KR102577107B1 - Adhesive composition having flame-resistance and non-flammable panel comprising the same - Google Patents

Abstract

The present invention includes a flame-retardant urethane-based binder, a solid flame retardant and a liquid flame retardant, wherein the flame-retardant urethane-based binder is prepared by reacting a halohydrin group-added polyol compound with an isocyanate-based compound, and a non-combustible sandwich containing the same. It's about panels.

Description

Flame retardant adhesive composition, and sandwich panel having incombustibility comprising the same {ADHESIVE COMPOSITION HAVING FLAME-RESISTANCE AND NON-FLAMMABLE PANEL COMPRISING THE SAME}

The present invention relates to a flame retardant adhesive composition and a sandwich panel including the same, which has excellent non-flammability, excellent insulation, and excellent mechanical properties and adhesion.

A sandwich panel is a construction material that has an insulating core material between two metal plates. It is inexpensive, simple to construct, can significantly shorten the construction period, and has excellent insulation effects. For this reason, sandwich panels are widely used in construction sites such as factories, warehouses, houses, and hangars. At this time, Styrofoam, urethane foam, glass wool, mineral wool, etc. are widely used as the core material. However, this core material is flammable and lacks incombustibility, and releases a large amount of organic matter in the event of a fire, making it vulnerable to fire and causing a lot of material and human loss in the event of a fire.

As a solution to this problem, sandwich panels using flame-retardant core materials such as PET and polyolefin have been proposed. Specifically, Korean Patent Publication No. 2012-0009033 (Patent Document 1) discloses a sandwich panel including a core material foamed with a silicate filler or a filler mixed with the silicate and an additive for improving water resistance and strength. However, panels containing core materials containing incombustible fillers, as shown in Patent Document 1, are vulnerable to moisture, making them difficult to apply in high temperature and high humidity environments, and lack incombustibility, so there is a problem in the long-term durability of structures to which they are applied.

As an alternative to this, sandwich panels using flame-retardant inorganic fiber core materials such as glass wool and mineral wool have been proposed. However, even if the flame-retardant inorganic fiber-based core material as described above is used, there is a problem that the manufactured sandwich panel lacks incombustibility due to the flammability of the adhesive that is essential for joining the metal plate and the core material during panel manufacturing.

Accordingly, Korean Patent No. 1619298 (Patent Document 2) includes a main portion containing a polyol component consisting of polyether polyol and polyester polyol; A polyurethane two-component semi-non-flammable adhesive consisting of a curing agent portion containing an isocyanate component is disclosed. However, the adhesive of Patent Document 2 is a semi-incombustible adhesive, and has a limitation in that the manufactured sandwich panel lacks incombustibility due to its lack of incombustibility.

Therefore, there is a need for research and development on a flame-retardant adhesive composition that has excellent incombustibility and adhesion, and a sandwich panel including the same with excellent incombustibility, insulation, mechanical properties, and adhesion.

Korean Patent Publication No. 2012-0009033 (Publication date: 2012.2.1.) Korean Patent No. 1619298 (Publication Date: May 10, 2016)

Accordingly, the present invention provides a flame retardant adhesive composition that has excellent incombustibility and adhesion, and a sandwich panel including the same, which has excellent heat resistance, insulation, mechanical properties, and adhesion.

The present invention includes a flame retardant urethane binder, a solid flame retardant, and a liquid flame retardant,

The flame retardant urethane binder provides a flame retardant adhesive composition prepared by reacting a halohydrin addition polyol compound and an isocyanate compound.

In addition, the present invention provides an inorganic fiber-based core material with an organic content of 3.0 to 9.5% by weight;

An adhesive layer formed on both sides of the core material; and

It includes a metal layer formed on the adhesive layer on both sides of the core material,

The adhesive layer provides a non-combustible sandwich panel, which is formed by applying 70 to 400 g of the flame retardant adhesive composition based on 1 m ² of the surface area of the core material.

The flame retardant adhesive composition according to the present invention has excellent non-flammability, adhesive strength, and wet adhesive strength. For this reason, the sandwich panel containing the flame retardant adhesive composition satisfies the judgment criteria of the non-combustibility test specified in KS F ISO 1182 and has excellent non-combustibility, as well as excellent insulation, mechanical properties, and adhesion.

1 is a cross-sectional view of a sandwich panel according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

In this specification, when a part “includes” a certain component, this means that it may further include other components rather than excluding other components, unless specifically stated to the contrary.

Additionally, in this specification, when a layer is said to be located “on” another layer, this includes not only the case where a layer is in contact with another layer, but also the case where another layer exists between the two layers.

Flame retardant adhesive composition

The flame retardant adhesive composition according to the present invention includes a flame retardant urethane binder, a solid flame retardant, and a liquid flame retardant.

Flame retardant urethane binder

The flame-retardant urethane-based binder maintains the strength of the sandwich panel by providing adhesion between the core material and the metal layer through a urethane curing reaction.

The flame-retardant urethane-based binder is manufactured, for example, by reacting an isocyanate-based compound with a halohydrin addition polyol compound.

The halohydrin addition polyol compound may be a halohydrin addition phosphoric acid polyol compound, a halohydrin addition phosphoric acid-ester polyol compound, etc.

The halohydrin addition polyol compound can be produced, for example, by reacting a phosphoric acid-based compound with a halohydrin-based compound.

The phosphoric acid-based compound is non-flammable and serves to improve flame retardant properties by reducing the spread of flame and forming non-combustible char under combustion conditions.

Additionally, the phosphoric acid-based compound may be one selected from the group consisting of phosphoric acid and phosphoric acid water hydrate. At this time, The phosphoric acid water hydrate may contain a small amount of moisture, and the moisture content may be less than 20% by mass. If the moisture content in the phosphoric acid aqueous hydrate exceeds the above range, the content of single-molecular side reactants and the amount of residual moisture in the prepared halohydrin group-added polyol compound may increase, causing instability in the urethane reaction.

The halohydrin-based compound contains a halogen atom and serves to reduce flame spread and improve flame retardancy when exposed to combustion conditions. Additionally, the halohydrin-based compound may be a halogen-substituted mono-epoxy-based compound, for example, epichlorohydrin, α-methyl epichlorohydrin, epifluorohydrin, epibromohydrin, etc. Specifically, the halohydrin-based compound may be epichlorohydrin.

The halohydrin addition polyol compound can be prepared by reacting 1 molar equivalent of a phosphoric acid-based compound with 3.5 to 9.0 molar equivalents, 4.0 to 8.0 molar equivalents, or 4.0 to 7.5 molar equivalents of the halohydrin-based compound. When the molar equivalent of the reaction between the phosphoric acid-based compound and the halohydrin-based compound is less than the above ratio, that is, when the molar equivalent of the halohydrin-based compound is low relative to the molar equivalent of the phosphoric acid-based compound, the acidity of the prepared halohydrin-addition polyol compound is low. Due to high reactivity with isocyanate-based compounds, problems with curing and poor strength may occur. In addition, when the molar equivalent of the phosphoric acid-based compound and the halohydrin-based compound exceeds the above ratio, that is, when the molar equivalent of the halohydrin-based compound is high relative to the molar equivalent of the phosphoric acid-based compound, the content of phosphoric acid groups in the prepared polyol compound is increased. Problems with deterioration of flame retardant performance and strength may occur due to deteriorated or unreacted halohydrin-based compounds remaining.

The halohydrin addition polyol compound may be included in an amount of 25 to 65 parts by weight, or 27 to 60 parts by weight, based on 100 parts by weight of the solid content of the flame-retardant urethane-based binder. If the content of the halohydrin addition polyol compound is less than the above range, the flame retardant performance of the urethane-based binder may be reduced, and if it exceeds the above range, the water resistance and adhesive strength of the adhesive composition containing it may be reduced.

The isocyanate-based compound may contain two or more isocyanate groups in one molecule. For example, the isocyanate-based compounds include 2,4-toluene diisocyanate (2,4-TDI), 2,6-toluene diisocyanate (2,6-TDI), and 4,4'-diphenylmethylene diisocyanate ( 4,4'-MDI), 2,4'-diphenylmethylene diisocyanate (2,4'-MDI), 1,4-phenylene diisocyanate, 1,5-naphthalene diisocyanate, ethylene diisocyanate, propylene diisocyanate Isocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, butylene diisocyanate, trimethylhexamethylene diisocyanate, bis(4-isocyanatocyclohexyl)methane, 1-methyltrimethylene diisocyanate, 1,3-cyclopentene diisocyanate, 1,4-cyclopentene diisocyanate, 1,2-cyclopentene diisocyanate, 5-isocyanato-1-(isocyanatomethyl)-1,3,3- Trimethyl-cyclohexane, triphenylmethane triisocyanate, tris(phenyl isocyanate) thiophosphate, 1,6,10-undecane triisocyanate and 1-isocyanato-4-[(4-isocyanatephenyl)methyl ]It may contain one or more types selected from the group consisting of benzene.

Additionally, the isocyanate-based compound may be reacted in an amount of 35 to 75 parts by weight or 40 to 73 parts by weight based on 100 parts by weight of solid content of the flame-retardant urethane-based binder. If the content of the isocyanate-based compound is less than the above range, the adhesive strength and water resistance of the adhesive composition may decrease due to uncuring, and if it exceeds the above range, the problem of insufficient non-flammable performance of the adhesive composition may occur.

The urethane-based prepolymer may have an unreacted isocyanate group content (NCO%) of 5 to 25% by weight, or 10 to 20% by weight. If the NCO% of the urethane-based prepolymer is less than the above range, the viscosity of the adhesive composition may increase excessively or the curing speed may be delayed, resulting in poor workability when manufacturing sandwich panels. Additionally, if the NCO% of the urethane-based prepolymer exceeds the above range, the adhesive layer may brittle, resulting in poor adhesive strength.

Additionally, the flame retardant urethane-based binder may be 10 to 50 wt%, 18 to 45 wt%, or 20 to 40 wt% based on the total solid weight of the flame retardant adhesive composition. If the content of the flame-retardant urethane-based binder is less than the above range, there is a problem that the adhesive strength of the adhesive layer is inferior, and if the content is more than the above range, the problem of deterioration of the non-combustible performance due to combustion of the flame-retardant urethane-based binder may occur.

solid flame retardant

The solid flame retardant serves to improve the flame retardancy and/or incombustibility of the adhesive layer.

Additionally, the solid flame retardant may be, for example, a metal-based solid flame retardant, a phosphorus-based solid flame retardant, or a nitrogen-based solid flame retardant. The metal-based solid flame retardant may include, for example, zinc borate, aluminum hydroxide, magnesium hydroxide, and antimony pentoxide. In addition, examples of the phosphorus-based solid flame retardant include ammonium polyphosphate, red phosphorus, and phosphate. The nitrogen-based solid flame retardant may include melamine, melamine cyanurate, etc. The solid flame retardant may be used alone or in combination of two or more types.

The solid flame retardant may be included in the composition in an amount of 30 to 70% by weight, 40 to 65% by weight, or 45 to 65% by weight based on the total solid weight of the flame retardant adhesive composition. If the content of the solid flame retardant is less than the above range, there is a problem that the non-combustibility of the adhesive layer is deteriorated, and if it exceeds the above range, the incombustibility of the adhesive layer becomes excellent, but storage and adhesion may be reduced.

liquid flame retardant

The liquid flame retardant improves the incombustibility of the adhesive layer, improves the dispersibility of the solid flame retardant in the adhesive composition by improving the miscibility between each component when mixing the adhesive composition, and improves the application workability of the adhesive composition when manufacturing sandwich panels. Do it.

In addition, the liquid flame retardant is compatible with a flame-retardant urethane-based binder and may be a phosphorus-based liquid flame retardant with flame retardant properties, for example, tris(chloroisopropyl)phosphate (TCPP), triethyl phosphate. (Triethylphosphate, TEP), Tricresylphosphate (TCP), and Tris(chloroethyl)phosphate (TCEP). The liquid flame retardant can be used alone or in combination of two or more types.

The liquid flame retardant may be included in the composition in an amount of 5 to 30% by weight, 10 to 30% by weight, or 10 to 25% by weight based on the total solid weight of the flame retardant adhesive composition. If the content of the liquid flame retardant is less than the above range, the miscibility and fluidity of the adhesive composition become poor, making uniform mixing difficult when manufacturing the adhesive composition, and the storage and application workability of the manufactured adhesive composition become poor. If it is excessive, the adhesion strength may be inferior due to a decrease in the incombustibility and strength of the adhesive layer.

The flame retardant adhesive composition may further include additives such as dispersants, wettability improvers, and leveling agents, if necessary.

The dispersant serves to improve the storage stability of the adhesive composition.

Additionally, the dispersant may be an ionic surfactant or a non-ionic surfactant. At this time, the ionic surfactant may include, for example, sodium dodecyl sulfite, and the non-ionic surfactant may include, for example, ethoxylated aliphatic alcohol and polyethylene oxide (PEO). ), Carboxylic ester, polyethylene glycol ester, fatty acid sorbitol ester, fatty acid glycol ester, fatty acid diethanol amine , fatty acids or glycol-based esters such as alkyl monoglyceryl ether and carboxylic amide; amide; amine; ether compounds; etc. can be mentioned.

The dispersant may be included in the composition in an amount of 0.1 to 5 parts by weight, 0.1 to 3 parts by weight, or 0.3 to 2 parts by weight based on the total solid weight of the flame retardant adhesive composition. If the content of the dispersant is less than the above range, there may be problems such as precipitation of the solid flame retardant and the storage properties of the adhesive composition are poor. If the content exceeds the above range, problems such as poor curability and/or excessive decrease in viscosity of the adhesive composition may occur. there is.

The flame retardant adhesive composition may be a one-component or two-component type.

When the flame retardant adhesive composition is a two-component type, the flame retardant adhesive composition includes an adhesive base comprising a flame retardant urethane-based binder, a solid flame retardant, and a liquid flame retardant; and an adhesive curing agent including a curing catalyst, a halohydrin addition polyol compound, a solid flame retardant, and a liquid flame retardant. At this time, the two-part adhesive composition can be used after mixing the adhesive base material and adhesive hardener before use.

The curing catalyst serves to promote the curing reaction of the adhesive main agent, and can be used without particular restrictions as long as it is generally applicable to urethane-based adhesives. The curing catalyst is, for example, triethylamine, tripropylamine, tributylamine, triamylamine, N-methyl morpholine, N,N-dimethyl cyclohexylamine, N,N-dimethyl benzylamine, 2- Amines such as methyl imidazole, pyrimidine, dimethylaniline, triethylene diamine, triethanolamine, N,N-dimethylethanolamine 2,2'-dimorpholinodiethyl ether; tetraalkyl ammonium hydroxide; alkaline compounds such as alkaline hydroxide, alkaline phenolate, and alkaline alcoholate; Organic tin compounds such as di-butyltindilaurate; etc. can be mentioned. Commercially available products of the amine-based curing catalyst include JEFFCAT DMDEE from Huntsman Corporation and DABCO EG from Econik Operations GmbH, and organic tin-based curing catalysts include The catalyst is Songwon Industrial's BDTDL.

When the flame retardant adhesive composition is a two-component type, the mixing weight ratio of the adhesive base material and the adhesive curing agent is determined by the ratio of the unreacted isocyanate group content in the adhesive base material and the hydroxyl group content in the adhesive curing agent, for example, 1 hydroxyl group in the adhesive curing agent. It can be mixed so that the molar equivalent of the isocyanate group in the adhesive base material is 0.9 to 2.0, or 0.95 to 1.8. If the molar equivalent is less than the above range, there is a problem that the adhesive strength and water resistance of the adhesive composition become poor, and if it exceeds the above range, there is a problem that the non-flammable performance of the adhesive composition deteriorates.

The flame retardant adhesive composition according to the present invention has excellent incombustibility and has the effect of improving the incombustibility of the manufactured sandwich panel. In addition, the flame retardant adhesive composition has excellent adhesion and improves the adhesion between the core material and the metal plate, thereby improving the mechanical properties of the sandwich panel.

sandwich panel

The sandwich panel according to the present invention includes an inorganic fiber-based core material; An adhesive layer formed on both sides of the core material; and a metal layer formed on the adhesive layer on both sides of the core material.

Referring to Figure 1, the sandwich panel 10 includes a core material 100; Adhesive layers (210, 220) formed on both sides of the core material; and metal layers 310 and 320 formed on the adhesive layer.

heartwood

The heartwood may have an organic content of 3.0 to 9.5% by weight, or 3.5 to 9.0% by weight. If the organic matter content of the core material is less than the above range, the strength of the core material may decrease and workability may become poor, and if it exceeds the above range, the non-combustible performance may be deteriorated. At this time, the organic content may be a value measured by the ignition loss measurement method (mass loss rate after heat treatment at 480°C for 2 hours).

In addition, the inorganic fiber-based core material can be used without particular limitation as long as it satisfies the above organic matter content and can generally be used as a core material for sandwich panels, and may include, for example, glass wool or mineral wool.

The core material may have a density of 25 to 100 kg/m ³ , or 40 to 80 kg/m ³ . If the density of the core material is less than the above range, the strength of the manufactured sandwich panel may deteriorate, and if it exceeds the above range, the insulation performance of the sandwich panel may deteriorate.

adhesive layer

The adhesive layer serves to adhere the metal layer to the core material.

The adhesive layer may be formed by applying 70 to 400 g, 100 to 350 g, or 200 to 300 g of the flame retardant adhesive composition based on 1 m ² of the surface area of the core material. If the application amount of the flame retardant adhesive composition is less than the above range, there is a problem that the adhesive strength between the core material and the metal layer becomes poor, and if it exceeds the above range, the non-combustible performance of the manufactured sandwich panel may be reduced due to excessive combustion of the adhesive layer. .

metal layer

The metal layer serves to improve the strength and incombustibility of the sandwich panel.

The metal layer is not particularly limited as long as it is generally applicable to improve the strength and incombustibility of the sandwich panel, and may include, for example, one or more types selected from the group consisting of iron, stainless steel, aluminum, and magnesium. Additionally, the metal layer may be, for example, a galvanized steel sheet or a metal layer coated with an organic coating layer.

Additionally, the metal layer may have an average thickness of 0.1 to 5.0 mm, or 0.3 to 1.0 mm.

The sandwich panel may have a temperature difference of 20K or less and a mass reduction rate of 30% by weight or less when evaluated for non-combustibility according to the method of KS F ISO 1182.

As described above, the sandwich panel according to the present invention satisfies the non-combustibility test criteria specified in KS F ISO 1182, has excellent non-combustibility, and is also excellent in insulation, mechanical properties, and adhesion.

Hereinafter, the present invention will be described in more detail through examples. However, these examples are only intended to aid understanding of the present invention, and the scope of the present invention is not limited to these examples in any way.

[Example]

Synthesis Example 1. Preparation of halohydrin addition polyol compound-1

230.6 g of phosphoric acid (Dongbu Farm Hannong Co., Ltd.; purity 85%) was added to a 2L four-neck flask equipped with a temperature control device, a stirring device, and a nitrogen input device under nitrogen supply, and the temperature was raised to 60 ± 3°C while stirring. Afterwards, 1,295.4 g of epichlorohydrin was added dropwise over 3 hours while stirring, and the temperature during dropwise addition was maintained at 70 ± 10°C through cooling. After epichlorohydrin was added dropwise, the reaction product was heated to 95 ± 3°C and aged for 2 hours. After completion of aging, the temperature was raised to 110 ± 3°C and the pressure was reduced to 150 torr or less for 30 minutes to recover unreacted epichlorohydrin and residual moisture, and then cooled to 50°C to obtain halohydrin addition polyol compound-1.

The prepared halohydrin addition polyol compound-1 was a light yellow transparent liquid and had a hydroxyl value of 365 mgKOH/g.

Synthesis Examples 2 to 4.

A halohydrin addition polyol compound was prepared in the same manner as in Synthesis Example 1 with the composition ratio shown in Table 1 below.

(part by weight) Synthesis Example 1 Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Phosphoric acid-based compound (purity%) Phosphoric acid (85%) 230.6 - 345.9 - Phosphoric acid (99%) - 207.9 - 178.2 epichlorohydrin 1,295.4 971.6 832.8 1665.5 Molar ratio (molar equivalent) of epichlorohydrin/phosphoric acid-based compound 7 5 3 10 Hydroxyl value of halohydrin addition polyol compound (mgKOH/g) 365 302 580 164

Synthesis Example 5. Preparation of urethane-based binder-1

Add 984.5 parts by weight of diphenylmethane diisocyanate (Cosmonate JG70K from Kumho Mitsui Chemicals) as an isocyanate compound under nitrogen supply to a 2L four-necked flask equipped with a temperature control device, stirring device, and nitrogen input device, and stir at 60 ± 3°C. The temperature was raised. Afterwards, 372.5 parts by weight of the halohydrin addition polyol compound of Synthesis Example 1 was added and stabilized for 30 minutes, then the temperature was raised to 75 ± 3°C and maintained for 3 hours. Afterwards, it was cooled to below 50°C to prepare urethane-based binder-1.

The produced urethane-based binder-1 had an unreacted isocyanate group content (NCO%) of 15.8% by weight.

Synthesis Examples 6 to 8.

A urethane-based binder was prepared in the same manner as in Synthesis Example 5 with the composition ratio shown in Table 2 below. At this time, as the polyol compound, bifunctional polyether polyol (equivalent weight: 1,000, PP-2000) manufactured by KPX Chemicals was used.

(part by weight) Synthesis Example 5 Synthesis Example 6 Synthesis Example 7 Synthesis Example 8 isocyanate Cosmonate JG70K 984.5 1,099.4 867.2 607.1 Halohydrin addition polyol compound Synthesis Example 1 372.5 - - - Synthesis Example 2 - 442.6 - - Synthesis Example 4 - - 474.8 - polyol compounds PP-2000 - - - 367.9 NCO group content of urethane binder (% by weight) 15.8 15.9 16.1 17.8

Preparation Examples 1 to 7. Preparation of adhesive composition (adhesive main agent)

An adhesive composition (main adhesive) was prepared by mixing the ingredients and composition ratios shown in Table 3 below.

At this time, TCPP is a liquid flame retardant, which is tris (chloroisopropyl) phosphate, BYK's BYK-220S was used as a dispersant, ATH is a solid flame retardant, which is aluminum tri-hydroxide, and the isocyanate-based compound is diphenylmethane diisocyanate. Annette (Cosmonate JG70K from Kumho Mitsui Chemicals) was used.

(part by weight) Manufacturing Example 1 Production example 2 Production example 3 Production example 4 Production example 5 Production example 6 Production example 7 liquid flame retardant TCPP 14.5 14.5 14.5 9.5 9.5 14.5 14.5 dispersant BYK-220S 0.5 0.5 0.5 0.5 0.5 0.5 0.5 solid flame retardant ATH 55 55 55 35 75 55 55 Urethane-based binder Synthesis Example 5 30 - - 55 15 - - Synthesis Example 6 - 30 - - - - - Synthesis Example 7 - - - - - 30 - Synthesis Example 8 - - - 30 Isocyanate-based compounds Cosmonate JG70K - - 30 - - - -

Preparation Example 5 had an excessive amount of solid flame retardant, a small amount of liquid flame retardant, and a small amount of urethane-based binder, so the viscosity increased excessively, making it impossible to manufacture an adhesive composition with a uniform composition.

Preparation Examples 8 and 9. Preparation of adhesive curing agent

An adhesive curing agent was prepared by mixing the ingredients and composition ratios shown in Table 4 below.

At this time, DBTDL is an organic tin-based urethane curing catalyst (dibutyltin dilaurate) from Songwon Industries, and DMDEE is an amine-based urethane curing catalyst (2,2'-dimorpholinodiethyl ether) from Huntsman Corporation.

(part by weight) Production example 8 Production example 9 liquid flame retardant TCPP 13 13 dispersant BYK-220S 0.5 0.5 solid flame retardant ATH 55 55 curing catalyst DBTDL 0.5 0.5 DMDEE One One Halohydrin addition polyol compound Synthesis Example 1 30 - Synthesis Example 3 - 30

Preparation Example 10. Preparation of two-component non-flammable urethane adhesive composition

As a general-purpose foamed urethane adhesive, a two-component urethane adhesive consisting of a hardener part (polymeric di-phenyl methane di-isocyanate) and a main part (polyol, water, additives) was used, and the hardener part was Kumho Mitsui Chemical's Cosmonate. M-200 was used, and Kukdo Chemical's KPF-2406 was used as the main part. At this time, 100 parts by weight of the hardener part was mixed with 100 parts by weight of the main part, and the two-component urethane adhesive did not contain a solid flame retardant or a liquid flame retardant.

Experimental Example 1.

A core material sample was prepared by cutting KCC's non-combustible glass wool core material (density: 64 kg/㎥, organic binder content: 8.3% by weight relative to the total weight of the core material) into a cylindrical shape with a diameter of 45 ± 1 mm and a height of 50 ± 2 mm. Afterwards, the adhesive composition of Preparation Example 1 was applied in an amount of 250 g/m2 to both sides of the core sample, and then a color steel sheet with a thickness of 0.4 ± 0.05 mm (manufacturer: KG Dongbu Steel, product name: NF non-combustible color steel sheet) was attached and stored at room temperature. A sandwich panel was manufactured by leaving it for 12 hours. At this time, the organic binder content in the core material was measured using the loss-on-ignition method.

Specifically, the ignition loss method heat-treated the core material at 480°C for 2 hours and then measured the mass loss rate (% by mass) before and after heat treatment based on the mass before heat treatment.

Experimental Examples 2 to 12.

A sandwich panel was manufactured in the same manner as Experiment 1, except that the type of adhesive composition was adjusted as shown in Table 5.

At this time, the content of the flame-retardant urethane-based binder in Table 5 is the sum of the content of the main flame-retardant urethane-based binder and the content of the halohydrin-addition polyol compound of the curing agent, and the content of the halohydrin-addition polyol compound of the curing agent is added to the content of the urethane-based binder. This is because the OH group of the polyol compound of the curing agent reacts with the NCO group of the main urethane-based binder to generate a urethane group.

In addition, the urethane-based binders of Preparation Examples 7 and 10 were non-flammable urethane-based binders.

Furthermore, the molar ratio of NCO/OH in Table 5 is the ratio of the molar equivalent of unreacted NCO in the main agent to the molar equivalent of hydroxyl group (OH) in the curing agent.

adhesive composition Content of urethane-based binder relative to the total weight of the adhesive composition Content of halohydrin addition polyol compound relative to the total weight of urethane binder liquid type subject
(part by weight) hardener
(part by weight) Molar ratio of NCO/OH Application amount (g/m ² ) Experimental Example 1 One Manufacturing Example 1 - - 250 30% by weight 27.5% by weight Experimental Example 2 One Production example 2 - - 250 30% by weight 28.7% by weight Experimental Example 3 2 Production example 2
(100) Production example 8
(50) 1.17 250 30% by weight 52.5% by weight Experimental Example 4 2 Production example 3
(100) Production example 8
(100) 1.15 250 30% by weight 50.0% by weight Experimental Example 5 2 Production Example 7 (100) Production example 8
(50) 1.30 250 30% by weight 33.3% by weight Experimental Example 6 One Production example 2 - - 50 30% by weight 28.7% by weight Experimental Example 7 One Production example 2 - - 500 30% by weight 28.7% by weight Experimental Example 8 One Production example 4 - - 250 55% by weight 27.5% by weight Experimental Example 9 One Production example 7 - - 250 30% by weight 0.0% by weight Experimental Example 10 One Production example 6 - - 250 30% by weight 35.4% by weight Experimental Example 11 2 Preparation Example 3 (100) Production Example 9 (50) 1.46 250 30% by weight 33.3% by weight Experimental Example 12 2 Production example 10 - 250 100% by weight 0% by weight

Test example: Characteristic evaluation

The sandwich panel of the experimental example was measured in the same manner as below, and the results are shown in Table 6.

(1) Adhesion strength

A steel plate and a core material were attached to a sandwich panel using an adhesive composition, left at room temperature for 12 hours, the steel plate and the core material were peeled, and the adhesive layer on the steel plate was visually inspected to measure the adhesive strength.

Specifically, if a uniform adhesive layer is formed on the steel plate and core material adhesion is good, Excellent (○); if the adhesive layer is partially detached within 30 area% of the steel plate and core material adhesion is generally good, average (△ ), if peeling of the adhesive layer was due to poor attachment of the embryonic core material, it was judged to be defective (X).

(2) Wet adhesive strength

In the same way as when measuring the adhesive strength in item (1), the sandwich panel was left at room temperature for 12 hours and immersed in water for 30 minutes, then the colored steel sheet as the metal layer was peeled off and the adhesive layer on the steel sheet was visually inspected to measure the wet adhesive strength. .

Specifically, if a uniform adhesive layer is formed on the steel plate and core material adhesion is good, Excellent (○); if the adhesive layer is partially detached within 30 area% of the steel plate and core material adhesion is generally good, average (△ ), if peeling of the adhesive layer occurred and core material adhesion was poor, it was judged as defective (X).

(3) Non-combustible evaluation-1: Temperature difference

A non-combustible evaluation was conducted on sandwich panels according to the method of KS F ISO 1182. At this time, sandwich panels were manufactured with a diameter of 45 mm and a thickness of 50 mm and used as specimens.

Specifically, the specimen was placed in a non-combustible tester preheated to 750°C, and the maximum temperature in the tester and the stable temperature after being left for 20 minutes were measured. If the temperature difference was 20K or less, the nonflammability was judged to be excellent.

(4) Non-combustible evaluation-2: Mass reduction rate

A non-combustible evaluation was conducted on sandwich panels according to the method of KS F ISO 1182. At this time, sandwich panels were manufactured with a diameter of 45 mm and a thickness of 50 mm and used as specimens.

Specifically, the initial mass of the specimen was measured, the specimen was placed in a heating furnace preheated to 750°C, and the mass of the specimen was measured after being prevented for 20 minutes. The mass reduction rate of the specimen after heat treatment was calculated based on the initial mass of the specimen, and if it was less than 30% by mass, it was judged to have excellent incombustibility.

adhesive strength Wet Adhesion Strength Non-combustible evaluation Temperature difference (K) Mass reduction rate (mass%) Experimental Example 1 ○ ○ 15.8 5.84 Experimental Example 2 ○ ○ 14.2 5.75 Experimental Example 3 ○ ○ 18.7 6.05 Experimental Example 4 ○ ○ 18.5 5.92 Experimental Example 5 ○ ○ 19.4 6.02 Experimental Example 6 X X 6.2 4.86 Experimental Example 7 ○ ○ 42.4 7.23 Experimental Example 8 ○ ○ 34.3 5.72 Experimental Example 9 ○ ○ 37.5 6.15 Experimental Example 10 ○ ○ 24.8 6.24 Experimental Example 11 X X 15.4 5.74 Experimental Example 12 ○ ○ 64.5 7.42

As shown in Table 6, the sandwich panels of Experimental Examples 1 to 5 had excellent adhesive strength and wet adhesive strength, and during nonflammability evaluation, the temperature difference was small at 20K or less and the mass reduction rate was small at 7% by weight or less, so they were very nonflammable. .

On the other hand, the curing agent of Preparation Example 9 including the halohydrin group-containing polyol compound of Experimental Example 6 with a small application amount of the flame retardant adhesive composition, and the halohydrin group-containing polyol compound of Synthesis Example 3 with insufficient reaction molar equivalent of the halohydrin group-containing compound to the phosphoric acid-based compound. Experimental Example 11 including was lacking in adhesive strength and wet adhesive strength.

In addition, Experimental Example 7 in which the application amount of the flame retardant adhesive composition was excessive, Experimental Example 8 using the adhesive of Preparation Example 4 with a small amount of solid flame retardant, Experimental Example 9 not containing a polyol compound containing a halohydrin group, and a phosphoric acid-based compound Experimental Example 10 including the halohydrin group-containing polyol compound of Synthesis Example 4 with an excessive molar equivalent reaction of the halohydrin group-containing compound, and Experimental Example 12 including the two-component non-flammable urethane adhesive composition of Preparation Example 1 The temperature difference in the non-combustible evaluation was over 20K, resulting in insufficient incombustibility.

Claims (7)

Contains a flame retardant urethane binder, a solid flame retardant, and a liquid flame retardant,
The flame-retardant urethane-based binder is manufactured by reacting a halohydrin group-added polyol compound with an isocyanate-based compound,
The halohydrin group-added polyol compound is a flame retardant adhesive composition prepared by reacting 1 molar equivalent of a phosphoric acid-based compound and 3.5 to 9.0 molar equivalents of a halohydrin group-containing compound. delete In claim 1,
A flame-retardant adhesive composition comprising 25 to 65 parts by weight of the halohydrin group-added polyol compound and 35 to 75 parts by weight of the isocyanate-based compound, based on 100 parts by weight of the flame-retardant urethane-based binder. In claim 1,
A flame retardant adhesive composition comprising 10 to 50% by weight of a flame retardant urethane-based binder, 30 to 70% by weight of a solid flame retardant, and 5 to 30% by weight of a liquid flame retardant. Inorganic fiber-based core material;
An adhesive layer formed on both sides of the core material; and
It includes a metal layer formed on the adhesive layer on both sides of the core material,
The adhesive layer is a non-flammable sandwich panel formed by applying 70 to 400 g of the flame retardant adhesive composition of any one of claims 1, 3, and 4 based on 1 m ² of the surface area of the core material. In claim 5,
The core material is a non-combustible sandwich panel comprising an inorganic fiber-based core material with an organic content of 3.0 to 9.5% by weight and a density of 25 to 100 kg/m ³ . In claim 5,
A non-combustible sandwich panel with a temperature difference of 20K or less and a mass reduction rate of 30% by weight or less when evaluated for noncombustibility according to the method of KS F ISO 1182.