JPS61174287A - Fire-resisting sealant - Google Patents

Abstract

PURPOSE:To provide a sealant consisting of specified inorganic and organic components, etc. which is excellent in fire and flame resistance, waterproofness, weathering resistance, durability, soil resistance, coatability, resistance to grain depression, etc., and produces a strongly adherent joint. CONSTITUTION:The sealent is prepared by blending an inorganic component consisting of (a) 20-300pts.wt. inorganic flame retarder made from an inorg. compd. which is decomposed by absorption of heat such as crystallization water releasing type, CO2 releasing type, heat absorption decomposing type and phase conversion type [e.g., Al(OH)3] and (b) 5-400pts.wt. fibrous potassium titanate which is a whisker surface coated with 0.05-1.0wt% silane coupling agent and having a diameter of 0.1-7mu and a length of 10-50mu, with 100pts.wt. organic component consisting of (c) 50-95wt% silicone resin such as polydimethylsiloxane which contains at least one group selected from among H, vinyl, allyl, OH, NH2 and 1-4C alkyl and (d) 50-5wt% modified silicone resin which amorphous at normal temp. and under normal pressure. When necessary, inorganic filler, hardener (curing accelerator), etc., are added.

Description

[Detailed Description of the Invention] The present invention relates to a fire-resistant sealing material used for windproofing, dustproofing, soundproofing, waterproofing, etc. in civil engineering, architecture, vehicles, ships, containers, etc., and it can be used simply by applying a primer treatment. It becomes a joint with good adhesion, and
It has excellent properties such as high fire resistance and flame resistance, waterproofness, weather resistance, durability, cold resistance, ozone resistance, stain resistance, paintability, etc., and is also excellent in resistance to resin fading. It provides a sealing material that exhibits properties.

Oil-based caulking materials and emulsions such as butyl-based, acrylic-based, and silicone-based sealants are used to provide windproof, dustproof, soundproof, waterproof, etc. to connection points in civil engineering, architecture, vehicles, ships, containers, etc. Although caulking materials and the like are used, the reality is that these sealing materials do not fully satisfy the fire and flame resistance requirements, especially in recent years for high-rise buildings.

The present invention provides a mixture containing an inorganic component of an inorganic flame retardant made of an endothermically decomposed inorganic compound and fibrous potassium titanate, and an organic component of a silicone resin and a modified silicone resin that is amorphous at room temperature and pressure. By using a sealing material made of a composition, it becomes a joint with good adhesion, and also has high fire resistance, flame resistance, waterproofness,
Weather resistant, durable, cold resistant, ozone resistant.

It is possible to provide a novel sealing material that has excellent properties such as stain resistance and suitability for painting, and also exhibits excellent properties against resin fading.

The mixed composition constituting the fire-resistant sealant of the present invention will be explained below.

The mixed composition constituting the fire-resistant sealant of the present invention is
The inorganic components are an inorganic flame retardant made of an endothermically decomposed inorganic compound and fibrous potassium titanate, and the organic components are a silicone resin and a modified silicone resin that is amorphous at room temperature and pressure. It is a paste-like composition containing a plasticizer, other inorganic fillers, a curing agent, a curing accelerator, a coloring agent, etc., which are added as desired.

The inorganic flame retardant made of an endothermically decomposed inorganic compound in the mixed composition constituting the fire-resistant sealant of the present invention imparts sufficient flame-retardant properties to the fire-resistant sealant of the present invention, such as calcined gypsum.

Alum, calcium carbonate, calcium hydroxide.

Uses inorganic flame retardants made of endothermic decomposition type inorganic compounds such as aluminum hydroxide, magnesium hydroxide, and hydrotalcite-based aluminum silicate, which release water of crystallization, release carbon dioxide, endothermic decomposition, and undergo phase change. be done.

Fibrous potassium titanate, which is the other essential inorganic component in the mixed composition, provides the fire-resistant sealant of the present invention with sufficient heat resistance, fire-resistant properties, and reinforcing effect. This fibrous potassium titanate is generally made of fibers whose components are represented by the general formula 2o-mTio2.nH2O (in the formula, m is a positive integer of 8 or less, and n is 0 or a positive integer of 4 or less). Diameter 0.1-0.7μm, fiber length 10-50
It is a μm whisker and is manufactured using titanium oxide and potassium carbonate as raw materials by a calcination method, a hydrothermal method, a fusics method, etc. The above-mentioned fibrous potassium titanate can be used as it is, but in order to achieve a better reinforcing effect, it is necessary to add 0.05 to 1.0% by weight based on the fibrous potassium titanate. It is preferable to use fibers whose surfaces have been treated with a silane coupling agent such as γ-aminopropyltriethoxysilane or γ-glycidoxyglobiltrimethoxysilane.

The silicone resin, which is an essential organic component in the mixed composition, generally contains hydrogen atoms.

For example, polydimethylsiloxane silicone resin, polydiphenylsiloxane containing at least one substituent such as vinyl group, allyl group, aryl group, hydroxyl group, alkoxyl group having 1 to 4 carbon atoms, amine group, or mercapto group. silicone resins, polymethylphenylsiloxane silicone resins, and epoxy-modified silicone resins obtained by modifying these with other resins.

Organopolysiloxane silicone resins such as polyester-modified silicone resins, fatty acid-modified silicone resins, alkyd-modified silicone resins, and amine resin-modified silicone resins, as well as heat-curing types such as polyacryloxyalkylalkoxysilane-based silicone resins and polyvinyl-based silicone resins. A room temperature curing resin in the presence of a resin or a catalyst is used.

The other essential organic component in the mixed composition, the modified silicone resin which is amorphous at room temperature and pressure, is, for example, a telechelic liquid polymer having a methyldimethoxysilyl functional group at the end of a polypropylene oxide main chain, or a mercaptoalkanone. a mercaptan-terminated liquid polymer obtained by reaction with an acid, a thiodiallic acid, and a polyoxypropylene polyol having three or more hydroxyl groups;
Polypropylene oxide, which has several unsaturated groups in the molecule, is cured with a nitrile oxide crosslinking agent, and allyl alcohol is added to a prepolymer with terminal incyanate groups obtained by the reaction of polyoxypropylene polyol and polyincyanate. A mercaptan-terminated liquid polymer obtained by reacting an allyl terminal with a polymercaptan compound and a prepolymer with terminal incyanate groups obtained by reacting PPG with a polyisocyanate are reacted with γ-aminopropyltrimethoxysilane. The resulting silyl group-terminated liquid polymer, etc.

The reason for using both a silicone resin and a modified silicone resin that is amorphous at room temperature and pressure as organic components in the mixed composition constituting the fire-resistant sealant of the present invention is as follows. It is as follows.

In the first place, silicone resin has excellent properties such as heat resistance, waterproofness, weather resistance, durability, cold resistance, and ozone resistance. is usually used in the form of a composition in which a low molecular weight silicone oil is mixed with the silicone resin, or a composition in which a solvent such as xylene is added.

However, when using sealants containing low molecular weight silicone oil, the silicone oil in the sealant migrates onto the adherend, making it easy for dust to be adsorbed. It easily contaminates the body and has weaknesses in stain resistance. Further, in the case where a solvent such as xylene is added, vaporization of the solvent progresses after the sealant is applied, and the problem of resin fading occurs depending on the amount of vaporized solvent. Furthermore, with the conventional silicone resin sealant mentioned above, the applied sealant surface (i.e., the hardened surface) is highly water repellent, so the adhesion of paint to the surface is very poor, and it is difficult to apply the sealant to external wall panels, for example. At the same time, it also has the disadvantage that the paint does not adhere well when painting the joints.

On the other hand, the above-mentioned modified silicone resin used in the present invention, which is in an amorphous state at room temperature and pressure, has a high viscosity by itself, but when it is blended into the silicone resin, it acts as a silicone oil. It also enables the addition and blending of a plasticizer, which also functions as silicone oil, and has the function of making it a high elongation type.

That is, the blend of silicone resin and modified silicone resin that is amorphous at room temperature and pressure in the fire-resistant sealant of the present invention has no problems such as stain resistance, unsuitability for painting, and resin fading as described above. Also, there is no problem of residual tack at the initial stage of curing that occurs with compositions containing only modified silicone resin as a resin component.
It exhibits good properties as a sealing material.

In the fire-resistant sealant of the present invention, the silicone resin and the modified silicone resin are compatible with each other, but in terms of uniform stability and storage stability of the mixed composition, the ratio of 50 to 95:
The most preferable range is about 50 to 5 (weight ratio).

The mixed composition constituting the fire-resistant sealing material of the present invention contains the above-mentioned essential components, namely, an inorganic flame retardant made of an endothermically decomposable inorganic compound, fibrous potassium titanate, a silicone resin, and the like at room temperature and pressure. In addition to the essential constituents consisting of amorphous modified silicone resin, in order to impart high elongation properties to the sealant, for example, phthalate esters, phosphate esters, fatty acid esters, aromatic hydrocarbons, etc. A plasticizer may be blended, and if desired, an inorganic filler, a flame retardant other than the inorganic flame retardant made of the endothermically decomposable inorganic compound, a curing agent, a curing accelerator, a coloring agent, etc. may be appropriately added or contained. It is something that exists. Examples of the inorganic filler include various inorganic substances such as titanium oxide, mica, alumina, talc, glass fiber powder, rock wool fine fibers, silica powder, and clay.

However, flame retardants other than the inorganic flame retardant made of the endothermally decomposable inorganic compound that are blended in order to obtain a mixed composition with superior flame retardant properties include, for example, phosphate ester type, organic halogen compound type, Organic flame retardants such as phosphazene compound types and inorganic flame retardants such as antimony compounds are used. Curing agents and curing accelerators that are well known to those skilled in the art are used, such as metal carboxylates, organic tin compounds, titanium chelate compounds, and tertiary amine compounds for silicone resins.

Peroxide and platinum-based catalysts are used, and for trench-modified silicone resins, for example, tertiary amine, tin (II) fatty acid salt-based catalysts, etc. are used.

As mentioned above, the fire-resistant sealant of the present invention is a mixed composition containing as essential components an inorganic flame retardant made of an endothermically decomposable inorganic compound, fibrous potassium titanate, a silicone resin, and a modified silicone resin. The amount of fibrous potassium titanate in the composition is determined so that the water repellent effect of the silicone resin and modified silicone resin in the composition and the flame retardant effect and reinforcing effect of the fibrous potassium titanate are expressed in a balance. Therefore, it is preferable that fibrous potassium titanate be contained in about 5 to 400 parts by weight per 100 parts by weight of the total amount of silicone resin and modified silicone resin. It is preferable to replace 10 to 90% by weight of potassium titanate with an inorganic filler. In addition, the amount of the inorganic flame retardant made of an endothermally decomposable inorganic compound, which is the other essential additive component, is determined by the total amount of silicone resin and modified silicone resin so that sufficient flame retardant performance is expressed by the flame retardant. It is preferable to contain about 20 to 300 parts by weight of an inorganic flame retardant made of an endothermically decomposable inorganic compound per 100 parts by weight, and when other flame retardants are used together, the flame retardant made of the endothermically decomposable inorganic compound is preferably contained. It is preferable to replace 10 to 50% by weight of the inorganic flame retardant with other flame retardants and use them together.

The fire-resistant sealant of the present invention is prepared using a solvent such as xylene, naphtha, gasoline, or a petroleum solvent such as benzene so that each component in the silicone resin composition can be uniformly dissolved or dispersed. Although it is also used in a form, the amount of solvent in the mixed composition is 10% by weight or less in order to avoid resin fading in the sealant.

The fire-resistant sealant of the present invention has the above-mentioned structure, and can exhibit good adhesion as a joint simply by applying a primer treatment, and has high fire and flame resistance, as well as waterproof and weather resistance. properties, durability, cold resistance, and ozone resistance.

It has excellent properties such as stain resistance and painting suitability, and also exhibits excellent properties against resin fading.

Hereinafter, the specific composition of the mixed composition constituting the fire-resistant sealant of the present invention will be explained using manufacturing examples thereof.

Example 1 A mixed composition consisting of the following (1) to (9) was placed in a small supermarket.
The mixture was stirred and mixed using a mixer to obtain a silicone resin-modified silicone resin varnish consisting of a substantially uniform highly viscous dispersion [viscosity: 350,000 cps (25° C.)].

(1) Silicone resin 7
0 parts by weight (molecular weight 70,000-74,000) (2)
Modified silicone resin (*1)・・・・・・・・・
30 parts by weight (molecular weight 7,000-9,000) (3) Fibrous potassium titanate
20 parts by weight (4) Wollastonite ・
...... 8 parts by weight (5) Aluminum hydroxide 120 parts by weight (6) Mica 30 parts by weight (
325 mesh pass) (7) Colorant・・・・・・・・・
3 parts by weight (8) Dispersant...
・1 part by weight (9) xylene...
...4 Weight part, modified silicone resin (*1
) is a telekeric liquid polymer [trade name ``Kanejiki MS Polymer ■'', manufactured by Kaneshiro Kagaku Kogyo Co., Ltd.] having a methyldimethoxysilyl functional group at the end of the polypropylene oxide main chain (the same applies hereinafter).

Subsequently, 11 parts by weight of a curing agent and curing accelerator for silicone resin, a curing agent for modified silicone resin (tin octylate), and a curing accelerator (lauryl amine) were added to 286 parts by weight of the obtained silicone resin-modified silicone resin face. )1
．． 4 parts by weight was added to obtain CI'3, an example of the fire-resistant sealant of the present invention for use in construction.

Example 2 A mixed composition consisting of the following (1) to (7) was stirred and mixed using a small super mixer to obtain a silicone resin-modified silicone resin varnish consisting of a substantially uniform highly viscous dispersion. A curing agent and a curing accelerator were added to this in the same manner as in Example 1 to obtain an example product [■] of the fire-resistant sealant of the present invention for use in construction.

(1) Silicone resin...
... 70 parts by weight (molecular weight 70,000-74,000
) (2) Modified silicone resin (*1) ・・・・・・・・・
... 30 parts by weight (molecular weight 7,000-9,000'
) (3) Fibrous potassium titanate ・・・・・・・・・
・28 parts by weight (4) Aluminum hydroxide...
・・・・・・150 parts by weight (5) Coloring agent
・・・・・・・・・ 3 parts by weight (6) Dispersant
・・・・・・・・・ 1 part by weight (7)
Xylene 4 parts by weight Example 3.

A plasticizer consisting of dioctyl phthalate is mixed with a modified silicone resin, and a composition obtained by adding a silicone resin to the resulting mixture is stirred with other fillers and a solvent in a small super mixer.

After mixing to obtain a silicone resin-modified silicone resin face consisting of a substantially uniform and highly viscous dispersion of the mixed composition from (1) to (8) below, this was mixed with Example 1 and Similarly, a curing agent and a curing accelerator were added to obtain an example product (m) of the fire-resistant sealant of the present invention for use in construction.

(1) Silicone resin...
・70 parts by weight (molecular weight 70,000-74,000)
(2) Modified silicone resin (*1) ・・・・・・・・・
- 30 parts by weight (molecular weight 7,000-9,000) (3) Fibrous potassium titanate 28 parts by weight (4) Aluminum hydroxide 150 parts by weight (5) Colorant 3 parts by weight (
6) Dispersant 1 part by weight (7
) Xylene 4 parts by weight (8) Plasticizer 15 parts by weight (dioctyl phthalate) Example 4 The procedure of Example 3 was repeated except that the amount of plasticizer (dioctyl phthalate) added was 7.5 parts by weight. A product [■] of the fire-resistant sealant of the present invention was obtained by formulating in the same manner as in Example 3.

Table 1 shows the tensile elongation and tensile strength of each of the above examples.

Table 1 Comparative Example 1 After stirring and mixing the following mixed compositions (1) to (6) in a small suit mixer to obtain a silicone resin face, 262 parts by weight of this silicone resin face was added with a third A comparative sealing material [1] for use in construction was obtained by adding 17 parts by weight of a curing agent and curing accelerator for silicone resin consisting of a class amine compound and a platinum-based catalyst.

(1) Silicone resin ・・・・・・・・・
100 parts by weight (molecular weight 70,000-74,000)
(2) Fibrous potassium titanate ・・・・・・・・・
28 parts by weight (3) Aluminum hydroxide...
...120 parts by weight (4) Coloring agent
・・・・・・・・・ 3 parts by weight (5) Dispersant
...... 1 part by weight (6) xylene ...... 10 parts by weight Comparative Example 2 A mixed composition consisting of the following (1) to (5) was prepared in Comparative Example 1.
A comparative solvent-free sealing material [11] was obtained by processing in the same manner as the mixed composition in .

(1) Low molecular weight silicone oil ・・・・・・・・・
100 parts by weight (molecular weight 30,000 or less) (2) Fibrous potassium titanate ・・・・・・・・・
・28 parts by weight (3) Aluminum hydroxide...
・・・・・・120 parts by weight (4) Coloring agent
・・・・・・・・・ 3 parts by weight (5) Dispersant
・・・・・・・・・ Fire resistance test results, stain resistance test results, coating suitability test results, resin fading resistance test results, and curing of each sealant obtained in each example and comparative example in amounts of 1 part by weight or more The initial residual tack resistance test results are summarized in Table 2.

The test method for each test is as follows.

Fire resistance test A simple small vertical fire resistance test furnace created in accordance with JIS-A 1304, that is, as shown in Figure 1 of the attached drawings, 1000 m long and 500 mm wide.

Two fireproof asbestos cement extruded plates 1.2 with a thickness of 60 mm are arranged with a gap (S) of 12 Nn between them,
100 rtan vertically on the back side of the gap (S).

3 cedar boards 100mm wide and 10mm thick
．． 3 in upper and lower directions at three locations (A), (B), and (C), and then apply a secondary fire prevention sealing material made of glass fiber nonwoven fabric to the position indicated by reference numeral 4 in the gap. (S
), fill with the sealing material obtained in each of the Examples and Comparative Examples using a caulking gun, and
After 4 hours have elapsed, a flame is applied to the surface of the primary sealing material 5, and the secondary seal is heated for 30 to 60 minutes along the heating standard curve based on the provisions of Article 107, Item 1 of the Building Standards Act. The temperature of the back surface of the material 4 was measured at the position where the cedar board 3 was in contact with the material.

Table 2 below shows the highest temperature among the measured temperatures.

Using Neopalier (artificial marble) manufactured by Nippon Electric Glass Co., Ltd. as the adherend, the test was conducted for three months at the edge of a road with heavy traffic, and outdoors where wood dust and debris such as volcanic ash soil are likely to occur. It was carried out in

A paint [Vini Deluxe-300, exterior acrylic emulsion, manufactured by Kansai Paint Co., Ltd.] was sprayed onto the surface of the paint film formed with the sealant, and its adhesion was visually evaluated.

The state of resin discoloration at the joints of the set during the stain resistance test described above was visually evaluated.

Tactile evaluation of the tack-free state was performed.

Regarding stain resistance, items with stain resistance were marked with a mark of ○. Items with significant stains were marked with a ×.

Items that are suitable for painting are those that are suitable for painting. ○ Items that are not suitable for painting are indicated by an ×.

Resin fading resistance means that there is almost no resin fading. ○Those that have a considerable amount of resin fading. They are indicated by ×.

Residual tack at the initial stage of curing is one with residual tack of less than 8 hours.
○Those with residual tack of 8 to 12 hours...
- Indicated by △.

Table 2 The fire-resistant sealant of the present invention has the above-mentioned structure, and can form joints with good adhesion just by applying a primer treatment, and has high fire and flame resistance, waterproofness, Weather resistance, durability, cold resistance, ozone resistance,
Stain resistance.

It has excellent properties such as coating suitability, and also exhibits excellent resin fading resistance.

However, the fire-resistant sealing material of the present invention can contain a plasticizer in the composition constituting the sealing material, and by adding this plasticizer, it can be made into a fire-resistant sealing material with high elongation. Therefore, it exhibits excellent functions and effects as a fire-resistant sealing material in fields that require elongation properties.

[Brief explanation of drawings]

FIG. 1 is a plan view of a testing apparatus used in a fire resistance test of sealing materials, and FIG. 2 is a reduced rear view thereof. 1.2 Fireproof asbestos cement extruded board, 3. Cedar board, 4. Secondary sealing material, 5. 1st sealing material, (A), (B)
, (C) Backside temperature measurement position.

Claims (2)

[Claims] (1) Essential constituents include an inorganic component consisting of an inorganic flame retardant made of an endothermically decomposed inorganic compound and fibrous potassium titanate, and an organic component consisting of a silicone resin and a modified silicone resin that is amorphous at room temperature and pressure. A fire-resistant sealant characterized by: (2) The fire-resistant sealing material according to claim 1, which contains a plasticizer such as a phthalate ester, a chlorinated paraffin, a fatty acid ester, a phosphate ester, or a process oil.