JPH03269077A - Adhesive composition and laminated inorganic board - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an adhesive composition and a laminated inorganic board using the same. More specifically, the present invention relates to an adhesive composition with excellent fire resistance and noncombustibility, and a noncombustible inorganic board using the adhesive composition.

[Prior Art 1] In recent years, with the increase in the number of high-rise buildings and underground malls, non-combustible building materials are required for disaster prevention. Under these circumstances, fire retardant and nonflammable properties have been desired for adhesives used in laminates and the like. Conventionally, such adhesives are mainly silicate-based,
Inorganic adhesives such as phosphate-based and colloidal silica-based adhesives have been proposed.

[Problems to be Solved by the Invention] However, the above-mentioned inorganic adhesives have a drawback of weak adhesive strength. In particular, when materials with different coefficients of thermal expansion, such as metal and inorganic board, are bonded together, repeated thermal stress in practical use causes distortion between the materials and tends to cause them to separate, making it impractical.

[Means for Solving the Problems 1] In view of the above-mentioned problems, the present inventors conducted intensive studies and found that castor oil-based polyol and/or hydrocarbon-based A polyurethane resin consisting of a polyol and an isocyanate group-containing compound,
The present inventors have discovered that the problem can be solved by using an adhesive composition containing at least 5% by weight.

The present invention will be explained in detail below.

The inorganic adhesive of the present invention is formed by blending a metal phosphate or a metal phosphate with appropriate amounts of a curing agent and a filler, if necessary.

The metal phosphates used as raw materials are mainly first metal phosphates and condensed phosphates thereof. Also, as a metal,
Calcium, magnesium, aluminum, zinc, copper,
Examples include iron and manganese, with calcium, magnesium, aluminum and zinc being particularly preferred. When preparing an adhesive, a metal phosphate is usually used as a compound, but it may also be used as a metal phosphate by adding phosphoric acid and a metal or a metal compound.

Hardening agents for the purpose of adjusting the hardening time of the metal phosphate as a binder and improving water resistance include: - Oxides of Group II and III metals of the periodic table such as magnesium, calcium, aluminum, and zinc; Hydroxides - Oxides and hydroxides of transition metals such as iron, titanium, and zirconium - Silicates of Group 1I metals of the periodic table such as calcium, magnesium, and zinc, and serpentinite, magnesian chlorite, lower grade talc, etc. Natural silicates (1) Hydrochlorides, sulfates, borates, organic acid salts (2) of group II metals of the periodic table - (2) metals of group II of the periodic table, borates, and carbonates of metals of group II of the periodic table. For the above purpose, the curing agent is added in an appropriate amount to the metal phosphate used as a raw material depending on the type of curing agent. Specifically, 1 for 100 parts by weight of metal phosphate.
Approximately 0 to 200 parts by weight of overlapping parts.

The polylyrethane resin that is blended with the inorganic adhesive, which is a major feature of the present invention, is obtained by the reaction of an organic compound having active hydrogen and an isocyanate group-containing compound.

Compounds having active hydrogen used in the present invention include:
Examples include relatively hydrophobic castor oil polyols and/or hydrocarbon polyols with low polarity. Examples of the hydrocarbon polyol include polyols having unsaturated hydrocarbon chains, such as polybutadiene polyols, and saturated hydrocarbon polyols obtained by hydrogenating them, with saturated hydrocarbon polyols being particularly preferred.

Isocyanate group-containing compounds include monomeric isocyanate compounds, modified isocyanates in which part of the isocyanate groups of the monomers are modified with alcoholic hydroxyl groups, amines, etc., isocyanate prepolymers such as polydiphenylmethane diisocyanate, and these. Block polymers obtained by reacting the isocyanate groups of the isocyanate compound with a blocking agent are used alone or as a mixture. As monomeric isocyanate compounds, those having two isocyanate groups are often used. Specific examples include diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, tolylene diisocyanate, hexamethylene diisocyanate,
Examples include inphorone diisocyanate and xylylene diisocyanate. A plasticizer is added to the polyurethane resin as necessary. Examples of the plasticizer include phthalate diesters such as dioctyl phthalate and dibutyl phthalate, paraffinic process oils, and the like.

In producing a polyurethane resin, the ratio of polyol to isocyanate-containing compound is: isocyanate group/hydroxyl group=1.0 to 3.0 molar ratio, preferably 1.1 to 3.0.
The molar ratio is set to 2.0. When adding a plasticizer, it is added in an amount of 0.2 to 0.4 parts by weight based on 1 part by weight of the total amount of the polyol and the isocyanate group-containing compound. The polyurethanization reaction is carried out by a known method, in which an isocyanate group-containing compound and a polyol are uniformly mixed, and
The process is carried out under conditions such that at least 1.0% by weight of isocyanate groups remains. For example, the reaction is carried out by stirring and mixing at 5 to 30°C for 3 to 10 minutes.

This polyurethane resin is blended in an amount of at least 5% by weight with respect to the inorganic adhesive. There is no practical problem even if the amount of polyurethane resin blended is large, but if nonflammability is required, it is undesirable to use a large amount of organic polyurethane resin. In this case, it is usually 5 to 20% by weight, and preferably The content is 5 to 15% by weight.

The adhesive of the present invention may contain a filler for the purpose of reducing shrinkage, improving adhesive strength, and preventing cracking. As the filler, heat-resistant inorganic powder and/or fibrous materials such as alumina, mica, and clay are used.

The size of the powder is 1 to 20 μm, preferably 1 to 10 μm.
pm is used, and is usually added in an amount of 1 to 200 parts by weight per 100 parts by weight of the metal phosphate.

In addition, fibrous materials added to prevent cracking and improve adhesive strength include inorganic fibers such as glass fiber, rock wool, asbestos, silica fiber, silica alumina fiber, and carbon fiber, as well as cellulose, acrylic, polypropylene, vinylon, etc. organic fibers can be used.

Moreover, inorganic fibers are preferable in order to improve fire resistance and nonflammability. The length of the fibrous material is 1 to 6 mm. Inorganic fibers are preferably surface-treated with a silane coupling agent or the like because they have affinity with polyurethane resins. For example, glass fibers may be treated with dimethyldichlorosilane. The amount of the fibrous material added is usually 1 to 40 parts by weight, preferably 5 to 20 parts by weight, based on 100 parts by weight of the metal phosphate.

The filler can also serve as the above-mentioned hardening agent depending on the material, that is, if it is reactive with the metal phosphate.

If the amount of filler added is too large, the workability of applying it to the adhesive surface will be poor, and if it is too small, the effect cannot be achieved.

When preparing the adhesive composition, the order in which the above components are added is not specified, but usually the metal phosphate, the curing agent, and the filler added as necessary are mixed together (mixture (A)).
, then water is added and kneaded. The amount of water varies depending on the blending ratio of each material, but is 0.1 to 100% of the mixture (A).
0.5 times the weight. As this kneading device, a kneader mixer, a Banbury mixer, an internal mixer, a pony mixer, a Muller mixer, etc. are usually used. Furthermore, the above-mentioned polyurethane resin is added to this kneaded material and kneaded. The crosstalk time varies depending on the blending ratio of each component, the crosstalk device, etc., but is usually carried out for 5 to 20 minutes. The temperature at the time of crosstalk is preferably about 20 to 30°C. The adhesive composition prepared in this manner cures when left to stand, so it can be used immediately.

This adhesive composition can be applied to all materials such as inorganic boards, plastics, rubber, and metals.

In particular, moisture permeable or hygroscopic materials are preferred.

Furthermore, since it has good fire resistance, it is desirable to apply it to bonding inorganic boards to each other or to bonding an inorganic board to metal. Examples of inorganic boards include cement calcium silicate boards, calcium silicate boards, cement boards such as GR slate, gypsum boards, slag gypsum boards, etc., which are often used as building materials. Further, examples of the metal include aluminum, iron, stainless steel, copper, and the like.

When bonding an inorganic board and metal, the adhesive composition is applied to the surface of the material to be bonded to a thickness of 50 to 300 νm using a roll coater or the like. Next, the surfaces to be bonded are pasted together and weighed 10 to 20 kg.
6 to 48 at room temperature to 60°C with a load of /cm2
By holding for a period of time, the adhesive is cured and a laminated inorganic board is obtained.

[Examples] The present invention will be described in more detail with reference to Examples and Comparative Examples below, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.

In the examples, parts represent parts by weight.

Production Example 1 In a reactor equipped with a stirrer 1, 100 parts of polyhydroxypolybutadiene hydrogenated product (hydroxyl value 50 KOH-mg/g, specific gravity 0.870, viscosity 100p) and diphenylmethane diisocyanate (NGO content 29.0%) were added. )15
and 30 parts of dioctyl phthalate at 23°.
The mixture was stirred and reacted at C for 5 minutes to obtain a polyurethane tree layer.

Production Example 2 100 parts of primary aluminum phosphate, 50 parts of aluminum hydroxide, 15 parts of magnesium hydroxide, and 65 parts of α-alumina were uniformly mixed. This was added to 70 parts of water and kneaded for about 10 minutes in a Banbury mixer to obtain a viscous inorganic adhesive (A).

Production Example 3 Production Example 1 was added to 100 parts of the inorganic adhesive (A) obtained in Production Example 2.
Add 9 parts of the polyurethane resin obtained from
The mixture was kneaded for 5 minutes to obtain an adhesive composition (B).

Production Example 4 In Production Example 2, glass fiber whose surface was treated with silane (
An inorganic adhesive (C) was obtained in the same manner except that 10 parts (fiber diameter: 10 to 13 μm, fiber length: 3 mm) was further added.

Production Example 5 9 parts of the polyurethane resin obtained in Production Example 1 was added to 100 parts by weight of the inorganic adhesive (C) obtained in Production Example 4, and the mixture was kneaded in a Banbury mixer for 5 minutes to obtain an adhesive composition (D). Ta.

Production Example 6 Inorganic adhesive (E) was prepared in the same manner as Production Example 2, except that 25 parts of aluminum hydroxide was used instead of 50 parts of aluminum hydroxide.
I got it.

Production Example 7 9 parts of the polyurethane resin obtained in Production Example 1 were added to 100 parts of the inorganic adhesive (E) obtained in Production Example 6 and kneaded for 5 minutes in a Banbury mixer to obtain an adhesive composition (F). Ta.

Production Example 8 50 parts of aluminum hydroxide to 100 parts of aluminum hydroxide
Inorganic adhesive (G) was prepared in the same manner as in Production Example 2 except that
I got it.

Production Example 9 9 parts of the polyurethane resin obtained in Production Example 1 were added to 100 parts of the inorganic adhesive (G) obtained in Production Example 8 and kneaded for 5 minutes in a Banbury mixer to obtain an adhesive composition (H). Ta.

Examples 1 to 4 and Comparative Examples 1 to 4 Two aluminum plates (0.2 mmt x 200 mm x 200
0.1-0.15 mm thick on one side of the asbestos-cement silica board (6 mmt x 200 mm).
mm x 200 mm) and 20 k
It was crimped for 1 minute at a pressure of g/cm2. Next, apply a load of 5 kg at 25°C for 24 hours, and then at 60°C for 24 hours.
I took time to heal. Table 1 shows the adhesive strength and heat cycle test results of this laminate.

In addition, each measurement method is as follows.

Adhesive Strength> Expressed as tensile shear strength measured in accordance with JIS A1613.

Heat cycle test〉 Heat the laminate at 25°C → -20'C → 25°C → 80°C →
The durability was visually evaluated by leaving it at 25°C (maintained at each temperature for 1 hour) and changing the temperature.

[Effects of the Invention] As described above, the adhesive composition of the present invention has excellent adhesiveness, fire retardancy, and noncombustibility, and can be widely used in building materials that require fire retardancy, such as laminated inorganic boards.

Claims (3)

[Claims] (1) Add at least 5% by weight of a polyurethane resin consisting of a castor oil polyol and/or hydrocarbon polyol and an isocyanate group-containing compound to an inorganic adhesive mainly composed of metal phosphates. An adhesive composition made of (2) The adhesive composition according to claim 1, wherein the inorganic adhesive contains a monolithic metal phosphate, a curing agent, and a filler. (3) The inorganic board and the metal plate are bonded using an inorganic adhesive mainly composed of a metal phosphate, and a polyurethane resin made of a castor oil-based polyol and/or a hydrocarbon-based polyol and an isocyanate group-containing compound. 1. A laminated inorganic board, characterized in that the board is bonded with an adhesive composition containing at least 5% by weight of the inorganic board.