JP2021161596A - Binder composition for inorganic fiber and inorganic fiber product - Google Patents

Abstract

To provide a binder composition for inorganic fibers that can give an inorganic fiber product having excellent workability and shape retention under a high temperature environment such as a fire, and provide an inorganic fiber product having excellent workability and shape retention under a high temperature environment such as a fire.SOLUTION: A binder composition for inorganic fiber products has an organic binder and an inorganic binder. An inorganic fiber product has a molding having inorganic fibers and the binder composition for inorganic fiber products, with the inorganic fibers bound together with the organic binder.SELECTED DRAWING: None

Description

The present invention relates to a binder composition for inorganic fibers and an inorganic fiber product.

Conventionally, as a fireproof coating method for a steel frame of a building, a method of attaching a calcium silicate molded plate as a fireproof coating material is known. However, in this method, since the calcium silicate molded plate is hard, it is difficult to process it according to the shape of the steel frame.
Therefore, a method of attaching a felt material obtained by molding an inorganic fiber such as rock wool to a steel frame as a refractory coating material has been proposed (Patent Document 1). Further, a method has been proposed in which a refractory coating material such as a rock wool blanket or a rock wool molded plate is attached to the surface of a steel frame, and then the refractory coating material is impregnated or coated with cement slurry to be solidified (Patent Document 2).

Japanese Unexamined Patent Publication No. 57-197349 Japanese Unexamined Patent Publication No. 7-189359

However, the method of Patent Document 1 does not have sufficient fire resistance. Felt materials used as fireproof coating materials are generally molded by bonding inorganic fibers with an organic binder from the viewpoint of ensuring strength and flexibility and improving workability. However, organic binders thermally decompose in the event of a fire. When the organic binder is thermally decomposed, the strength of the felt material is reduced, and the felt material is peeled off at a place where the felt material is not applied to a sufficient thickness to expose the steel frame. Even if the felt material is thick enough, the felt material may come off due to the wind generated during a fire.
In the method of Patent Document 2, since the cement slurry is impregnated or applied to solidify after the construction of the refractory coating material, the construction period is increased.

INDUSTRIAL APPLICABILITY The present invention is an inorganic fiber binder composition capable of obtaining an inorganic fiber product having excellent workability and shape retention in a high temperature environment such as fire, and excellent workability and shape retention in a high temperature environment such as fire. The purpose is to provide inorganic fiber products.

The present invention has the following aspects.
[1] A binder composition for an inorganic fiber product, which comprises an organic binder and an inorganic binder.
[2] The binder composition for an inorganic fiber product according to the above [1], wherein the organic binder is a thermosetting organic binder.
[3] The binder composition for inorganic fiber products according to the above [1] or [2], wherein the organic binder contains at least one selected from the group consisting of sugars, phenol resins, polyvinyl alcohol resins and polycarboxylic acid resins. ..
[4] A hydroxide or oxide of a metal selected from the group consisting of lithium, sodium, potassium, magnesium, calcium, barium, titanium, chromium, manganese, iron, copper, silver, zinc and aluminum. The invention according to any one of claims 1 to 3, which comprises at least one selected from the group consisting of chlorides, silicates, carbonates, sulfates, nitrates, aluminates, borates and phosphates. Binder composition for inorganic fiber products.
[5] The binder composition for an inorganic fiber product according to any one of [1] to [4], wherein the ratio of the inorganic content of the inorganic binder to 100% by mass of the organic content of the organic binder is 1 to 300% by mass.
[6] The binder composition for an inorganic fiber product according to any one of [1] to [5] above, further comprising a silane coupling agent.
[7] A binder composition for an inorganic fiber product, which comprises an organic binder, an inorganic binder, and a carbamide group or a thiocarbamide group-containing compound.
[8] The binder composition for inorganic fiber products according to the above [7], wherein the organic binder is a thermosetting organic binder.
[9] The binder composition for inorganic fiber products according to the above [7] or [8], wherein the organic binder contains at least one selected from the group consisting of sugars, phenol resins, polyvinyl alcohol resins and polycarboxylic acid resins. ..
[10] A hydroxide or oxide of a metal selected from the group consisting of lithium, sodium, potassium, magnesium, calcium, barium, titanium, chromium, manganese, iron, copper, silver, zinc and aluminum. Any of the above [7] to [9], which comprises at least one selected from the group consisting of chlorides, silicates, carbonates, sulfates, nitrates, aluminates, borates and phosphates. Binder composition for inorganic fiber products.
[11] The carbamide group or thiocarbamide group-containing compound is urea, ethylene urea, thiourea, (mono, di, tri or tetra) methyl urea, (mono, di, tri or tetra) hydroxymethyl urea, (mono, di, tri or tetra). Group consisting of di, tri or tetra) ethyl urea, (mono, di, tri or tetra) hydroxyethyl urea, (mono, di, tri or tetra) propyl urea, (mono, di, tri or tetra) butyl urea and biuret The binder composition for an inorganic fiber product according to any one of [7] to [10] above, which comprises at least one selected from the above.
[12] The binder composition for an inorganic fiber product according to any one of [7] to [11], wherein the ratio of the inorganic content of the inorganic binder to 100% by mass of the organic content of the organic binder is 1 to 300% by mass.
[13] Any of the above [7] to [12], wherein the content of the carbamide group or the thiocarbamide group-containing compound is 0.1 to 100% by mass with respect to 100% by mass of the solid content of the inorganic binder. Binder composition for inorganic fiber products.
[14] The binder composition for an inorganic fiber product according to any one of [7] to [13] above, further comprising a silane coupling agent.
[15] The content of the silane coupling agent is 0.1 to 100 with respect to a total of 100% by mass of the solid content of the organic binder, the solid content of the inorganic binder, and the carbamide group or thiocarbamide group-containing compound. The binder composition for an inorganic fiber product according to the above [14], which is by mass%.
[16] An inorganic fiber product comprising an inorganic fiber and a binder composition for an inorganic fiber product according to any one of the above [1] to [6], and comprising a molded product in which the inorganic fiber is bonded by the organic binder.
[17] The inorganic fiber product according to [16], wherein the molded product is a cotton-like body.
[18] The inorganic fiber product according to the above [16] or [17], which is a refractory coating material.
[19] The inorganic fiber product according to the above [16] or [17], which is a heat insulating material.
[20] An inorganic fiber product comprising an inorganic fiber and a binder composition for an inorganic fiber product according to any one of [7] to [15], and comprising a molded product in which the inorganic fiber is bonded by the organic binder.
[21] The inorganic fiber product according to [20], wherein the molded product is a cotton-like body.
[22] The inorganic fiber product according to the above [20] or [21], which is a refractory coating material.
[23] The inorganic fiber product according to the above [20] or [21], which is a heat insulating material.

According to the present invention, a binder composition for an inorganic fiber capable of obtaining an inorganic fiber product having excellent workability and suppressed decrease in strength in a high temperature environment such as a fire, and an excellent workability in a high temperature environment such as a fire. It is possible to provide an inorganic fiber product in which a decrease in strength underneath is suppressed.

It is a graph which shows the result of Test Example 1. It is a photograph which shows the result of Test Example 1. It is a graph which shows the result of Test Example 2. It is a photograph which shows the result of Test Example 2. It is a graph which shows the result of Test Example 3. It is a photograph which shows the result of Test Example 3. It is a photograph which shows the result of Test Example 4. It is a photograph which shows the result of Test Example 5. It is a graph (base material: rock wool (1)) which shows the result of Test Example 6. It is a graph (base material: rock wool (2)) which shows the result of Test Example 6. It is a graph and a photograph which show the result of Test Example 7. It is a graph and a photograph which show the result of Test Example 8. It is a graph and a photograph which show the result of Test Example 9. It is a photograph which shows the result of Test Example 10.

In the present invention, the solid content indicates the non-volatile content when dried at 135 ° C. for 1 hour.
The inorganic content indicates the non-volatile content when firing at 800 ° C. for 1 hour.
The organic content of the organic binder indicates the balance obtained by subtracting the inorganic content from the solid content of the organic binder.
The volatile content of the inorganic binder indicates the balance obtained by subtracting the inorganic content from the solid content of the inorganic binder.

The non-volatile content after drying at 135 ° C. for 1 hour is measured by the following measuring method.
Measurement method of non-volatile content when dried at 135 ° C. for 1 hour: _{Weigh the mass C 1} (g) of an aluminum foil plate (inner diameter 50 mm, height 15 mm), and weigh the sample into 1.5 ± 0.1 g. Weigh accurately and let the specific mass of the sample be the sample mass S ₁ (g) before drying. This aluminum foil dish is placed in an incubator kept at 135 ± 1 ° C in advance, dried for 60 ± 2 minutes, allowed to cool in a desiccator, and its mass C ₂ (g) is measured. .. From the result, the sample mass D ₁ (mass of the sample remaining on the aluminum foil dish after the drying treatment) (g) after drying was calculated by the following formula (1), and 135 ° C. for 1 hour by the following formula (2). Calculate the non-volatile content during drying.
D ₁ = C _2- C ₁ ... (1)
Non-volatile content (%) when dried at 135 ° C for 1 hour = D ₁ / S ₁ × 100 ・ ・ ・ (2)

The non-volatile content after firing at 800 ° C. for 1 hour is measured by the following measuring method.
Measurement method of non-volatile content during firing at 800 ° C. for 1 hour: _{Weigh the mass C 3} (g) of the pot, weigh the sample into 10 ± 0.1 g, and burn the specific mass of the sample. Let the previous sample mass be S ₂ (g). This crucible is placed in an electric furnace, fired for 60 ± 2 minutes, allowed to cool in a desiccator, and its mass C ₄ (g) is weighed. From the result, the sample mass D ₂ (mass of the sample remaining in the crucible after the firing treatment) (g) after firing was calculated by the following formula (3), and when firing at 800 ° C. for 1 hour by the following formula (4). Calculate the non-volatile content.
D ₂ = C _4- C ₃ ... (3)
Non-volatile content (%) when firing at 800 ° C. for 1 hour = D ₂ / S ₂ × 100 ・ ・ ・ (4)

[Binder composition for inorganic fiber products]
The binder composition for inorganic fiber products according to one aspect of the present invention (hereinafter, also referred to as "composition (1)") includes an organic binder and an inorganic binder.
The composition (1) may further contain other components, if necessary, as long as the effects of the present invention are not impaired.

<Organic binder>
The organic binder binds the inorganic fibers. By binding the inorganic fibers with an organic binder, the inorganic fiber products can be processed with deformation such as winding around a steel frame. The binding of inorganic fibers by the organic binder is well maintained unless it is exposed to high temperatures due to fire or the like.

During the production of inorganic fiber products, binders are often used in the form of aqueous solutions or aqueous dispersions. Therefore, the organic binder is preferably water-soluble or water-dispersible, and more preferably water-soluble. For example, the solubility in ion-exchanged water at 25 ° C. is preferably 10 g / 100 mL or more in terms of solid content.

Examples of the organic binder include a thermoplastic organic binder and a thermosetting organic binder. A thermosetting organic binder is preferable in terms of excellent heat resistance of the inorganic fiber product.

The thermoplastic organic binder contains a thermoplastic resin.
Examples of the thermoplastic resin include polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, polychloroprene, styrene butadiene copolymer, acrylonitrile butadiene styrene resin, acrylonitrile copolymer, polyisoprene, polybutadiene, polyvinyl chloride, polyvinyl acetate, polyamide, and polyacetal. Examples thereof include polycarbonate and polyester. One type of these thermoplastic resins may be used alone, or two or more types may be used in combination.

The thermosetting organic binder contains a thermosetting resin.
The thermosetting resin may be any resin that can be increased in molecular weight by heat alone or in the presence of a curing agent. For example, sugar, phenol resin, urea resin, melamine resin, epoxy resin, polyurethane resin, resorcinol resin, etc. Examples thereof include unsaturated polyester resin, silicone resin, polyvinyl alcohol resin (hereinafter, also referred to as “PVA”), and polycarboxylic acid resin. Among these, sugars, phenol resins, PVAs, and polycarboxylic acid resins are preferable because they have excellent water solubility and excellent binding performance of inorganic fibers. One of these thermosetting resins may be used alone, or two or more thereof may be used in combination.
The thermosetting organic binder may further contain a curing agent (catalyst, cross-linking agent, etc.), if necessary. As the curing agent, a known curing agent can be used depending on the type of the thermosetting resin.

Hereinafter, a thermosetting organic binder containing a sugar (hereinafter, also referred to as a “sugar-based binder”), a thermosetting organic binder containing a phenol resin (hereinafter, also referred to as a “phenol resin-based binder”), and PVA. The thermocurable organic binder containing (hereinafter, also referred to as “PVA-based binder”) and the thermocurable organic binder containing a polycarboxylic acid resin (hereinafter, also referred to as “polycarboxylic acid-based binder”) will be described in more detail. However, the thermosetting organic binder is not limited to these.

(Sugar-based binder)
Examples of sugars include monosaccharides, oligosaccharides, polysaccharides, and derivatives thereof.
Examples of the monosaccharide include glucose, fructose, mannose, galactose, ribose, xylose and the like.
The oligosaccharide is a combination of 2 or more and 10 or less monosaccharides, for example, disaccharides such as sucrose, maltose, lactose, trehalose, and isomaltose; trisaccharides such as maltotriose and raffinose; maltooligosaccharides. Isomaltose oligosaccharides; fructo-oligosaccharides; manno-oligosaccharides; galactooligosaccharides and the like.
The polysaccharide is a combination of 11 or more monosaccharides, and examples thereof include starch, pullulan, dextrin, and polydextrose.
Derivatives of monosaccharides, oligosaccharides or polysaccharides include, for example, sugar alcohols, glycosides, modified starch and the like.

Modified starch includes, for example, starch that has been subjected to any one or more treatments of esterification, etherification, oxidation and cross-linking, or a mixture thereof. Examples of the esterified modified starch include esterified starches such as starch acetate, phosphorylated starch, and octenyl succinate starch. Examples of the modified starch subjected to the etherification treatment include etherified starch such as hydroxyethyl starch and hydroxypropyl starch. Examples of the modified starch that has been subjected to the oxidation treatment include oxidized starch. Examples of the modified starch that has been subjected to the cross-linking treatment include cross-linked starch such as phosphoric acid cross-linked starch. As the modified starch (composite processed starch) that has been subjected to any two or more treatments of esterification, etherification, oxidation and cross-linking, examples thereof include adipic acid acetate cross-linked starch, phosphate-phosphate cross-linked starch and acetate-oxidized starch. Examples thereof include hydroxypropyl phosphoric acid cross-linked starch and phosphoric acid monoesterified phosphoric acid cross-linked starch.
These sugars may be used alone or in combination of two or more.
Among the above, at least one sugar selected from the group consisting of monosaccharides, disaccharides and trisaccharides is preferable.

The sugar-based binder may further contain phenols.
Phenols are aromatic hydroxy compounds in which the hydrogen atom of the aromatic hydrocarbon nucleus is replaced with a hydroxy group. Phenols, together with sugars, form the skeleton of the cured product. The phenol resin is not included in the phenols.

Examples of phenols include plant-derived phenols and fossil fuel-based phenols. Examples of plant-derived phenols include flavonoid-based tannins, catechins, anthocyanins, rutins, isoflavones, phenolic acid-based chlorogenic acids, ellagic acids, lignans, curcumin, coumarin, lignin and other polyphenols, cardanol, cashew nut shell liquid and the like. Can be mentioned. Fossil fuel-based phenols include phenol, cresol, xylenol, trimethylphenol, ethylphenol, propylphenol, butylphenol, butylcresol, phenylphenol, cumylphenol, methoxyphenol, bromophenol, bisphenol A, bisphenol F, bisphenol S, Examples thereof include catechol, resorcinol, hydroquinone, pyrogallol, fluoroglucolcinol and the like. Any one of these phenols may be used alone or in combination of two or more.
Among these, polyhydric phenols (phenols having two or more hydroxyl groups) are preferable from the viewpoint of more excellent binder performance.

Phenols are preferably water-soluble. When the phenols are water-soluble, the phenols are easily miscible with the sugar, and the binder performance is more excellent.
Examples of water-soluble phenols include tannin, phenol, cresol, catechol, resorcinol, hydroquinone, pyrogallol, phloroglucinol and the like.

When the sugar-based binder contains phenols, the content of the phenols is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, based on 100% by mass of the sugar. When the content of phenols is at least the above lower limit value, the binder performance is more excellent, and the properties such as the strength of the obtained inorganic fiber product are more excellent. When the content of phenols is not more than the above upper limit value, properties such as strength of the inorganic fiber product can be maintained better, and the composition (1) and the inorganic fiber product can be produced at a more economical cost.

Sugar-based binders usually contain ammonium salts. The ammonium salt functions as a source of ammonia that reacts with the sugar in the curing reaction of the sugar-based binder, and as a source of an acidic substance that functions as a catalyst in the subsequent reaction.
Examples of the ammonium salt include an inorganic ammonium salt and an organic ammonium salt. Examples of the inorganic ammonium salt include ammonium sulfate, ammonium phosphate, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium hydrogen phosphate, ammonium borate, ammonium carbonate, ammonium hydrogencarbonate and the like. Examples of the organic ammonium salt include ammonium acetate, ammonium oxalate, ammonium citrate and the like. These ammonium salts may be used alone or in combination of two or more.

The content of the ammonium salt is preferably 1 to 30% by mass, more preferably 5 to 25% by mass, based on 100% by mass of the total of sugars and phenols. When the content of the ammonium salt is at least the above lower limit value, when molding the inorganic fiber product, curing is completed within predetermined molding conditions (temperature, time), and the required performance can be easily exhibited. When the content of the ammonium salt is not more than the above upper limit value, the binder performance is efficiently exhibited, and the properties such as the strength of the obtained inorganic fiber product are good.

As the thermosetting mechanism of the sugar-based binder, a mechanism similar to caramelization can be considered. When the sugar-based binder is heated, first, when the sugar is a reducing sugar, it reacts with ammonium ions as it is to become glucosylamine, and when the sugar is a non-reducing sugar, the non-reducing sugar is hydrolyzed to become a reducing sugar. The reducing sugar reacts with ammonium ions to form glucosylamine. Then, with ring opening, 1-amino-1-deoxy-2-ketose is formed. This is commonly referred to as the Amadori rearrangement. Subsequently, under the influence of anions (acid catalyst) and heating, the ring is closed with dehydration to produce hydroxymethylfurfural (hereinafter referred to as HMF). HMF is a thermally unstable compound, and the produced HMF reacts with other HMFs and phenols under continuous heating with further dehydration. As the reaction progresses, curing progresses and is eventually completed. It is presumed that the resulting cured product has a structure in which a phenolic skeleton is introduced into a part of the caramel-like structure.
It is considered that only water is produced as a by-product in the above reaction. Therefore, when the organic binder is a sugar-based binder, it is considered that the gas generated when the composition (1) is cured in the manufacturing process of the inorganic fiber product is generally only water vapor.

(Phenol resin binder)
Phenol resins are reaction products of phenols and aldehydes in the presence of catalysts.

Phenols are compounds having an aromatic ring and a hydroxyl group bonded to the aromatic ring. Examples of phenols include phenols, alkylphenols (o, m, p cresols, o, m, p ethylphenols, xylenol isomers, etc.), and polyaromatic ring phenols (α, β). Naphthol, etc.), polyphenols (bisphenol A, bisphenol F, bisphenol S, pyrogallol, resorcin, catechol, hydroquinone, etc.) and the like. One of these phenols may be used alone, or two or more of these phenols may be used in combination. Of these, practical substances are phenol, o, m, and p cresols, xylenol isomers, resorcin, and catechol.

Aldehydes are at least one compound selected from the group consisting of a compound having a formyl group and a multimer thereof. Examples of aldehydes include formaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, salicylaldehyde, glyoxal and the like. One of these aldehydes may be used alone, or two or more of these aldehydes may be used in combination. Of these, the practical substance is formaldehyde.

As the phenol resin, a resol type phenol resin using an alkali as a catalyst is preferable. When phenols and aldehydes are reacted in the presence of an alkali catalyst, an addition reaction occurs in which the aldehydes are added to the aromatic ring of the phenols, and then the phenols are polymerized through a condensation reaction.

The resole-type phenol resin may be urea-modified. By using the urea-modified resol-type phenol resin, the amount of formaldehyde volatilization in the manufacturing process of the inorganic fiber product is reduced as compared with the case of using the urea-modified resol-type phenol resin.

The weight average molecular weight of the resole-type phenol resin is preferably 800 or less, more preferably 600 or less, still more preferably 400 or less, from the viewpoint of water dilution and stability over time.
The weight average molecular weight of the resole-type phenol resin is preferably 150 or more. If the weight average molecular weight is less than 150, there is a risk that the yield and strength of the binder in the inorganic fiber product may decrease.
The weight average molecular weight of the resole-type phenol resin is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

The resol type phenol resin is preferably liquid.
The solid content of the resole-type phenol resin is preferably 30% by mass or more, more preferably 40% by mass or more, from the viewpoint of transportation cost.

(PVA-based binder)
PVA has a vinyl alcohol unit. The PVA may further have a monomer unit other than the vinyl alcohol unit (for example, a vinyl acetate unit).
The PVA preferably has a degree of polymerization of 500 or less in that it has a low viscosity. Examples of PVA having a degree of polymerization of 500 or less include "JL-05E" manufactured by Japan Vam & Poval Co., Ltd.

The PVA-based binder usually contains a cross-linking agent (curing agent).
Examples of the cross-linking agent include aliphatic carboxylic acid compounds and boron compounds.
Examples of the aliphatic carboxylic acid compound include polymers and copolymers of aliphatic monocarboxylic acids, aliphatic monocarboxylic acids, and polymers and copolymers thereof. Examples of the aliphatic monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid. Examples of the aliphatic dicarboxylic acid include maleic acid, fumaric acid, itaconic acid and the like.
Examples of the boron compound include borax, boric acid, and a boric acid complex.
These cross-linking agents may be used alone or in combination of two or more.
The content of the cross-linking agent is, for example, 4 to 100 parts by mass with respect to 100 parts by mass of PVA.

(Polycarboxylic acid resin binder)
A polycarboxylic acid resin is a resin having at least two carboxy groups or acid anhydride groups.
Examples of the polycarboxylic acid resin include resins having a monomer unit having a carboxy group or an acid anhydride group. The polycarboxylic acid resin may further have other monomeric units.

Examples of the monomer having a carboxy group include unsaturated monocarboxylic acids having 3 to 20 carbon atoms (hereinafter abbreviated as C) and unsaturated dicarboxylic acids having C4 to 20 (preferably C4 to 16). Examples of unsaturated monocarboxylic acids include (meth) acrylic acid, crotonic acid, cinnamic acid, vinyl benzoic acid, and alkenoic acid [C4 to 20 (preferably C4 to 13), such as vinyl acetate and 3-methyl-3-butenoic acid. , 3-Pentenoic acid, 4- and 5-hexenoic acid], monoalkyl (C1-8) esters of unsaturated dicarboxylic acids [C4-16, such as maleic acid monoalkyl esters, fumaric acid monoalkyl esters, citraconate monoalkyl Esters], unsaturated dicarboxylic acid monoesters [C5-20, for example, ethyl carbitol monoesters of maleic acid, ethyl carbitol monoesters of fumaric acid, glycol monoesters of itaconic acid] and the like. (Meta) Acrylic acid means acrylic acid or methacrylic acid. Examples of unsaturated dicarboxylic acids include maleic acid, fumaric acid, citraconic acid, itaconic acid and the like.
Examples of the monomer having an acid anhydride group include the above-mentioned anhydrides of unsaturated dicarboxylic acids, such as maleic anhydride and itaconic anhydride.
One of these monomers may be used alone, or two or more of these monomers may be used in combination.

The other monomer may be copolymerizable with a monomer having a carboxy group or an acid anhydride group, and examples thereof include the following.
(Meta) acrylamide, N-alkyl (C1-5) (meth) acrylamide, alkoxy (C1-4) alkyl (C1-5) (meth) acrylamide, N, N-dialkyl (C1-5) (meth) acrylamide, Aminoalkyl (C1-5) (meth) acrylamide, N-alkyl (C1-5) Aminoalkyl (C1-5) (meth) acrylamide, N, N-dialkyl (C1-5) Aminoalkyl (C1-5) ( C3-18 unsaturated amide compounds such as meta) acrylamide, diacetone (meth) acrylamide, N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone;
Alkyl (C1-18) (meth) acrylates and their lower alkyl (C1-4) ethers, aminoalkyl (C1-5) (meth) acrylates, N-alkyl (C1-5) aminoalkyls (C1-5) ( C3-30 such as meta) acrylate, N, N-dialkyl (C1-5) (meth) acrylate, N-alkyl (C1-5) aminoalkyl (C1-5) aminoalkyl (C1-5) (meth) acrylate (Meta) acrylate;
Vinylalkyl (C1-20) ether, N-alkyl (C1-5) vinylamine, N, N-dialkyl (C1-5) vinylamine, N-vinylpyridine, N-vinylimidazole, N- (alkyl) aminoalkyl (C1) -5) C3-30 vinyl compounds such as vinylamine;
Allyl compounds such as C3-10, for example N-allylamine, N-alkyl (C1-5) allylamine, N, N-dialkyl (C1-5) allylamine;
C3-10, for example, nitrile compounds such as (meth) acrylonitrile;
C2-30 aliphatic unsaturated hydrocarbons such as ethylene, propylene, isobutylene, isoprene, and butadiene;
C8-30 aromatic vinyl compounds such as styrene, α-methylstyrene, p-methoxystyrene, vinyltoluene, p-hydroxystyrene, p-acetoxystyrene;
A vinyl ester compound of C3 to 30 such as vinyl acetate and vinyl propionate.
One of these monomers may be used alone, or two or more of these monomers may be used in combination.

The ratio of the monomer unit having a carboxy group or an acid anhydride group to 100% by mass of all the monomer units constituting the polycarboxylic acid resin is, for example, 20% by mass or more, further 40% by mass or more, and further 60% by mass. % Or more, and may be 100% by mass.

The weight average molecular weight of the polycarboxylic acid resin is, for example, 500 to 100,000, further 1,000 to 80,000, and further 5,000 to 50,000.
The weight average molecular weight of the polycarboxylic acid resin is a value measured by gel permeation chromatography (GPC) using polyethylene oxide as a standard substance.

The polycarboxylic acid resin-based binder usually contains a cross-linking agent (curing agent).
Examples of the cross-linking agent include C2-20 hydroxylamine and amine alkylene oxide (hereinafter abbreviated as “AO”) adducts.
The hydroxylamine includes C2-20, for example, one having one hydroxyl group [for example, a primary amine such as monoethanolamine and 2- (2-aminoethylamino) ethanol], and one having two hydroxyl groups [diisopropanolamine, Secondary amines such as diethanolamine] and those having three hydroxyl groups [for example, tertiary amines such as triethanolamine and tris (hydroxyethyl) aminomethane] can be mentioned.
Examples of amines include aliphatic amines [C1-10, such as methylamine, ethylamine, n- and i-propylamine, ethylenediamine, diethylenetriamine], aromatic amines [C6-12, such as aniline, toluidine], and alicyclic-containing amines. [C4-10, for example cyclopentylamine, cyclohexylamine], heterocyclic amine-containing amine [C4-10, for example piperazine] can be mentioned.
Examples of AO include ethylene oxide, 1,2-propylene oxide, 1,2-, 2,3- or 1,3-butylene oxide, tetrahydrofuran, 3-methyl-tetrahydrofuran, 1,3-propylene oxide, isobutylene oxide and the like. Unsubstituted AO; Substituted AO such as styrene oxide can be mentioned.
The AO added to the amine may be one type or two or more types. In the case of two or more types, random addition or block addition may be performed. The number of moles added with AO is preferably 1 to 20 moles.

<Inorganic binder>
The inorganic binder binds the inorganic fibers when the inorganic fiber product is exposed to a high temperature (for example, 500 ° C. or higher) equal to or higher than the thermal decomposition temperature of the organic binder due to a fire or the like. When the inorganic fiber product is exposed to a high temperature, the organic binder is thermally decomposed, but the inorganic binder bonds the inorganic fibers to each other and maintains the shape of the inorganic fiber product.

The inorganic binder typically includes an inorganic compound that solidifies or condenses at a high temperature (for example, 500 ° C. or higher) equal to or higher than the thermal decomposition temperature of the organic binder (hereinafter, also referred to as “solidified / condensed inorganic compound”). In this case, when the inorganic fiber product is exposed to a high temperature, the solidified / condensed inorganic compound is solidified or condensed, and the inorganic fibers are bonded to each other by the solidified or condensed product.

The solidified / condensed inorganic compound is selected from hydroxides, oxides, chlorides, oxoacids, and oxoacids. For example, hydroxides, oxides, chlorides, silicates of metals selected from the group consisting of lithium, sodium, potassium, magnesium, calcium, barium, titanium, chromium, manganese, iron, copper, silver, zinc and aluminum. , Carbonate, Sulfate, Nitrate, Aluminate, Borate, Phosphate and the like. Specific examples include acid, trisodium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, tripotassium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium monohydrogen phosphate, and phosphoric acid. Examples thereof include magnesium, sodium sulfate, potassium sulfate, sodium carbonate, potassium carbonate, sodium silicate, potassium silicate, sodium chloride, potassium chloride and the like. One of these solidified / condensed inorganic compounds may be used alone, or two or more thereof may be used in combination.

The inorganic binder preferably contains a phosphate because it is water-soluble and has excellent condensability at a relatively low temperature (about 500 ° C.). Phosphate may be used in combination with other solidified / condensed inorganic compounds.
The ratio of the phosphate to 100% by mass of the total amount of the solidified / condensed inorganic compound is preferably 1% by mass or more, more preferably 5% by mass or more.

When a phosphate is used in combination with another solidified / condensed inorganic compound, a sulfate is preferable as the other solidified / condensed inorganic compound. By using the phosphate and the sulfate in combination, the strength of the inorganic fiber product when exposed to a high temperature of 1000 ° C. or higher is more excellent than that of the phosphate alone.
The ratio of the sulfate salt to 100 parts by mass of the phosphate is preferably 1 to 100 parts by mass, more preferably 1 to 60 parts by mass.

<Other ingredients>
As the other components, those known as components that can be blended in the binder of inorganic fiber products can be appropriately selected and used. For example, water, a curing accelerator, and an additive (silane coupling agent, softener, antistatic agent) can be used. Agents, mold release agents, adhesion improvers, viscosity regulators, antioxidants, UV absorbers, stabilizers, plasticizers, waxes, pigments, dyes, antistatic agents, antibacterial agents, fungicides, fragrances, flame retardants , Dispersants, film-forming aids, pH adjusters, wetting agents, etc.). Any one of these may be used alone or two or more thereof may be used in combination.

The composition (1) preferably contains a silane coupling agent from the viewpoint of the strength of the inorganic fiber product.
Examples of the silane coupling agent include an amino group-containing silane coupling agent, an epoxy group-containing silane coupling agent, a vinyl group-containing silane coupling agent, a methacryloyl group-containing silane coupling agent, an acryloyl group-containing silane coupling agent, and a ureido group. Examples thereof include a silane coupling agent and an isocyanate group-containing silane coupling agent. Examples of the amino group-containing silane coupling agent include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and 3-aminopropyltrimethoxy. Silane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2 Examples thereof include a hydrochloride of −aminoethyl-3-aminopropyltrimethoxysilane. Examples of the epoxy group-containing silane coupling agent include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxy. Examples thereof include propylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane. Examples of the vinyl group-containing silane coupling agent include vinyltriethoxysilane and the like. Examples of the methacryloyl group-containing silane coupling agent include 3-methacryloxypropyltrimethoxysilane. Examples of the acryloyl group-containing silane coupling agent include 3-acryloyloxypropyltrimethoxysilane. Examples of the ureido group-containing silane coupling agent include 3-ureidopropyltriethoxysilane. Examples of the isocyanate group-containing silane coupling agent include 3-isocyanatepropyltriethoxysilane. Any one of these silane coupling agents may be used alone, or two or more thereof may be used in combination.

<Composition>
In the composition (1), the ratio of the inorganic content of the inorganic binder to 100% by mass of the organic content of the organic binder is preferably 1 to 300% by mass, more preferably 2 to 200% by mass, still more preferably 3 to 100% by mass. , 5-80% by mass is particularly preferable. When the ratio of the inorganic content of the inorganic binder is at least the above lower limit value, the shape retention of the inorganic fiber product in a high temperature environment such as a fire is more excellent. When the ratio of the inorganic content of the inorganic binder is not more than the above upper limit value, the strength and workability of the inorganic fiber product are more excellent.

In the composition (1), the ratio of the solid content of the inorganic binder to 100% by mass of the solid content of the organic binder is preferably 1 to 300% by mass, more preferably 2 to 200% by mass, still more preferably 3 to 100% by mass. , 5-80% by mass is particularly preferable. When the ratio of the solid content of the inorganic binder is at least the above lower limit value, the shape retention of the inorganic fiber product in a high temperature environment such as a fire is more excellent. When the ratio of the inorganic content of the inorganic binder is not more than the above upper limit value, the strength and workability of the inorganic fiber product are more excellent.

The total ratio of the solid content of the organic binder and the solid content of the inorganic binder to 100% by mass of the solid content of the composition (1) is preferably 60% by mass or more, more preferably 80% by mass or more, and 100% by mass. May be good.

The water content is set according to the solid content concentration of the composition (1).
The solid content concentration of the composition (1) can be appropriately set in consideration of the solubility of the organic binder or the inorganic binder, the usage pattern of the composition (1), etc., and is, for example, relative to the total mass of the composition (1). , 1-80% by mass.

The content of the silane coupling agent in the composition (1) is preferably 0 to 5% by mass, more preferably 0 to 1% by mass, based on 100% by mass of the solid content of the organic binder.

Since the composition (1) described above contains an organic binder and an inorganic binder, an inorganic fiber product having excellent workability and shape retention in a high temperature environment such as a fire can be obtained.
In the inorganic fiber product using the composition (1), the inorganic fiber is bonded by an organic binder before being exposed to a high temperature (for example, 500 ° C. or higher) due to a fire or the like. Therefore, the inorganic fiber product has sufficient strength and can be processed with deformation such as winding around a steel frame. In addition, if it is installed at a construction site such as a steel frame, the construction will be completed and the construction period will be short.
When the inorganic fiber product is exposed to a high temperature, the organic binder is thermally decomposed, and the inorganic binder bonds the inorganic fibers to each other. Therefore, the decrease in strength of the inorganic fiber product can be suppressed, and the shape of the inorganic fiber product can be maintained.

The binder composition for inorganic fiber products according to another aspect of the present invention (hereinafter, also referred to as “composition (2)”) is an organic binder, an inorganic binder, and a carbamide group or a thiocarbamide group-containing compound (hereinafter, “composition (2)”). Also referred to as "compound (A)").
The composition (2) may further contain other components, if necessary, as long as the effects of the present invention are not impaired.

<Organic binder>
Examples of the organic binder include the same as described above.

<Inorganic binder>
Examples of the inorganic binder include the same as described above.
As the inorganic binder in the composition (2), among the solidified / condensed inorganic compounds described above, lithium, sodium, potassium, magnesium, calcium, barium, and the like, because the effect of improving the moisture resistance strength of the compound (A) can be easily obtained. Hydrooxides, oxides, chlorides, silicates, carbonates, sulfates, nitrates, aluminates, hobos of metals selected from the group consisting of titanium, chromium, manganese, iron, copper, silver, zinc and aluminum. At least one selected from the group consisting of acid salts and phosphates is preferable, and at least one selected from the group consisting of silicates, borates and phosphates is more preferable.

Among the above, the inorganic binder is more preferably containing a phosphate because it is excellent in water solubility and condensability at a relatively low temperature (about 500 ° C.). Phosphate may be used in combination with other solidified / condensed inorganic compounds.
The ratio of the phosphate to 100% by mass of the total amount of the solidified / condensed inorganic compound is preferably 50% by mass or more, more preferably 80% by mass or more.

<Compound (A)>
Compound (A) is a compound having a carbamide group (> NC (= O) -N <) or a thiocarbamide group (> NC (= S) -N <) in the molecule.
When the composition (2) contains the compound (A), the moisture resistance of the inorganic fiber product is improved.

The molecular weight of compound (A) is, for example, 60 to 300.
Specific examples of compound (A) include urea, ethylene urea, thiourea, (mono, di, tri or tetra) methyl urea, (mono, di, tri or tetra) hydroxymethyl urea, (mono, di, tri or tetra). Examples thereof include tetra) ethyl urea, (mono, di, tri or tetra) hydroxyethyl urea, (mono, di, tri or tetra) propyl urea, (mono, di, tri or tetra) butyl urea, biuret and the like. These compounds may be used alone or in combination of two or more.

Among the above, the compound (A) includes urea, ethylene urea, thiourea, (mono, di, tri or tetra) methylurea, and (mono, di, tri or tetra) hydroxymethyl from the viewpoint of water dilatability. At least one selected from the group consisting of urea, (mono, di, tri or tetra) hydroxyethyl urea is preferred.

<Other ingredients>
Examples of other components include the same components as described above.

From the viewpoint of the strength of the inorganic fiber product, the composition (2) preferably contains a silane coupling agent among the other components described above. Examples of the silane coupling agent include the same as described above.

<Composition>
In the composition (2), the ratio of the inorganic content of the inorganic binder to 100% by mass of the organic content of the organic binder is preferably 1 to 300% by mass, more preferably 2 to 200% by mass, still more preferably 3 to 100% by mass. , 5-80% by mass is particularly preferable. When the ratio of the inorganic content of the inorganic binder is at least the above lower limit value, the shape retention of the inorganic fiber product in a high temperature environment such as a fire is more excellent. When the ratio of the inorganic content of the inorganic binder is not more than the above upper limit value, the strength and workability of the inorganic fiber product are more excellent.

In the composition (2), the ratio of the solid content of the inorganic binder to 100% by mass of the solid content of the organic binder is preferably 1 to 300% by mass, more preferably 2 to 200% by mass, still more preferably 3 to 100% by mass. , 5-80% by mass is particularly preferable. When the ratio of the solid content of the inorganic binder is at least the above lower limit value, the shape retention of the inorganic fiber product in a high temperature environment such as a fire is more excellent. When the ratio of the inorganic content of the inorganic binder is not more than the above upper limit value, the strength and workability of the inorganic fiber product are more excellent.

The content of the compound (A) in the composition (2) is preferably 0.1 to 100% by mass, more preferably 1 to 80% by mass, and 2 to 50% by mass with respect to 100% by mass of the solid content of the inorganic binder. % Is more preferable, and 5 to 30% by mass is particularly preferable. When the content of the compound (A) is within the above range, the moisture resistance of the inorganic fiber product is more excellent.
When the compound (A) contains water of crystallization, the content of the compound (A) shall indicate the amount excluding the water of crystallization.

The total ratio of the solid content of the organic binder, the solid content of the inorganic binder and the compound (A) to 100% by mass of the solid content of the composition (2) is preferably 60% by mass or more, more preferably 80% by mass or more, and 100%. It may be% by mass.

The water content is set according to the solid content concentration of the composition (2).
The solid content concentration of the composition (2) can be appropriately set in consideration of the solubility of the organic binder, the inorganic binder, the compound (A) and the like, the usage pattern of the composition (2), and the like. ) May be 1 to 80% by mass.

The content of the silane coupling agent in the composition (2) is preferably 0.1 to 100% by mass with respect to a total of 100% by mass of the solid content of the organic binder, the solid content of the inorganic binder and the compound (A). , 1 to 80% by mass, more preferably 2 to 50% by mass, and particularly preferably 5 to 30% by mass. When the content of the silane coupling agent is at least the above lower limit value, the strength (normal strength, moisture resistance) of the inorganic fiber product is more excellent, and when it is at least the above upper limit value, the shape is retained in a high temperature environment such as a fire. Better in sex.

Since the composition (2) described above contains an organic binder, an inorganic binder, and the compound (A), it is an inorganic fiber product having excellent workability, shape retention in a high temperature environment such as a fire, and moisture resistance. Is obtained.
In the inorganic fiber product using the composition (2), the inorganic fiber is bonded by an organic binder before being exposed to a high temperature (for example, 500 ° C. or higher) due to a fire or the like. Therefore, the inorganic fiber product has sufficient strength and can be processed with deformation such as winding around a steel frame. In addition, if it is installed at a construction site such as a steel frame, the construction will be completed and the construction period will be short.
When the inorganic fiber product is exposed to a high temperature, the organic binder is thermally decomposed, and the inorganic binder bonds the inorganic fibers to each other. Therefore, the decrease in strength of the inorganic fiber product can be suppressed, and the shape of the inorganic fiber product can be maintained.

The compound (A) contributes to the improvement of the moisture resistance before the inorganic fiber product is exposed to a high temperature due to a fire or the like. The reason why the compound (A) exerts such an effect is presumed as follows.
In the absence of compound (A), it is considered that the inorganic binder is dispersed and arranged without being bonded to each other in the inorganic fiber product before being exposed to high temperature due to fire or the like. The inorganic binder has a relatively high hydrophilicity, and it is considered that the moisture resistance strength is lowered when the inorganic binder is dispersed and arranged as described above.
The portion of the carbamide group or the thiocarbamide group of the compound (A) is decomposed by the heat during the production of the inorganic fiber product. For example, urea is decomposed into isocyanic acid and ammonia by heat. The decomposition product acts on the inorganic binder, and the hydrophilic groups of the inorganic binder react with each other (for example, the hydroxyl group of the phosphate undergoes a condensation reaction). As a result, it is considered that the moisture resistance strength is improved by forming a network of inorganic binders and suppressing the influence of hydrophilic groups.

[Inorganic fiber products]
The inorganic fiber product of the present invention comprises a molded product containing the inorganic fiber and the present composition. It can be said that the molded product contains an inorganic fiber, an organic binder, and an inorganic binder.

The inorganic fiber is not particularly limited, and examples thereof include glass wool, rock wool, and ceramic fiber. Any one of these may be used alone or two or more thereof may be used in combination. As the inorganic fiber, glass wool or rock wool is preferable from the viewpoint of versatility and heat insulating performance.

In the molded product, the inorganic fibers are bound by an organic binder. As a result, the molded body has flexibility, and processing such as winding an inorganic fiber product around the surface of a steel frame is possible.
When the organic binder of the present composition is a thermosetting organic binder, the organic binder that binds the inorganic fibers is a cured product of the thermosetting organic binder.
Inorganic fibers are usually not bound by the inorganic binder.

The molded body is preferably a cotton-like body from the viewpoint of wrapping processability.
Examples of the cotton-like body include felt, mat, board and the like. These are usually distinguished by density. In the case of rock wool, the density of felt is generally 20-40 kg / m ³ , the density of mat ^{is 40-80 kg / m 3} , and the density of board is 80-250 kg / m ³ . In the case of glass wool, the density of felt is generally 10 to 16 kg / m ³ , the density of mat is 10 to 32 kg / m ³ , and the density of board is 32 to 96 kg / m ³ .
The thickness of the cotton-like body is preferably 25 to 100 mm, more preferably 25 to 50 mm.

The inorganic fiber product of the present invention may be made of the molded product, or may further include members other than the molded product. Examples of other members include a skin material for packaging and the like.

<Manufacturing method of inorganic fiber products>
The inorganic fiber product of the present invention can be produced, for example, by a production method comprising the step of molding the inorganic fiber at a temperature lower than the thermal decomposition temperature of the organic binder to obtain a molded product using the present composition.
As a method for producing the molded product, a known method conventionally used for producing an inorganic fiber product can be used except that the present composition is used as a binder.

An example of a method for producing a molded product will be described by taking the case where the organic binder is a thermosetting organic binder as an example.
The manufacturing method of this example is a step of adhering the present composition to the inorganic fiber (hereinafter referred to as an adhering step) and an accumulation of the shape corresponding to the inorganic fiber product to be manufactured by accumulating the inorganic fiber to which the present composition is attached. After forming the body, it has a step of heating the aggregate to cure the thermosetting organic binder in the present composition (hereinafter referred to as a molding step). Hereinafter, each step will be described in more detail.

(Adhesion process)
The fiber length and fiber diameter of the inorganic fiber may be appropriately set according to the inorganic fiber product to be manufactured, and are not particularly limited. Usually, those having a fiber diameter in the range of 3 to 10 μm are used.
As the inorganic fiber, a commercially available one may be used, or one produced by a known method may be used as it is. Inorganic fibers are generally produced by fiberizing raw materials (waste glass, basalt, iron furnace slag, etc.). Examples of the fibrosis method include a flame method and a centrifugation method. Fibrosis by these various methods can be carried out using a corresponding fibrosis device.

Examples of the method of adhering the present composition to the inorganic fiber include a method of spraying the present composition on the inorganic fiber using a spray device and the like, a method of impregnating the present composition with the inorganic fiber, and the like. The method may be used.
The amount of the composition to be attached to the inorganic fiber is not particularly limited, but is usually in the range of 0.5 to 20% by mass as the solid content (nonvolatile content) of the composition with respect to the inorganic fiber (100% by mass). Is inside. This amount affects the physical properties (mechanical strength, etc.) of the obtained molded product. For example, the larger the amount of the present composition attached to the inorganic fiber, the higher the mechanical strength of the obtained molded product tends to be.

(Molding process)
Next, the inorganic fibers to which the composition is attached are accumulated to form an aggregate having a shape corresponding to the inorganic fiber product to be produced, and then the aggregate is heated to cure the composition.
The molding step can be carried out by a known method. For example, in the case of producing a cotton-like molded product as an example, inorganic fibers are deposited on a conveyor, and the deposit is pressed from the vertical direction of the conveyor and compressed to form an aggregate, which is then accumulated. A cotton-like molded product is obtained by sending the body to a heating furnace (curing furnace) and heating to cure the composition.
The amount of inorganic fibers used (the amount of inorganic fibers deposited on the conveyor) and compression conditions are set according to the thickness, bulk density, etc. of the inorganic fiber product to be manufactured.
The heating conditions (heating temperature, heating time) of the aggregate are not particularly limited as long as they are lower than the thermal decomposition temperature of the thermocurable organic binder and within the range in which the thermocurable organic binder is cured, but the heating temperature is 180. It is preferably in the range of ~ 270 ° C. If the temperature is lower than 180 ° C., the curing may be insufficient and the mechanical strength may be insufficient. If the temperature exceeds 270 ° C., the thermosetting organic binder may be decomposed, resulting in a decrease in yield and a decrease in mechanical strength. The heating time varies depending on the size of the aggregate, the heating temperature, and the like, and is not particularly limited.

The obtained molded product may be used as it is as an inorganic fiber product, and may be further subjected to processing such as cutting and packing with a skin material, if necessary.

The inorganic fiber product of the present invention can be used as, for example, a fireproof coating material, a heat insulating material, a sound absorbing material, and various other molded products (automobile roof, bonnet liner, etc.).
As described above, the inorganic fiber product of the present invention has excellent shape retention in a high temperature environment such as a fire. Therefore, the inorganic fiber product of the present invention is suitable as a fireproof coating material or a heat insulating material used for buildings, and is particularly suitable as a fireproof coating material. When this inorganic fiber product is used as a fire-resistant coating material, it is possible to prevent the fire-resistant coating material from peeling off from the steel frame and deteriorating the fire resistance performance in the event of a fire.

The fireproof coating material covers the steel frame (beams, columns, etc.) of the building. By covering the steel frame with a fireproof coating material, it is possible to prevent the steel frame from melting due to the heat of a fire.
The method of constructing the fireproof coating material may be the same as that of a known method. For example, when the refractory coating material is felt-like, a method of wrapping the refractory coating material around a steel frame and fixing it with a pin or the like can be mentioned.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the examples. In each of the following examples, "parts" and "%" indicate "parts by mass" and "% by mass", respectively, unless otherwise specified.

(Production Example 1: Preparation of sugar-based binder)
2.7 g of an 85% aqueous phosphoric acid solution and 7.3 g of a 65% aqueous phenol sulfonic acid solution were dissolved in 13.2 g of ion-exchanged water. While checking the pH (inserted the electrode of the pH meter and carried out with stirring), a 25% aqueous ammonia solution was added, and finally the pH was adjusted to 5.5. Then, 2.7 g of tannin was added and dissolved. Then, 69.0 g of an aqueous solution of isomerized sugar having a solid content concentration of 75% was added and dissolved uniformly. Then, ion-exchanged water was finally added so that the total amount of the binder composition was 100 g to obtain a sugar-based binder (solid content concentration 47%).
Tannins are powdered UCL Company Pty Ltd. , Mimosa NT, 85% phosphate aqueous solution manufactured by Katakura Corp. Agri, 65% phenolsulfonic acid aqueous solution manufactured by Nippon Kagaku Sangyo Co., Ltd., 25% ammonia aqueous solution manufactured by Mitsubishi Chemical Co., Ltd., isomerized sugar. "75FG" manufactured by Gunei Chemical Industry Co., Ltd. (containing 25% of water content, 45% of glucose and 42% of fructose with respect to the total sugar content) was used.

<Test Example 1>
(Preparation of binder composition)
A sugar-based binder (organic binder) of 100 parts in terms of solid content and an aqueous solution of 36% sodium dihydrogen phosphate (inorganic binder) in the amount shown in Table 1 in terms of solid content were mixed and diluted with ion-exchanged water. The binder composition of Examples 1-1 to 1-5 was prepared. The composition of ion-exchanged water was set so that the total solid content concentration after dilution was 36%. The sodium dihydrogen phosphate manufactured by Kanto Chemical Co., Inc. was used.
The binder composition of Comparative Example 1 was prepared by diluting the sugar-based binder with ion-exchanged water so that the total solid content concentration after dilution was 36%.
The 36% aqueous sodium dihydrogen phosphate solution was used as it was as the binder composition of Comparative Example 2.

(Measurement of inorganic and organic components)
The solid content (nonvolatile content when dried at 135 ° C. for 1 hour) (%) of the binder composition was measured.
The inorganic content (nonvolatile content at 800 ° C. for 1 hour) (%) of the binder composition was measured.
The value obtained by subtracting the inorganic content (%) from the solid content (%) of the binder composition was defined as the organic content (%) of the binder composition.
When measuring the inorganic content of this composition (when baking at 800 ° C. for 1 hour), the organic binder decomposes and volatilizes, and also the water and metal components generated by the condensation of the inorganic binder also volatilize. The organic content of the present composition includes the organic content of the organic binder and the volatile content of the inorganic binder.
The results are shown in Table 2.

The solid content (parts) of the binder composition was determined by the mass (parts) × solid content (%) / 100 of the binder composition.
The inorganic content (parts) of the binder composition was determined by the mass (parts) of the binder composition x the inorganic content (%) / 100.
The value obtained by subtracting the inorganic content (part) from the solid content (part) of the binder composition was taken as the organic content (part) of the binder composition.
The results are shown in Table 3.

The solid content (parts) of the binder composition was determined by the mass (parts) × solid content (%) / 100 of the binder composition.
The inorganic content (%) of the binder composition of Comparative Example 1 was measured. This value corresponds to the inorganic content (part) of the sugar-based binder (organic binder) in the binder compositions of Comparative Examples 1 and Examples 1-1 to 1-5. The value obtained by subtracting the inorganic content (part) of the sugar-based binder from the inorganic content (part) of the binder composition of Comparative Examples 1 and 1-1 to 1-5 was taken as the inorganic content (part) of the inorganic binder.
The organic content in Comparative Example 2 corresponds to the volatile content of the inorganic binder. The ratio (16.99 / 85.65) of the organic content (= volatile content) to the inorganic content in Comparative Example 2 was defined as the volatile content ratio of the inorganic binder. For the binder composition of Examples 1-1 to 1-5, the volatile content (part) of the inorganic binder was determined by the ratio of the inorganic content (part) × the volatile content of the inorganic binder.
The value obtained by subtracting the volatile content (part) of the inorganic binder from the organic content (part) of the binder composition was taken as the organic content (part) of the sugar-based binder (organic binder).
The results are shown in Table 4.

(evaluation)
The binder composition was added and mixed with respect to 150 g of the base material so that the solid content of the sugar-based binder was 3%. Sand (Cera beads manufactured by Itochu Ceratech, average particle size 300 μm) was used as the base material. The obtained mixture was uniformly filled in a dogbone mold (length 75 mm × width 25 to 42 mm × thickness 7 mm) to prepare a test piece. The test piece was fired at 200 ° C. for 30 minutes assuming the production of a refractory coating material, and then refired at 800 ° C. for 30 minutes assuming the occurrence of a fire. The tensile strength (N) of the test piece was measured after firing and after re-baking. The tensile strength was measured at a load speed of 5 mm / min.
The tensile strength is generally a value (N / mm ² ) calculated by a measured value (N) / breaking area 25 × 7 (mm ² ), but in this evaluation, the breaking area is 175 (mm ² ). Since it is constant, only the measured value (N) is described.

The measurement results are shown in Table 5. Further, FIG. 1 shows a graph in which the ratio of the solid content of the inorganic binder to the solid content of the organic binder (inorganic binder mixing ratio) (%) is taken on the horizontal axis and the tensile strength is taken on the vertical axis.
Further, FIG. 2 shows the appearance (photograph) of the test piece after measuring the tensile strength. The test piece after re-baking in Example 1-1 was divided into three parts and partially collapsed. In this case, the tester split one of the two divided test pieces by hand to check the condition. This is because of the firing. The state immediately after re-baking was equivalent to that of Examples 1-2 to 1-4.

As shown in the above results, in Examples 1-1 to 1-5 in which the inorganic binder was blended with the organic binder, the shape of the test piece was maintained after re-baking at 800 ° C. Further, as the mixing ratio of the inorganic binder increased, the tensile strength after re-baking increased.

<Test Example 2>
(Preparation of binder composition)
The binder composition of Examples 2-1 to 2-4 is obtained by mixing 100 parts of a sugar-based binder (organic binder) in terms of solid content and 25 parts of an inorganic binder in terms of solid content and diluting with ion-exchanged water. I got something. The inorganic binder was prepared by adding 100 parts of a 36% sodium dihydrogen phosphate aqueous solution in terms of solid content to the amount of sodium sulfate shown in Table 6 in terms of solid content. The composition of ion-exchanged water was set so that the total solid content concentration after dilution was 36%. Sodium sulfate used was manufactured by Kanto Chemical Co., Inc.
Separately, the binder composition of Comparative Example 1 was prepared in the same manner as in Test Example 1.

(evaluation)
Each binder composition was evaluated in the same manner as in Test Example 1. However, re-baking was performed at 550 ° C, 800 ° C and 1100 ° C.
The measurement results are shown in Table 6. FIG. 3 shows a graph in which the ratio of sodium sulfate (solid content) to 100% of sodium dihydrogen phosphate (solid content) (sodium sulfate mixture ratio) (%) is on the horizontal axis and the tensile strength is on the vertical axis. ..
Further, FIG. 4 shows the appearance (photograph) of the test piece after measuring the tensile strength.

As shown in the above results, in Examples 2-1 to 2-4 in which the inorganic binder was mixed with the organic binder, the shape of the test piece was maintained after re-baking at 550 to 1100 ° C.
When the sodium sulfate mixing ratio in the inorganic binder was 33.3%, the tensile strength after firing and after re-baking was improved as compared with the case where the sodium sulfate mixing ratio was 0%.
When the sodium sulfate mixing ratio in the inorganic binder was 100%, the tensile strength after re-baking at 1100 ° C. was improved as compared with the case where the sodium sulfate mixing ratio was 0%.

<Test Example 3>
(Preparation of binder composition)
100 parts of sugar-based binder (organic binder) in terms of solid content, 25 parts of inorganic binder in terms of solid content, and 1 part of silane coupling agent in terms of solid content ("KBE-903" manufactured by Shin-Etsu Chemical Co., Ltd. ) And diluted with ion-exchanged water to prepare the binder composition of Examples 3-1 to 3-6. The inorganic binder was prepared by adding 100 parts of a 36% sodium dihydrogen phosphate aqueous solution in terms of solid content to the amount of sodium sulfate shown in Table 7 in terms of solid content. The composition of ion-exchanged water was set so that the total solid content concentration after dilution was 36%.
Separately, 100 parts of a sugar-based binder (organic binder) in terms of solid content and 1 part of a silane coupling agent (“KBE-903” manufactured by Shin-Etsu Chemical Co., Ltd.) in terms of solid content are mixed to form ion-exchanged water. The binder composition of Comparative Example 1 was prepared by diluting with. The composition of ion-exchanged water was set so that the total solid content concentration after dilution was 36%.

(evaluation)
Each binder composition was evaluated in the same manner as in Test Example 1. However, re-baking was performed at 550 ° C.
The measurement results are shown in Table 7. FIG. 5 shows a graph in which the ratio of sodium sulfate (solid content) to 100% of sodium dihydrogen phosphate (solid content) (sodium sulfate mixture ratio) (%) is on the horizontal axis and the tensile strength is on the vertical axis. ..
Further, FIG. 6 shows the appearance (photograph) of the test piece after measuring the tensile strength.

As shown in the above results, in Examples 3-1 to 3-6 in which the inorganic binder was mixed with the organic binder, the shape of the test piece was maintained after re-baking at 550 ° C.
When the sodium sulfate mixing ratio in the inorganic binder was 25%, the tensile strength at 200 ° C. firing was improved as compared with the case where the sodium sulfate mixing ratio was 0%.
When the sodium sulfate mixing ratio in the inorganic binder was 42.9%, the strength at 550 ° C. recalcination was improved as compared with the case where the sodium sulfate mixing ratio was 0%.

<Test Example 4>
(Preparation of binder composition)
The binder composition of Comparative Example 1 was prepared in the same manner as in Test Example 1.
The binder composition of Comparative Example 1 and the diluted solution of sodium dihydrogen phosphate diluted with pure water and having a solid content of 36% were mixed at the solid content mass ratio shown in Table 8 to form the binder composition of Example 4-1. The thing was prepared.
The binder composition of Comparative Example 4 was prepared by diluting a phenol (PF) resin (PL-6757 manufactured by Gun Ei Chemical Industry Co., Ltd.) (organic binder) with pure water so that the total solid content after dilution was 36%. bottom.
The binder composition of Comparative Example 4 and the diluted solution of sodium dihydrogen phosphate diluted with pure water and having a solid content of 36% were mixed at the solid content mass ratio shown in Table 8 to form the binder composition of Example 4-2. The thing was prepared.

(evaluation)
The binder composition was added and mixed with respect to 150 g of the base material so that the solid content of the binder composition was 3%. Sand (Cera beads manufactured by Itochu Ceratech, average particle size 300 μm) was used as the base material. The obtained mixture was uniformly filled in a dogbone mold (length 75 mm × width 25 to 42 mm × thickness 7 mm) to prepare a test piece. The test piece was fired at 200 ° C. for 30 minutes assuming the production of a refractory coating material, and then refired at 800 ° C. for 30 minutes assuming the occurrence of a fire.
The tensile strength (N) of the test piece after firing at 200 ° C. was measured, and the value was taken as the normal strength. Separately, the tensile strength (N) when the test piece after firing at 200 ° C. was held in an environment of 60 ° C. and 90% RH for 12 hours was measured, and the value was taken as the moisture resistance strength. The tensile strength was measured at a load speed of 5 mm / min. The tensile strength is generally a value (N / mm ² ) calculated by a measured value (N) / breaking area 25 × 7 (mm ² ), but in this evaluation, the breaking area is 175 (mm ² ). Since it is constant, only the measured value (N) is described.
It was visually confirmed whether or not the test piece retained its shape during re-baking at 800 ° C., and the heat resistance was evaluated.
Table 8 shows the measurement results of the normal strength and the moisture resistance of each example. Further, FIG. 7 shows the appearance (photograph) of the test piece after re-baking at 800 ° C.

As shown in the above results, in Examples 4-1 to 4-2 in which the inorganic binder was mixed with the organic binder, the shape of the test piece was maintained after re-baking at 800 ° C.
From this result, it was confirmed that the inorganic binder contributes to the improvement of the shape retention in a high temperature environment not only when the organic binder is a sugar-based binder but also when it is a PF resin.

<Test Example 5>
(Preparation of binder composition)
A sugar-based binder (organic binder) and sodium dihydrogen phosphate (inorganic binder) were each diluted with pure water to obtain a diluted solution having a solid content of 36%.
The diluted solution of each raw material shown in Table 9 and the following aminosilane (silane coupling agent) were mixed at the solid content mass ratio shown in Table 9 to obtain the binder composition of Examples 5-1 to 5-2.
Aminosilane: KBE-903, 3-aminopropyltriethoxysilane manufactured by Shin-Etsu Chemical.
Separately, the binder composition of Comparative Example 1 was prepared in the same manner as in Test Example 1.

(evaluation)
Each binder composition was evaluated in the same manner as in Test Example 4.
Table 9 shows the measurement results of the normal strength and the moisture resistance of each example. Further, FIG. 8 shows the appearance (photograph) of the test piece after re-baking at 800 ° C.

As shown in the above results, in Examples 5-1 to 5-2 in which the inorganic binder was mixed with the organic binder, the shape of the test piece was maintained after re-baking at 800 ° C.
Further, in Example 5-2 containing the silane coupling agent, the moisture resistance strength and the normal strength at 200 ° C. firing were improved as compared with Example 5-1 not containing the silane coupling agent.

<Test Example 6>
In this test, the binder composition was actually impregnated into the inorganic fiber and its performance was evaluated.

(Inorganic fiber)
The following two types of rock wool were prepared as inorganic fibers.
Rock wool (1): Density 80 kg / m ³ , thickness 20 mm.
Rock wool (2): Density 32 kg / m ³ , thickness 120 mm.
Table 10 shows the results of metal elemental analysis by an inductively coupled plasma (ICP) emission spectrophotometer for each rock wool.
Each rock wool was used after removing the adhering binder by firing at 600 ° C. for 30 minutes.

(Making a molded product 1)
The following three types of binders were prepared.
PF resin: Phenol resin, PL-6757 manufactured by Gun Ei Chemical Industry Co., Ltd.
Sugar-based binder: The one obtained in Production Example 1.
High heat-resistant binder: A mixture of the above-mentioned sugar-based binder and sodium dihydrogen phosphate in a solid content mass ratio of sugar-based binder: sodium dihydrogen phosphate = 90:10.

Each binder was diluted with ion-exchanged water so that the total solid content after dilution was 2% to obtain a diluted solution. The rock wool (1) is cut into a width of 100 × a length of 100 × a thickness of 20 mm, and the thickness is up to 10 mm so that the binder adheres at a ratio of 2% in terms of solid content to the total mass of the rock wool (1). The diluted solution was uniformly impregnated while being compressed. This was sandwiched between punching metals and dried at 110 ° C. for 1 hour. During this time, it was turned inside out every 30 minutes. Then, heat pressing was performed at 200 ° C. for 30 minutes at a thickness of 10 mm to prepare a molded product. The area A was calculated from the dimensions in the width direction and the length direction of the obtained molded product.
The molded product was then fired in an electric furnace preheated to 1050 ° C. for 1 hour. The area B was calculated from the dimensions in the width direction and the length direction of the molded product after firing.
The area A before firing and the area B after firing of the molded product were applied to the following formula to calculate the shrinkage rate. The results are shown in Table 11 and FIG.
Shrinkage rate (%) = {(AB) / A} x 100

(Making a molded product 2)
The following two types of binders were prepared.
Sugar-based binder: The one obtained in Production Example 1.
High heat-resistant binder: A mixture of the above-mentioned sugar-based binder and sodium dihydrogen phosphate in a solid content mass ratio of sugar-based binder: sodium dihydrogen phosphate = 90:10.

Each binder was diluted with ion-exchanged water so that the total solid content after dilution was 0.5% to obtain a diluted solution. The rock wool (2) is cut into a width of 120 × a length of 120 × a thickness of 120 mm, and the thickness is up to 20 mm so that the binder adheres at a ratio of 4% in terms of solid content to the total mass of the rock wool (2). The diluted solution was uniformly impregnated while being compressed. This was sandwiched between punching metals and dried at 110 ° C. for 1 hour. During this time, it was turned inside out every 30 minutes. Then, heat pressing was performed at 200 ° C. for 30 minutes at a thickness of 20 mm to prepare a molded product. The area A was calculated from the dimensions in the width direction and the length direction of the obtained molded product.
The molded product was then fired in an electric furnace preheated to 1050 ° C. for 1 hour. The area B was calculated from the dimensions in the width direction and the length direction of the molded product after firing.
The area A before firing and the area B after firing of the molded product were applied to the above formula to calculate the shrinkage rate. The results are shown in Table 12 and FIG.

As shown in the above results, the molded products of Examples 6-1 to 6-2 using a binder in which an inorganic binder is mixed with an organic binder are a molded product that does not use a binder or an organic binder (PF resin, sugar). Compared with the molded product using the system binder alone), the shrinkage rate at the time of firing at 1050 ° C. was low, and the heat resistance was excellent.

<Test Example 7>
(Preparation of binder composition)
A sugar-based binder (organic binder), sodium dihydrogen phosphate (inorganic binder), and urea (compound (A)) were each diluted with pure water to obtain a diluted solution having a solid content of 36%.
Diluted solutions of each raw material shown in Table 13 were mixed at the solid content mass ratio shown in Table 13 to obtain a binder composition of Examples 7-1 to 7-4.
Separately, the binder composition of Comparative Example 1 was prepared in the same manner as in Test Example 1.

(evaluation)
Each binder composition was evaluated in the same manner as in Test Example 4.
The measurement results of the normal strength and the moisture resistance of each example are shown in Tables 13 and 11. In addition, FIG. 11 also shows the appearance (photograph) of the test piece after re-baking at 800 ° C.

As shown in the above results, in Examples 7-1 to 7-4 in which the inorganic binder was mixed with the organic binder, the shape of the test piece was maintained after re-baking at 800 ° C.
Further, in Examples 7-2 to 7-4 containing urea, the moisture resistance strength at 200 ° C. firing was improved as compared with Example 7-1 not containing urea.

<Test Example 8>
(Preparation of binder composition)
A sugar-based binder (organic binder), sodium dihydrogen phosphate (inorganic binder), urea, ethylene urea, thiourea, and 1,3-dimethylurea (above, compound (A)) are each diluted with pure water. A diluted solution having a solid content of 36% was obtained.
Diluted solutions of each raw material shown in Table 14 were mixed at the solid content mass ratio shown in Table 14 to obtain a binder composition of Examples 8-1 to 8-5.
Separately, the binder composition of Comparative Example 1 was prepared in the same manner as in Test Example 1.

(evaluation)
Each binder composition was evaluated in the same manner as in Test Example 4.
The measurement results of the normal strength and the moisture resistance strength of each example are shown in Table 14 and FIG. In addition, FIG. 12 also shows the appearance (photograph) of the test piece after re-baking at 800 ° C.

As shown in the above results, in Examples 8-1 to 8-5 in which the inorganic binder was mixed with the organic binder, the shape of the test piece was maintained after re-baking at 800 ° C.
Further, in Examples 8-2 to 8-5 in which the compound (A) was blended, the moisture resistance strength at 200 ° C. firing was improved as compared with Example 8-1 in which the compound (A) was not blended.
Among Examples 8-2 to 8-5, Example 8-4 in which thiourea was used as the compound (A) had the best moisture resistance.

<Test Example 9>
(Preparation of binder composition)
A sugar-based binder (organic binder), sodium dihydrogen phosphate (inorganic binder), and urea (compound (A)) were each diluted with pure water to obtain a diluted solution having a solid content of 36%.
The diluted solution of each raw material shown in Table 15 and the following aminosilane (silane coupling agent) were mixed at the solid content mass ratio shown in Table 15 to obtain the binder composition of Examples 9-1 to 9-5.
Aminosilane: KBE-903, 3-aminopropyltriethoxysilane manufactured by Shin-Etsu Chemical.
Separately, the binder composition of Comparative Example 1 was prepared in the same manner as in Test Example 1.

(evaluation)
Each binder composition was evaluated in the same manner as in Test Example 4.
The measurement results of the normal strength and the moisture resistance of each example are shown in Tables 15 and 13. In addition, FIG. 13 also shows the appearance (photograph) of the test piece after re-baking at 800 ° C.

As shown in the above results, in Examples 9-1 to 9-5 in which the inorganic binder was mixed with the organic binder, the shape of the test piece was maintained after re-baking at 800 ° C.
Further, in Examples 9-2 to 9-5 in which the compound (A) was blended, the moisture resistance strength and the normal strength at 200 ° C. firing were improved as compared with Example 9-1 in which the compound (A) was not blended. .. Further, in Examples 9-3 to 9-5 in which the silane coupling agent was blended, the moisture resistance strength and the normal strength were improved as compared with Example 9-2. In particular, in Examples 9-5, the same moisture resistance as in Comparative Example 1 in which the inorganic binder was not blended was obtained.

<Test Example 10>
(Preparation of binder composition)
A sugar-based binder (organic binder), sodium dihydrogen phosphate (inorganic binder), urea, and ethylene urea (above, compound (A)) were each diluted with pure water to obtain a diluted solution having a solid content of 36%. ..
The binder composition of Examples 10-1 to 10-4 is prepared by mixing the diluents of each raw material shown in Table 16, the following aminosilane and epoxysilane (hereinafter, silane coupling agents) at the solid content mass ratio shown in Table 16. Got
Aminosilane: KBE-903, 3-aminopropyltriethoxysilane manufactured by Shin-Etsu Chemical.
Epoxysilane: KBM-403, 3-glycidoxypropyltrimethoxysilane manufactured by Shin-Etsu Chemical.
Separately, the binder composition of Comparative Example 1 was prepared in the same manner as in Test Example 1.

(evaluation)
Each binder composition was evaluated in the same manner as in Test Example 4.
Table 16 shows the measurement results of the normal strength and the moisture resistance of each example. Further, FIG. 14 shows the appearance (photograph) of the test piece after re-baking at 800 ° C.

As shown in the above results, in Examples 10-1 to 10-4 in which the inorganic binder was mixed with the organic binder, the shape of the test piece was maintained after re-baking at 800 ° C.
Further, in Examples 10-2 to 10-4 in which the compound (A) and the silane coupling agent were blended, firing at 200 ° C. was performed as compared with Example 10-1 in which the compound (A) and the silane coupling agent were not blended. Moisture resistance and normal strength have been improved.
Comparing Examples 10-2 and 10-3, Example 9-2 using aminosilane was superior in moisture resistance and normal strength to Example 10-3 using epoxysilane.
Comparing Examples 10-2 and 10-4, Example 10-4 using ethylene urea was superior in moisture resistance and normal strength to Example 10-2 using urea.

Claims (23)

A binder composition for inorganic fiber products, which comprises an organic binder and an inorganic binder. The binder composition for an inorganic fiber product according to claim 1, wherein the organic binder is a thermosetting organic binder. The binder composition for an inorganic fiber product according to claim 1 or 2, wherein the organic binder contains at least one selected from the group consisting of sugars, phenol resins, polyvinyl alcohol resins and polycarboxylic acid resins. The inorganic binder is a hydroxide, oxide, chloride, or a metal selected from the group consisting of lithium, sodium, potassium, magnesium, calcium, barium, titanium, chromium, manganese, iron, copper, silver, zinc and aluminum. The inorganic fiber according to any one of claims 1 to 3, which contains at least one selected from the group consisting of silicates, carbonates, sulfates, nitrates, aluminates, borates and phosphates. Binder composition for products. The binder composition for an inorganic fiber product according to any one of claims 1 to 4, wherein the ratio of the inorganic content of the inorganic binder to 100% by mass of the organic content of the organic binder is 1 to 300% by mass. The binder composition for an inorganic fiber product according to any one of claims 1 to 5, further comprising a silane coupling agent. A binder composition for an inorganic fiber product, which comprises an organic binder, an inorganic binder, and a carbamide group or a thiocarbamide group-containing compound. The binder composition for an inorganic fiber product according to claim 7, wherein the organic binder is a thermosetting organic binder. The binder composition for an inorganic fiber product according to claim 7 or 8, wherein the organic binder contains at least one selected from the group consisting of sugars, phenol resins, polyvinyl alcohol resins and polycarboxylic acid resins. The inorganic binder is a hydroxide, oxide, chloride, or a metal selected from the group consisting of lithium, sodium, potassium, magnesium, calcium, barium, titanium, chromium, manganese, iron, copper, silver, zinc and aluminum. The inorganic fiber according to any one of claims 7 to 9, which comprises at least one selected from the group consisting of silicates, carbonates, sulfates, nitrates, aluminates, borates and phosphates. Binder composition for products. The carbamide group or thiocarbamide group-containing compound is urea, ethylene urea, thiourea, (mono, di, tri or tetra) methyl urea, (mono, di, tri or tetra) hydroxymethyl urea, (mono, di, tri). Alternatively, it is selected from the group consisting of (tetra) ethyl urea, (mono, di, tri or tetra) hydroxyethyl urea, (mono, di, tri or tetra) propyl urea, (mono, di, tri or tetra) butyl urea and biuret. The binder composition for an inorganic fiber product according to any one of claims 7 to 10, which comprises at least one kind. The binder composition for an inorganic fiber product according to any one of claims 7 to 11, wherein the ratio of the inorganic content of the inorganic binder to 100% by mass of the organic content of the organic binder is 1 to 300% by mass. The inorganic according to any one of claims 7 to 12, wherein the content of the carbamide group or the thiocarbamide group-containing compound is 0.1 to 100% by mass with respect to 100% by mass of the solid content of the inorganic binder. Binder composition for textile products. The binder composition for an inorganic fiber product according to any one of claims 7 to 13, further comprising a silane coupling agent. The content of the silane coupling agent is 0.1 to 100% by mass based on 100% by mass of the total of the solid content of the organic binder, the solid content of the inorganic binder and the carbamide group or the thiocarbamide group-containing compound. The binder composition for an inorganic fiber product according to claim 14. An inorganic fiber product comprising an inorganic fiber and a binder composition for an inorganic fiber product according to any one of claims 1 to 6, wherein the inorganic fiber is bound to a molded product by the organic binder. The inorganic fiber product according to claim 16, wherein the molded product is a cotton-like body. The inorganic fiber product according to claim 16 or 17, which is a refractory coating material. The inorganic fiber product according to claim 16 or 17, which is a heat insulating material. An inorganic fiber product comprising an inorganic fiber and a binder composition for an inorganic fiber product according to any one of claims 7 to 15, and comprising a molded product in which the inorganic fiber is bonded by the organic binder. The inorganic fiber product according to claim 20, wherein the molded product is a cotton-like body. The inorganic fiber product according to claim 20 or 21, which is a refractory coating material. The inorganic fiber product according to claim 20 or 21, which is a heat insulating material.

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