KR102154864B1 - Semi-nonflammable Polyurethane Foam Block Composition And Manufacturing Method of the Same - Google Patents

Abstract

The present invention relates to a semi-noninflammable polyurethane foam block composition and a method for manufacturing the same. More specifically, the present invention relates to a semi-noninflammable polyurethane foam block composition which contains polyol, MDI, liquid paraffin chloride, phosphoric acid, calcium silicate, and a dispersant. The present invention is to provide: a polyurethane foam block composition which has high flame retardancy, is environmentally friendly, and also has excellent thermal insulation performance; and the method for manufacturing the same.

Description

Semi-nonflammable Polyurethane Foam Block Composition And Manufacturing Method of the Same}

The present invention relates to a semi-non-combustible polyurethane foam block composition and a method for producing the same, and more particularly, to a semi-non-combustible polyurethane foam block composition comprising polyol, MDI, liquid paraffin chloride, phosphoric acid, calcium silicate and a dispersant.

Polyurethane foam blocks attached to walls, etc. have excellent insulation performance and are used in many structures, but have a disadvantage of being vulnerable to fire.

Conventional polyurethane foam blocks are generally manufactured by mixing a resin premix and polyisocyanate prepared in advance by mixing polyether polyol, foaming agent, catalyst, flame retardant, foaming agent, etc., and then putting them in a certain frame and molding.

At this time, tris (chloroisopropyl) phosphate and Daihichi's CR-530 are mainly used as flame retardants, but it is known that there is no significant improvement in flame retardancy.

As the blowing agent, as a physical blowing agent, 1.1-dichloro-1-1-fluoro-ethane (trade name 141b) of low boiling point hydrochlorofluorocarbon (HCFC) was used, but recently, 141b type blowing agent is bad for global warming. As it turned out to have an effect, its use was limited.

Japanese Patent Publication No. Hei 5-176817 Japanese Patent Publication No. Hei 5-253402

In order to solve the above problems, it is an object of the present invention to provide a semi-non-combustible polyurethane foam block composition having high flame retardancy, eco-friendly, and excellent thermal insulation performance, and a method of manufacturing the same.

In order to achieve the above object, the present invention provides a semi-non-combustible polyurethane foam block composition comprising polyol, MDI, liquid chlorinated paraffin, phosphoric acid, calcium silicate and a dispersant.

At this time, the content of each component, polyol 40-50% by weight, MDI 10-15% by weight, liquid paraffin chlorinated 10-15% by weight, phosphoric acid 5-10% by weight, calcium silicate 10-15% by weight, and dispersant 1 to It is preferably 5% by weight.

In addition, in order to achieve the above object, the present invention comprises the steps of mixing and stirring MDI and phosphoric acid at RPM 300 to 500 for 10 to 30 minutes; After adding liquid paraffin chloride to the mixture of MDI and phosphoric acid, mixing and stirring at an RPM of 500 to 1000 for 30 to 60 minutes; Adding calcium silicate and a dispersant to the liquid paraffin-containing mixture, followed by mixing and stirring at RPM 1500 to 2000 for 30 to 60 minutes; And after adding the polyol to the mixture to which the calcium silicate and the dispersant are added, mixing and stirring at RPM 3000 to 3500 for 1 to 2 minutes; provides a method of preparing a semi-non-flammable polyurethane foam block composition comprising.

The semi-non-combustible polyurethane foam block composition according to the present invention is to solve the problems caused by low heat resistance, flame retardancy, and emission of harmful gases of a general polyurethane foam block, and has high flame retardancy, eco-friendly, and excellent insulation performance. It is an object of the present invention to provide a foam block composition and a method of manufacturing the same.

Hereinafter, the present invention will be described in detail with reference to embodiments of the present invention and drawings. These examples are only illustratively presented to explain the present invention in more detail, and it will be apparent to those of ordinary skill in the art that the scope of the present invention is not limited by these examples. .

In addition, unless otherwise defined, all technical and scientific terms used in the present specification have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs, and in case of conflict, the present specification including definitions The description of will take precedence.

In order to clearly describe the invention proposed in the drawings, parts not related to the description are omitted, and similar reference numerals are attached to similar parts throughout the specification. And, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components unless specifically stated to the contrary. In addition, "unit" described in the specification means one unit or block that performs a specific function.

In each step, the identification code (first, second, etc.) is used for convenience of description, and the identification code does not describe the order of each step, and each step does not clearly describe a specific sequence in the context. It may be implemented differently from the order specified above. That is, each of the steps may be performed in the same order as the specified order, may be performed substantially simultaneously, or may be performed in the reverse order.

The semi-non-combustible polyurethane foam block composition of the present invention is characterized by comprising polyol, MDI, liquid paraffin chloride, phosphoric acid, calcium silicate, and a dispersant. At this time, the content of each component, polyol 40-50% by weight, MDI 10-15% by weight, liquid paraffin chlorinated 10-15% by weight, phosphoric acid 5-10% by weight, calcium silicate 10-15% by weight, and dispersant 1 to It is preferably 5% by weight.

In addition, the semi-non-combustible polyurethane foam block composition of the present invention comprises the steps of mixing and stirring MDI and phosphoric acid at RPM 300 to 500 for 10 to 30 minutes; After adding liquid paraffin chloride to the mixture of MDI and phosphoric acid, mixing and stirring at an RPM of 500 to 1000 for 30 to 60 minutes; Adding calcium silicate and a dispersant to the liquid paraffin-containing mixture, followed by mixing and stirring at RPM 1500 to 2000 for 30 to 60 minutes; And after adding the polyol to the mixture to which the calcium silicate and the dispersant are added, mixing and stirring at RPM 3000 to 3500 for 1 to 2 minutes; provides a method of preparing a semi-non-flammable polyurethane foam block composition comprising. Hereinafter, take a closer look.

The MDI (4,4-diphenylmethane diisocyanate) is a representative isocyanate compound, which reacts with a polyol to foam, hexamethylene diisocyanate, m-phenylene diisocyanate, 2,4-toluene diisocyanate (TDI) , Dianisidine diisocyanate, tolidin isocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane, chlorophenylene-2,4-diisocyanate, 1,5-naphthalene diisocyanate, ethylene diisocyanate, die Tyridene diisocyanate, propylene-1,2-diisocyanate, cyclohexylene-1,2-diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy -4,4'-biphenylene diisocyanate, 3,3'-diphenyl-4,4'-biphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dichloro-4 ,4′-biphenylene diisocyanate, furfurylidene diisocyanate, and the like, and the catalyst may be at least one selected from the group consisting of triethylenediamine (TEDA), 1,4-diazabicyclo[2.2.2 ]Octane (DABCO), dimethylcyclohexylamine (DMCHA), or dimethylethanolamine (DMEA) may be substituted.

The content of the MDI is preferably 10 to 15% by weight of the polyurethane foam block composition, and if it is more or less than this, foaming may not be properly performed or the hardness of the foam block may be too low.

The phosphoric acid is added to add plasticity and non-combustibility to the foam block, and is preferably 5 to 10% by weight of the total foam block composition, and if it is less than this, the functional effect of phosphoric acid may be reduced, and if it exceeds this, the foam The foaming and insulating properties of the block may be poor.

The phosphoric acid may be used alone, but may be used in combination with a phosphorus-containing organic flame retardant in order to increase miscibility and workability with other components, and to enhance plasticity and non-flammability.

At this time, the mixing ratio of phosphoric acid and phosphorus-containing flame retardant is preferably about 1 to 2: 1 (w/w). The phosphorus-containing organic flame retardant may be a variety of commercially available phosphorus-containing flame retardants, but preferably tris(2,6-dimethylphenyl)phosphine, tetrakis-(2,6-xylyl)resorcinol bisphosphate, tetra Phenyl resorcinol diphosphate, triphenyl phosphate, phosphazene flame retardant, 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-( 2,5-dihydroxynaphthyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide or 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- Any one or a mixture of at least two selected from oxide flame retardants may be used.

At this time, in order to solve the problem of decay and deterioration due to the organic flame retardant, it is preferable to add cardanol having an antibacterial effect. The cardanol may be obtained by distilling a cashew nut shell liquid (CNSL) extracted from a cashew nut. The amount of cardanol used is not particularly limited, but an amount of 1 to 10% by weight based on the weight of the phosphorus-containing organic flame retardant may be used.

The prepared MDI and phosphoric acid are mixed and stirred for 10 to 30 minutes at 300 to 500 RPM. At this time, since heat is generated in the stirrer over 200℃, it is preferable to operate the cooling system and stir until the temperature inside the stirrer drops to 30℃.

When the stirring is complete, 40% liquid paraffin chloride is added to the mixture of MDI and phosphoric acid, followed by mixing and stirring at an RPM of 500 to 1000 for 30 to 60 minutes. The content of the chlorinated paraffin is preferably 10 to 15% by weight of the total foam block composition, and if it is less than this, the functional effect of the chlorinated paraffin may be deteriorated, and if it exceeds this, the foaming property and thermal insulation properties of the foam block may be deteriorated.

The chlorinated paraffin may be used alone, but preferably, it may be used together with graphite to increase the rigidity of the foam block and prevent cracking while adding flame retardancy to the foam block. The graphite is preferably 1 to 5% by weight of the total foam block composition, and if it is less than this, the functional effect of graphite may be reduced, and if it exceeds this, the overall physical properties of the foam block may be deteriorated.

At this time, in order to increase miscibility with other components and increase incombustibility, the graphite may be a composite with zinc. The composite is obtained by dispersing an organometallic coupling agent and graphite in an aqueous medium, adding zinc chloride or zinc iodide to the dispersion, and drying to obtain a zinc/coupling agent/graphite composite, and then firing the dried composite. I can.

It is preferable to use the graphite modified by surface oxidation.For example, 1) a dry oxidation method in which an oxidizing agent gas such as water vapor, carbon dioxide, oxygen and ozone is brought into contact with graphite at a high temperature, and 2) graphite and an oxidizing agent (e.g. Hydrogen peroxide, nitric acid, sulfuric acid, etc.) There is wet oxidation in which a reagent solution reacts. In addition, there are electrochemical oxidation, ozone treatment, annealing, and microwave cooling plasma heat treatment.

의 화학식을 가지는 커플링제가 사용될 수 있으며, 상기 식에서, RO는 가수분해기 또는 기질 반응성기로, 상기 R은 탄소수 2 내지 10개이고, 상기 Z는 알루미늄, 실리콘, 티타늄, 아연 및 지르코늄으로 구성된 군에서 선택되는 1종 이상의 원소이며, 상기 R'는 지방족, 나프텐계 또는 방향족의 열가소성 작용기로서, 탄소수 10 내지 40을 가지고, Y는 비닐, 알릴, 아크릴 또는 메타크릴의 열반응성 또는 열경화성 관능기이며, n은 1 내지 3의 정수이다. 상기 유기금속계 커플링제의 사용량은 특별히 한정되지 않지만, 흑연 중량을 기준으로, 0.1~5 중량%의 양이 사용될 수 있다. The organometallic coupling agent

A coupling agent having the formula of may be used, wherein RO is a hydrolyzable group or a substrate reactive group, R is 2 to 10 carbon atoms, and Z is selected from the group consisting of aluminum, silicon, titanium, zinc and zirconium. It is one or more elements, wherein R'is an aliphatic, naphthenic or aromatic thermoplastic functional group, has 10 to 40 carbon atoms, Y is a thermally reactive or thermosetting functional group of vinyl, allyl, acrylic or methacrylic, and n is 1 to It is an integer of 3. The amount of the organometallic coupling agent is not particularly limited, but an amount of 0.1 to 5% by weight based on the weight of graphite may be used.

The use conditions and reaction conditions, such as the addition temperature, the addition method, the addition rate and the stirring rate of the organometallic coupling agent, are not particularly limited, and may be determined from the ordinary knowledge and level of a person skilled in the art.

When the stirring is complete, calcium silicate and a dispersant are additionally added to the liquid paraffin-added mixture, followed by mixing and stirring at RPM 1500 to 2000 for 30 to 60 minutes.

The calcium silicate is added to improve the thermal insulation and sound-absorbing properties of the foam block, and the content is preferably 10 to 15% by weight of the total foam block composition, and if it is less than this, the functional effect of calcium silicate may be reduced, If this is exceeded, overall physical properties may deteriorate.

The dispersant serves to help the various ingredients to be uniformly mixed, and various commercially available dispersants may be used. The content is preferably 1 to 5% by weight of the total foam block composition, and if it is less than this, the functional effect of the dispersant may be deteriorated, and if it exceeds this, the overall physical properties may deteriorate.

At this time, in order to further increase the miscibility and stability of the respective components, 1 to 3% by weight of cyclodextrin may be additionally added. The cyclodextrin is a cyclic compound composed of a glucose group as a repeating unit, and forms a complex with additive components such as calcium silicate or flame retardant, and attracts and immobilizes the additional components by hydrogen bonding to the outside, so that the foam block has durability and stability. Can be given.

As the cyclodextrin, various commercially available cyclodextrins may be used, and as an example, 2,3,6-tri-O-naphthoyl-beta-cyclodextrin may be used.

When the stirring is complete, the polyol is finally added to the mixture to which the calcium silicate and dispersant are added, followed by high-speed stirring at RPM 3000 to 3500 for 1 to 2 minutes to mix.

As the polyol, various polyols used in the foam block may be used, but preferably i) an alkylene oxide such as ethylene oxide (EO) or propylene oxide (PO) in sucrose in order to increase the strength of the foam block. Polyols with a functional group of 5 to 6 and a hydroxyl value of 400 to 450 mgKOH/g and ii) ethylene oxide and propylene oxide on an amine base such as toluene diamine and ethylene diamine to lower the thermal conductivity of the foam block and increase thermal insulation properties. It is preferable to use a mixture of a polyol having a hydroxyl value of 550 to 650 mgKOH/g made by polymerization of an alkylene oxide such as 1: 1 in a volume ratio.

The content of the polyol is preferably 40 to 50% by weight of the total weight of the polyurethane foam block composition, and if it is more or less than this, foaming may not be properly performed or the hardness may be too low.

In this way, the polyol-added mixture is finally poured into a foam block mold and molded.

Hereinafter, examples and experimental examples of the present invention will be described. However, the scope of the present invention is not limited to the following preferred embodiments, and those skilled in the art can implement various modified forms of the contents described in the present specification within the scope of the present invention.

<Example 1>

15g of MDI and 5g of phosphoric acid were stirred for 10 minutes at RPM 300, but the cooling system was operated to lower the temperature inside the stirrer to 30°C. When the stirring was completed, 10 g of 40% liquid paraffin chloride was added, followed by stirring at RPM 500 for 30 minutes. Thereafter, 15 g of calcium silicate and 5 g of a dispersant were added, followed by stirring at RPM 1500 for 30 minutes. Finally, 50 g of polyol was added and agitated at high speed for 2 minutes at RPM 3000, and then poured into a foam block mold to form.

<Example 2>

12 g of MDI, 2 g of phosphorus, and 3 g of tris(2,6-dimethylphenyl)phosphine were stirred at RPM 300 for 10 minutes, but the cooling system was operated to lower the temperature inside the stirrer to 30°C. When the stirring was completed, 10 g of 40% liquid paraffin and 3 g of graphite were added, followed by stirring at RPM 500 for 30 minutes. Thereafter, 15 g of calcium silicate and 5 g of a dispersant were added, followed by stirring at RPM 1500 for 30 minutes. Finally, 50 g of polyol was added and agitated at high speed for 2 minutes at RPM 3000, and then poured into a foam block mold to form.

<Example 3>

12 g of MDI, 2 g of phosphorus, and 3 g of tris(2,6-dimethylphenyl)phosphine were stirred at RPM 300 for 10 minutes, but the cooling system was operated to lower the temperature inside the stirrer to 30°C. When the stirring was completed, 10 g of 40% liquid paraffin chloride and 3 g of zinc graphite composite were added, followed by stirring at RPM 500 for 30 minutes. Thereafter, 15 g of calcium silicate, 4 g of dispersant, and 1 g of cyclodextrin were added, followed by stirring at RPM 1500 for 30 minutes. Finally, 50 g of polyol was added and agitated at high speed for 2 minutes at RPM 3000, and then poured into a foam block mold to form.

<Comparative Example>

MDI 20g was stirred at RPM 300 for 10 minutes, but the cooling system was operated to lower the temperature inside the stirrer to 30°C. When the stirring was completed, 10 g of 40% liquid paraffin chloride was added, followed by stirring at RPM 500 for 30 minutes. Thereafter, 15 g of calcium silicate and 5 g of a dispersant were added, followed by stirring at RPM 1500 for 30 minutes. Finally, 50 g of polyol was added and agitated at high speed for 2 minutes at RPM 3000, and then poured into a foam block mold to form.

<Experimental Example>

The flame retardant performance was evaluated through a heat release rate test after constructing a polyurethane foam block test body, and the results are shown in Table 1.

The heat release rate test was performed in accordance with KS F ISO 5660-1:2008. Specifically, after setting and maintaining the radiant heat of the cone heater at about 50 kW/㎡ and the discharge flow rate at about 0024 ㎥/s, the specimen and the specimen holder Was placed on the mass measuring device, the radiant heat shield was removed, heated for 5 minutes, the maximum heat release rate and the total amount of heat emitted were measured, and after the heating was completed, the specimen holder was removed from the mass measuring device and the specimen was observed.

Test Items Details Example 1 Example 2 Example 3 Comparative example Heat release rate Total calories released
(MJ/m2) 2.7 2.3 1.5 7.5 200 kW/m2
Time to exceed (seconds) 0 0 0 7

As can be seen from the above table, it was confirmed that Example 3 of the present invention has the most excellent flame retardant performance.

The present invention is not limited to the specific embodiments and description described above, and any person having ordinary knowledge in the technical field to which the present invention pertains without departing from the gist of the present invention claimed in the claims can implement various modifications. And, such modifications are within the scope of protection of the present invention.

Claims (3)

delete delete Semi-non-combustible poly comprising 40-50% by weight of polyol, 10-15% by weight of MDI, 10-15% by weight of liquid paraffin, 5-10% by weight of phosphoric acid, 10-15% by weight of calcium silicate, and 1-5% by weight of dispersant As a method for producing a urethane foam block composition,
Mixing and stirring MDI and phosphoric acid at RPM 300 to 500 for 10 to 30 minutes;
After adding liquid paraffin chloride to the mixture of MDI and phosphoric acid, mixing and stirring at an RPM of 500 to 1000 for 30 to 60 minutes;
Adding calcium silicate and a dispersant to the liquid paraffin-containing mixture, followed by mixing and stirring at RPM 1500 to 2000 for 30 to 60 minutes; And
Adding polyol to the mixture to which the calcium silicate and dispersant are added, and then mixing and stirring at RPM 3000 to 3500 for 1 to 2 minutes;
Method for producing a semi-non-combustible polyurethane foam block composition comprising a.