JP3261016B2 - Polyurethane resin composition and fire-resistant sealing material using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyurethane resin composition and a fire-resistant sealing material using the same, and more particularly, to a joint portion of a curtain wall of a building,
Filled into the joints of the partition walls, etc.
Demonstrates excellent performance such as deformation followability and durability, and also has a function to form a solid refractory ashing layer when encountering a flame and to prevent the penetration of the flame from the above seam, a new The present invention relates to a polyurethane resin composition and a fire-resistant sealing material using the same.

[0002]

2. Description of the Related Art Conventionally, architectural sealing materials of various compositions have been provided for filling seams of curtain walls. As a sealing material for such applications, there is a polyurethane-based composition, and a sealing material made of the polyurethane-based composition has a good filling workability to a curtain wall joint portion and the like, an adhesive property unique to a polyurethane resin,
It has favorable properties as a building sealing material such as waterproofness, airtightness, deformation followability, durability, abrasion resistance, weather resistance and the like based on rubber elasticity.

[0003] However, these sealing materials melt, ignite, and fall off very easily when they encounter a flame, facilitating the invasion of the flame from the curtain wall seam and causing the spread of the fire. That is, even in a refractory building such as a steel frame or a reinforced concrete structure, the joint portion of the curtain wall is a weak point in fire prevention and is considered as one of the causes of the spread of fire.

[0004] For this reason, in current buildings, a sealing material for a building, which is provided with waterproofness, conformability to deformation, etc., is filled in a joint portion of a curtain wall, and asbestos foam is used as a fire protection measure for the joint portion. Usually, it is filled as a secondary sealing material.

[0005] Such fire prevention measures at the curtain wall joint have problems such as an increase in the number of construction steps. Also,
There are also health and safety issues due to asbestos.

[0006]

DISCLOSURE OF THE INVENTION The present invention relates to a polyurethane-based sealing material which has inherent adhesiveness and rubber elasticity, such as waterproofness, airtightness, deformation followability, durability, abrasion resistance and weather resistance. An object of the present invention is to provide a sealing material provided with fire resistance and a polyurethane resin composition used for the sealing material without impairing preferable properties as a building sealing material. That is, when a flame is encountered, it does not melt off even if ignited, forms a solid ashing layer, and does not collapse for a long time, for example, the ability to prevent the invasion of the flame from the seam of the curtain wall It is an object of the present invention to provide a polyurethane resin composition suitable for architectural purposes and a fire-resistant sealing material using the same.

[0007]

Means for Solving the Problems In order to solve the above-mentioned problems and achieve the object of the present invention, the present inventors have repeatedly studied a polyurethane resin composition. As a result, (a) a prepolymer containing an isocyanate group at a terminal,
(B) a hardener containing active hydrogen, and (c) an average length of 0.5
mm to 5 mm of a fibrous inorganic substance;
Or, by blending with an organic flame retardant, they found that carbonization and incineration without melting and falling off even when ignited, and that even when incinerated, they had the effect of maintaining their shape firmly in a flame atmosphere and not falling down. Was.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The polyurethane resin composition of the present invention comprises (a) a prepolymer having an isocyanate group at the terminal, (b) an active hydrogen-containing curing agent, and (c) an average length of 0.5 mm. It is characterized by containing a fibrous inorganic substance of about 5 mm and (d) an inorganic and / or organic flame retardant.

(A) The terminal isocyanate group-containing prepolymer is obtained by reacting a known diisocyanate compound or polyisocyanate compound with a known active hydrogen-containing compound such as polyol or polyamine. For example, the number of functional groups is 2-3, and the molecular weight is 25,000-60,00.
0, an isocyanate (NCO) group-containing prepolymer having a terminal isocyanate group content of 2 to 4%.

As the isocyanate compound used for preparing these prepolymers, for example, tolylene diisocyanate (TDI), vitriylene diisocyanate, methylene diisocyanate, naphthylene diisocyanate, phenylene diisocyanate, 1,6-hexane diisocyanate, xylylene Diisocyanate, hydrogenated methylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, diphenylmethane-4,4-diisocyanate (also referred to as MDI), ethylene diisocyanate, propylene diisocyanate, 1-methyl-2,4-diisocyanatecyclohexane, triisocyanate Phenylmethane diisocyanate, dicyclohexylmethane diisocyanate, their epoxy-modified products, etc. One or more aromatic or aliphatic polyisocyanates. Especially, T
DI and / or MDI isocyanates are preferably used.

Examples of the active hydrogen-containing compound used for preparing the prepolymer include low molecular weight polyols such as ethylene glycol, propylene glycol, butadiene polyol, hexanediol, diethylene glycol, trimethylolpropane, glycerin and hexanetriol. One or two kinds of polyoxyalkylene glycols such as polyethylene glycol and polyoxide / propylene oxide copolymer, alkylene oxides such as propylene oxide, ethylene oxide, butylene oxide and tetrahydrofuran, and olefin polyols such as polybutadiene polyol and polyisoprene polyol. The above is mentioned.

Further, ethylenediamine, hexamethylenediamine, phenylenediamine, aniline, methylenebisorthochloroaniline, methylenedianiline, methylenedianisidine, dibutylaminopropylamine, bis (hexamethylene) triamine, a mixture of tall oil and triethylenetetramine Amidopolyamines, polyamines such as amide polyamines of ricinoleic acid and triethylenetetramine, alkanolamines such as ethanolamine and propanolamine, and one or more polyhydric phenols such as resorcinol and bisphenols also contain active hydrogen. It can be exemplified as a compound.

(B) As the active hydrogen-containing curing agent for curing the prepolymer having terminal isocyanate groups, polyols having a molecular weight of 1,000 to 4,000 and having 2 to 3 hydroxyl groups are preferred. .

The mixing ratio of the terminal isocyanate group-containing prepolymer to the polyols is such that the equivalent ratio of NCO groups to OH groups (NCO / OH equivalent ratio) is 1.02 to 1.40, and especially 1.07 to 1.40. .37. If the equivalent ratio is less than 1.02, the hardness of the cured product will be low, and if it is more than 1.40, the hardness of the cured product will be too high, which tends to cause practical problems.

[0015] The refractory sealing material of the present invention comprises:
(B) when mixing with an active hydrogen-containing curing agent, (c) a fibrous inorganic substance having an average length of 0.5 mm to 5 mm, (d)
Inorganic and / or organic flame retardants, more preferably (e) a triazine compound and (f) a phosphate ester plasticizer, are appropriately mixed with the curing agent of (b) so as to coexist.

(C) a fibrous inorganic substance having an average length of 0.5 mm to 5 mm, preferably 1 mm to 3 mm [hereinafter referred to as (c)
Ingredients. ] Is exemplified by a glass fiber having a diameter of 5 μm to 15 μm.

The compounding amount is preferably 2 to 12 parts by weight, more preferably 4 to 8 parts by weight, based on 100 parts by weight of the curing agent (b). If it is less than 2 parts by weight, it will easily collapse during combustion, and if it exceeds 12 parts by weight, the viscosity will increase, and the filling workability and the appearance of the cured product may be impaired. On the other hand, if the average length is more than 5 mm, the viscosity increases and the workability is impaired. If the average length is less than 1 mm, the effect of preventing the ash layer from collapsing is poor.

(D) Examples of the inorganic flame retardant include alumina hydrate such as aluminum hydroxide, magnesia hydrate such as magnesium hydroxide, calcium oxide hydrate such as calcium hydroxide, and oxide such as barium hydroxide. Barium hydrate, lead oxide hydrate such as lead hydroxide, manganese oxide hydrate such as manganese hydroxide, zirconium oxide hydrate, tin oxide hydrate, zinc borate hydrate, basic magnesium carbonate Or 2 types of known inorganic flame retardants such as hydrated metal oxides such as sand, shelf sand, hydrotalcite and dawsonite, alumina, silica, magnesia, clay, talc, zinc borate, aluminum borate and antimony oxide More than one species can be exemplified. Among the inorganic flame retardants, magnesium hydroxide and / or aluminum borate are preferred from the viewpoint of fire resistance.

As the organic flame retardant, known bromine flame retardants and chlorine flame retardants are used. For example, hexabromobenzene, decabromodiphenyl oxide, chlorinated paraffin and the like are exemplified, and hexabromobenzene is preferred from the viewpoint of fire resistance.

Inorganic and / or organic flame retardant [hereinafter referred to as component (d). ] Is the amount of the curing agent 10 (b).
40 to 400 parts by weight, especially 50 to 2 parts by weight per 0 parts by weight
50 parts by weight are preferred. If the compounding amount of the component (d) is less than 40 parts by weight, flame retardancy is poor, and no ash layer is formed.
Alternatively, even if formed, the incinerated layer is liable to collapse, and if it exceeds 400 parts by weight, the viscosity increases and the workability at the time of mixing and the workability of filling may become poor. In the present invention, it is preferable to combine magnesium hydroxide, aluminum borate and hexabromobenzene.

(E) Triazine compound [hereinafter referred to as component (e). ] Can be exemplified by melamine, melamine isocyanurate and the like, and preferably melamine isocyanurate. These have an average particle size of 300 μ or less, preferably 100 μ or less, particularly preferably 50 μ or less.

The component (e) is preferably used in an amount of 5 to 80 parts by weight, more preferably 10 to 40 parts by weight, based on 100 parts by weight of the curing agent (b). If the compounding amount is less than 5 parts by weight, it may easily collapse during combustion, and a solid ash layer may not be formed.
If the amount is more than 0 parts by weight, the viscosity may increase, and the mixing or filling workability may be poor.

(F) Phosphate ester plasticizer [hereinafter referred to as component (f)]. ], Alkyl phosphates, tricresyl phosphate, tri (2,3 dibromopropyl) phosphate and the like are used. (F)
From the viewpoint of fire resistance, the compounding amount of the component is 100% of the curing agent (b).
10 to 200 parts by weight, especially 20 to 10 parts by weight,
0 parts by weight is preferred.

The polyurethane resin composition of the present invention can be provided with a thixotropic agent by adding a sagging agent as required. Thixotropic is easy to apply such as coating work and filling sealing work, but hard to flow, and can prevent dripping when applied to a vertical seam or an inclined surface. As the anti-sagging agent, colloidal silica, calcium carbonate, bentonite and the like can be used.

The anti-sagging agent which can be preferably used from the viewpoint of storage stability which does not impair the rubber elasticity and chemical resistance of the sealing material is calcium carbonate having an average particle size of 10 μm or less, particularly 0.02 to 2 μm. 8 carbon atoms such as aebicinic acid
It is preferable to apply a surface treatment with the above carboxylic acid or alcohol to provide a coating layer. Surface treatment, for example, dissolve the carboxylic acid or alcohol in the solvent as needed, mix the solution and anti-sagging agent, after coating on the surface,
It can be performed by a method of drying treatment or the like.

In preparing the refractory sealing material of the present invention, each of the components (c) and (d), more preferably the component (e) and / or the component (f), preferably contains the active hydrogen containing component (b). It is mixed with the curing agent, and the mixing operation may be performed by a method such as a normal planetary mixer, three rolls, or a vacuum kneader. At that time, if necessary, carbon or other pigments, fillers, antioxidants, ultraviolet rays Appropriate additives such as an absorbent, a flame retardant aid, a fungicide, and a catalyst can be compounded. (B), (c) and (d) thus obtained.
By mixing a mixture containing at least each of the above components with the prepolymer having terminal isocyanate groups of (a), the prepolymer of (a) is cured, and the refractory sealing material of the present invention is prepared. The treatment temperature in the curing treatment of the prepolymer (a) is not particularly limited, but is usually performed at room temperature.

[0027]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In order to explain the effects and objects of the present invention in more detail, embodiments of the present invention will be described below with reference to the drawings.

Various sealing materials were prepared according to the formulations shown in Tables 1 and 2 below. These sealants were examined for fire resistance, durability, and mechanical properties.

[0029]

[Table 1]

[0030]

[Table 2]

The amounts of the compounding agents shown in Tables 1 and 2 indicate parts by weight, and the physical properties of some of the compounding agents are described below.

TDI prepolymer: having 2-3 functional groups,
Prepolymer having a molecular weight of 25,000-35,000, a viscosity of 20,000 CP, and an NCO group content of 2.45%.

MDI prepolymer: In Examples 6 and 7, a prepolymer having 2-3 functional groups, a molecular weight of 30,000-50,000 and an NCO group content of 2.6% was used. In Examples 8, 9 and Comparative Example 2, an NCO group was used. A prepolymer with a content of 4.7% was used.

Polyether polyol: bifunctional, molecular weight
3,000, except that in Examples 8, 9 and Comparative Example 2, 3
Functional, molecular weight 1,500 polyether polyol (20 parts by weight) and trifunctional, molecular weight 3,000 (40 parts by weight)
And a mixture of a bifunctional compound having a molecular weight of 1,000 (40 parts by weight).

Glass fiber: 1.5 mm long and 3.0 mm
The long ones have a diameter of 10 μm, and the 6.0 mm long ones have a diameter of 11 μm.

Glass fiber powder: average particle size 10 μm

Magnesium hydroxide: average particle size of about 3 μm

Chlorinated paraffin: chlorine content 45%

Melamine isocyanurate: particle size 0.9
3 μm

Calcium carbonate: What was surface-treated with aevitic acid was used.

[Evaluation of Fire Resistance] The fire resistance of the various sealing materials was evaluated as follows. A concrete wall seam model as shown in FIG. 1 is created, a sealing material is filled into the seam portion to a certain thickness, and the seam is cured at room temperature to obtain a test body. The test body is provided with two rows of joints assuming heating from inside and outside, and is filled with a backup material made of foamed polyethylene as shown in the figure, and a sealing material is filled on the outside thereof. Heating was applied from one side of the specimen to J
Heat for 2 hours according to the heating standard curve of IS A 1304 (fire resistance test method for building structure), and heat from room temperature to a maximum of 1010 ° C. at temperature measurement point A.

In the meantime, when the sealing material does not fall down, the flame does not penetrate from the joint, and the temperature does not exceed 260 ° C. at the temperature measurement point B on the back side (indoor side) of the joint of the outdoor heating section, “◎” is attached in the table. Also, JIS A
Heating is performed for 1 hour in accordance with the heating standard curve of 1304 (fire resistance test method for building structural parts), and at temperature measurement point A, from room temperature to a maximum of 925 ° C. During this time, if the sealing material does not collapse, no flame penetrates from the seam portion, and the temperature does not exceed 260 ° C. at the temperature measurement point B on the back surface side (indoor side) of the seam of the outdoor heating section, “○” In the table,
When any of the conditions was not satisfied, “X” was added in the table.

[Evaluation of General Properties of Sealing Material] After being applied, the sealing material normally adheres well to the curtain wall, and follows the dimensional change of the seam throughout the year to continuously exhibit the water stopping function. Must. Therefore,
It has appropriate mechanical properties and JIS A 57
58 (building sealing material) must pass the durability test.

For hardness, strength, elongation and 100% modulus, JIS K6301 (Vulcanized rubber physical test method)
Was measured by The durability test was performed on the mortar adhesive test piece having the shape shown in FIG.
And in the case of rejection, “×” is given in the table.

[Evaluation of joint filling workability] JIS A5
758 (Building Sealing Material) 4.2 Extrusion workability (20 sec. Or less), 4.2 slump test (2 mm in length, 1 mm or less in width) and appearance after filling (with no visual irregularities) ) Is good, "表" is given in the table, and if any of the conditions is not satisfied, "x" is given in the table.

[0046]

According to the fire-resistant sealing material using the polyurethane resin composition of the present invention, waterproofness, airtightness, deformation followability and durability based on the inherent adhesiveness and rubber elasticity of the polyurethane sealing material are provided. Preferred properties as a building sealing material such as water resistance, abrasion resistance and weather resistance are not impaired. Further, when a flame is encountered, the flame does not fall off even when ignited, and a solid ashing layer is formed, so that the flame can be prevented from entering from a joint portion of a curtain wall, for example, without collapsing for a long time. Therefore, the polyurethane resin composition of the present invention is suitably used for architectural purposes, particularly as a sealing material to be filled in a joint portion of a curtain wall, a joint portion of a partition wall, and the like.

[Brief description of the drawings]

FIG. 1 is a view showing a concrete wall joint model for examining fire resistance performance of a sealing material.

FIG. 2 is a perspective view of a mortar adhesive test piece for examining durability of a sealing material.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08K 5/521 C08K 5/521 7/04 7/04 C09K 3/10 C09K 3/10 D 21/14 21/14 (72) Inventor Kiyoshi Furukawa 1-8-1 Kotakecho, Nerima-ku, Tokyo Ryosei Denso Co., Ltd. (72) Inventor Yoichi Koide 3-4-1 Marunouchi, Chiyoda-ku, Tokyo (Shin Kokusai Building) Mitsubishi Cable Industries Co., Ltd. Company Tokyo Office (72) Inventor Shinji Tsukamoto 3-5-1, Uchimachi, Takatsuki-shi, Osaka Sanyuresin Co., Ltd. (72) Inventor Naokatsu Kunaga 3-5-1, Doumachi, Takatsuki-shi, Osaka Sanyuresin (72) Inventor Yoshimichi Takei 3-5-1 Doumachi, Takatsuki-shi, Osaka Sanyuresin Co., Ltd. (56) References JP-A-57-121021 (JP, A) (58) Fields investigated Int.Cl. ⁷ , DB name) C08L 75/04-75/12 C08K 3/00-7/28 C09K 3 / 10,21 / 14

Claims (8)

(57) [Claims] 1. A prepolymer having an isocyanate group at a terminal, an active hydrogen-containing curing agent, and an average length of 0.5
A polyurethane resin composition containing a fibrous inorganic substance having a size of 5 mm to 5 mm and an inorganic and / or organic flame retardant. 2. The polyurethane resin composition according to claim 1, comprising an inorganic and an organic flame retardant. 3. The polyurethane resin composition according to claim 1, wherein the inorganic flame retardant is magnesium hydroxide and / or aluminum borate. 4. The polyurethane resin composition according to claim 1, wherein the organic flame retardant is hexabromobenzene. 5. The polyurethane resin composition according to claim 1, further comprising a phosphate ester plasticizer. 6. The composition according to claim 1, which contains a triazine compound.
6. The polyurethane resin composition according to any one of claims 1 to 5. 7. The polyurethane resin composition according to claim 6, wherein the triazine compound is melamine isocyanurate. 8. A fire-resistant sealing material comprising the polyurethane resin composition according to claim 1.