flame retardancy satisfying semi-flame retardancy performance due to strong carbonization protection and subsequent flame penetration prevention.

In addition, the spray foaming composition according to one aspect of the present invention can be applied not only to spray foaming using a high-pressure foaming nozzle, but also to general polyurethane foam foaming methods, i.e., a two-component foaming method using an injection molding machine, a low-pressure foaming method, etc.

Figure 1 is a photograph showing the evaluation of the semi-fireproof characteristics using an organic semi-fireproof PIR spray foam according to an embodiment of the present invention using the cone calorimeter method according to KS F ISO 5660-1.
Figure 2 is a photograph showing the evaluation of the semi-fireproof characteristics by the cone calorimeter method according to KS F ISO 5660-1 using an organic semi-fireproof PIR spray foam according to a comparative example of the present invention.
Figure 3 is a report on the performance compliance test results for semi-combustible materials conducted by the Korea Construction Living Environment Testing & Research Institute using an organic semi-combustible PIR spray foam according to an embodiment of the present invention.
Figure 4 is a report on the performance compliance test results for semi-combustible materials conducted by FITI Testing & Research Institute using an organic semi-combustible PIR spray foam according to an embodiment of the present invention.
Figure 5 shows the results of a KS M 3809 evaluation conducted by the Korea Testing & Research Institute for Chemical Industry using an organic semi-combustible PIR spray foam according to an embodiment of the present invention. According to the results, it was confirmed that the KS M 3809 Type 1, No. 2 standard was satisfied.

Hereinafter, the present invention will be described in more detail. However, the following specific examples or examples are only a reference for describing the present invention in detail, and the present invention is not limited thereto, and may be implemented in various forms.

Also, unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of this invention is only for the purpose of effectively describing particular embodiments and is not intended to be limiting of the invention.

Additionally, the singular forms used in the specification and the appended claims are intended to include the plural forms as well, unless the context clearly dictates otherwise.

Additionally, when a part is said to "include" a component, this does not mean that it excludes other components, but rather that it may include other components, unless otherwise specifically stated.

Additionally, unless otherwise specifically defined, when a layer or element is said to be “on” another layer or element, this includes not only cases where the layer or element is in contact with the other layer or element, but also cases where another layer or element exists between the two layers or elements.

In addition, the terms “about,” “substantially,” etc. are used in a meaning that is at or close to the numerical value when manufacturing and material tolerances inherent in the meanings mentioned are presented, and are used to prevent unscrupulous infringers from unfairly exploiting the disclosure contents in which exact or absolute numerical values are mentioned to aid the understanding of the present invention.

In addition, “quasi-non-combustible” means that, according to Article 2 of the Enforcement Decree of the Building Act, it has properties equivalent to non-combustible materials, and according to KS F ISO 5660-1 [Combustion performance test - Heat release, smoke generation, mass loss rate - Part 1: Heat release rate (cone calorimeter method)], the total heat release amount is 8 MJ/㎡ or less for 10 minutes after the start of the heating test, the maximum heat release rate for 10 minutes does not exceed 200 kW/㎡ for 10 seconds or more continuously, and after 10 minutes of heating, there should be no cracks, holes, or melting (including complete melting and disappearance of the core material in the case of composite materials) penetrating the test piece that are hazardous to fire protection, and there should be no partial melting or shrinkage exceeding 20% of the test piece thickness.

Additionally, “OH value” is an indicator of the amount of reactive hydroxyl groups that can participate in a reaction, and refers to the number of mg of KOH required to neutralize acetic acid bound to an acetyl compound obtained from 1 g of polyol.

Additionally, the “NCO content” is the content of NCO terminal groups of the isocyanate compound, which can be calculated as follows:

NCO % = [100 × 2 × NCO chemical formula weight × (capping ratio - 1)] / (diisocyanate molecular weight × capping ratio) + polyol molecular weight

In the above formula, the capping ratio is the molar ratio of diisocyanate/molar ratio of polyol.

One aspect of the present invention is a foam foam prepared by foaming a spray foam composition in which 130 to 180 parts by weight of an isocyanate compound is mixed with 100 parts by weight of a polyol composition comprising an organic substance including an aromatic polyester polyol, a blowing agent, an organic flame retardant, a catalyst, and a foam stabilizer,

The above aromatic polyester polyol comprises a structure derived from phthalic anhydride, terephthalic acid, benzoic acid, trimellitic acid and adipic acid, and has a hydroxyl value (OH value) of 100 to 300 mgKOH/g.

The above polyol composition provides an organic semi-combustible PIR spray foam insulation having a viscosity measured at 20° C. of 100 to 600 cps.

In addition, one aspect of the present invention comprises the steps of preparing a polyol composition comprising an aromatic polyester polyol having a structure derived from phthalic anhydride, terephthalic acid, benzoic acid, trimellitic acid and adipic acid, a blowing agent, an organic flame retardant, a catalyst and a foaming agent, and having a viscosity of 100 to 600 cps measured at 20° C.

A step of foaming by mixing 130 to 180 parts by weight of an isocyanate compound with respect to 100 parts by weight of the above polyol composition;

A method for manufacturing an organic semi-combustible PIR spray foam insulation material including:

In addition, one aspect of the present invention comprises a polyol composition comprising an aromatic polyester polyol having a structure derived from phthalic anhydride, terephthalic acid, benzoic acid, trimellitic acid and adipic acid and having an OH value of 100 to 300 mgKOH/g, an organic substance including a blowing agent, an organic flame retardant, a catalyst and a foaming agent, and having a viscosity measured at 20° C. of 100 to 600 cps; and an isocyanate compound;

A spray foaming composition is provided, wherein 130 to 180 parts by weight of an isocyanate compound is mixed with 100 parts by weight of the above polyol composition.

Below, each component of the present invention is described in more detail.

[Composition for spray foaming]

A spray foaming composition according to one aspect of the present invention is a foaming composition capable of spray foaming and having semi-fireproof properties, although it is not limited to spray equipment.

Specifically, the polyol composition is used as solution A, and the isocyanate compound is used as solution B, and the content ratio of solutions A and B is adjusted to mix and foam.

The spray foaming composition of the present invention uses a higher content of an isocyanate compound than a polyol composition, and specifically, the spray foaming can be performed by mixing 130 to 180 parts by weight, 140 to 170 parts by weight, or 150 to 160 parts by weight of an isocyanate compound with respect to 100 parts by weight of the polyol composition.

Accordingly, a foam including a PIR structure can be provided, and an effect of further improving flame retardancy can be achieved. However, in order to increase the content of the isocyanate compound, the hydroxyl value and viscosity of the polyol composition mixed together need to be controlled, and in order to satisfy the semi-flame retardancy characteristic, the introduction of a new polyol was required.

As a result of research for this purpose, a polyol composition was developed comprising an aromatic polyester polyol having an OH value of 100 to 300 mgKOH/g, a blowing agent, an organic flame retardant, a catalyst, and a foaming agent, and having a viscosity measured at 20°C of 100 to 600 cps. It was also discovered that a foamed product obtained by mixing this with an isocyanate compound satisfies semi-flame retardancy properties and exhibits the surprising effect of showing almost no shrinkage even after a semi-flame retardancy test.

[Polyol composition]

In one aspect of the present invention, the polyol composition means a composition in which a polyol, a blowing agent, an organic flame retardant, a catalyst, and a foaming agent are mixed. In addition, additives commonly used in the relevant field may be further included, and although the present invention does not exclude the use of inorganic particles, the semi-flammability characteristics can be satisfied even without using inorganic particles.

The polyol composition may have a viscosity measured at 20° C. of 100 cps or more, 200 cps or more, 300 cps or more, 400 cps or more, 500 cps or more, 600 cps or less, or a value between the above values, for example, 100 to 600 cps, and the mixing ratio of the isocyanate compound may be increased to 130 to 180 parts by weight within a range satisfying this range.

In one aspect, the polyol means an organic molecule having an average of greater than 1.0 hydroxyl groups per molecule.

The above polyol is characterized by using an aromatic polyester polyol that simultaneously contains structures derived from phthalic anhydride, terephthalic acid, benzoic acid, trimellitic acid, and adipic acid.

By simultaneously including the above structures, it is possible to further increase the content of isocyanate compounds, and to satisfy the semi-fireproof properties without including inorganic substances.

The above aromatic polyester polyol includes a structure derived from phthalic anhydride, terephthalic acid, benzoic acid, trimellitic acid, and adipic acid, and may have a hydroxyl value (OH value) of 100 mgKOH/g or more, 150 mgKOH/g or more, 200 mgKOH/g or more, 400 mgKOH/g or less, 300 mgKOH/g or less, or a value between the above values, for example, 100 to 300 mgKOH/g. When the hydroxyl value satisfies the above range, the content ratio of the isocyanate compound can be used in a higher content than that of the polyol composition.

In addition, the present invention may further include other polyols, such as polyether-based polyols or aliphatic polyester polyols, in addition to the aromatic polyester polyol, but from the viewpoint of satisfying the semi-flame retardancy properties and ensuring that shrinkage hardly occurs after the semi-flame retardancy evaluation, it is preferable to use the aromatic polyester polyol alone.

The above aromatic polyester polyol can be produced by reacting an acid component including phthalic anhydride, terephthalic acid, benzoic acid, trimellitic acid, and adipic acid with a glycol component.

The above acid component may further include one or more acid components selected from trimellitic anhydride, suberic acid, sebacic acid, isophthalic acid, succinic acid, adipic acid, fumaric acid, etc.

More preferably, it may contain phthalic anhydride, terephthalic acid, benzoic acid, trimellitic acid and adipic acid as essential components, and a combination of these can provide a foam that satisfies semi-fireproof properties and has a lower shrinkage rate.

The above glycol component may be, for example, one or a mixture of two or more selected from ethylene glycol, diethylene glycol, triethylene glycol, 1,4-butanediol, glycerin, trimethylolpropane, propylene glycol, pentaerythritol, and the like.

More preferably, the aromatic polyester polyol may be polymerized at once to include phthalic anhydride, terephthalic acid, benzoic acid, trimellitic acid and adipic acid structures, but in the present invention, in order to express the properties of each component, it may be polymerized as three polyols and then mixed and used.

Specifically, for example, the first polyol may be a mixture of: a first polyol in which phthalic anhydride, terephthalic acid, and benzoic acid are reacted as acid components, and diethylene glycol and triethylene glycol are reacted as glycol components; a second polyol in which phthalic anhydride and adipic acid are reacted as acid components, and diethylene glycol as glycol components; and a third polyol in which phthalic anhydride, terephthalic acid, and trimellitic acid are reacted as acid components, and trimethylolpropane and diethylene glycol as glycol components.

More specifically, the first polyol may be a product obtained by reacting 3 to 4 mol of phthalic anhydride, 1 to 2 mol of terephthalic acid, 0.2 to 0.8 mol of benzoic acid, 3 to 4 mol of diethylene glycol, and 3 to 4 mol of triethylene glycol in the presence of a catalyst. At this time, the reaction catalyst is not limited, but a tin-based catalyst such as butyltartaric acid may be used. The first polyol exhibits excellent flame retardancy by including a structure derived from benzoic acid, and by using a high content of terephthalic acid, improves the curing speed and polyurethane foam strength during polyurethane reaction, thereby playing a role in reinforcing shrinkage and dimensional stability. The first polyol may have an acid value of 1.0 or less, a hydroxyl value of 130 mgKOH/g or less, and a viscosity measured at 25°C of 25,000 to 35,000 cps.

The above second polyol may be a product obtained by reacting 1 to 2 mol of phthalic anhydride, 4 to 5 mol of adipic acid, and 8 to 9 mol of diethylene glycol in the presence of a catalyst. At this time, the reaction catalyst is not limited, but a titanate catalyst such as tetraisopropyl titanate (TIPT) may be used. The second polyol has excellent crosslinking properties by imparting ductility due to its relatively high molecular weight, thereby improving the adhesiveness of the polyurethane foam, and its low hydroxyl value increases the polyurethane foam INDEX, thereby preventing cracking of the foam. The acid value may be 2.0 or less, the hydroxyl value (OH value) may be 95 mgKOH/g or less, and the viscosity measured at 25°C may be 5,000 to 7,000 cps.

The above third polyol may be a product obtained by reacting 1 to 2 mol of phthalic anhydride, 2 to 3 mol of terephthalic acid, 0.5 to 1 mol of trimellitic acid, 0.2 to 0.8 mol of trimethylolpropane as a glycol component, and 8 to 10 mol of diethylene glycol in the presence of a catalyst. At this time, the reaction catalyst is not limited, but a tin-based catalyst such as butyltartaric acid may be used. The above third polyol is an ester polyol having a high functionality and a high acid group, and serves to improve the overall physical properties of the polyurethane foam, and may have an acid value of 1.0 or less, a hydroxyl value (OH value) of 300 mgKOH/g or less, and a viscosity measured at 25°C of 9,000 to 12,000 cps.

In one embodiment, the mixing ratio of the first polyol: the second polyol: the third polyol may be 30 to 40:25 to 35:30 to 40 by weight, and may be suitable for expressing the desired physical properties at the mixing ratio.

In one embodiment, the aromatic polyester polyol may have a hydroxyl value (OH value) of 100 to 300 mgKOH/g and a viscosity measured at 25°C of 10,000 to 20,000 cps in a mixed state of the first polyol, the second polyol, and the third polyol. In a range satisfying the above properties, the viscosity can be lowered when producing a polyol composition, and the content of the isocyanate compound can be increased. In addition, the number of functional groups may be 2 to 4, or 2 to 3, in a mixed state of the first polyol, the second polyol, and the third polyol, but is not limited thereto.

In one embodiment, the polyol composition may include, but is not limited to, 45 to 60 wt% of an aromatic polyester polyol, 15 to 25 wt% of a blowing agent, 15 to 30 wt% of an organic flame retardant, 5 to 15 wt% of a catalyst, and 0.2 to 1 wt% of a foaming agent.

The above-mentioned foaming agent may be a chemical foaming agent or a physical foaming agent, or may be a mixture thereof, but is not limited thereto.

Examples of the chemical foaming agent that can be used include, but are not limited to, water, azodicarbonamide, azobisisobutyronitrile, diazoaminoazobenzene, N,N'-dinitro-sopentamethylenetetramine p-toluenesulfonylhydrazide, and p,p'-oxybis(benzenesulfonylhydrazide) p-toluene-sulfonylsemicarba, sodium dicarbonate.

The above physical blowing agent may be a hydrocarbon blowing agent, a hydrochlorofluorocarbon (HCFC) blowing agent, a hydrofluorocarbon (HFC) blowing agent, a hydrofluoroolefin (HFO) blowing agent, or a mixture thereof, and specifically, may be c-pentane, iso-pentane, n-pentane, HCFC-141b (1,1-dichloro-1-fluoroethane), HFC-242fa (1,1,1,3,4-pentafluoropropane), HFC-365mfc, mixed HFC-365mfc/227ea, or a mixture thereof, but is not limited thereto. In particular, HCFC-141b and c-pentane, iso-pentane, n-pentane, etc. used in the manufacture of “closed cell foam” can be used.

The content of the above-mentioned foaming agent is preferably 15 to 25 wt%, and when included within the above range, it is possible to appropriately satisfy the required characteristics, such as density, of the semi-fireproof polyurethane foam to be manufactured while having excellent semi-fireproof properties. Specifically, when the above-mentioned foaming agent is used within the above range, it is preferable because it is possible to form a polyurethane foam having excellent semi-fireproof properties.

The above organic flame retardant may include halogen-based, phosphorus-based, inorganic-based, and nitrogen-based flame retardants, and may specifically be a phosphorus-based flame retardant, but is not limited thereto. Specific examples of the phosphorus-based flame retardant include dimethyl methylphosphonate, triethyl phosphate (TEP), tris-2-chloroethyl phosphate, tris(1-chloro-2-propyl) phosphate (TCPP), isopropylphenyldiphenyl phosphate, tricresyl phosphate, triphenyl phosphate, triethyl phosphate, melamine phosphate, and ammonium phosphate, and may be any one or more phosphorus-based flame retardants selected from the group consisting of:

More preferably, in order to exhibit even better semi-fireproof properties of the all-organic composition of the present invention, and to exhibit compatibility with the aromatic polyester polyol and even better semi-fireproof properties, it is preferable to include dimethyl methylphosphonate. Alternatively, it may include one selected from triethyl phosphate (TEP) and dimethyl methylphosphonate, or a mixture thereof. For example, it may be a mixture of dimethyl methylphosphonate (DMMP) and tris(1-chloro-2-propyl)phosphate (TCPP). For example, it may be a mixture of dimethyl methylphosphonate (DMMP), triethyl phosphate (TEP), and tris(1-chloro-2-propyl)phosphate (TCPP).

The content of dimethyl methyl phosphonate (DMMP) among the total content of the organic flame retardant may be 50 wt% or more, 60 wt% or more, 70 wt% or more, 80 wt% or more, specifically 50 to 90 wt%, and may be any value between the above values. Although it is preferred because the intended semi-flame retardant property can be satisfied within the above range, it is not limited thereto.

The content of the organic flame retardant is preferably 15 to 30 wt%, and the intended semi-flame retardant properties can be satisfied within the above range.

The above catalyst may use a trimerization catalyst, and the trimerization catalyst is a material for promoting the production of isocyanurate through a trimerization reaction of an isocyanate group included in the isocyanate compound. The trimerization catalyst may be, for example, a nitrogen-containing aromatic compound, an alkali metal salt, a tertiary ammonium salt or a quaternary ammonium salt, and a mixture thereof, and specifically, may be at least one compound selected from tris(dimethylaminomethyl)phenol, 2,4-bis(dimenylaminomethyl)phenol, 2,4,6-tris(dialkylaminoalkyl)helsahydro-S-trizine, potassium acetate, potassium 2-ethylhexanoate, potassium 2-ethylhexanoate, potassium octylate, trimethylammonium salt, triethylammonium salt, triphenylammonium salt, tetramethylammonium salt, tetraethylammonium, and tetraphenylammonium salt, but is not limited thereto.

The content of the above catalyst is preferably 5 to 15 wt%, and within the above range, there is an advantage in that the reaction rate of the isocyanate compound can be appropriately controlled while suppressing the phenomenon of the semi-fireproof performance being deteriorated.

The above-mentioned foam stabilizer is a component that affects the cell structure in the semi-fireproof polyurethane foam by means of a surface-active action, and can perform functions such as stabilizing the mixing of the reaction raw materials, generating bubbles, and stabilizing bubbles. As the above-mentioned foam stabilizer is included, the size of the foam cells can be reduced, thereby increasing the surface area, and surface elasticity can also be increased, thereby enabling the recovery of a film that critically expands before cell destruction occurs, thereby enhancing the stability of the foam. In addition, the surface viscosity, which reduces deformation of the cell structure, can be increased.

The type of the above-mentioned surfactant is not limited to a commonly used surfactant, and specifically, a silicone-based surfactant can be used, and specifically, a polysiloxane ether can be used, but is not limited thereto. The polysiloxane ether may have a molecular weight of 1,000 to 10,000 g/mol, and specifically, may have a molecular weight of 3,000 to 7,000 g/mol, but is not limited thereto.

The content of the above-mentioned foaming agent is preferably 0.2 to 1 wt%, and the stability of the foam cell can be increased within the above range.

[isocyanate compounds]

The above isocyanate compound reacts with polyol to form a urethane bond within the foam, and includes a compound in which an aromatic, cycloaliphatic and/or aliphatic group is linked to an isocyanate group.

The above isocyanate compounds are known in the art and may include polyisocyanates, for example, ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate), 2,4-hexahydrotoluene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI, or HMDI), 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4- and 2,6-toluene diisocyanate (TDI), diphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), naphthylene-1,5-diisocyanate, triphenyl-methane-4,4',4”-triisocyanate, polyphenyl-polymethylene-polyisocyanate (crude MDI), norbornane diisocyanate, m-isocyanatophenyl sulfonylisocyanate, p-isocyanatophenyl sulfonylisocyanate, perchlorated arylpolyisocyanates, carbodiimide-modified polyisocyanates, urea-modified polyisocyanates, biuret-containing polyisocyanates, isocyanate-terminated prepolymers or mixtures thereof.

Even better, it may be possible to use a mixture of 4,4'-MDI, 2,4'-MDI and 2,2'-MDI.

The above isocyanate compound may be used having an average number of functional groups of 2 to 3, an NCO content of 25 to 35%, and a viscosity measured at 25° C. of 100 to 400 cps. The NCO% refers to the weight% of NCO contained in the isocyanate. In the above range, when mixed with the polyol composition of the present invention, it is preferable because it has excellent foaming properties, enables the formation of PIR, and exhibits semi-fireproof properties.

[Organic semi-combustible PIR spray foam insulation]

In one aspect of the present invention, the organic semi-combustible PIR spray foam insulation satisfies the semi-combustible characteristics of the cone calorimeter method according to KS F ISO 5660-1, and after the semi-combustible evaluation according to KS F ISO 5660-1, the shrinkage rate of the foam is 20% or less, 10% or less, 5% or less, 3% or less, 2% or less, 1% or less, or substantially no shrinkage occurs.

Specifically, in the semi-combustibility evaluation according to KS F ISO 5660-1, for a 50 mm thick specimen, the material can satisfy the property that the total heat release for 10 minutes (600 seconds) is 8 MJ/㎡ or less, 7 MJ/㎡ or less, 6 MJ/㎡ or less, and specifically 6 to 8 MJ/㎡.

In addition, in the Heat Release Rate (HRR) evaluation, which means the heat release rate per unit area, the average heat release rate (Average HRR) can satisfy the property of being 12 KW/m ² or less, 11 KW/m ² or less, 10 KW/m ² or less, and more specifically, 10 to 12 KW/m ² . In addition, the property can satisfy the property of being the highest maximum heat release rate (Peak HRR) at the time of evaluation of being 60 KW/m ² or less, 58 KW/m ² or less, 55 KW/m ² or less, 50 KW/m ² or less, and more specifically, 40 to 60 KW/m ² .

In addition, it can satisfy the property that the self-extinguishing time is 8 seconds or less, 7 seconds or less, 6 seconds or less, 5 seconds or less, and more specifically 1 to 8 seconds.

In addition, after the cone calorimeter method quasi-combustibility characteristic evaluation according to the above ISO 5660-1, the shrinkage may be 30% or less, 20% or less, 10% or less, 5% or less, 1% or less, or substantially 0%, so that no shrinkage occurs.

In addition, it may satisfy a property of having a weight reduction rate of 30 to 50% after evaluation of semi-combustibility characteristics by the cone calorimeter method according to the above ISO 5660-1.

[Method for manufacturing organic semi-combustible PIR spray foam insulation]

A method for manufacturing an organic semi-combustible PIR spray foam insulation according to one embodiment of the present invention comprises the steps of: preparing a polyol composition comprising an organic substance by mixing an aromatic polyester polyol having a structure derived from phthalic anhydride, terephthalic acid, benzoic acid, trimellitic acid and adipic acid, a blowing agent, an organic flame retardant, a catalyst and a foam stabilizer; and mixing and foaming 130 to 180 parts by weight of an isocyanate compound with respect to 100 parts by weight of the polyol composition.

The above components are the same as described above.

In one embodiment, the mixing and foaming step may utilize spray equipment. At this time, a nozzle for injecting a polyol composition and a nozzle for injecting an isocyanate compound may be provided, respectively. In addition, the spraying speed of the nozzle may be adjusted so that the isocyanate compound is mixed in an amount of 130 to 180 parts by weight, 140 to 170 parts by weight, or 150 to 160 parts by weight, per 100 parts by weight of the polyol composition.

The above polyol composition may have a viscosity measured at 20° C. of 100 to 600 cps and includes an aromatic polyester polyol having a hydroxyl value (OH value) of 100 to 300 mgKOH/g.

The above isocyanate compound may have an NCO content of 25 to 35%, an average number of functional groups of 2 to 3, and a viscosity measured at 25° C. of 100 to 400 cps.

In order to satisfy the above properties, the isocyanate compound can be mixed in an amount of 130 to 180 parts by weight, 140 to 170 parts by weight, or 150 to 160 parts by weight per 100 parts by weight of the polyol composition, and the foam can satisfy the semi-non-flammable characteristic.

The present invention will be described in more detail based on the following examples and comparative examples. However, the following examples and comparative examples are only examples for describing the present invention in more detail, and the present invention is not limited by the following examples and comparative examples.

The following physical properties were evaluated as follows.

<Conditions for evaluating the physical properties of polyol>

[ACID VALUE]

Measured according to JIS K 6751.

[OH-VALUE]

Measured according to JIS K 1525.

[viscosity]

Viscosity was measured at 20°C and 25°C using a BROOKFIELD viscometer (model number: BROOKFIELD DV3TRVCJ0) with spindle 6.

<Semi-combustible test method and evaluation conditions>

[Total heat release test]

According to the results of the heating test in accordance with the Korean Industrial Standard KS F ISO 5660-1 [Combustion performance test - Heat release, smoke generation, mass loss rate - Part 1: Heat release rate (cone calorimeter method)], all of the following items must be satisfied in all tests in accordance with Article 28, Paragraph 2, Subparagraph 1.

A. The total heat release for 10 minutes after the start of heating shall be 8 MJ/m2 or ^less .

B. The maximum heat release rate shall not exceed 200 kW/m2 for 10 consecutive seconds or more during 10 minutes.

After heating for 10 minutes, there shall be no fire-hazardous cracks penetrating the test piece (this refers to a deformation in which the test piece is split and the bottom surface is visible), holes (this refers to a deformation in which the bottom surface is visible from the surface of the test piece), and melting (this refers to a case in which the test piece melts and the bottom surface is visible), and there shall be no partial melting or shrinkage exceeding 20% of the test piece thickness.

[Gas toxicity test]

In the gas toxicity test results of the Korean Industrial Standard KS F 2271 (flammability test method for interior materials and structures of buildings), the average behavioral suspension time of laboratory mice must be 9 minutes or longer in all tests according to Article 28, Paragraph 3, Subparagraph 2.

The test is conducted in two repetitions, and the specimen is 220 × 220 mm in width and length, with three holes of 25 mm diameter drilled from the front to the back of the specimen.

Heating is performed with a secondary heat source for 3 minutes, and then with a primary heat source for 3 minutes. During heating, air is supplied at 3 L/min from the primary supply device and 25 L/min from the secondary supply device. Combustion products are discharged through the exhaust device of the test box, and the discharge amount is 10 L/min.

Combustion products were introduced into the test box containing test mice (DD or ICR strain, female, 5 weeks old, 18–22 g) in a rotating basket, and the average behavioral cessation time of eight mice was calculated.

[Shrinkage evaluation after semi-combustibility evaluation]

After the semi-combustibility evaluation according to the above KS F ISO 5660-1, the shrinkage rate of the foam was evaluated.

Shrinkage = Thickness of foam before semi-combustible evaluation - Thickness of foam after semi-combustible evaluation / Thickness of foam before semi-combustible evaluation × 100

<Evaluation of foam properties>

The evaluation of the physical properties of the foam shown in Fig. 5 was performed by the following method.

[Apparent density]

Density is measured as follows:

The measurement of apparent density is in accordance with KS M ISO 845 and the following. The insulation board is cut into three test pieces of approximately 100 mm X 100 mm from the sample while maintaining the thickness of the sample. The insulation tube is cut into three test pieces of a shape that is easy to obtain the volume of approximately 50 cm3 or more.

- Measuring equipment: PEACOCK DIGITAL COUNTER C-5S (dimensions), METTLER TOLEDO XSR6002S (weight)

[Thermal Conductivity]

The measurement of thermal conductivity follows the method specified in KS L 9016.

a) The insulation board shall comply with 6.1 (flat plate direct method), 6.2 (flat plate comparison method) or 6.3 (flat plate heat flow meter method) specified in KS L 9016.

b) The insulation cylinder shall be manufactured according to 6.4 (cylinder method) specified in KS L 9016 or an insulation board manufactured under the same conditions shall be used as a sample in accordance with a).

It's okay to do that.

- Measuring equipment: TA FOX200

[Bending failure load]

The flexural failure load is tested according to KS M ISO 1209-1, with the test specimen dimensions being 250 mm X 100 mm X 20 mm and the support spacing being 200 mm.

and the load concentration speed should be 50 mm/min. However, the number of test specimens should be three.

- Measuring equipment: SHIMAZU AG-IS

[Compressive strength]

The measurement of compressive strength is as follows:

a) The test piece shall be a rectangular solid, and one side of the bottom surface of the sample shall be (100±1) mm or (50±1) mm, and the thickness shall be the length of one side of the bottom surface.

Cut out three pieces so that they do not exceed the thickness. The parallelism of the upper and lower surfaces of the test piece should be within 1% of the thickness.

b) The test method and calculation shall be in accordance with KS M ISO 844. The load shall be the load at the yield strain, and the yield point shall be at the specified strain of 0.1.

If this does not occur, the load is applied at a specified strain of 0.1.

- Measuring equipment: SHIMAZU AGX-V

[Absorption]

The measurement of absorption is as follows:

a) Remove the epidermis from the sample using a sharp blade, cut out three test pieces measuring 100 mm X 100 mm X 25 mm, and measure the dimensions.

b) Immerse the test piece 50 mm below the surface of a container containing clear water at (23±3)℃. Then, take out the test piece after 10 seconds, place it on a wire mesh with a mesh size of approximately 3 mm and tilted 30° from the vertical, leave it for 30 seconds, and measure its weight with an accuracy of 0.01 g, and use this as the reference weight (C). Then, immerse it again in clear water, let it absorb water for 24 hours, and measure the weight (B) in the same way as when measuring the reference weight.

The absorption amount is calculated according to the following formula.

[combustibility]

The combustibility test uses the test equipment specified in KS M ISO 9772, and the test method is as follows.

Cut five test pieces from the sample, each with a thickness of (13±1) mm, a length of (150±10) mm, and a width of (50±1) mm. However, if the sample thickness is less than 13 mm, use the sample thickness as is. Apply a flame to one end of the test piece for 60 seconds, and the time until the flame goes out, including the heating time, is the combustion time (seconds). After the flame goes out, the length from the end of the test piece where the flame was applied to the longest part of the burnt part is the combustion length (mm).

[Synthesis Example 1] Preparation of first aromatic polyester polyol

A 2 L four-necked flask was charged with 3.21 mol of phthalic anhydride, 1.92 mol of terephthalic acid, 0.53 mol of benzoic acid, 3.73 mol of diethylene glycol, 3.74 mol of triethylene glycol, and 200 ppm of the catalyst butyl tartaric acid (BuSnOOH, ESCAT 5500) and stirred for 30 minutes. After that, the temperature of the reactor was increased to 140 ℃ and stirred for 1 hour. After that, the temperature of the reactor was increased to 160 ℃ and stirred for 1 hour. After that, the temperature of the reactor was increased to 190 ℃ and stirred for 2 hours. After that, the temperature of the reactor was increased to 210 ℃ and stirred for 2 hours. After that, the temperature of the reactor was increased to 220 ℃ and stirred for 2 hours. When the acid value reached 1.0 or less, the viscosity reached 30,000 cps at 25° C., and the hydroxyl value reached 130 mgKOH/g, the reaction was terminated to obtain the first polyol.

[Synthesis Example 2] Preparation of Second Aromatic Polyester Polyol

A 2L four-necked flask was charged with 1.89 mol of phthalic anhydride, 4.50 mol of adipic acid, 8.14 mol of diethylene glycol, and 50 ppm of the catalyst TIPT (Tetra Isopropyl Titanate) and stirred for 30 minutes. After that, the temperature of the reactor was increased to 140 ℃ and stirred for 2 hours. After that, the temperature of the reactor was increased to 150 ℃ and stirred for 2 hours. After that, the temperature of the reactor was increased to 160 ℃ and stirred for 1 hour. After that, the temperature of the reactor was increased to 190 ℃ and stirred for 2 hours. After that, the temperature of the reactor was increased to 220 ℃ and stirred for 2 hours. The reaction was terminated when the acid value was 2.0 or less, the viscosity was 6,500 cps at 25°C, and the hydroxyl value was 95 mgKOH/g, thereby obtaining the second polyol.

[Synthesis Example 3] Production of a third aromatic polyester polyol

A 2 L four-necked flask was charged with 1.34 mol of phthalic anhydride, 2.27 mol of terephthalic acid, 0.98 mol of trimellitic acid, 0.41 mol of trimethylolpropane, 9.35 mol of diethylene glycol, and 200 ppm of the catalyst butyl tartaric acid (BuSnOOH, ESCAT 5500) and stirred for 30 minutes. After that, the temperature of the reactor was increased to 150 ℃ and stirred for 1 hour. After that, the temperature of the reactor was increased to 170 ℃ and stirred for 1 hour. After that, the temperature of the reactor was increased to 190 ℃ and stirred for 2 hours. After that, the temperature of the reactor was increased to 200 ℃ and stirred for 2 hours. After that, the temperature of the reactor was increased to 220 ℃ and stirred for 2 hours. The reaction was terminated when the acid value was 1.0 or less, the viscosity was 10,000 cps at 25° C., and the hydroxyl value was 300 mgKOH/g, thereby obtaining the third polyol.

[Example 1]

Using the polyols manufactured in the above Synthetic Examples 1 to 3, the mixing ratio of the first polyol:the second polyol:the third polyol was mixed in a weight ratio of 35.3:29.4:35.3 as shown in Table 1 below. To this, 0.6 wt% of the foaming agent, 21.5 wt% of the flame retardant, 6.6 wt% of the catalyst, and 0.7 wt% of water were added, and stirred for 30 minutes under the conditions of 25°C and 1,500 RPM. Then, 18.4 wt% of a blowing agent (HCFC-141b, SANMEI) was mixed into the polyol compound after stirring, and stirred at 1,000 RPM for 10 minutes to prepare a polyol composition A.

After putting the prepared Liquid A into a plastic container, an isocyanate compound (Huntsman SUPRASEC®5005, NCO (%) 31.5, viscosity (25 ℃) 200 cps, 4,4'-MDI 92%, 2,4'-MDI 7.7%, 2,2'-MDI 0.3%) was added to the plastic container containing Liquid A so that the weight ratio of Liquid A : isocyanate compound was 100 : 150, and the mixture was stirred at 9,000 RPM for 1 second using a stirrer. Afterwards, the mixture was poured into a mold to foam and harden the semi-combustible polyurethane resin composition, thereby manufacturing an organic semi-combustible PIR spray foam. The properties of the manufactured foam were evaluated and are shown in Table 2 below.

The types of stabilizers, flame retardants, catalysts, and blowing agents used in Table 1 below are as described below.

The stabilizer used was EVONIK’s B-8409 product (silicon-based stabilizer).

Flame retardants used were 9.2 wt% TCPP (Jiangsu Changyu Chemical) and 12.3 wt% DMMP (DIMETHYL METHYLPHOSPHONATE, LIANMEI).

The catalysts used were 1.2 wt% PC-5 (PMDETA, Evonik Korea), 3.0 wt% T-45 (Potassium 2-ethylhexanoate + Dipropylene glycol, SD Korea), and 2.2 wt% TEDA-33E (1,2-Ethanediol + 1,4-Diazabicyclo[2.2.2]octane, P&I Materials).

The blowing agent used was 0.7 wt% water and 18.4 wt% HCFC-141b (SANMEI).

[Examples 2 and 3]

Except that the mixing ratio of the first polyol:second polyol:third polyol was changed as shown in Table 1 below, the same process as in Example 1 was performed.

The properties of the manufactured foam were evaluated and are shown in Table 2 below.

[Example 4]

In the above Example 1, the same process as in Example 1 was performed except that 21.5 wt% of TCPP (Jiangsu Changyu Chemical Company) was used alone as a flame retardant.

The properties of the manufactured foam were evaluated and are shown in Table 2 below.

[Example 5]

In the above Example 1, it was manufactured in the same manner as in Example 1, except that 10.75 wt% of TCPP (Jiangsu Changyu Chemical) and 10.75 wt% of DMMP (DIMETHYL METHYLPHOSPHONATE, LIANMEI) were used as flame retardants.

The properties of the manufactured foam were evaluated and are shown in Table 2 below.

[Example 6]

In the above Example 1, the content of the isocyanate compound was changed to 130 parts by weight per 100 parts by weight of the polyol composition as shown in Table 1 below, and the same process as in Example 1 was performed, except that the content was changed to 130 parts by weight per 100 parts by weight of the polyol composition.

The properties of the manufactured foam were evaluated and are shown in Table 2 below.

[Example 7]

In the above Example 1, the content of the isocyanate compound was changed to 180 parts by weight per 100 parts by weight of the polyol composition as shown in Table 1 below, and the same process as in Example 1 was performed, except that the content was changed to 180 parts by weight per 100 parts by weight of the polyol composition.

The properties of the manufactured foam were evaluated and are shown in Table 2 below.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 1st polyol (weight%) 18.4 20.1 17 18.4 18.4 18.4 18.4 Secondary polyol (weight%) 15.3 15 15 15.3 15.3 15.3 15.3 3rd polyol (weight%) 18.4 17 20.1 18.4 18.4 18.4 18.4 Stabilizer (weight%) 0.6 0.6 0.6 0.6 0.6 0.6 0.6 Flame retardant (weight %) 21.5 21.5 21.5 21.5 21.5 21.5 21.5 Catalyst (wt%) 6.6 6.6 6.6 6.6 6.6 6.6 6.6 Foaming agent (weight%) 19.2 19.2 19.2 19.2 19.2 19.2 19.2 Total (weight %) 100 100 100 100 100 100 100 Isocyanate content (weight parts) 150 150 150 150 150 130 180 Viscosity at 20°C (cps) of polyol composition A solution 340 430 370 360 350 340 340 Viscosity at 25°C (cps) of isocyanate compounds 200 200 200 200 200 200 200

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Density (kg/m ³ ) 32.1 32.8 30.2 32.7 32.5 28.5 34.4 Weight of specimen before carbonization (g) 16.0 16.4 15.1 16.4 16.2 14.3 17.2 Weight of specimen after carbonization (g) 9.8 9.3 7.8 7.9 9.8 8.2 9.9 Weight loss rate (%) 38.9 43.4 48.4 51.7 39.7 42.5 42.4 Thickness of specimen before carbonization (mm) 50 50 50 50 50 50 50 Specimen thickness after carbonization (mm) 50 45 45 30 45 45 45 Thickness reduction rate (%) 0 10 10 20 10 10 10 Total heat release (MJ/ ^m2 )300 seconds cumulative 3.3 3.2 2.7 6.4 4.5 5.5 5.2 Total heat released (MJ/ ^m2 ) 600 seconds accumulated 4.0 4.3 4.6 8.0 6.1 7.0 6.9 HRR(KW/ ^m2 ) Real-time emission (average) 10.7 7.2 7.6 10.7 7.6 11.5 10.6 Peak HRR (KW/m ² ) Highest emission 58.2 67.1 57.5 58.2 62.5 49.4 65.0 Peak HRR Time (sec) 8 9 8 8 7 8 8 Self-extinguishing time (sec) 1~6 1~7 1~8 1~12 1~8 1~7 1~9

As shown in Table 2 above, it can be confirmed that the foams of Examples 1 to 7 can exhibit quasi-fireproof performance while satisfying the total heat release and thickness shrinkage ratio, and it can also be confirmed that the foams of Examples 6 to 7 exhibit quasi-fireproof performance when the content of the isocyanate compound is in the range of 130 to 180 parts by weight.

In addition, the appearance of the foam of Example 1 after the semi-fireproof test is shown in Fig. 1. As can be seen in Fig. 1, it was confirmed that no shrinkage occurred at all after the semi-fireproof test. In addition, as shown in Figs. 3 and 4, it was judged to have satisfactory semi-fireproof performance by the Korea Construction Living Environment Testing & Research Institute and the FITI Testing & Research Institute, respectively. In addition, as shown in Fig. 5, it was confirmed that it satisfied the KS M 3809 Type 1 No. 2 standard in the KS M 3809 evaluation result conducted by the Korea Testing & Research Institute for Chemical Industry.

In addition, when comparing Example 1 with Examples 4 and 5, it was confirmed that when TCPP and DMMP were mixed and used as a flame retardant, the flame retardancy was superior in terms of total heat release and heat release rate (HRR), thickness, and weight reduction rate compared to when TCPP was used alone as a flame retardant.

In this way, it was confirmed that the spray foaming composition of the present invention can be applied to various fields requiring semi-fireproof properties.

[Comparative examples 1 to 3]

A polyol composition was prepared by mixing in the same manner as in Example 1, but at a mixing ratio as shown in Table 3 below. The properties of the prepared foam were evaluated and are shown in Table 4 below.

[Comparative examples 4 and 5]

The composition content was changed as shown in Table 3 below, and the product was manufactured in the same manner as in Example 1, except that polyether polyol was added and used.

In Table 3 below, polyether polyol 1 is KONIX KR-403 (initiator o-TDA, number of functional groups 4) from KPX, and polyether polyol 2 is KONIX KR-500 (initiator o-TDA/TEOA, number of functional groups 4).

The properties of the manufactured foam were evaluated and are shown in Table 4 below.

[Comparative Example 6]

As shown in Table 3 below, the content of the isocyanate compound was changed to 100 parts by weight per 100 parts by weight of the polyol composition, and the same process as in Example 1 was used.

The properties of the manufactured foam were evaluated and are shown in Table 4 below.

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 1st polyol (weight%) 52.1 - - 18.5 18.5 18.4 Secondary polyol (weight%) - 52.1 - 12.3 12.3 15.3 3rd polyol (weight%) - - 52.1 18.5 18.5 18.4 Polyether polyol 1 - - - 3.1 - - Polyether polyol 2 - - - - 3.1 - Stabilizer (weight%) 0.6 0.6 0.6 0.6 0.6 0.6 Flame retardant (weight %) 21.5 21.5 21.5 21.6 21.6 21.5 Catalyst (wt%) 6.6 6.6 6.6 7.4 7.4 6.6 Foaming agent (weight%) 19.2 19.2 19.2 18.0 18.0 19.2 Total (weight %) 100 100 100 100 100 100 Isocyanate content (weight parts) 150 150 150 150 150 100 Viscosity at 20°C (cps) of polyol composition A solution 680 80 220 340 320 340 Viscosity at 25°C (cps) of isocyanate compounds 200 200 200 200 200 200

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Density (kg/m ³ ) 32.8 31.6 30.2 35.5 32.9 30.2 Weight of specimen before carbonization (g) 16.4 15.8 15.1 17.8 16.5 15.1 Weight of specimen after carbonization (g) 8.8 8.3 7.8 8.6 8.0 7.7 Weight loss rate (%) 46.3 47.5 48.4 51.6 51.4 49.0 Thickness of specimen before carbonization (mm) 50 50 50 50 50 50 Specimen thickness after carbonization (mm) 35 35 30 55 55 30 Thickness reduction rate (%) 30 30 40 -10 -10 40 Total heat release (MJ/ ^m2 )300 seconds cumulative 3.9 5.8 4.9 6.9 8.2 7.8 Total heat released (MJ/ ^m2 ) 600 seconds accumulated 8.1 8.2 8.4 8.8 9.8 10.1 HRR(KW/ ^m2 ) Real-time emission (average) 7.2 7.6 6.8 11.5 13.7 11.5 Peak HRR (KW/m ² ) Highest emission 67.1 57.5 52.5 56.2 44.5 49.4 Peak HRR Time (sec) 10 11 9 11 13 8 Self-extinguishing time (sec) 1~7 1~7 1~8 55~220 70~140 50~160

As shown in Table 4 above, the foams of Comparative Examples 1 to 3 did not satisfy the standard in terms of total heat release, and did not pass the semi-fireproof test due to high thickness reduction rate (shrinkage rate). The foams of Comparative Examples 4 to 6 were measured to have total heat release rates exceeding the standard in terms of high thickness release rate, and it was confirmed that the upper surface expanded significantly while the lower surface shrank significantly, and thus they did not pass the semi-fireproof test. The thickness reduction rate of -10% in Comparative Examples 4 and 5 means that the upper surface expanded significantly, resulting in an overall thickness expansion compared to the initial state. In this case as well, the semi-fireproof test is not satisfied.

In addition, the appearance of the foam of Comparative Example 4 after the semi-fireproof test is shown in Fig. 2. As seen in Fig. 2, it was confirmed that shrinkage occurred after the semi-fireproof test, and it was confirmed that the shrinkage rate exceeded 30%.

Although the present invention has been described through specific matters and limited examples as described above, these have been provided only to help a more general understanding of the present invention, and the present invention is not limited to the above examples, and those skilled in the art to which the present invention pertains can make various modifications and variations from this description.

Therefore, the idea of the present invention should not be limited to the described embodiments, and all things that are equivalent or equivalent to the claims described below as well as the claims are included in the scope of the idea of the present invention.

Claims (27)

A foam foam is produced by foaming a composition for spray foaming in which 130 to 180 parts by weight of an isocyanate compound is mixed with 100 parts by weight of a polyol composition comprising an organic substance including an aromatic polyester polyol, a blowing agent, an organic flame retardant, a catalyst and a foam stabilizer.
The above aromatic polyester polyol comprises a structure derived from phthalic anhydride, terephthalic acid, benzoic acid, trimellitic acid and adipic acid, and has a hydroxyl value (OH value) of 100 to 300 mgKOH/g.
The above aromatic polyester polyol is a mixture of a first polyol comprising a structure derived from phthalic anhydride, terephthalic acid and benzoic acid; a second polyol comprising a structure derived from phthalic anhydride and adipic acid; and a third polyol comprising a structure derived from phthalic anhydride, terephthalic acid and trimellitic acid.
The above polyol composition is an organic semi-combustible PIR spray foam insulation having a viscosity measured at 20° C. of 100 to 600 cps.
In the first paragraph,
The above organic semi-fireproof PIR spray foam insulation satisfies the semi-fireproof characteristics according to the cone calorimeter method according to KS F ISO 5660-1, and has a shrinkage rate of 20% or less of the foam after the semi-fireproof evaluation according to KS F ISO 5660-1.
In the first paragraph,
The above first polyol is a product produced by reacting phthalic anhydride, terephthalic acid and benzoic acid as acid components and diethylene glycol and triethylene glycol as glycol components.
The above second polyol is a product produced by reacting phthalic anhydride and adipic acid as acid components and diethylene glycol as glycol components.
The above third polyol is an organic semi-combustible PIR spray foam insulation material in which acid components such as phthalic anhydride, terephthalic acid and trimellitic acid are reacted with glycol components such as trimethylolpropane and diethylene glycol.
In the third paragraph,
The above first polyol has an acid value of 1.0 or less, a hydroxyl value of 130 mgKOH/g or less, and a viscosity measured at 25°C of 25,000 to 35,000 cps,
The above second polyol has an acid value of 2.0 or less, a hydroxyl value of 95 mgKOH/g or less, and a viscosity measured at 25°C of 5,000 to 7,000 cps.
The third polyol is an organic semi-combustible PIR spray foam insulation having an acid value of 1.0 or less, an OH value of 300 mgKOH/g or less, and a viscosity measured at 25°C of 9,000 to 12,000 cps.
In paragraph 4,
An organic semi-combustible PIR spray foam insulation material having a mixing ratio of the first polyol: the second polyol: and the third polyol of 30 to 40: 25 to 35: 30 to 40 by weight.
In the first paragraph,
The above polyol composition is an organic semi-fireproof PIR spray foam insulation comprising 45 to 60 wt% of an aromatic polyester polyol, 15 to 25 wt% of a blowing agent, 15 to 30 wt% of an organic flame retardant, 5 to 15 wt% of a catalyst, and 0.2 to 1 wt% of a foaming agent.
In the first paragraph,
An organic semi-combustible PIR spray foam insulation material wherein the organic flame retardant comprises one selected from dimethyl methylphosphonate and triethyl phosphate (TEP) or a mixture thereof.
In Article 7,
The above organic flame retardant is a mixture of dimethyl methyl phosphonate (DMMP) and tris (1-chloro-2-propyl) phosphate (TCPP), or a mixture of dimethyl methyl phosphonate (DMMP), triethyl phosphate (TEP), and tris (1-chloro-2-propyl) phosphate (TCPP).
Organic semi-combustible PIR spray foam insulation having a content of dimethyl methyl phosphonate (DMMP) of 50 wt% or more of the total organic flame retardant content.
In the first paragraph,
The above isocyanate compounds include 4,4'-MDI, 2,4'-MDI and 2,2'-MDI,
Organic semi-combustible PIR spray foam insulation having an NCO content of 25 to 35 wt%, an average number of functional groups of 2 to 3, and a viscosity measured at 25°C of 100 to 400 cps.
In the first paragraph,
The above-mentioned blowing agent is selected from a chemical blowing agent selected from water, azodicarbonamide, azobisisobutyronitrile, diazoaminoazobenzene N,N'-dinitro-sopentamethylenetetramine p-toluenesulfonylhydrazide and p,p'-oxybis(benzenesulfonylhydrazide) p-toluene-sulfonylsemicarba and sodium dicarbonate; and a physical blowing agent selected from a hydrocarbon blowing agent, a hydrochlorofluorocarbon (HCFCs) blowing agent, a hydrofluorocarbon (HFC) blowing agent and a hydrofluoroolefin (HFO) blowing agent; An organic semi-combustible PIR spray foam insulation, wherein the organic semi-combustible PIR spray foam insulation is one or a mixture of two or more thereof.
In the first paragraph,
The above-mentioned organic semi-combustible PIR spray foam insulation material wherein the surfactant is a silicone-based surfactant.
A step of preparing a polyol composition comprising an aromatic polyester polyol having a structure derived from phthalic anhydride, terephthalic acid, benzoic acid, trimellitic acid and adipic acid and having an OH value of 100 to 300 mgKOH/g, a blowing agent, an organic flame retardant, a catalyst and a foaming agent, and comprising an organic substance and having a viscosity of 100 to 600 cps measured at 20°C;
A step of foaming by mixing 130 to 180 parts by weight of an isocyanate compound with respect to 100 parts by weight of the above polyol composition;
Including,
A method for producing an organic semi-fireproof PIR spray foam insulation material, wherein the aromatic polyester polyol comprises a first polyol comprising a structure derived from phthalic anhydride, terephthalic acid, and benzoic acid; a second polyol comprising a structure derived from phthalic anhydride and adipic acid; and a third polyol comprising a structure derived from phthalic anhydride, terephthalic acid, and trimellitic acid.
In Article 12,
The above organic semi-fireproof PIR spray foam insulation satisfies the semi-fireproof characteristics according to the cone calorimeter method according to KS F ISO 5660-1, and a method for manufacturing an organic semi-fireproof PIR spray foam insulation having a shrinkage rate of 20% or less after a semi-fireproof evaluation according to KS F ISO 5660-1.
In Article 12,
A method for producing an organic semi-fireproof PIR spray foam insulation, wherein the polyol composition comprises 45 to 60 wt% of an aromatic polyester polyol, 15 to 25 wt% of a blowing agent, 15 to 30 wt% of an organic flame retardant, 5 to 15 wt% of a catalyst, and 0.2 to 1 wt% of a foaming agent.
In Article 12,
A method for manufacturing an organic semi-fireproof PIR spray foam insulation, wherein the organic flame retardant comprises one selected from dimethyl methylphosphonate and triethyl phosphate (TEP) or a mixture thereof.
In Article 12,
The above organic flame retardant is a mixture of dimethyl methyl phosphonate (DMMP) and tris (1-chloro-2-propyl) phosphate (TCPP), or a mixture of dimethyl methyl phosphonate (DMMP), triethyl phosphate (TEP), and tris (1-chloro-2-propyl) phosphate (TCPP).
A method for manufacturing an organic semi-fireproof PIR spray foam insulation material, wherein the content of dimethyl methyl phosphonate (DMMP) among the total content of organic flame retardants is 50 wt% or more.
In Article 12,
The above isocyanate compounds include 4,4'-MDI, 2,4'-MDI and 2,2'-MDI,
A method for producing an organic semi-combustible PIR spray foam insulation having an NCO content of 25 to 35 wt%, an average number of functional groups of 2 to 3, and a viscosity measured at 25° C. of 100 to 400 cps.
In Article 12,
A method for manufacturing an organic semi-combustible PIR spray foam insulation, wherein the mixing and foaming step uses spray equipment.
A polyol composition comprising an aromatic polyester polyol having a structure derived from phthalic anhydride, terephthalic acid, benzoic acid, trimellitic acid and adipic acid and having an OH value of 100 to 300 mgKOH/g, an organic substance including a blowing agent, an organic flame retardant, a catalyst and a foaming agent, and having a viscosity measured at 20°C of 100 to 600 cps; and an isocyanate compound,
The above aromatic polyester polyol is a mixture of a first polyol comprising a structure derived from phthalic anhydride, terephthalic acid and benzoic acid; a second polyol comprising a structure derived from phthalic anhydride and adipic acid; and a third polyol comprising a structure derived from phthalic anhydride, terephthalic acid and trimellitic acid.
A spray foaming composition comprising 130 to 180 parts by weight of an isocyanate compound mixed with 100 parts by weight of the above polyol composition.
In Article 19,
The above first polyol is a product produced by reacting phthalic anhydride, terephthalic acid and benzoic acid as acid components and diethylene glycol and triethylene glycol as glycol components.
The above second polyol is a product produced by reacting phthalic anhydride and adipic acid as acid components and diethylene glycol as glycol components.
The above third polyol is a spray foaming composition prepared by reacting phthalic anhydride, terephthalic acid and trimellitic acid as acid components and trimethylolpropane and diethylene glycol as glycol components.
In Article 20,
The above first polyol has an acid value of 1.0 or less, a hydroxyl value of 130 mgKOH/g or less, and a viscosity measured at 25°C of 25,000 to 35,000 cps,
The above second polyol has an acid value of 2.0 or less, a hydroxyl value of 95 mgKOH/g or less, and a viscosity measured at 25°C of 5,000 to 7,000 cps.
A spray foaming composition wherein the third polyol has an acid value of 1.0 or less, an OH value of 300 mgKOH/g or less, and a viscosity measured at 25°C of 9,000 to 12,000 cps.
In Article 20,
A spray foaming composition having a mixing ratio of the first polyol: the second polyol: the third polyol of 30 to 40:25 to 35:30 to 40 by weight.
In Article 19,
The polyol composition is a spray foaming composition comprising 45 to 60 wt% of an aromatic polyester polyol, 15 to 25 wt% of a blowing agent, 15 to 30 wt% of an organic flame retardant, 5 to 15 wt% of a catalyst, and 0.2 to 1 wt% of a foaming agent.
In Article 19,
A spray foaming composition comprising the organic flame retardant selected from dimethyl methylphosphonate, tris(1-chloro-2-propyl)phosphate (TCPP), or triethyl phosphate (TEP), or a mixture thereof.
In Article 19,
The above organic flame retardant is a mixture of dimethyl methyl phosphonate (DMMP) and tris (1-chloro-2-propyl) phosphate (TCPP), or a mixture of dimethyl methyl phosphonate (DMMP), triethyl phosphate (TEP), and tris (1-chloro-2-propyl) phosphate (TCPP).
A spray foaming composition having a content of dimethyl methyl phosphonate (DMMP) of 50 wt% or more of the total content of organic flame retardants.
In Article 19,
The above isocyanate compounds include 4,4'-MDI, 2,4'-MDI and 2,2'-MDI,
A spray foaming composition having an NCO content of 25 to 35 wt%, an average number of functional groups of 2 to 3, and a viscosity measured at 25° C. of 100 to 400 cps.
In Article 19,
A spray foaming composition wherein the above-mentioned surfactant is a silicone-based surfactant.