JPH09132731A - Inorganic oxide-containing adhesive, hardening composition, hardened material and forming made of the hardened material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition containing a compound having at least one isocyanate group and inorganic oxide powder as essential components, having excellent adhesive strength and useful as an adhesive for building and construction such as a binder or a concrete, a paint, etc., SOLUTION: The adhesive contains (A) a compound having at least one isocyanate group (e.g. methacryloylethyl isocyanate, hexamethylene diisocyanate or 4,4'-diphenylmethane diisocyanate) and (B) inorganic oxide powder (e.g. silicon oxide, aluminum oxide, indium tin oxide or lithium manganese oxide) as essential components. Further, the compounding ratio of the component A to the component B is 0.5-80wt.% component A to 95.5-20wt.% component B, preferably 1-60wt.% component A to 99-40wt.% component B.

Description

Detailed Description of the Invention

[0001]

The present invention relates to an adhesive composition containing an inorganic oxide powder, a curable composition containing an inorganic oxide powder and a cured product,
The present invention relates to a molding material and a molded product made of the cured product. More specifically, the present invention provides an adhesive composition containing at least one compound having an isocyanate group and an inorganic oxide powder, a coating composition, the compound having an isocyanate group and the inorganic oxide powder. The present invention relates to a curable composition containing the composition, a cured product obtained from the composition, a molding material and a molded article. The composition containing an inorganic oxide powder according to the present invention has excellent adhesive strength and can be used as a binder, an adhesive for building civil engineering such as concrete or mortar, a paint, a filler, etc., and is obtained from the cured composition according to the present invention. The cured product obtained is excellent in heat resistance, water resistance, curability, and workability, and can be used as a molding material or molded body for various applications.

[0002]

2. Description of the Related Art Inorganic oxide powders typified by ceramics have durability as a unique feature, and have been used as pottery and bricks for a long time. In recent years, it has been attempted to use ceramics for structural materials as a material particularly useful for the development of energy saving and pollution prevention techniques, but in order to impart a shape to the inorganic oxide powder, generally a binder as an adhesive must be used. I won't. For example, in order to adhere a tile to concrete, a pressure-bonding cement for tiles is used, but its adhesive strength is low and its corrosion resistance, durability, heat resistance and reliability are insufficient, and their improvement is required. . For this purpose, various binders as adhesives are currently developed and marketed, but no one satisfying the adhesive strength, corrosion resistance, durability, heat resistance and reliability has been obtained so far. .

Regarding the adhesion of the inorganic oxide powder, there is an alkali metal silicate type such as water glass. For example, water glass does not need heat resistance or water resistance so much, glass to glass, glass to metal. It is used for bonding various materials such as glass, stone, and ceramics (Japanese Patent Laid-Open No. 2-31)
1582, JP-A-5-17722). However, since these usually consist of only alkali metal silicate and aggregate,
It cannot be used in a place where moisture resistance and heat resistance are required because the curing is slow and sufficient strength is not obtained and the water resistance is low.

[0004]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present invention has found a new substance as a binder of an inorganic oxide powder capable of overcoming the disadvantages of the above-mentioned adhesive binder of alkali metal silicate type, and has a heat resistance, It has excellent water resistance, curability, workability, and high adhesive strength, and can be used for molding materials, binders, adhesives for building civil engineering such as concrete or mortar, paints, fillers, etc. It is intended to provide a cured product, a molding material and a molded product that are used.

[0005]

The present inventors have made a material having a curing action and a cured product having the above-mentioned preferable features,
As a result of repeated research to develop an adhesive, a molding material using the same, and a molded body, conventional curing was achieved when an inorganic oxide powder containing a compound having at least one isocyanate group was used. Based on this finding, it was found that a cured product having excellent physical properties can be obtained by improving the drawbacks of the organic binder and the present invention has been completed.

That is, the present invention is: 1) an adhesive composition comprising a compound having at least one isocyanate group and an inorganic oxide powder as essential components, and 2) at least one isocyanate group. A coating composition, characterized in that a compound having the formula (1) and an inorganic oxide powder are essential components, and 3) consisting essentially of the inorganic oxide powder and a compound having at least one isocyanate group as the essential components. A curable composition characterized by: 4) a cured product obtained by reacting a compound having at least one or more isocyanate groups with an inorganic oxide powder; and 5) an inorganic oxide powder and at least 1 as essentially essential components. A molded article characterized by comprising a compound having at least one isocyanate group.

Hereinafter, the present invention will be described in detail. [Inorganic Oxide] The inorganic oxide used in the present invention is not particularly limited as long as it has a group that reacts with an isocyanate group, for example, a hydroxyl group on its surface, and is a compound in which oxygen is coordinated to various elements. The single substance or the complex oxide may be used. As a single substance, silicon oxide, aluminum oxide, germanium oxide, chromium oxide, copper oxide, iron oxide, vanadium oxide, manganese oxide,
Nickel oxide, cobalt oxide, magnesium oxide, zinc oxide, cadmium oxide, tungsten oxide, molybdenum oxide, antimony oxide, tantalum oxide, titanium oxide, niobium oxide, tin oxide, bismuth oxide, zirconium oxide,
Strontium oxide, calcium oxide, barium oxide,
Lead oxide etc. are mentioned. As the composite oxide, indium tin oxide, lithium manganese oxide, a compound selected from a combination of the above elements such as barium titanate, clay, kaolin, bentonite, porcelain stone, various cements, for example, Portland cement (e.g., ordinary Portland cement, Early Strength Portland Cement, Super Early Strength Portland Cement, Moderate Heat Portland Cement, Sulfate Resistant Portland Cement, White Cement), Mixed Cement (Example: Silica Cement, Blast Furnace Cement, Fly Ash Cement), Special Cement (Example: Super Fast Cement) ,
Alumina cement), calcium sulfate hemihydrate cement (eg, hemihydrate gypsum cement) and the like. These inorganic oxide powders may be used alone or in combination. The particle size of the inorganic oxide powder to be used is not particularly limited either, but it depends on the characteristics required from the intended use, but it is 10 ⁻³ to 10 ⁻⁷ m from the viewpoint of ease of production.
Is used, preferably in the range of 10 ⁻⁴ to 10 ⁻⁶ m.

[Compound Having Isocyanate Group] The compound having at least one isocyanate group used in the present invention is not particularly limited, and examples thereof include monoisocyanates (eg, methacryloyloxyethyl isocyanate, methacryloyl isocyanate, phenyl). Isocyanate, p-chlorophenyl isocyanate, o-chlorophenyl isocyanate, m-chlorophenyl isocyanate, 3,4-dichlorophenyl isocyanate, 2,5-dichlorophenyl isocyanate, methyl isocyanate, ethyl isocyanate, n
-Butyl isocyanate, n-propyl isocyanate, octadecyl isocyanate), diisocyanate (eg 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, dianisidine diisocyanate, o
-Toluylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, trans vinylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, diaryl diisocyanate, trimethylhexamethylene diisocyanate, 3,3'-dimethylphenylmethane-4,4 ′ -Diisocyanate, isopropylidene bis (4-cyclohexyl isocyanate), hydrogenated 4,4′-diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate), triisocyanate (eg: triphenylmethane triisocyanate, tris (4-phenyl isocyanate) Thiophosphate)), polyisocyanate (eg polymethylene polyphenyl isocyanate) Polyisocyanate methacrylate, polyisocyanate methacrylate),
And dimers thereof (eg, N, N (4,4′-dimethyl-3,3′-diphenyldiisocyanate) uretdione) and trimers (eg, 4,4 ′, 4 ″ -trimethyl),
3,3 ′, 3 ″ -triisocyanate, 2,4,6-triphenylcyanurate), their derivatives (eg carbodiimide-modified isocyanate), compounds obtained by reacting an isocyanate compound with a polyol (eg polyurethane) Prepolymers), blocked isocyanates and mixtures thereof.When the toxicity of the isocyanate compound used is a problem, 4,4'-diphenylmethane diisocyanate having a relatively low vapor pressure, polyisocyanate, an isocyanate compound derivative, Polyurethane prepolymers, blocked isocyanates and the like can be used.

[Diluting solvent] When the compound having at least one isocyanate group has a high viscosity or is a solid, a solvent in which the isocyanate group does not react, for example, hexane, heptane, cyclohexane, benzene,
Toluene, xylene and other hydrocarbon solvents, dichloromethane, chloroform, carbon tetrachloride and other halogenated hydrocarbon solvents, diethyl ether, dioxane, furan and other ether solvents, acetone, methyl ethyl ketone, cyclohexanone and other ketone solvents, acetic acid Ester solvents such as methyl, ethyl acetate and butyl acetate, nitrogen compound solvents such as nitromethane and acetonitrile, and high boiling point solvents such as 2-methoxyethyl acetate, 2-ethoxyethyl acetate and 2-butoxyethyl acetate can be used. .

[Compounding Ratio of Isocyanate Compound and Inorganic Oxide Powder] The mixing ratio of the isocyanate compound and the inorganic oxide powder varies depending on the types of the isocyanate compound and the inorganic oxide powder. -80 wt% (inorganic oxide powder 95.5-20 wt%), preferably 1-60 wt% (inorganic oxide powder 9
9 to 40% by weight). Isocyanate compound content less than 0.5 wt% or 8
If it exceeds 0% by weight, the physical strength of the cured product decreases.

[Catalyst] A catalyst may be added in order to accelerate the reaction rate of the isocyanate compound. The catalyst can be selected from catalysts that promote the reaction between isocyanate groups and hydroxyl groups, and a catalyst for polyurethane production is preferably used. As the catalyst, for example, an amine-based (eg:
1,4-diazabicyclo [2.2.2] octane, N,
N-dimethylcyclohexylamine, N-methyldicyclohexylamine, N, N, N'N'-tetramethyl-
1,3-butanediamine, N, N, N'N'-tetramethylpropylenediamine, N, N, N'N'-tetramethylhexamethylenediamine, N-ethylmorpholine,
N-methylmorpholine, N, N-dimethylethanolamine, triethylamine), 1,8-diaza-bicyclo [5.4.0] undecene-7 and its salts, metal systems (eg stanas octoate, dibutyltin dilaurate). , Trimethyltin hydroxide, dimethyltin dichloride, tin octate), and others (butadiene sulfonic acid, inorganic acid, oxy acid, phosphoric acid ester, boric acid ester, monobutyl phthalate, p-toluene sulfonic acid) and the like.

[Preparation Method of Adhesive and Curing Composition, Molding of Curing Composition] The inorganic oxide powder-containing adhesive or curing composition of the present invention can be prepared by sufficiently mixing the components used. If it is, there is no particular limitation, but the following method can be given as an example. The inorganic oxide powder is put into an ordinary mixer such as a planetary mixer, and at least one compound having an isocyanate group and, if necessary, a diluting solvent are added and mixed, and the resulting mixture is mixed with a powerful mixer. For example, the kneader is transferred to a kneader, a Banbury mixer, a wet pan mixer, a mixing roll, a knnet machine, a pack mill, a screw extruder or the like, and further kneaded.

When a cured product of the inorganic oxide powder of the present invention is obtained in the form of a thin film such as a paint, a usual method for forming a coating film can be used. That is, after adding a solvent and a compound having at least one isocyanate group to the inorganic oxide powder, they are mixed with a mixer such as a paint shaker, and the resulting suspension is mixed with a bar coater or a spray atomizer. Create a coating film.

[Curing Method] Curing of the adhesive, paint or cured composition in the present invention is usually carried out by heating.
The heating temperature is not particularly limited, but in general, the higher the reaction temperature is, the faster the curing proceeds, so the higher temperature is preferable. However, considering the type, boiling point, safety or thermal stability of the compound having an isocyanate in the present invention, it is 20
It is common to cure in the range of ℃ to 250 ℃.
The heating time depends on the temperature, but is about 1 to 48 hours. The molding material obtained by curing in this way can be further molded into an arbitrary shape.

[0015]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Examples 1 to 5: Cured product of indium tin oxide powder 100 parts by weight of indium tin oxide powder and 15 parts by weight of the isocyanate compound shown in Table 1 were mixed in a planetary mixer for 10 minutes. This mixture was molded at a room temperature for 15 minutes at a pressure of 300 kgf / cm ² using a tablet molding machine to obtain a molded product having a diameter of 10 mm and a thickness of 1 mm, which was further dried at 120 ° C. for 6 hours with a heating dryer to obtain a cured product. It was The surface electric resistance value of this product was measured at room temperature by Loresta (manufactured by Mitsubishi Chemical Corporation). The results obtained are shown in Table 1.

[0017]

[Table 1] Table 1 Examples Isocyanate compound Surface electric resistance [Ω / cm ² ] 1 Methacryloylethyl isocyanate 5 × 10 ⁴ 2 Hexamethylene diisocyanate 8 × 10 ⁴ 3 Polyisocyanate ethyl methacrylate 1 × 10 ⁴ 4 Hexamethylene diisocyanate isocyanurate Sumidule N -3500 (Sumitomo Bayer Urethane Co., Ltd.) 9 × 10 ⁵ 5 Hexamethylene diisocyanate block isocyanate coronate 2515 (Nippon Polyurethane Co., Ltd.) 8 × 10 ⁵

Examples 6 to 10: Hardened barium titanate A hardened barium titanate was prepared in the same manner as in Examples 1 to 5 and had a relative dielectric constant of 25 ° C. and a precision LCR meter (Hewlett Packard Company). Manufactured). The results obtained are shown in Table 2.

[0019]

[Table 2] Table 2 Example Isocyanate compound Dielectric constant 6 Methacryloyl ethyl isocyanate 1100 7 Hexamethylene diisocyanate 800 8 Polyisocyanate ethyl methacrylate 900 9 Hexamethylene diisocyanate isocyanurate Sumidule N-3500 (Sumitomo Bayer Urethane Co., Ltd.) 1000 10 Hexamethylene diisocyanate Nate block isocyanate Coronate 2515 (manufactured by Nippon Polyurethane Co.) 600

Examples 11 to 30: Adhesion test of various inorganic materials 100 parts by weight of various inorganic oxide powders and arbitrary parts by weight of Sumijour N-3500 were used in a planetary mixer for 15 times.
Mix for minutes. A test piece was prepared from this mixture according to JIS K 6850, and the tensile shear adhesive strength was measured using Tensilon. The cured product was obtained by drying at 120 ° C. for 6 hours with a heat dryer. The results obtained are shown in Table 3.

[0021]

[Table 3] Table 3 Tensile shear Example Inorganic oxide Isocyanate Adherend strength [wt%] [kg f / cm ² ] 11 Portland cement 0 Aluminum 0 12 Portland cement 0 Iron 0 13 Portland cement 5 Aluminum 1 14 Portland cement 5 Iron 2 15 Portland Cement 9 Aluminum 3 16 Portland Cement 9 Iron 4 17 Portland Cement 17 Aluminum 33 18 Portland Cement 17 Iron 58 19 Portland Cement 29 Aluminum 39 20 Portland Cement 29 Iron 72 21 Early Strength Cement 17 Iron 26 22 White Cement 17 Iron 51 23 Alumina Cement 17 Iron 54 24 Jet cement 17 Iron 44 25 Manganese oxide 17 Iron 60 26 Smectite 17 Iron 25 27 Alumina 17 Iron 40 28 Portland Cem DOO manganese oxide 1: 1 mixture of 17 iron 50 29 Portland cement and manganese oxide 1: 1 mixture of 17 glass 20 30 Portland cement smectite 1: 1 mixture of 17 iron 30

Examples 31 to 35: Durability Test of Adhesion Test Pieces The durability of the test pieces prepared in Examples 18, 23, 25, 27 and 29 was tested by heat resistance (400 ° C./1 in air).
Time left) and environmental test (at 90% relative temperature-
10 cycles were changed in the temperature range of 10 ° C to 50 ° C)
Was evaluated by tensile shear adhesive strength. Table 4 shows the obtained results.

[0023]

[Table 4] Table 4 Tensile shear adhesive strength Example Inorganic oxide Isocyanate Adherend [kg f / cm ² ] Concentration [wt%] After heat resistance test After environmental test 31 Portland cement 17 Iron 34 43 32 Alumina cement 17 Iron 29 41 33 Manganese oxide 17 Iron 17 45 34 Alumina 17 Iron 30 32 35 Portland Cement 17 Glass 38 40 Manganese oxide 1: 1 mixture

[0024]

EFFECTS OF THE INVENTION A cured product obtained from a curing composition comprising the compound having at least one isocyanate group and the inorganic oxide powder according to the present invention as essential components is excellent in heat resistance, water resistance and curability. . In particular, the adhesive containing the isocyanate compound and the inorganic oxide powder according to the present invention as essential components is suitable for bonding ceramic structural materials and bonding glass, metal, concrete, cement, mortar and the like. By using the composition according to the present invention, it is possible to use the inorganic oxide powder in the fields of conductors, dielectrics and coatings, and the industrial utility value is great.

Claims (5)

[Claims] 1. An adhesive composition comprising a compound having at least one or more isocyanate groups and an inorganic oxide powder as essential components. 2. A coating composition comprising a compound having at least one or more isocyanate groups and an inorganic oxide powder as essential components. 3. A curable composition comprising an inorganic oxide powder and a compound having at least one or more isocyanate groups as substantially essential components. 4. A cured product obtained by reacting a compound having at least one isocyanate group with an inorganic oxide powder. 5. A molded product comprising an inorganic oxide powder and a compound having at least one isocyanate group as substantially essential components.