JPH0625333B2 - Sealing material - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a sealing material, and more specifically, in the field of civil engineering, construction, vehicles, ships, containers, etc., windproof, dustproof,
The present invention relates to a sealing agent used for the purpose of soundproofing and waterproofing.

[Prior Art] Conventionally, as a sealing material used for the purpose of imparting windproof, dustproof, soundproof, waterproof, etc. to a connection point of civil engineering, construction, vehicles, ships, containers, etc., butyl series, acrylic series,
Silicone-based oil-based caulking materials, emulsion caulking materials, etc. are used, but these sealing materials are especially required in recent years for high-rise buildings, etc. with fire resistance, flame resistance, stain resistance, and coating suitability (on sealing materials). The coating property of the paint on) was not sufficiently satisfactory.

In order to improve the drawbacks of the above organic sealing material, a sealing material in which an inorganic component is added to an organic resin component has also been investigated. For example, Japanese Patent Laid-Open No. 61-174287 discloses an organic resin containing a silicone resin and a modified silicone resin. A sealing material is disclosed in which an inorganic component of an endothermic decomposition type inorganic flame retardant and fibrous potassium titanate is added to a resin component.

[Problems to be Solved by the Invention] The organic-inorganic mixed sealant described in JP-A No. 61-174287 has considerably improved fire and flame resistance, stain resistance and coating suitability as compared with the organic sealant. However, it is still insufficient, and it has been desired to further improve these properties.

Therefore, an object of the present invention is to provide a sealant having further improved properties such as fire resistance, stain resistance, and coating suitability.

[Means for Solving the Problems] The present invention has been made to achieve the above object, and the present invention is to provide rock wool having a fiber length of 70 to 200 μm of 24.3 to 31.3% by weight, 1. One or more inorganic sintering promoters selected from montmorillonite, sepiolite, wollastonite, glass fibers
0-2.4% by weight, calcined gypsum, alum, calcium carbonate, calcium hydroxide,
15.0 to 19.0% by weight of one or more inorganic flame retardants selected from aluminum hydroxide, magnesium hydroxide, hydrotalcite-based aluminum silicate, modified silicone resin 25.1 to 33.3% by weight, and plastic Ingredient 14.0 to 18.7% by weight, the weight ratio of the inorganic component (P) containing rock wool, inorganic sintering promoter and inorganic flame retardant and the organic component (R) containing modified silicone resin and plasticizer ( A sealing material having a P / R ratio of 0.8 or more.

The present invention will be described in detail below.

The sealing material of the present invention is composed of an inorganic component and an organic component, and the inorganic component contains rock wool, an inorganic sintering accelerator and an inorganic flame retardant as essential components. Rockwool, which is the first inorganic component, is a high-speed rotating body that melts synthetic or natural ores such as steel slag, silica stone, genki stone, dolomite, chlorite, olivine at a high temperature of 1500 ° C or higher. Using the centrifugal force of, fiber diameter 1-10
μm, a fiber length of about 0.01 mm to several tens of mm, and after removing the unfibrinated material (commonly called shot) normally contained in 20 to 40% by weight, the fiber length is adjusted to 70 to 200 μm. is there.

As described above, the fiber length of rockwool, which is the first inorganic component, is limited to 70 to 200 μm. The reason is that when the fiber length of rock wool is 70 to 200 μm, when the rock wool hits a flame, the action of the inorganic sintering accelerator, which is the inorganic second component, is combined with the rock wool to sinter strongly. The sealing material of the joint forms a strong coating film to block the invasion of the flame into the inside, while the fiber length is 70
If it is less than μm and is too short, a strong sintering phenomenon does not occur and the sealing material at the joint portion does not form a strong coating film. Therefore, the sealing material scatters due to the wind pressure of the fire and This is because the thinning of the meat deteriorates the fire resistance and flame resistance, and when the fiber length exceeds 200 μm and is too long, the surface property of the coating film deteriorates.

Further, rock wool may be surface-treated with a silane coupling agent or the like, if necessary, to improve the dispersibility and the adhesiveness with the modified silicone resin, and then used. The components and properties of the rock wool used in the present invention are generally as follows, but are not limited thereto.

Chemical composition SiO ₂ 40 to 50 wt% CaO 15 to 40 Al ₂ O ₃ 5 to 15 MgO 5 to 25 Fe ₂ O ₃ 0.5 to 1.0 Properties Melting point 1100 to 1200 ° C. Fiber diameter 1 to 10 μm It is preferably 24.3 to 31.3% by weight based on the total solid content of the sealing material.

The inorganic sintering accelerator, which is the inorganic second component used together with the above-mentioned inorganic wool, the rockwool, is for promoting the sintering of rockwool as described above. , Montmorillonite, sepiolite, wollastonite, glass fiber, and other inorganic layered compounds. The amount of the inorganic sintering accelerator used is preferably 1.0 to 2.4% by weight based on the weight of the total solid content of the sealing material.

The inorganic flame retardant used as the inorganic third component together with the inorganic first component rockwool and the inorganic second component inorganic sintering accelerator is a flame retardant sufficient for the sealing material of the present invention containing an organic component. It imparts properties such as calcined gypsum, alum, calcium carbonate, calcium hydroxide, aluminum hydroxide, magnesium hydroxide, hydrotalcite-based aluminum silicate, etc. Type and phase inversion type inorganic flame retardants are used. It should be noted that it is effective to mix two or more kinds having different properties in use. The amount of the inorganic flame retardant used is 15.0 with respect to the total solid content of the sealing material.
It is preferable to be ˜19.0% by weight.

The rock wool, the inorganic sintering accelerator, and the inorganic flame retardant used as the inorganic component have been described above. However, the sealing material of the present invention contains an organic component together with the above inorganic component, and the organic component is a modified silicone resin and a plastic. It contains an agent.

As the modified silicone resin, an oxyalkylene polymer having an ether type allyl olefin group at the end is used
General formula in the presence of Group VIII transition metals [In the formula, R is a group selected from a monovalent hydrocarbon group and a halogenated monovalent hydrocarbon group, a is an integer of 0, 1 or 2,
X represents a hydrolyzable group or atom selected from a halogen, an alkoxy group, an acyloxy group and a ketoximate group] to a terminal obtained by reacting with a hydrosilicone compound represented by Examples thereof include a silicon-terminated organic polymer having a group.

Also, at the end of the above X of the silicon-terminated organic polymer having a group is replaced with another hydrolyzable group Y (Y is an alkoxy group, an acyloxy group, an amide group,
A modified silicone resin converted to an acid amide group, an aminooxy group or a ketoximate group) can also be used. These modified silicone resins are described in JP-A-50-156599. In the modified silicone resin, the hydrolyzable group X or Y group on the terminal silicon atom is hydrolyzed by the action of water or a catalyst to generate a silanol group,
Then, by forming a siloxane bond by a silanol condensation reaction, the crosslinking reaction proceeds and becomes a rubber elastic body. Since this crosslinking reaction proceeds at room temperature in several hours, it can be applied on site. The amount of the modified silicone resin used is 25.1 based on the total weight of solids in the sealing material.
It is preferably ˜33.3% by weight.

The plasticizer used together with the modified silicone resin as an organic component is for imparting high elongation property to the sealing material, and for example, phthalic acid ester, phosphoric acid ester, fatty acid ester, aromatic hydrocarbon, etc. are used. To be done. The amount of the plasticizer used is preferably 14.0 to 18.7% by weight based on the weight of the total solid content of the sealing material.

The sealing material of the present invention may appropriately contain, in addition to the above-mentioned essential components, a curing accelerator, a filler, a flame retardant other than the inorganic flame retardant which is an essential component, a colorant, and the like. Of these, the curing accelerator is one that accelerates the curing of the modified silicone resin, and specific examples thereof include organic amines and tin (II) fatty acid salts. In the former case, relative to 100 parts by weight of the modified silicone resin. Preferably 0.5
In the latter case, it is preferably used in an amount of 1 to 10 parts by weight per 100 parts by weight of the modified silicone resin.

Examples of the filler include various inorganic substances such as titanium oxide, mica, alumina, talc, silica powder and clay.

As the flame retardant other than the inorganic flame retardant, for example, an organic flame retardant such as a phosphoric acid ester, an organic halogen compound or a phosphazene compound, an antimony compound, or an inorganic flame retardant such as borax is used.

As the colorant, for example, pigments such as carbon black and titanium oxide are used within a range that does not impair the object of the present invention.

In the sealing agent of the present invention, the weight ratio of inorganic component / organic component (hereinafter referred to as P / R) needs to be 0.8 or more. The reason is that if P / R is smaller than 0.8,
This is because, in the fire resistance test according to JIS A 1304, the back surface temperature exceeds 260 ° C. without being able to withstand 30 minutes of fire resistance, and the sealing material burned by the gas pressure of the flame will be scattered. It is particularly preferable that P / R is 1.0 or more.

[Operation and Effect] The sealing material of the present invention, when exposed to a flame, is the inorganic first component constituting the sealing material, 70 to 200.
The rock wool of μm is combined with the action of the inorganic sintering accelerator, which is the second inorganic component, to form a strong sintered body. As a result, a strong coating film is formed on the joints and the penetration of flames into the interior is blocked. In addition, the coating film will not be peeled off or peeled from the joint due to the pressure of the flame. The inorganic third flame retardant acts on the flammable organic component to enhance the flame retardancy of the coating film. Therefore, the fire resistance and flame resistance of the sealing material of the present invention is extremely excellent due to these three inorganic components.

Further, the sealing material of the present invention does not use a low molecular weight silicone resin that gradually migrates to the surface to absorb dust and deteriorates stain resistance, and has a silicon-containing group only at the end of the polyalkylene oxide main chain. Since the modified silicone resin is used as the organic component, the resin component does not migrate to the surface and has excellent stain resistance.

In addition, since the modified silicone resin has an affinity for the coating material, the sealing material of the present invention is not difficult to adhere to the coating material applied on the sealing material unlike the conventional silicone-based sealing material. Compared to other surfaces, there are no drawbacks such as being difficult to paint, different colors, or conspicuous stains, and it has excellent coating suitability.

Further, since the sealing material of the present invention uses rock wool having a fiber length of 200 μm or less, there is no deterioration of the smoothness of the coating film due to the surface exposure of the fiber, which is observed when the fiber length is long, and Since the plasticizer used at the same time has the effect of expanding the sealing material, it has excellent surface smoothness.

[Examples] Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples. In the examples, "parts" means "parts by weight".

Example 1 73 parts of rock wool having a fiber length of 70 to 200 μm, 3 parts of wollastonite which is an inorganic sintering accelerator, 28 parts of calcium carbonate which is an inorganic flame retardant, and 1 part of aluminum hydroxide.
7 parts, 100 parts of modified silicone resin having a molecular weight of 9000 to 10000, 50 parts of di-2-ethylhexyl phthalate which is a plasticizer, 6 parts of titanium oxide as a colorant and a stabilizer [UV absorber (manufactured by Sumitomo Chemical Co., Ltd.) , Smith soap # 1
10) and an antioxidant (a mixture of Nocrac NS-6 manufactured by Ouchi Shinko Chemical Co., Ltd. in a weight ratio of 1/1)] were mixed with stirring with a small mixer. This was further kneaded with a three-roll roll for experiment, and 3 parts of tin octylate and 1 part of laurylamine as a hardening accelerator, 6 parts of di-2-ethylhexyl phthalate as a plasticizer and titanium oxide as a filler were used. A mixed composition consisting of 11 parts was added and mixed to form a table.
A sealing material having a distribution composition shown in 1 was obtained. The P / R of this sealing material was 0.85.

Using the obtained sealing material, various physical properties of the sealing material (JIS A 5758), stain resistance, sinterability (1 hour fire resistance test), residual tack at the initial stage of curing, surface properties and coating suitability are tested. However, as shown in Table-2, good results were obtained in all the tests.

Examples 2 to 5 The compounding amount of rock wool having a fiber length of 70 to 200 μm as an inorganic component, the type and the compounding amount of the inorganic sintering accelerator, the type and the compounding amount of the inorganic flame retardant, and the filler / colorant ((titanium oxide Was carried out in the same manner as in Example 1 except that the compounding amount of () was changed (the kinds and the compounding amounts of the organic components are exactly the same as those in Example 1) to obtain sealing materials of Examples 2 to 5 (details). (See Table 1 for the composition of various compounds.) P / R of these sealing materials is in the range of 1.10 to 1.46, which satisfies the P / R limit value (0.8 or more) of the present invention. Was.

Using the obtained sealing material, various tests were conducted in the same manner as in Example 1, but as shown in Table-2, good results were obtained in all the tests.

Comparative Example 1 The same kinds of inorganic and organic components as in Example 3 were used, but the P / R was 0.66, which was the limit value (0.8
A sealing material which does not satisfy the above) was obtained in the same manner as in Example 1 (see Table 1 for detailed compounding composition).

When various tests were conducted using the obtained sealing material in the same manner as in Example 1, there was a problem in sinterability as shown in Table 2. About 45 minutes after the 1 hour fire resistance test, the sealing material began to scatter due to the wind pressure of the flame.
The result was that when the minutes passed, only a small amount remained in the joint.

Comparative Example 2 A sealing material was obtained in the same manner as in Example 1 except that rockwool and the inorganic sintering accelerator were not used (see Table 1 for detailed compounding composition).

Using the obtained sealing material, various tests were carried out in the same manner as in Example 1, and as shown in Table 2, the elongation at break in the general physical properties (JIS A 5758) of the sealing material was 300.
%, And the maximum tensile stress was very low, around 3 kg / cm ² . Regarding the sinterability, the sealing material began to scatter about 30 minutes after the fire resistance test with the wind pressure of the flame.
As a result, it was found that there was almost no remaining when the minutes passed.

Comparative Examples 3 to 4 As rockwool, a fiber length of 10 to 50, which is not included in the fiber length range (70 to 200 μm) specified in the present invention.
μm (Comparative Example 3) and fiber length 250 to 1000 μm
A sealing material was obtained in the same manner as in Example 2 except that the m (m) (Comparative Example 4) was used (see Table 1 for detailed compounding composition).

Various tests were carried out using the obtained two kinds of sealing materials in the same manner as in Example 1, but the sealing material of Comparative Example 3 was inferior in sinterability (1 hour fire resistance test) as shown in Table 2. It was a thing. That is, in this 1-hour fire resistance test, heat on the flame side was easily transferred to the back side, the cedar board burned, and the back surface temperature could not be measured. Further, the sealing material of Comparative Example 4 had poor surface properties as shown in Table 2.

Comparative Example 5 Rock wool having a fiber length not regulated within the range (70 to 200 μm) specified in the present invention was used, fibrous potassium titanate was used, and a silicone resin was used together with a modified silicone resin. A sealing material was obtained in the same manner as in Example 2 except for the above (see Table 1 for detailed compounding composition).

Using the obtained sealing material, various tests were conducted in the same manner as in Example 1, but as shown in Table 2, stain resistance, sinterability (fire resistance 1 hour test), residual tack at the initial stage of curing, surface The result was inferior to that of Example 1 in the coating property and the coating suitability.

The test methods for various physical properties shown in Table 2 are as follows.

1. General physical properties of sealing materials The general physical properties of sealing materials are specified in JIS A 5758.
It was performed in accordance with. The evaluation criteria are as follows.

Those that passed the standard ... ○ Those that did not pass the standard ... × 2. Contamination resistance test NEOVARIER (artificial marble) manufactured by Nippon Electric Glass Co., Ltd. is used as the adherend, and it is performed at the road end where traffic is heavy, and outdoors where dust and dust such as volcanic ash soil easily occur.
It was evaluated after 1 year and 3 years. The evaluation criteria are as follows.

No contamination at all ◎ Contaminated but not marked ... ○ Markedly contaminated ... × 3. Sinterability test (fireproof 1 hour test) As shown in FIG. 1 and FIG. 2, two fireproof asbestos-cement extruded plates 1 and 2 having a length of 1000 mm, a width of 500 mm and a thickness of 60 mm are provided between the two. Arranged so that a gap S of 12 mm is formed, and three cedar boards 100 mm long, 100 mm wide, and 10 mm thick are provided on the opposite side of the gap S shown in FIG.
3, 3 are brought into contact with three locations A, B, C in the upward and downward directions, and then a secondary fireproof sealing material made of glass fiber non-woven fabric is provided at a position indicated by reference numeral 4 for about half of the gap S. , The sealing material obtained in each of the examples and comparative examples was filled as a primary sealing material at a position indicated by reference numeral 5 with a caulking gun, and after 24 hours, the sealing material 5 surface was exposed to flame. Apply the Building Standard Act Construction Order No. 102
The back surface temperature of the secondary sealing material 4 when heated for 1 hour along the heating standard curve based on the provisions of Article 1
It was carried out by measuring at the contact position. The evaluation criteria are as follows.

A product in which the sea rig material 5 is in a very good sintered state and has excellent fire resistance ... ◎ A product in which the sea rig material 5 is in a good sintered state and the fire resistance is almost satisfactory. , With poor fire resistance ……
…………… × 4. Residual tack test at the initial stage of curing The tack state was evaluated by touch. The evaluation criteria are as follows.

Those without tacks ……………… ◎ Those with tacks but not marked… ○ Those marked with tacks ………… × 5. Surface property test The appearance of the coating film based on JIS K 5400 (test relating to physical properties of the coating film) was evaluated by visually observing the coated surface under diffused daylight. The evaluation criteria are as follows.

Very good surface properties of coating film ◎◎ Good surface properties of coating film ……………… ○ Poor surface property of coating film ……………… × 6. Coating Suitability Test A paint (Kansai Paint Co., Ltd .: Vini Deluxe-300, acrylic emulsion for exterior) was sprayed onto the surface of the coating film formed of the sealing material, and its adhesion was visually evaluated. The evaluation criteria are as follows.

Very good paintability …… ◎ Good paintability ………… ○ ○ Poor paintability ………… ×

[Brief description of drawings]

FIG. 1 is a partial plan view of a sample piece used in a fire resistance test of a sealing material, and FIG. 2 is a rear view thereof. 1, 2 ... Fireproof asbestos-cement extruded board, 3 ... Cedar board, 4
…… Secondary sealing material, 5 …… Primary sealing material, A, B,
C: Backside temperature measurement position, S: Gap.

Claims (1)

[Claims] 1. A rock wool having a fiber length of 70 to 200 μm, 24.3 to 31.3% by weight, at least one inorganic sintering accelerator selected from montmorillonite, sepiolite, wollastonite, and glass fiber.
0-2.4% by weight, calcined gypsum, alum, calcium carbonate, calcium hydroxide,
15.0 to 19.0% by weight of one or more inorganic flame retardants selected from aluminum hydroxide, magnesium hydroxide, hydrotalcite-based aluminum silicate, modified silicone resin 25.1 to 33.3% by weight, and plastic Ingredient 14.0 to 18.7% by weight, the weight ratio of the inorganic component (P) containing rock wool, inorganic sintering promoter and inorganic flame retardant and the organic component (R) containing modified silicone resin and plasticizer ( A sealing material having a P / R) of 0.8 or more.