KR20230028996A - Adhesive composition having flame-resistance and non-flammable panel comprising the same - Google Patents

Abstract

The present invention relates to a flame retardant adhesive composition, and a non-combustible sandwich panel including the same, wherein the flame retardant adhesive composition includes a silicone-modified urethane-based prepolymer, a solid flame retardant and a liquid flame retardant, the silicone-modified urethane-based prepolymer is manufactured by reacting an isocyanate compound with an active hydrogen-containing siloxane compound, the content of an unreacted isocyanate group (NCO%) is 5 to 25% by weight, and the content of a siloxane compound is 15 to 70% by weight.

Description

Flame retardant adhesive composition, and a sandwich panel having incombustibility comprising the same

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

Sandwich panel is a building material in which a thermal insulation material is inserted as a core material between two metal plates. It is inexpensive and simple to construct, so the construction period can be greatly reduced and the insulation effect is excellent. For this reason, sandwich panels are widely used in construction sites such as factories, warehouses, houses, and hangars. At this time, as the core material, styrofoam, urethane foam, glass wool, mineral wool, and the like are widely used. However, such a core material has problems in that it lacks incombustibility due to its flammability and releases a large amount of organic matter during a fire, making it vulnerable to fire and causing a lot of physical and human losses in the event of a fire.

As an alternative to this, a sandwich panel using a flame retardant core material such as PET or polyolefin has 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, as in Patent Document 1, a panel including a core material containing an incombustible filler is vulnerable to moisture and is difficult to apply to a high temperature and high humidity environment, lacks incombustibility, and has a problem of insufficient long-term durability of a structure to which it is applied.

In addition, Korean Patent Registration No. 1619298 (Patent Document 2) is prepared by reacting a curing agent part containing an isocyanate group with a main part containing a polyol composed of polyether polyol and polyester polyol, and a flame retardant, thermally expandable graphite, catalyst, silicone-based Disclosed is a two-component polyurethane adhesive containing a foam stabilizer and a silicone-based emulsifier. However, when the semi-incombustible adhesive of Patent Document 2 is included as the adhesive of the sandwich panel, there is a limit to controlling the content of the combustible organic material in the sandwich panel manufactured by using the core material containing the organic material, thereby making the sandwich panel incombustible There was a limit to the lack of performance.

Therefore, there is a need for research and development on a sandwich panel having excellent incombustibility, excellent thermal insulation properties, and excellent mechanical properties and adhesion.

Korean Patent Publication No. 2012-0009033 (published date: 2012.2.1.) Korean Registered Patent No. 1619298 (Public date: 2016.5.10.)

Accordingly, the present invention provides a flame retardant adhesive composition and a sandwich panel having excellent incombustibility, excellent heat insulation, and excellent mechanical properties and adhesiveness, including the flame retardant adhesive composition.

The present invention includes a silicone-modified urethane-based prepolymer, a solid flame retardant and a liquid flame retardant,

The silicone-modified urethane-based prepolymer is prepared by reacting an isocyanate compound with an active hydrogen-containing siloxane compound, and has an unreacted isocyanate group content (NCO%) of 5 to 25% by weight and a siloxane compound content of 15 to 70% by weight, A flame retardant adhesive composition is provided.

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

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; includes,

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

The sandwich panel according to the present invention satisfies the incombustibility performance that satisfies the criteria for incombustibility test stipulated in KS F ISO 1182 and has excellent incombustibility, and also has excellent thermal insulation properties, 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 the present specification, when a certain component is said to "include", it means that it may further include other components without excluding other components unless otherwise stated.

Also, in this specification, when a layer is said to be located “on” another layer, this includes not only the case where a certain 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 silicone-modified urethane-based prepolymer, a solid flame retardant and a liquid flame retardant.

Silicone modified urethane prepolymer

The silicone-modified urethane-based prepolymer is a main component of the composition and serves to impart adhesive strength to the composition.

In addition, the silicone-modified urethane-based prepolymer may be prepared, for example, by reacting an isocyanate compound with an active hydrogen-containing siloxane compound.

The isocyanate compound may include two or more isocyanate groups in one molecule. For example, the isocyanate-based compound is 2,4-toluene diisocyanate (2,4-TDI), 2,6-toluene diisocyanate (2,6-TDI), 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(isocyanatephenyl) thiophosphate, 1,6,10-undecane triisocyanate and 1-isocyanato-4-[(4-isocyanatophenyl)methyl ] may include one or more selected from the group consisting of benzene.

The active hydrogen-containing siloxane compound may include an active hydrogen group that reacts with an isocyanate compound and may include a siloxane structure in a main chain. Due to the flame retardant properties of the active hydrogen-containing siloxane compound, the urethane-based propolymer combined with the isocyanate compound has flame retardant properties. That is, in the case of adhesives using conventional urethane-based prepolymers, they do not have flame retardant properties and are easily burned. However, adhesives using silicone-modified urethane-based prepolymers using the active hydrogen-containing siloxane compound have excellent flame retardancy.

In addition, the active hydrogen-containing siloxane compound may be, for example, a carbinol group-containing siloxane compound, an amine group-containing siloxane compound, or a mercaptan group-containing siloxane compound. Examples of the carbinol group-containing siloxane compound include bis-hydroxypropyl dimethicone and bis-hydroxyethoxypropyl dimethicone, and the amine group-containing siloxane compound, for example, bis-3-amino Examples of the mercaptan group-containing siloxane compound include bis-3-mercaptopropyl dimethicone and the like.

The silicone-modified urethane-based prepolymer may have an unreacted isocyanate group content (NCO%) of 5 to 25% by weight or 8 to 20% by weight. When the NCO% of the silicone-modified urethane-based prepolymer is less than the above range, the viscosity of the adhesive composition is excessively increased or the curing rate is delayed, resulting in poor workability during manufacture of the sandwich panel. In addition, when the NCO% of the silicone-modified urethane-based prepolymer exceeds the above range, the adhesive layer may become brittle, resulting in poor adhesive strength.

In addition, the silicone-modified urethane-based prepolymer may have a siloxane compound content of 15 to 70% by weight, or 20 to 60% by weight. When the content of the siloxane compound in the silicone-modified urethane-based prepolymer is less than the above range, there is a problem that the flammability of the urethane-based prepolymer is increased and the incombustibility performance is lowered. A problem of inferiority may occur.

The adhesive composition may include 15 to 60% by weight, or 15 to 40% by weight of the silicone-modified urethane-based prepolymer based on the total weight of the solid content. When the content of the silicone-modified urethane-based prepolymer is less than the above range, there is a problem in that the adhesive strength of the adhesive layer is inferior, and when it exceeds the above range, the combustion of the silicone-modified urethane-based prepolymer causes a problem in that incombustible performance is lowered. May occur.

solid flame retardant

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

In addition, the solid flame retardant may be, for example, a metal-based solid flame retardant, a phosphorus-based solid flame retardant, a nitrogen-based solid flame retardant, and the like. 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, and the like. The solid flame retardants may be used alone or in combination of two or more.

The solid flame retardant may be included in the composition in an amount of 40 to 500 parts by weight, 50 to 400 parts by weight, or 100 to 300 parts by weight based on 100 parts by weight of the silicone-modified urethane-based prepolymer. When the content of the solid flame retardant is less than the above range, there is a problem in that the incombustible performance of the adhesive layer is lowered, and when it exceeds the above range, the incombustibility of the adhesive layer is excellent, but storability and adhesion may be deteriorated.

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 serves to improve the coating workability of the adhesive composition when manufacturing a sandwich panel. do

In addition, the liquid flame retardant may be a phosphorus-based liquid flame retardant having compatibility with a silicone-modified urethane-based prepolymer and having flame retardant properties, for example, tris (chloroisopropyl) phosphate (TCPP), triethyl Phosphate (Triethylphosphate, TEP), Tricresylphosphate (TCP), Tris (chloroethyl) phosphate (Tris (chloroethyl) phosphate, TCEP) and the like. The liquid flame retardant may be used alone or in combination of two or more.

The liquid flame retardant may be included in the composition in an amount of 10 to 150 parts by weight, 20 to 100 parts by weight, or 35 to 70 parts by weight based on 100 parts by weight of the urethane-based prepolymer. When the content of the liquid flame retardant is less than the above range, the miscibility and fluidity of the adhesive composition are poor, making it difficult to uniformly mix during preparation of the adhesive composition, and the storage stability and coating workability of the prepared adhesive composition are poor. If it exceeds, the adhesive strength may deteriorate due to incombustibility and strength reduction of the adhesive layer.

additive

The adhesive composition may further include a dispersing agent, a wettability improving agent, a leveling agent, and the like, if necessary.

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

In addition, the dispersing agent may be an ionic surfactant or a nonionic surfactant. At this time, the ionic surfactant may include, for example, sodium dodecyl sulfite, and the nonionic surfactant may include, for example, ethoxylated aliphatic alcohol, polyethylene oxide (PEO), ), Carboxylic ester, polyethylene glycol ester, fatty acid sorbitol ester, fatty acid glycol ester, fatty acid diethanol amine , fatty acid or glycol-based esters such as alkyl monoglyceryl ethers and carboxylic amides; 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, 0.5 to 4 parts by weight, or 1 to 2.5 parts by weight based on 100 parts by weight of the silicone-modified urethane-based prepolymer. When the content of the dispersant is less than the above range, there is a problem that the storage property of the adhesive composition is poor, such as precipitation of the solid flame retardant, and when it exceeds the above range, problems such as poor curability and / or excessive decrease in viscosity of the adhesive composition may occur there is.

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

When the adhesive composition is a two-component type, the adhesive composition includes an adhesive main component including a silicone-modified urethane-based prepolymer, a solid flame retardant, and a liquid flame retardant; and a curing agent unit including a curing catalyst and an active hydrogen-containing compound capable of curing reaction with isocyanate. At this time, the two-component adhesive composition may be used after mixing the adhesive main part and the curing agent part before use.

The curing catalyst serves to accelerate the curing reaction of the main adhesive part, and can be used without particular limitation as long as it is generally applicable to urethane-based adhesives. The curing catalyst is, for example, triethylamine, tripropylamine, tributylamine, triamylamine, 2,2'-dimorpholinodiethyl ether (DMDEE), N-methylmorpholine, N,N- amines such as dimethyl cyclohexylamine, N,N-dimethyl benzylamine, 2-methyl imidazole, pyrimidine, dimethylaniline, triethylene diamine, triethanolamine, and N,N-dimethylethanol amine; tetraalkyl ammonium hydroxide; alkali compounds such as alkali hydroxides, alkali phenolates and alkali alcoholates; organotin systems such as dibutyltin dilaurate (DBTDL); etc. can be mentioned. Specifically, the curing catalyst may include an amine-based curing catalyst and an organotin-based curing catalyst.

Commercially available products of the amine-based curing catalyst include JEFFCAT DMDEE from Huntsman Corporation and DABCO EG from Econik Operations GmbH, and organotin-based curing catalysts. The catalyst includes DBTDL from Songwon Industry.

Examples of the active hydrogen-containing compound that can undergo a curing reaction with the isocyanate include water or organic and inorganic compounds containing two or more functional groups such as a hydroxyl group, a mercaptan group, an amine group, and a urea group.

The curing agent part may include 0.3 to 3.0 wt % or 0.5 to 1.5 wt % of an amine-based curing catalyst, and 0.05 to 1.00 wt % or 0.10 to 0.80 wt % of an organotin-based curing catalyst. When the content of the amine-based curing catalyst and the organotin-based curing catalyst is less than the above range, the curing rate of the adhesive composition is delayed, resulting in a decrease in productivity. When the content exceeds the above range, the curing reaction of the adhesive composition is excessively fast A problem may occur in which the application of the composition and the bonding process become impossible.

The content ratio of the adhesive main part and the curing agent part in the adhesive composition may be appropriately adjusted according to the active hydrogen equivalent of the active hydrogen-containing compound in the curing agent part.

The flame retardant adhesive composition according to the present invention has the advantage of improving the incombustibility of a sandwich panel including the same.

sandwich panel

A sandwich panel according to the present invention includes a 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 FIG. 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 has an organic matter content of 3.0 to 9.5% by weight. Specifically, the core material may be 3.5 to 9.0% by weight. When the content of organic matter in the core material is less than the above range, strength of the core material is lowered and workability is deteriorated, and when it exceeds the above range, incombustible performance may be deteriorated. In this case, the organic matter content may be a value measured by an ignition loss measurement method (mass loss rate after heat treatment at 480 ° C. for 2 hours).

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

The core material may have a density of 25 to 100 kg/m ³ , or 30 to 80 kg/m ³ . When the density of the core material is less than the above range, there is a problem in that the strength of the manufactured sandwich panel is lowered, and when it exceeds the above range, a problem in that the insulation performance of the sandwich panel is lowered may occur.

adhesive layer

The adhesive layer serves to adhere the metal layer to the core material, and is formed by applying the flame retardant adhesive composition as described above.

The adhesive layer may be formed by applying 70 to 400 g, 100 to 350 g, or 200 to 350 g of the flame retardant adhesive composition based on 1 m ² of surface area of the core material. When the application amount of the adhesive composition is less than the above range, there is a problem in that the adhesive strength between the core material and the metal layer is poor, and when it exceeds the above range, the incombustible performance of the manufactured sandwich panel may be deteriorated 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 generally not particularly limited as long as it is applicable to improve the strength and incombustibility of the sandwich panel, and may include, for example, at least one selected from the group consisting of iron, stainless steel, aluminum, and magnesium. In addition, the metal layer may be, for example, a galvanized steel sheet or a metal layer coated with an organic coating layer.

In addition, 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 evaluating incombustibility according to the method of KS F ISO 1182.

As described above, the sandwich panel according to the present invention satisfies the non-combustible performance that satisfies the criteria for non-combustibility test specified in KS F ISO 1182, has excellent incombustibility, and has excellent heat insulation, mechanical properties and adhesion.

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

[Example]

Preparation Example 1. Preparation of silicone-modified urethane-based prepolymer-1

319.6 parts by weight of SM2330P (manufactured by KCC Silicone Co., bifunctional carbinol group-modified polydimethylsiloxane, equivalent: 1000) as an active hydrogen-containing siloxane compound under nitrogen supply in a 2L four-necked flask equipped with a temperature control device, a stirring device, and a nitrogen injection device. After adding and stirring, the temperature was raised to 60 ± 3 ° C. Thereafter, 527.4 parts by weight of diphenylmethane diisocyanate (Cosmonate JG70K from Kumho-Mitsui Chemical Co., Ltd.) was added as an isocyanate compound, and after stabilization for 30 minutes, the temperature was raised to 75±3° C. and maintained for 3 hours. Thereafter, the mixture was cooled to 50° C. or less to prepare silicone-modified urethane-based prepolymer-1.

The prepared silicone-modified urethane-based prepolymer-1 had an unreacted isocyanate group content (NCO%) of 17.7 wt% and a siloxane compound content of 37.7 wt%.

Preparation Example 2. Preparation of silicone-modified urethane-based prepolymer-2

Except for using 393.8 parts by weight of SM2310P (KCC Silicone Co., Ltd., bifunctional carbinol group-modified polydimethylsiloxane, equivalent: 1500) as an active hydrogen-containing siloxane compound, and using the contents of each component as the contents shown in Table 1, Silicone-modified urethane-based prepolymer-2 was prepared in the same manner as in Example 1.

The prepared silicone-modified urethane-based prepolymer-2 had an unreacted isocyanate group content (NCO%) of 16.9 wt% and a siloxane compound content of 42.6 wt%.

Preparation Examples 3 to 6.

A silicone-modified urethane-based prepolymer or an unmodified urethane-based prepolymer was prepared in the same manner as in Preparation Example 1 or 2 with the composition ratios shown in Table 1 below. At this time, as the polyol compound, KPX Chemical's bifunctional polyether polyol (equivalent weight: 1,000) was used.

(parts by weight) Preparation Example 1 Preparation Example 2 Preparation Example 3 Production Example 4 Preparation Example 5 Preparation Example 6 Siloxane compounds containing active hydrogen SM2330P 319.6 - - - 1047.4 146.3 SM2310P - 393.8 250.5 - - - polyol compound PP-2000 - - 208.7 367.9 - - isocyanate Cosmonate JG70K 527.4 531.6 688.8 607.1 297.6 965.7 Content of unreacted NCO groups (% by weight) 17.7 16.9 17.6 17.8 4.6 26.7 Content of siloxane compound (% by weight) 37.7 42.6 21.8 does not contain 77.9 13.2

Preparation Examples 7 to 22. Preparation of adhesive composition (adhesive main part)

An adhesive composition (adhesive main part) was prepared by mixing the components and composition ratios shown in Tables 2 to 4 below.

At this time, TCPP is tris (chloroisopropyl) phosphate as a liquid flame retardant, BYK-220S from BYK was used as a dispersant, ATH is aluminum tri-hydroxide, APP is ammonium polyphosphate, and MCA is melamine-cya It is Nurate.

(parts by weight) Preparation Example 7 Preparation Example 8 Preparation Example 9 Preparation Example 10 Preparation Example 11 Preparation Example 12 liquid flame retardant TCPP 14.5 14.5 14.5 14.5 14.5 14.5 dispersant BYK-220S 0.5 0.5 0.5 0.5 0.5 0.5 solid flame retardant ATH 55 30 55 30 55 30 APP - 15 - 15 - 15 MCA - 15 - 15 - 15 Silicone modified urethane prepolymer Preparation Example 1 30 25 - - - - Preparation Example 2 - - 30 25 - - Preparation Example 3 30 25

(parts by weight) Preparation Example 13 Preparation Example 14 Preparation Example 15 Preparation Example 16 Preparation Example 17 Preparation Example 18 liquid flame retardant TCPP 14.5 14.5 14.5 14.5 14.5 14.5 dispersant BYK-220S 0.5 0.5 0.5 0.5 0.5 0.5 solid flame retardant ATH 55 30 55 30 55 30 APP - 15 - 15 - 15 MCA - 15 - 15 - 15 Production Example 4
(unmodified urethane-based prepolymer) 30 25 - - - - Silicone modified urethane prepolymer Preparation Example 5 - - 30 25 - - Preparation Example 6 30 25

(parts by weight) Preparation Example 19 Production Example 20 Production Example 21 Production Example 22 liquid flame retardant TCPP 14.5 14.5 34.5 34.5 dispersant BYK-220S 0.5 0.5 0.5 0.5 solid flame retardant ATH 20 20 55 55 APP - - - - MCA - - - - Silicone modified urethane prepolymer Preparation Example 1 65 - 10 - Preparation Example 2 65 - 10

Preparation Example 23. Preparation of curing agent part

492.5 g of glycerin (LG Household & Health Care; Glycerin 95%, active hydrogen-containing compound) was added to a 1L beaker, and 2.5 g of dibutyltin dilaurate (Songwon Industry; DBTDL) and 2,2'-dimorpholino were stirred at room temperature. 5.0 g of diethyl ether (Huntsman Corporation, DMDEE) was sequentially added and stirred for 10 minutes to prepare a curing agent part.

Preparation Example 24. Preparation of two-component urethane adhesive composition

A two-component urethane adhesive consisting of a curing agent (polymeric di-phenyl methane di-isocyanate) and a main component (polyol, water, additives) was used, and Kumho Mitsui Chemicals Cosmonate M-200 was used as the curing agent, For the subject part, KPF-2406 of Kukdo Chemical was used. At this time, 100 parts by weight of the curing agent part was mixed and used with respect to 100 parts by weight of the main part, and the two-component urethane adhesive did not contain a solid flame retardant and a liquid flame retardant.

Experimental example 1.

As a core material, KCC's nonflammable glass wool core material (density: 64 kg/m3, organic binder content: 8.3% by weight relative to the total weight of the core material) was cut into a cylindrical shape with a diameter of 45 ± 1 mm and a height of 50 ± 2 mm to prepare a core material sample. Thereafter, the adhesive composition of Preparation Example 8 was applied in an amount of 300 g / m 2 to both sides of the core sample, and then a color steel sheet having a thickness of 0.4 ± 0.05 mm (manufacturer: KG Dongbu Steel, product name: NF non-flammable color steel sheet) was attached and room temperature left for 12 hours to prepare a sandwich panel. At this time, the organic binder content in the core material was measured by an ignition loss method.

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

Experimental Examples 2 to 21.

As shown in Table 5, a sandwich panel was manufactured in the same manner as in Experimental Example 1, except that the type of core material and the type of adhesive composition were adjusted.

At this time, as the general glass wool core material, KCC's general glass wool core material for panels (density: 64 kg/m 3 , organic binder content: 11.5% by weight relative to the total weight of the core material) was used.

heartwood adhesive composition liquid type Adhesive subject part (weight ratio) curing agent
(weight ratio) Application amount (g/m ² ) Experimental Example 1 Non-combustible glass wool core One Preparation Example 7 - 300 Experimental Example 2 Non-combustible glass wool core One Preparation Example 8 - 300 Experimental Example 3 Non-combustible glass wool core One Preparation Example 9 - 300 Experimental Example 4 Non-combustible glass wool core One Preparation Example 10 - 300 Experimental Example 5 Non-combustible glass wool core One Preparation Example 11 - 300 Experimental Example 6 Non-combustible glass wool core One Preparation Example 12 - 300 Experimental Example 7 Non-combustible glass wool core 2 Preparation Example 7
(10 parts by weight) Production Example 23
(1 part by weight) 300 Experimental Example 8 Non-combustible glass wool core 2 Preparation Example 10
(10 parts by weight) Production Example 23
(1 part by weight) 300 Experimental Example 9 Ordinary glass wool core One Preparation Example 7 - 300 Experimental Example 10 General glass wool core One Preparation Example 9 - 300 Experimental Example 11 Non-combustible glass wool core 2 Production Example 24 300 Experimental Example 12 Non-combustible glass wool core One Preparation Example 13 - 300 Experimental Example 13 Non-combustible glass wool core One Preparation Example 14 - 300 Experimental Example 14 Non-combustible glass wool core One Preparation Example 15 - 300 Experimental Example 15 Non-combustible glass wool core One Preparation Example 16 - 300 Experimental Example 16 Non-combustible glass wool core One Preparation Example 17 - 300 Experimental Example 17 Non-combustible glass wool core One Preparation Example 18 - 300 Experimental Example 18 Non-combustible glass wool core One Preparation Example 19 - 300 Experimental Example 19 Non-combustible glass wool core One Production Example 20 - 300 Experimental Example 20 Non-combustible glass wool core One Production Example 21 - 300 Experimental Example 21 Non-combustible glass wool core One Production Example 22 - 300

Test example: Characteristic evaluation

The sandwich panels of the experimental examples were measured in the following manner, and the results are shown in Table 6.

(1) adhesive strength

The steel sheet and the core material were attached to the sandwich panel using an adhesive composition, and after being left at room temperature for 12 hours, the steel sheet and the core material were peeled off, and the adhesive layer on the steel sheet was visually checked to measure the adhesive strength.

Specifically, when a uniform adhesive layer is formed on the steel sheet and core material adhesion is good, it is excellent (○), and when the adhesive layer is partially detached at a level of less than 30 area% on the steel sheet and core material adhesion is generally good, it is normal (△ ), when the peeling of the adhesive layer was poor in attachment to the developmental core material, it was judged as defective (X).

(2) wet adhesion strength

In the same way as when measuring the adhesive strength of item (1), the sandwich panel was left at room temperature for 12 hours and immersed in water for 30 minutes. .

Specifically, when a uniform adhesive layer is formed on the steel sheet and core material adhesion is good, it is excellent (○), and when the adhesive layer is partially detached at a level of less than 30 area% on the steel sheet and core material adhesion is generally good, it is normal (△ ), when peeling of the adhesive layer occurred and the attachment of the core material was poor, it was judged as defective (X).

(3) Nonflammable evaluation-1: temperature difference

Incombustibility was evaluated for the sandwich panel according to the method of KS F ISO 1182, and at this time, a sandwich panel with a diameter of 45 mm and a thickness of 50 mm was used as a specimen.

Specifically, the specimen was put into a nonflammable tester preheated to 750 ° C., and the maximum temperature in the tester and the stable temperature after being left for 20 minutes were measured.

(4) Nonflammable evaluation-2: mass reduction rate

Incombustibility was evaluated for the sandwich panel according to the method of KS F ISO 1182, and at this time, a sandwich panel with a diameter of 45 mm and a thickness of 50 mm was used as a specimen.

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 incombustibility was judged to be excellent when it was 30% by mass or less.

adhesive strength Wet Adhesion Strength nonflammable rating Temperature difference (K) Mass reduction rate (% by mass) Experimental Example 1 ○ ○ 14.8 5.92 Experimental Example 2 ○ ○ 15.2 6.05 Experimental Example 3 ○ ○ 12.7 5.87 Experimental Example 4 ○ ○ 13.1 5.72 Experimental Example 5 ○ ○ 18.5 6.15 Experimental Example 6 ○ ○ 19.4 6.24 Experimental Example 7 ○ ○ 15.4 5.95 Experimental Example 8 ○ ○ 14.8 6.01 Experimental Example 9 ○ ○ 22.4 6.52 Experimental Example 10 ○ ○ 24.8 6.75 Experimental Example 11 ○ ○ 78.2 8.95 Experimental Example 12 ○ ○ 24.6 6.23 Experimental Example 13 ○ ○ 22.8 6.41 Experimental Example 14 △ X 12.8 5.48 Experimental Example 15 △ X 11.2 5.41 Experimental Example 16 ○ △ 21.8 6.24 Experimental Example 17 ○ △ 23.5 6.34 Experimental Example 18 ○ ○ 48.5 7.25 Experimental Example 19 ○ ○ 46.8 7.35 Experimental Example 20 X X 13.2 5.04 Experimental Example 21 X X 11.7 5.11

As shown in Table 6, the sandwich panels of Experimental Examples 1 to 8 were excellent in adhesive strength and wet adhesive strength, and had a low temperature difference of 20K or less and a low mass loss rate of 7% by weight or less during nonflammability evaluation, so they had excellent incombustibility. .

On the other hand, Experimental Example 9 and Experimental Example 10 using a general glass wool core material, Experimental Example 11 including the two-component urethane adhesive of Preparation Example 25 without a solid flame retardant and a liquid flame retardant, and Experimental Example 12 including an unmodified urethane-based prepolymer And Experimental Example 13 lacked incombustibility with a temperature difference of 20K or more in nonflammability evaluation.

In addition, Experimental Examples 14 and 15 including the prepolymer of Preparation Example 5 having an excessive amount of siloxane compound, and Experimental Examples 20 and 21 including the adhesive compositions of Preparation Examples 21 and 22 containing a small amount of the silicone-modified urethane-based prepolymer Adhesive strength and wet adhesive strength were insufficient.

Experimental Examples 16 and 17 including the prepolymer of Preparation Example 6 having an excessive amount of the siloxane compound, and Experimental Examples 18 and 19 including the adhesive compositions of Preparation Examples 19 and 20 containing an excess of the silicone-modified urethane-based prepolymer were evaluated as nonflammable The temperature difference was more than 20K, and the incombustibility was insufficient.

Claims (6)

Including a silicone-modified urethane-based prepolymer, a solid flame retardant and a liquid flame retardant,
The silicone-modified urethane-based prepolymer is prepared by reacting an isocyanate compound with an active hydrogen-containing siloxane compound, and has an unreacted isocyanate group content (NCO%) of 5 to 25% by weight and a siloxane compound content of 15 to 70% by weight, Flame retardant adhesive composition. The method of claim 1,
A flame retardant adhesive composition comprising the silicone-modified urethane-based prepolymer in an amount of 15 to 60% by weight based on the total weight of the solid content. The method of claim 1,
A flame retardant adhesive composition comprising 100 parts by weight of a silicone-modified urethane-based prepolymer, 40 to 500 parts by weight of a solid flame retardant and 10 to 150 parts by weight of a liquid flame retardant. An inorganic fiber-based core material having an organic content of 3.0 to 9.5% by weight;
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; includes,
The adhesive layer is formed by applying 70 to 400 g of the flame retardant adhesive composition according to any one of claims 1 to 3 based on 1 m ² of the surface area of the core material, a sandwich panel having incombustibility. The method of claim 4,
The core material has a density of 25 to 100 kg / m ³ and includes an inorganic fiber-based core material, a sandwich panel having incombustibility. The method of claim 4,
A sandwich panel having incombustibility with a temperature difference of 20K or less and a mass reduction rate of 30% by weight or less when evaluated incombustibility according to the method of KS F ISO 1182.

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