JPH03212478A - Flame-retardant sealing material - Google Patents

Abstract

PURPOSE:To obtain a sealing material containing a liquid polychloroprene, liquid polyurethane, hydrated metal oxide, silica and amines at a specific ratio, having good weather resistance, adhesion, flame-retardation and self-curing property in air after application and suitable for construction. CONSTITUTION:The objective sealing agent consisting of 100 pts.wt. liquid polychloroprene (preferably having 3500-10000 number-average molecular weight, 30000-150000cp Brookfield viscosity at ambient temperature and one or more OH groups), 50-500 pts.wt., preferably 100-250 pts.wt. liquid polyurethane, 50-500 pts.wt., preferably 100-400 pts.wt. hydrated metal oxide (e.g. magnesium hydroxide, preferably having <=10mum average grain size), 5-150 pts.wt., preferably 5-50 pts.wt. silica (preferably having 0.1-10mum average grain size) and 1-50 pts.wt., preferably 2-30 pts.wt. amines (preferably activated triethanolamine).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a flame-retardant sealing material that can be used in various fields, and is particularly suitable for architectural use.

[Conventional technology]

Urethane-based, acrylic-based,
Silicone-based sealants are commercially available, but urethane-based and acrylic-based sealants generally have poor flame retardancy.
On the other hand, silicone-based sealants have problems such as weather resistance, especially black staining due to mold, and insufficient adhesion to mortar and the like.

[Problems that need to be solved]

In consideration of the above circumstances, the present invention aims to develop a sealing material that has good weather resistance (black staining due to mold) and adhesion to mortar, etc., and is also excellent in flame retardancy and fire resistance.

[Means for solving problems]

The above problems are caused by liquid polychloroprene, and per 100 parts by weight of liquid polychloroprene, 50 to 500 parts by weight of liquid polyurethane, 50 to 500 parts by weight of hydrated metal oxide, 5 to 150 parts by weight of silica, and 1 to 500 parts by weight of silica. The problem is solved by a flame-retardant sealant characterized by comprising 50 parts by weight of amines.

[Effect]

The sealant of the present invention has good weather resistance, adhesion, and flame retardancy due to the interaction between the ingredients, and also has good self-curing properties in the atmosphere after being applied to a desired location. Furthermore, there is no dripping during combustion, and an ash is formed that substantially retains its pre-combustion form, and this ash also exhibits fire resistance and spread prevention properties.

As liquid polychloroprene, for example, the number average molecular weight is about 1,000 to 100,000, particularly 3.500 to 100,000.
10.000, with a Brookfield viscosity of 10.000 to 200,000 cp at room temperature, especially 30.00
A nonvolatile liquid having a concentration of 0 to 150.0 Ocp is used, and those having one or more hydroxyl groups at the end or in the molecule are particularly preferred.

Examples of liquid polyurethanes include common two-component polyurethanes consisting of isocyanate and polyol. In that case, the weight ratio of isocyanate to polyol is the former/
The latter ratio is suitably in the range of 0.5/1.0 to 2.0/1.0, preferably 0.7/1.0 to 1.5/1.0. As the isocyanate, tolylene diisocyanate, diphenylmethane diisocyanate (.), hexamethylene diisocyanate, and urethane prepolymers of the above-mentioned isocyanates are used, and commercially available products have an EC26
10B (Polyurethane Kasei Co., Ltd.), IIRICN-202
3 (Ito Oil Co., Ltd.) is exemplified.

Examples of polyols include low molecular weight polyols (ethylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, etc.), polyether polyols (polyethylene glycol, polyoxypropylene glycol, ethylene oxide-propylene oxide copolymer, etc.), and polyester polyols. (polyβ-methyl-δ-valerolactone, polycaprolactone, polyester from diol-dibasic acid, etc.), silicone polyol, castor oil, etc. are used, and commercially available products have an EC261
OA (Polyurethane Kasei Co., Ltd.), URICH-30 (
Ito Oil Co., Ltd.) is an example.

As the hydrated metal oxide, an agent that exhibits a flame retardant effect through a dehydration reaction at high temperatures is used, such as magnesium hydroxide, aluminum hydroxide, and the like. The hydrated metal oxide has an average particle size of 0.05 to 50 μm, especially 10 μm.
Fine particles of micrometers or less are preferred. The hydrated metal oxide may or may not be surface-treated, but surface-treated ones are generally preferable because they give good results in properties such as dispersibility in the material of the present invention and fire resistance. Particularly preferred hydrated metal oxides are magnesium hydroxide surface-treated with saturated fatty acids, unsaturated fatty acids, silane coupling agents, titanium coupling agents, and silicon oligomers.

The silica may be produced by any method such as a wet method or a dry method, but the average particle size is 50
Fine particles with a diameter of 1 μm or less, particularly about 0.1 to 10 μm are preferable. For example, wet silica such as Nip Seal VN3 (product name of Nippon Silica Co., Ltd.), Jiruton R2 (product name of Mizusawa Chemical Co., Ltd.), Aerosil R972 (product name of Nippon Aerosil Co., Ltd.)
Examples include dry silica such as

Amines include aliphatic primary amines (methylamine,
ethylamine, propylamine, monoethanolamine, etc.), aliphatic secondary amines (dimethylamine, diethylamine, dipropylamine, jetanolamine, etc.),
Aliphatic tertiary amines (trimethylamine, triethylamine, tripropylamine, triethanolamine, etc.)
, various alicyclic amines, aromatic amines, and the like. Among these, ethanolamines, especially activated triethanolamine, and mixtures of activated triethanolamine and silicates are preferred.

In the present invention, ordinary flame retardants, colorants, processing aids, antioxidants, adhesive agents, etc. may be added in addition to the above-mentioned components. In particular, it is preferable to incorporate common flame retardants and adhesive agents to improve flame retardancy and adhesive properties, respectively.

Common flame retardants include inorganic flame retardants such as antimony trioxide, zinc borate, red phosphorous, lead borosilicate, decabromodiphenyl oxide, trifluorophenol, tetrabromobisphenol A1, tetrabromoxylene, brominated polyols, and dibromoneone. Pentyl glycol, perchloropentane clodecane, chlorinated paraffin, etc.
Examples include organic phosphorus-based flame retardants such as ammonium-based organic flame retardants, phosphoric acid esters, condensed ammonium phosphates, melamine phosphates, polyphosphoric acid carbamates, and aliphatic phosphonic acid esters. Particularly preferred are inorganic flame retardants, especially antimony trioxide.

Examples of adhesive agents include adhesives such as tackifiers, silane compounds, titanium coupling agents, and reactive silicone oligomers.

Next, to explain the usage amount of each component, liquid polyurethane is 50 parts by weight per 100 parts by weight of liquid polychloroprene.
-500 parts by weight, especially 100-250 parts by weight. 5
If it is less than 0 parts by weight, the self-curing property in the atmosphere after application to a desired location is poor, and if it is more than 500 parts by weight, flame retardancy is decreased.

The amount of hydrated metal oxide is from 50 to 500 parts by weight, in particular from 100 to 400 parts by weight, per 100 parts by weight of liquid polychloroprene. If it is less than 50 parts by weight, flame retardancy is poor;
If the amount exceeds 0.00 parts by weight, elongation properties and adhesion properties will deteriorate.

Gluing force is 5 per 100 parts by weight of liquid polychloroprene.
~150 parts by weight, especially 5 to 50 parts by weight.

If it is less than 5 parts by weight, the fire resistance will be poor, while if it is more than 150 parts by weight, the elongation properties and elasticity of the sealant will be lost and it will become hard.

The amines are used in an amount of 1 to 50 parts by weight, particularly 2 to 30 parts by weight, per 100 parts by weight of liquid polychloroprene. If it is less than 1 part by weight, there will be a strong tendency for drips to occur during combustion, while if it is more than 50 parts by weight, the anti-drip effect will be saturated and the problem of bleeding will occur.

When using a common flame retardant as described above, the physical properties of the sealing material of the present invention will be deteriorated if an excessive amount is used, so the amount used is 5 parts by weight per 100 parts by weight of liquid polychloroprene.
It is preferably 0 parts by weight or less, particularly 2 to 30 parts by weight. Within this range, the flame retardance and fire resistance of the sealing material of the present invention can be further improved without adversely affecting the weather resistance and adhesiveness.

〔effect〕

As described above, the sealing material of the present invention has various excellent performances and is inexpensive, so it is extremely useful as a sealing material for various fields, especially for construction.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples, and at the same time, the excellent effects of the present invention will be shown. All numerical values below are parts by weight or weight %.

Examples 1 to 8, Comparative Examples 1 to 3 Each component shown in Table 1 was thoroughly mixed in the amount ratio shown in the same table using a triple roll, and the seals of Examples 1 to 8 and Comparative Examples 1 to 3 were prepared. I got the material.

Next, the characteristics of each sealing material were evaluated by the method shown below. The results are shown together in the same table.

Self-curing property: Immediately after sufficiently mixing the sealing material using a triple roll, the obtained sealing material is formed into a 1 mm thick sheet and left in the air at room temperature for 24 hours, after which the degree of curing is examined. If there is some damage, mark it as ×, and if there is no damage, mark it as ○.

Mechanical properties: A No. 3 Dangel specified in JIS K6301 is punched out from the sheet obtained in the above self-curing test after being left in the atmosphere for 24 hours, and a tensile test is performed on it.

A case where the elongation is less than 100% is marked as ×, and a case where the elongation is 100% or more is marked as ○.

Flame retardancy: Oxygen index is measured according to the method specified in JIS K7201.

Fire resistance: Thickness 3WM, length 50m at approximately 1000℃ burner,
A sample with the size and shape of 6 cranes in width is burned for 5 minutes and turned into ashes. A sample that ashes while retaining its pre-combustion shape or a shape close to it is rated as ○, and a sample that loses its shape significantly due to combustion is marked as ×.

Weather resistance: After each composition was left to cure at room temperature for 24 hours, it was exposed to a sunshine weather meter for 2000 hours. Those with black contamination due to mold are marked as ×, and those with no mold growth are marked as O.

Adhesion: After pre-treating a mortar block with a urethane primer, each composition was coated to a thickness of 2 WM and a width of 101 mm, and after being left at room temperature for 24 hours, evaluation was made on the presence or absence of peeling between the mortar and each composition. If the sealing material is uncured and stretches, or if the sheet bends and is easily peeled off, it is marked as ×, and if it is not easily peeled off, it is marked as ○.

Fire resistance: Thickness 3fi, length 50u1 at approximately 1000℃ burner
A sample having a size and shape of 6n in width is burned and incinerated over 5 minutes. A sample that ashes while retaining its pre-combustion shape or a shape close to it is rated as ○, and a sample that is significantly deformed by combustion is marked as ×.

Weatherability: Each composition was exposed (at room temperature, after 24 hours of curing) to a sunshine weather meter for 2,000 hours. Those with black contamination due to mold are marked as ×, and those with no mold are marked as ○.

Adhesion: After pre-treating the mortar block with a urethane primer, each composition was coated to a thickness of 21 m and a width of 10 wm, and after being left at room temperature for 24 hours, the presence or absence of peeling between the mortar and the sealant of each composition was determined. The sealant is uncured and stretches, and the sealer is brittle and easily peels off.
, Those that do not peel off easily are marked as ○.

The details of the materials indicated by *1 to *10 in Table 1 are as follows.

*1 Denka LCRFH-50: trade name manufactured by Denki Kagaku Co., Ltd. *2
EC2610A: Product name manufactured by Polyurethane Kasei Co., Ltd. *3
URICH-30: Product name manufactured by Ito Oil Co., Ltd., $4 EC
2610B: Product name manufactured by Polyurethane Kasei Co., Ltd. *5 UR
ICN-2023: Trade name manufactured by Ito Oil Co., *6 Kisuma 5B = Trade name manufactured by Kyowa Chemical Co., Ltd. *7 Decabromodiphenyl oxide, *8 Nipsil VN-3:
Product name manufactured by Nippon Silica Co., *9 Aerosil R972: Product name manufactured by Degusser Co., Ltd. *10 Nattro Cel
5050 (mixture of reethanolamine and silicate): Manufactured by Berwick Chemical.

[Margin below]

Claims (1)

[Claims] (1) Liquid polychloroprene, and 50 to 500 parts by weight of liquid polyurethane and 50 to 500 parts by weight of hydrated metal oxide per 100 parts by weight of the liquid polychloroprene.
A flame-retardant sealing material comprising ~150 parts by weight of silica and 1-50 parts by weight of amines.