JP2003119449A - Adhesive for inorganic fiber, mineral fiber board and inorganic board using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an isocyanate group-bearing adhesive that has increased adhesion to inorganic fibers, and to efficiently provide a mineral fiber board and an inorganic board light in weight, high in strength and excellent in fire retardant properties by using the same. SOLUTION: The adhesive for inorganic fibers comprises a prepolymer including at least an ionic hydrophilic group, a nonionic hydrophilic group and an isocyanate group. In another case, a slurry including at least mineral fibers and the adhesive is made into sheets and the sheets are cured to give the objective mineral fiber board. In addition, an upper layer, one or more intermediate layers and a lower layer are integrally laminated to produce an inorganic board. The upper layer and the lower layer are prepared by making a slurry including the mineral fibers and the adhesive into sheets and curing the resultant sheets to obtain a mineral fiber board part. At least one layer among the intermediate layers is an inorganic foam board part prepared by curing at least an inorganic foam with the adhesive.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a mineral fiber plate and an inorganic plate, and an adhesive for efficiently producing them.

[0002]

2. Description of the Related Art As a method for producing a lightweight, high-strength, and fireproof inorganic plate as a building material, it is obtained by making a slurry containing mineral fiber, inorganic powder and a binder as essential components. A method is known in which a wet inorganic plate is used as the upper and lower layers, and a mixture containing an inorganic foam, a fibrous substance and a binder as essential components is laminated between them, and the mixture is pressed and dried. In this method, in order to obtain sufficient strength, an adhesive that prevents springback due to the high density of the upper and lower layers and a hot press that cures the adhesive are required. However, in this method, since the upper and lower layers obtained by papermaking have a high water content, it takes a very long time of hot pressing to dry the upper and lower layers and cure the adhesive, resulting in poor production efficiency. There is.

In order to solve the above problems, Japanese Unexamined Patent Publication No.
JP-A-217216 discloses a method for efficiently producing an inorganic plate-like body by blending an adhesive containing at least an isocyanate group and curing the adhesive in a short time hot pressing and a subsequent drying step. It is disclosed.

However, in the above-mentioned method, since the isocyanate group-containing adhesive is in a liquid state, it easily flows out during the papermaking process, and in order to fix the desired amount of the isocyanate group-containing adhesive to the inorganic fiber, the addition amount thereof should be increased. There is a problem that has to be. At the same time due to the occurrence of this problem,
There is a problem in that white water is contaminated by the isocyanate group-containing adhesive that has flowed out, and that the reaction product of the isocyanate group-containing adhesive and water causes clogging of pipes and nets, and that the production efficiency of the inorganic plate-shaped body is poor.

[0005]

DISCLOSURE OF THE INVENTION The present invention solves the above problems and provides an isocyanate group-containing adhesive having an improved fixing rate to inorganic fibers, and a lightweight, high-strength and fire-proof adhesive using the same. It is an object of the present invention to provide an excellent mineral fiber plate and inorganic plate with high production efficiency.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, by introducing an ionic hydrophilic group and a nonionic hydrophilic group into polyisocyanate, an adhesive containing the same is introduced. The inventors have found that the fixing rate of the agent to the inorganic fibers can be improved and the mineral fiber plate and the inorganic plate can be efficiently produced, and have completed the present invention.

That is, the present invention is an adhesive for inorganic fibers, which comprises a prepolymer having at least an ionic hydrophilic group, a nonionic hydrophilic group and an isocyanate group.

[0008] The present invention is a mineral fiber plate, characterized in that a slurry containing at least mineral fibers and the adhesive is formed into a paper and the adhesive is cured.

Further, the present invention is an inorganic plate-like body in which an upper layer portion, one or more intermediate layer portions and a lower layer portion are integrally laminated, wherein the upper layer portion and the lower layer portion are mineral fibers and the above A slurry containing at least an adhesive is formed into a paper, which is a mineral fiber plate-shaped portion obtained by curing the adhesive, and at least one layer of the middle layer portion is formed by adhering and curing at least an inorganic foam with an adhesive. The above-mentioned inorganic plate-shaped body is an inorganic foamed plate-shaped portion.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The prepolymer used in the adhesive for inorganic fibers of the present invention has at least an ionic hydrophilic group such as a cation group and an anion group, a nonionic hydrophilic group, and an isocyanate group. Specifically, (a mixture of) an active hydrogen compound containing at least an ionic hydrophilic group-containing active hydrogen compound and a nonionic hydrophilic group-containing active hydrogen compound.
Is a prepolymer obtained by reacting with an organic polyisocyanate. In the adhesive for inorganic fibers of the present invention, a urethane system having an anion group, a nonionic hydrophilic group, and an isocyanate group, which is mainly obtained by using an alcohol compound (mixture of) among the active hydrogen compounds (mixture) Prepolymers are preferred.

As this organic polyisocyanate,
4,4'-diphenylmethane diisocyanate, 2,
4'-diphenylmethane diisocyanate, 2,2'-
Diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenyl ether diisocyanate,
4,4'-diphenylpropane diisocyanate, 1,
Aroma such as 2-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,4-naphthalene diisocyanate, 1,5-naphthalene diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate Aliphatic diisocyanates such as group diisocyanates, 1,6-hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate and lysine diisocyanate, aromatic fats such as o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate and tetramethyl xylene diisocyanate Group diisocyanates, isophorone diisocyanates, hydrogenated toluene diisocyanates, hydrogenated xylene diisocyanates,
Examples thereof include alicyclic diisocyanates such as hydrogenated diphenylmethane diisocyanate. Further, adduct modified products of these organic diisocyanates, buret modified products,
Modified polyisocyanates such as isocyanurate modified products, uretonimine modified products, uretdione modified products, and carbodiimide modified products can also be used. Furthermore, polyisocyanates such as polyphenylene polymethylene polyisocyanate and crude toluene diisocyanate can also be used. These may be used alone or in combination of two or more. Of these organic polyisocyanates, polyphenylene polymethylene polyisocyanate is most preferred.

The cation group-containing active hydrogen compound is preferably formed, for example, from a cation group-forming group-containing active hydrogen compound and an acidic neutralizing agent or a quaternizing agent. That is,
The cation group comprises a cation group-forming group such as a tertiary amino group and an acidic neutralizing agent or a quaternizing agent. As the cationic group-forming group-containing active hydrogen compound, N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dipropylethanolamine, N, N
-Diphenylethanolamine, N-methyl-N-ethylethanolamine, N-methyl-N-phenylethanolamine, N, N-dimethylpropanolamine, N
-Methyl-N-ethylpropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine,
N-methyldipropanolamine, N-phenyldiethanolamine, N-phenyldipropanolamine, N
-Hydroxyethyl-N-hydroxypropyl-methylamine, N, N'-dihydroxyethylpiperazine, triethanolamine, trisisopropanolamine,
N-methyl-bis (3-aminopropyl) amine, N-
Methyl-bis (2-aminopropyl) amine and the like can be mentioned. Also, primary amines such as ammonia and methylamine, and secondary amines such as dimethylamine to which alkylene oxide is added can be used. As the acidic neutralizing agent for forming a cationic group, for example, hydrochloric acid, acetic acid, propionic acid, lactic acid, cyanoacetic acid, phosphoric acid,
Examples thereof include inorganic acids such as sulfuric acid and organic acids. Examples of the quaternizing agent include dimethyl sulfate, benzyl chloride, bromoacetamide, chloroacetamide, and alkyl halides such as ethyl bromide, propyl bromide, and butyl bromide. The cation group-forming group-containing active hydrogen compound, the acidic neutralizing agent and the quaternizing agent may be used alone or in combination of two or more.

The anion group-containing active hydrogen compound is preferably formed, for example, from an anion group-forming group-containing active hydrogen compound and a basic neutralizing agent. That is, the anionic group is composed of an anionic group-forming group such as carboxylic acid, sulfonic acid, phosphoric acid, phosphonic acid, phosphinic acid and thiosulfonic acid, and a basic neutralizing agent. As the anion group-forming group-containing active hydrogen compound, α-hydroxypropionic acid, hydroxysuccinic acid, dihydroxysuccinic acid, ε
-Hydroxypropane-1,2,3-tricarboxylic acid,
Hydroxy acetic acid, α-hydroxybutyric acid, hydroxystearic acid, ricinoleic acid, ricinoelaidic acid, ricinostearolic acid, salicylic acid, mandelic acid, etc., hydroxylated unsaturated fatty acids such as oleic acid, ricinoleic acid, linoleic acid Fatty acid or 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid,
Carboxylic acid-containing polyol such as 2,2-dimethylolvaleric acid, polyester polyol having a 5-sulfoisophthalic acid skeleton introduced therein, polycaprolactone having water or an active hydrogen compound having a carboxyl group as an initiator, polyester polyol and a carboxyl group Examples thereof include transesterification products with active hydrogen compounds and transesterification products with polycarbonate polyols and active hydrogen compounds having a carboxyl group. Further, a half-ester mixture containing a carboxyl group, which is obtained by reacting a long-chain polyol, a low-molecular polyol, and the like, which will be described later, with a polycarboxylic acid anhydride can also be used. In particular, when a polyol is added to a dianhydride such as pyromellitic dianhydride, two carboxylic acids are produced, so that an anion group-forming group can be introduced into the molecular chain of the polyester polyol.
Of these, sulfonic acid group-containing polyols are preferred. As a basic neutralizing agent for forming an anion group, ethylamine, trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N
-Phenyldiethanolamine, monoethanolamine, dimethylethanolamine, diethylethanolamine, morpholine, N-methylmorpholine, 2-amino-2-ethyl-1-propanol, organic amines such as pyridine, sodium hydroxide, potassium hydroxide, etc. Inorganic alkalis, ammonia, and the like. Among these, preferred are inorganic alkalis such as sodium hydroxide and potassium hydroxide. In addition, these anion group-forming group-containing active hydrogen compounds and basic neutralizing agents, respectively,
You may use it individually or in mixture of 2 or more types.

As the nonionic hydrophilic group-containing active hydrogen compound, poly (oxyalkylene) ether alcohol,
Preference is given to poly (oxyalkylene) fatty acid ester alcohols and the like. The nonionic hydrophilic group is a portion of the repeating unit of the oxyalkylene group introduced into the main chain or side chain of the resin. Poly (oxyalkylene) ether alcohol is obtained by addition-polymerizing alkylene oxide with an initiator. Examples of the initiator include methanol, ethanol, propanol, n-butanol, cyclohexanol, phenol, ethylene glycol, propylene glycol, aniline, trimethylolpropane, glycerin, pentaerythritol and the like. Among these, those having a small molecular weight such as ethylene glycol are preferable. Examples of the alkylene oxide include ethylene oxide and propylene oxide. A compound having an epoxy group such as styrene oxide, epichlorohydrin, and butylglycidyl ether may be used as a part of the alkylene oxide. Moreover, acetic acid, propionic acid, butyric acid, etc. are mentioned as a fatty acid used for manufacture of poly (oxyalkylene) fatty acid ester alcohol. Any of these may be used alone or in combination of two or more. It should be noted that the polyether chains present in the above-mentioned raw material have a viscosity of 3 to 300.
It is preferable to have one, especially 5 to 200, oxyethylene groups and have 50 mol% or more, particularly 60 mol% or more of oxyethylene groups.

The amounts of ionic hydrophilic groups such as cationic groups and anionic groups and nonionic hydrophilic groups introduced into the urethane prepolymer of the present invention are as follows. The amount of anion group or cation group introduced is 0.
It is preferably 001 to 1.0 mmol / g, and particularly preferably 0.003 to 0.1 mmol / g. The amount of the nonionic hydrophilic group (preferably ethylene oxide unit) introduced is 0.1 to 40 mass% with respect to the prepolymer.
Is preferable, and 0.5 to 30 mass% is particularly preferable.

Other active hydrogen compounds that can be used in combination with the ionic hydrophilic group-containing active hydrogen compound and the nonionic hydrophilic group-containing active hydrogen compound include those known as long-chain polyols in the polyurethane industry and those having chain extension. Examples include so-called agents. Any of these may be used alone or in combination of two or more.

Examples of the long-chain polyols include polyester polyols, polycarbonate polyols, polyether polyols, polyolefin polyols, animal / vegetable polyols, and copolyols thereof.
Specific examples of the chain extender include low molecular weight polyols, low molecular weight polyamines and low molecular weight amino alcohols.

Next, the production of the prepolymer will be described. The prepolymer in the present invention is, for example, an organic polyisocyanate, an ionic hydrophilic group-containing active hydrogen compound, a nonionic hydrophilic group-containing active hydrogen compound, and optionally other active hydrogen compounds are reacted sequentially or simultaneously. Can be manufactured. The final equivalent ratio of all isocyanate groups and all active hydrogen groups at this time, the target number average molecular weight, depending on factors such as the average number of functional groups of the organic polyisocyanate and the average number of functional groups of the active hydrogen compound, conditions under which gelation does not occur during the reaction Is calculated and determined so as to satisfy this condition. The method of reacting at the same time is preferable because the number of manufacturing steps is reduced. The reaction is a molten state, a bulk state, or a solvent commonly used in the polyurethane industry, if necessary, for example, an aromatic hydrocarbon solvent, an ester solvent, a ketone solvent, a glycol ether ester solvent, an ether solvent, an alcohol solvent. Solvent, polar solvent 1
One kind or a mixture of two or more kinds can be used. Also,
During the reaction, a catalyst can be used if necessary.
Specific examples thereof include organic metal compounds such as dibutyltin dilaurate and dioctyltin dilaurate, organic amines such as triethylenediamine and triethylamine, and salts thereof. The number average molecular weight of the prepolymer is 1,
000 to 50,000, especially 3,000 to 40,000
Is preferred. When the number average molecular weight is less than 1,000, the reaction is insufficient, so that the number of hydrophilic groups is inevitably reduced and it becomes difficult to disperse in water, and the inorganic fiber is used for obtaining the target product. The retention rate for When the number average molecular weight exceeds 50,000, the viscosity of the prepolymer itself becomes high, the handling workability of the prepolymer deteriorates, and the number of isocyanate groups contained in the prepolymer decreases, so The physical properties such as strength of the resulting plate-shaped body are deteriorated. In the present invention, the number average molecular weight is a value measured by gel permeation chromatography in terms of polystyrene using a refractive index detector. The isocyanate group (NCO) content of the prepolymer is preferably 20 to 30% by mass.

Next, the mineral fiber plate and the inorganic plate of the present invention will be described. First, examples of the mineral fibers used for forming the upper and lower layers of the mineral fiber plate or the inorganic plate include rock wool, slag wool, mineral wool, nickel wool and glass fiber. These can be used alone or in combination of two or more kinds. The amount of the mineral fiber used is preferably 20 to 80 mass% of the entire upper and lower layer portions of the mineral fiber plate or the inorganic plate. If it is less than 20% by mass, it is difficult to obtain the desired bending strength, and if it exceeds 80% by mass, the ratio of other compounding ingredients such as the inorganic powder is relatively reduced, so that the desired surface hardness is secured. Hard to do.

In order to form the upper and lower layers of the mineral fiber plate or the inorganic plate, in addition to the mineral fiber, if necessary,
Inorganic powders can be used. The inorganic powdery material is for increasing hardness and screwing performance while maintaining fire resistance, for example, calcium carbonate,
Mention may be made of silica sand, microsilica, slag and aluminum hydroxide. These may be used alone or in combination of two or more. The blending amount of the inorganic powder is
2 of the whole upper and lower layers of mineral fiber plate or inorganic plate
It is preferably from 0 to 80% by mass. If it is less than 20% by mass, the desired surface hardness cannot be obtained, and if it exceeds 80% by mass, the proportion of the mineral fiber that imparts strength decreases.
It becomes difficult to obtain the desired bending strength.

The role of the adhesive in the upper and lower layers of the mineral fiber plate or the inorganic plate is to combine and integrate the mineral fibers with each other and the inorganic powder to achieve the final practical strength. In order to express strength, and to bond and fix the upper and lower layers of the mineral fiber plate or the inorganic plate by a hot press for a short time to achieve sufficient strength that can be handled. It is to be. Therefore, the adhesive used for the upper and lower layer portions of the mineral fiber plate or the inorganic plate so that the plate can be handled such as being transported,
It is an adhesive (isocyanate group-containing adhesive) containing a prepolymer having at least the above-mentioned ionic hydrophilic group, nonionic hydrophilic group, and isocyanate group capable of exhibiting primary strength in a short time.

When the isocyanate group-containing adhesive of the present invention is used, it is preferable to use an ionic or amphoteric coagulant (ionic coagulant) together. In the isocyanate group-containing adhesive of the present invention, since the prepolymer has an ionic hydrophilic group, it is ionically bound to the ionic coagulant, the coagulation efficiency is improved, and the yield of the adhesive or the like during papermaking is improved. As a result, it becomes possible to further enhance the strength of the mineral fiber plate or the inorganic plate. Examples of such an ionic coagulant include an inorganic coagulant and an organic polymer coagulant. Examples of the compound that can be used as the inorganic flocculant include polyaluminum chloride, a sulfuric acid band, ferric chloride, ferrous sulfate, and polyiron sulfate. Examples of the organic polymer flocculant include aminoalkyl acrylate quaternary salt (co) polymer, aminoalkyl methacrylate quaternary salt (co) polymer, polyaminomethylacrylamide salt or quaternary salt, chitosan acetate, acrylamide / aminoalkyl. Acrylic copolymer salt or quaternary salt, acrylamide / aminoalkyl methacrylate copolymer salt or quaternary salt, cationic starch, cationic flocculant such as polyethyleneimine, acrylamide / sodium acrylate copolymer, Acrylamide / sodium methacrylate copolymer, acrylamide / sodium acrylate / 2-acryloylamino-2-methylpropanesulfonic acid soda copolymer, acrylamide / sodium methacrylate / 2-acryloylamino-2-methylpropanesulfonic acid soda Polymers, sodium polyacrylate, anionic flocculants such as poly methacrylic acid sodium,
Further, the molecular weight of the cationic group and the anionic group is 200 to
There are 3 million polyacrylamides or polymethacrylamides such as amphoteric flocculants. Among these, those having a ratio of the number of functional groups of the cation group and the anion group of 0.5 to 1.0 are preferable. Further, it is more preferable to use an inorganic coagulant and an organic polymer coagulant together.

The isocyanate group-containing adhesive of the present invention is
It is preferable to use 5 to 50 parts by mass, more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the mineral fiber. The ionic flocculant is preferably used in a mass ratio of 100: 0.01 to 100: 10 with respect to the isocyanate group-containing adhesive of the present invention.

In addition, the isocyanate group-containing adhesive of the present invention may be used in combination with one or more of powdered phenolic resins, epoxies, starches and the like so as to develop secondary strength and add strength. You can These substances that gel in hot water also have the function of adding primary strength. These do not exhibit strength unless they are sufficiently heat-cured, but a plate-shaped body that exhibits primary strength and retains its shape by the isocyanate group-containing adhesive is efficiently dried by heating and drying in a state where it is released from the press. It can be sufficiently heat-cured to develop the secondary strength required as a building material such as a base plate and an outer wall base material. In addition, the isocyanate group-containing adhesive of the present invention also develops secondary strength by heating and drying after developing primary strength.

Further, in order to accelerate the reaction of the isocyanate group-containing adhesive, various amine compounds and catalysts such as organometallic compounds such as lead octylate may be appropriately added.
In addition, in order to suppress the reaction before entering the hot-pressing process as much as possible, the catalyst does not exhibit activity at normal temperature, so that the temperature-sensitive catalyst that exhibits activity near the pressing temperature and the effect in the pressing process Preferably, the catalyst is embedded in microcapsules that break down upon compression and release the contents.

Further, an organic silicone monomer can be added to increase the strength. Organosilicone monomers generally have weak bonding strength because they have a functional group that bonds to the surface of inorganic materials such as mineral fibers and inorganic powders, and a functional group that bonds to organic materials such as isocyanate group-containing adhesives. A strong adhesive force can be created as an inclusion of an inorganic material and an organic material.

Further, if necessary, in order to perform wet papermaking from the slurry, papermaking additives such as a sizing agent and a defoaming agent may be added.

As the inorganic foam for forming the middle layer portion of the inorganic plate-like body of the present invention, perlite, shirasu foam, silica flower, glass foam, vermiculite, obsidian foam or the like may be used alone or in combination of two or more kinds. Can be used. In this case, the inorganic foam used as the material for the intermediate layer is preferably prepared by mixing the adhesive and water while spraying. The lower layer mineral matter of the inorganic plate-like body is uniformly sprayed on the upper surface of the fiber plate-like section (wet mat), the middle layer section is laminated by a method such as stacking and laminating, and the upper layer mineral matter is further stacked thereon. The fibrous plate parts (wet mat) are laminated.

The thus obtained three-layered inorganic plate-like body is dried, for example, with a hot air dryer at 100 to 250 ° C., and the adhesive contained in the inorganic plate-like body, for example, the isocyanate group-containing adhesive of the present invention. Or by sufficiently reacting other adhesives such as phenolic adhesives,
A strong dry inorganic plate-like body can be obtained. Regarding the method of adding the isocyanate group-containing adhesive or other adhesives, it is preferable to add all of them and then to aggregate with an ionic coagulant, because the yield is good, but in addition to that, other materials are added. Each of the above adhesives may be added after the ionic coagulant is added.

It is also preferable to interpose the adhesive on the interface between the upper and lower layers and the middle layer by spraying, spraying or coating. Thereby, the adhesive strength at the interface between the upper and lower layer portions and the middle layer portion can be increased, and various strengths such as bending strength and peeling strength can be improved. If the isocyanate group-containing adhesive of the present invention is added to the adhesive to be added to the interface, the added adhesive is chemically bonded to a substance that reacts with the isocyanate groups contained in the upper and lower layers or the middle layer by hot pressing for a short time. In addition, strong interfacial adhesion can be performed.

Although the inorganic plate-shaped body has a three-layer structure so far, the present invention is not limited to this, and the middle layer may have a plurality of layers, and an adhesive is interposed at the interface between the middle layers. Of course, it is also good.

[0032]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. In addition, "part" and "%" in a synthetic example, an Example, and a comparative example mean a "mass part" and "mass%" unless there is particular notice.

The evaluations carried out in Examples and Comparative Examples were based on the following methods. (1) The fixing rate of the isocyanate group-containing adhesive was measured by finely crushing the mineral fiber board obtained by papermaking or scraping off the surface layer of the inorganic board, putting it in a crucible, burning organic matter, and measuring the mass before and after combustion. Was calculated by the following formula. Fixing rate (%) = (mass of plate before combustion (g) -mass of residue after combustion (g)) / mass of plate before combustion (g) x 100 (2) Bending strength is JIS A It measured according to 1408.

Synthesis Example 1 Polymeric MDI95 was placed in a reactor having a capacity of 2,000 ml equipped with a stirrer, a thermometer, a cooling tube and a nitrogen gas introducing tube.
5 parts were charged, and 25 parts of polyol A and polyol B were further added.
20 parts were charged and reacted at 80 to 90 ° C. for 3 hours to obtain an isocyanate group-containing urethane prepolymer (isocyanate group-containing adhesive). This isocyanate group-containing adhesive has an NCO content of 28.8%, a viscosity at 25 ° C. of 290 mPa · s, and a sodium sulfonate content of 0.0.
It was 1 mmol / g. Polymeric MDI: M manufactured by Nippon Polyurethane Industry Co., Ltd.
R-200 NCO content = 30.5% Viscosity at 25 ° C. = 180 mPa · s Polyol A: Hexane adipate polyester polyol containing Na sulfonate Number average molecular weight = 1000 Average number of functional groups = 2 Na sulfonate content = 0.4 mmol / g Polyol B: Methoxypolyethylene glycol number average molecular weight = 700 Average number of functional groups = 1

Example 1 Rock wool 50%, calcium carbonate 40%, Synthesis Example 1
The raw materials were added to water so that the composition ratio of the isocyanate group-containing adhesive obtained in step 1 was 10%, and the mixture was stirred and mixed.
Flocked 7% slurry was prepared by adding 15%. Next, this slurry is poured into a forming box laid with a 25 × 25 cm 40-mesh wire mesh,
A wet mat was produced by suction dehydration. The wet mat was pressed at 95 ° C. for 90 seconds, dried at 180 ° C. for 40 minutes in a hot air circulation dryer, and cured to obtain a mineral fiber board. The prepared mineral fiber board has a thickness of 2.0 mm,
The density was 0.48 g / cm ³ . The evaluation results are shown in Table 1.

Comparative Example 1 Rock wool 50%, calcium carbonate 40%, self-emulsifying polymeric MDI (WC-300 manufactured by Nippon Polyurethane Industry Co., Ltd., NCO content = 29.5%, viscosity at 25 ° C. = 170 mPa · s, Na sulfonate content = 0 mmo
1 / g) Each raw material was added to water so as to have a composition ratio of 10%, and the mixture was stirred and mixed.
Amphoteric polyacrylamide 0.15% was added to prepare a floc-like 7% slurry. Next, this slurry was poured into a forming box on which a 25 × 25 cm 40-mesh wire net was laid and suction-dewatered to prepare a wet mat. The wet mat was pressed at 95 ° C. for 90 seconds, dried at 180 ° C. for 40 minutes in a hot air circulation dryer, and cured to obtain a mineral fiber board. The prepared mineral fiber board has a thickness of 2.0 mm and a density of 0.46 g / cm ^3.
Met. The evaluation results are shown in Table 1.

Comparative Example 2 In the same manner as in Comparative Example 1, a mineral fiber board was obtained by using the self-emulsifying polymeric MDI used in Comparative Example 1 in an amount corresponding to 3 times that in Comparative Example 1. The produced mineral fiber board had a thickness of 2.1 mm and a density of 0.48 g / cm ³ . The evaluation results are shown in Table 1.

[0038]

[Table 1]

Example 2 As the upper and lower layer materials, each raw material was made to have a composition ratio of rock wool 50%, calcium carbonate 40%, powdered phenol resin 8%, and isocyanate group-containing adhesive 2% obtained in Synthesis Example 1. Was added to water and mixed by stirring, and then 0.1% of polyaluminum chloride and 0.15% of amphoteric polyacrylamide were added to prepare a floc-like 7% slurry. Next, this slurry was poured into a forming box on which a 25 × 25 cm 40-mesh wire mesh was laid and suction-dewatered to produce two wet mats.

As the material for the middle layer, 75% of shirasu foam,
Powdered phenol resin 8% and water 17% were uniformly mixed as an adhesive. The material for the middle layer is uniformly sprayed and deposited on the wet mat to be the lower layer, and the wet mat to be the upper layer is further laid on the wet mat.
After pressing for 1 minute, it was dried and cured in a hot air dryer at 180 ° C. for 40 minutes to obtain a three-layered inorganic plate. The prepared inorganic plate has a thickness of 7.4 mm and a density of 0.71 g / cm.
^{Was 3} . The evaluation results are shown in Table 2.

Comparative Example 3 As the upper and lower layer materials, each raw material was made to have a composition ratio of rock wool 50%, calcium carbonate 40%, powdered phenol resin 8%, and self-emulsifying polymeric MDI 2% used in Comparative Example 1. Add to water, stir and mix, then 0.1% polyaluminum chloride and 0.15% amphoteric polyacrylamide
Was added to prepare a floc-like 7% slurry. Next, this slurry was poured into a forming box on which a 25 × 25 cm 40-mesh wire mesh was laid and suction-dewatered to produce two wet mats.

75% Shirasu foam as the material for the middle layer,
Powdered phenol resin 8% and water 17% were uniformly mixed.
The material for the middle layer is uniformly sprayed and deposited on the wet mat to be the lower layer portion, the wet mat to be the upper layer portion is further stacked thereon, and this is pressed at 95 ° C. for 5 minutes, and then hot air at 180 ° C. It was dried for 40 minutes in a dryer and cured to obtain a three-layered inorganic plate. The produced inorganic plate had a thickness of 7.5 mm and a density of 0.69 g / cm ³ . The evaluation results are shown in Table 2.

[0043]

[Table 2]

[0044]

As described above, by using the isocyanate group-containing adhesive of the present invention, the fixing rate of the isocyanate group-containing adhesive to the inorganic fiber at the time of papermaking is improved. There is no need to add more than necessary. Therefore, white water can be prevented from being contaminated, and clogging of pipes and nets due to a reaction product of the isocyanate group-containing adhesive and water can be reduced. As a result, it has become possible to extremely efficiently manufacture and provide a mineral fiber plate-like body or an inorganic plate-like body that is lightweight, has high strength, and is excellent in fire protection.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Kazushi Minamiba             1 Ina, Inami-cho, Tonami-gun, Toyama Prefecture             Ken Kogyo Co., Ltd. (72) Inventor Toshihiko Tsuchida             440 Akihacho, Totsuka-ku, Yokohama-shi, Kanagawa             This Polyurethane Industry Co., Ltd.             In-house (72) Inventor Ken Enoda             440 Akihacho, Totsuka-ku, Yokohama-shi, Kanagawa             This Polyurethane Industry Co., Ltd.             In-house F-term (reference) 4G052 GA14 GB81                 4J040 EF051 EF061 EF091 EF111                       EF121 EF131 EF181 EF321                       GA03 GA07 GA16 GA25 GA27                       MA01 MA02 MA05 MB02 NA12                 4L055 AF01 AF02 AF04 AG11 AG12                       AG77 AG79 AG85 AG96 AG98                       AH01 AH37 BF02 BF03 BF04                       FA19 FA22 FA30 GA24

Claims (4)

[Claims] 1. An adhesive for inorganic fibers, comprising a prepolymer having at least an ionic hydrophilic group, a nonionic hydrophilic group and an isocyanate group. 2. A prepolymer having at least an ionic hydrophilic group, a nonionic hydrophilic group and an isocyanate group,
The inorganic material according to claim 1, which is a prepolymer obtained by reacting an active hydrogen compound containing at least an ionic hydrophilic group-containing active hydrogen compound and a nonionic hydrophilic group-containing active hydrogen compound with an organic polyisocyanate. Adhesive for fibers. 3. A mineral fiber plate-shaped body, characterized by being formed by making a slurry containing at least a mineral fiber and the adhesive according to claim 1 or 2, and curing the adhesive. 4. An inorganic plate-like body obtained by integrally laminating an upper layer portion, one or more intermediate layer portions and a lower layer portion, wherein the upper layer portion and the lower layer portion are mineral fibers. Papermaking a slurry containing at least the adhesive described in 2,
A mineral fiber plate-shaped part obtained by curing the adhesive, and at least one layer of the middle layer part is an inorganic foam plate-shaped part obtained by bonding and curing at least an inorganic foam. The said inorganic plate-shaped body characterized.