JP2017165859A - Thermosetting binder composition and inorganic fiber product using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting binder composition capable of obtaining excellent normal strength and water resistant properties even without using formaldehyde as raw material, and an inorganic fiber product using the same.SOLUTION: Provided is a thermosetting binder composition comprising: a first component as glucide or a mixture between glucide and phenol; at least one kind of ammonium salt selected from the group consisting of ammonium sulfate, triammonium citrate, diammonium citrate and ammonium phenol sulfonic acid; a surfactant; a silane coupling agent; and a water repellent.SELECTED DRAWING: None

Description

  The present invention relates to a thermosetting binder composition and an inorganic fiber product using the same.

Conventionally, inorganic fiber products formed by bonding inorganic fibers such as glass wool, rock wool, and ceramic fibers with binders are used for heat insulating materials, sound absorbing materials, and other various molded products (automobile roofs, bonnet liners, etc.) It has been.
In general, inorganic fiber products are produced by attaching a binder to inorganic fibers and accumulating them to obtain an aggregate in the shape of the desired inorganic fiber product, followed by heating and curing the binder. As a binder, a resin mainly composed of a phenol resin obtained by reaction of phenols with formaldehyde (hereinafter sometimes referred to as a phenol resin binder) is relatively inexpensive and has excellent performance such as mechanical strength. It is widely used because it can be obtained.

However, when a phenol resin binder is used, there is a problem that formaldehyde is diffused in the manufacturing process of inorganic fiber products and the like. The cause is that formaldehyde used as a raw material in the production of the phenol resin remains unreacted and is generated during thermosetting. Formaldehyde is a substance that adversely affects the human body. For example, formaldehyde released from building materials is considered to be one of the causative substances of sick house syndrome. Therefore, in 2003, the revised Building Standard Law that regulates the amount of formaldehyde emitted was enforced in Japan.
In the revised Building Standard Law, the amount of formaldehyde emission is 5 μg / m ² · h or less as the formaldehyde emission rate measured according to JIS A1901, or the one that does not use formaldehyde as a raw material is not regulated. . Therefore, the binder is required to have a formaldehyde emission rate of 5 μg / m ² · h or less, or one that does not use formaldehyde as a raw material.

  As a so-called non-formaldehyde type binder that does not use formaldehyde as a raw material, conventionally, a combination of a dehydrating organic polyol such as sugar and a dehydrating agent such as ammonium phosphate (Patent Document 1), a reducing sugar Are combined with a specific inorganic ammonium salt, optionally further combined with a carboxylic acid or ammonia (Patent Document 2), combined with a monosaccharide and / or polysaccharide and an organic carboxylic acid having a molecular weight of 1000 or less ( Patent Document 3), a combination of a saccharide, an ammonium salt, and a phenol (Patent Document 4) has been proposed.

European Patent Application No. 0044614 Special table 2010-535864 Special table 2011-506781 gazette JP 2014-173085 A

However, although the binder composition of patent documents 1-3 does not use formaldehyde as a raw material, there is a problem that the performance as a binder is inferior to a phenol resin binder. For example, after thermosetting, there are problems such as low normal strength and low water resistance (low strength retention, which is a ratio of water resistance to normal strength, high water absorption, etc.).
The binder composition of Patent Document 4 is superior to the binder compositions of Patent Documents 1 to 3 in terms of normal strength after heat curing and good water resistance, but it is still not sufficient.
Therefore, a non-formaldehyde type binder composition that can exhibit excellent binder performance equal to or higher than that of a phenol resin binder is required.

  The present invention has been made in view of the above circumstances, and provides a thermosetting binder composition capable of obtaining excellent normal strength and water resistance without using formaldehyde as a raw material, and an inorganic fiber product using the same The purpose is to do.

  As a result of intensive studies, the present inventors have improved the normal strength by further adding a surfactant to a combination of a saccharide and an ammonium salt, or a combination of a saccharide, a phenol and an ammonium salt. Found to get. In addition, as a result of further studies, it has been found that by selecting a specific ammonium salt and further incorporating a silane coupling agent and a water repellent, water resistance can be improved in addition to normal strength. Completed the invention.

The present invention has the following aspects.
[1] A first component which is a carbohydrate or a mixture of a carbohydrate and a phenol, and at least one ammonium salt selected from the group consisting of ammonium sulfate, triammonium citrate, diammonium citrate and ammonium phenolsulfonate A thermosetting binder composition containing a surfactant, a silane coupling agent, and a water repellent.
[2] The thermosetting binder composition according to [1], which is substantially free of formaldehyde.
[3] The thermosetting binder composition according to [1] or [2], wherein the sugar includes at least one selected from the group consisting of glucose, fructose, and sucrose.
[4] The thermosetting binder composition according to any one of [1] to [3], wherein the surfactant includes an ionic surfactant.
[5] The thermosetting binder composition according to any one of [1] to [4], wherein the surfactant includes one or both of sodium dodecyl sulfate and sodium dodecylbenzenesulfonate.
[6] The first component is a mixture of a saccharide and a phenol,
The thermosetting binder composition according to any one of [1] to [5], wherein the phenol is a polyhydric phenol.
[7] The thermosetting binder composition according to [6], wherein the polyhydric phenol includes at least one selected from the group consisting of resorcinol, tannin, catechol, hydroquinone, pyrogallol, phloroglucinol, and lignin.
[8] The thermosetting binder according to any one of [1] to [7], wherein a ratio of the surfactant to a total of the first component and the ammonium salt is 0.01 to 1.0% by mass. Composition.
[9] The first component is a mixture of sugar and phenols,
The thermosetting binder composition according to any one of [1] to [8], wherein a ratio of the phenols to the saccharide is 0.1 to 30% by mass.
[10] The heat according to any one of [1] to [9], wherein the silane coupling agent is at least one selected from the group consisting of an amino group-containing silane coupling agent and an epoxy group-containing silane coupling agent. A curable binder composition.
[11] The thermosetting binder composition according to any one of [1] to [10], wherein the water repellent is a silicone water repellent.
[12] The thermosetting binder composition according to any one of [1] to [11], further containing at least one selected from the group consisting of a dust prevention oil, a curing regulator, a curing accelerator, and water.
[13] A curing regulator is contained, and the curing regulator is composed of ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol having an average molecular weight of 160 to 500, propylene glycol, 1,4-butylene glycol, glycerin and diglycerin. The thermosetting binder composition according to [12], which is at least one selected from the group.
[14] An inorganic fiber product including a molded body in which inorganic fibers are bonded with a binder, wherein the binder is a cured product of the thermosetting binder composition according to any one of [1] to [13]. An inorganic fiber product.
[15] The inorganic fiber product according to [14], wherein the inorganic fiber is glass wool or rock wool.

  According to the present invention, it is possible to provide a thermosetting binder composition capable of obtaining excellent normal strength and water resistance without using formaldehyde as a raw material, and an inorganic fiber product using the same.

In the present invention, normal strength refers to mechanical strength (tensile strength, bending strength, etc.) in a dry state, and water resistant strength refers to mechanical strength in a wet state.
The water resistance property indicates high strength retention and low water absorption.
The strength retention indicates a ratio of water resistance strength to normal strength (water resistance strength / normal strength × 100 (%)). In the calculation of the strength retention, the normal strength and the water resistance strength are values measured by the same measurement method, except that the measurement is performed in a dry state or a wet state.

<Thermosetting binder composition>
The thermosetting binder composition of the present invention (hereinafter also simply referred to as a binder composition) contains a first component, an ammonium salt, a surfactant, a silane coupling agent, and a water repellent.
The first component is a saccharide or a mixture of a saccharide and a phenol.
If necessary, the binder composition of the present invention contains other components other than carbohydrates, phenols, ammonium salts, surfactants, silane coupling agents, and water repellents as long as the effects of the present invention are not impaired. Furthermore, you may contain.

[Sugar]
Examples of the saccharide include monosaccharides, oligosaccharides, polysaccharides, and derivatives thereof.
In the present invention, “oligosaccharides” are those in which 2 to 10 monosaccharides are bound, and “polysaccharides” are those in which 11 or more monosaccharides are bound.

Examples of monosaccharides include glucose, fructose, mannose, galactose, ribose, xylose and the like.
Examples of the oligosaccharide include disaccharides such as sucrose, maltose, lactose, trehalose, and isomaltose; trisaccharides such as maltotriose and raffinose; maltooligosaccharides; isomaltoligosaccharides; fructooligosaccharides; mannooligosaccharides; Etc.
Examples of the polysaccharide include starch, pullulan, dextrin, polydextrose and the like.
Examples of monosaccharide, oligosaccharide or polysaccharide derivatives include glycosides and modified starches.

Examples of the modified starch include those obtained by subjecting starch to any one or more of esterification, etherification, oxidation and crosslinking, or a mixture thereof. Examples of the modified starch subjected to the esterification treatment 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 starches such as hydroxyethyl starch and hydroxypropyl starch. Examples of the modified starch subjected to the oxidation treatment include oxidized starch. Examples of the modified starch that has been subjected to crosslinking treatment include crosslinked starch such as phosphate-crosslinked starch. In addition, as modified starch (combined modified starch) subjected to any two or more of esterification, etherification, oxidation, and crosslinking, adipic acid crosslinked starch, acetic phosphate crosslinked starch, acetate oxidized starch, Hydroxypropyl phosphate crosslinked starch, phosphate monoesterified phosphate crosslinked starch and the like.
These carbohydrates may be used alone or in combination of two or more. Of these, monosaccharides are preferred.

  In the present invention, it is preferable that the saccharide contains at least one selected from the group consisting of glucose, fructose and sucrose (hereinafter also referred to as a specific saccharide) from the viewpoint of excellent effects of the invention. Any one of these specific carbohydrates may be used alone, or two or more thereof may be used in combination.

  The proportion of the specific carbohydrate in the saccharide (100% by mass) is preferably 20% by mass or more, more preferably 50% by mass or more, more preferably 55% by mass or more, more preferably 60% by mass or more, and 65% by mass. Or more, more preferably 70% by mass or more, more preferably 75% by mass or more, more preferably 80% by mass or more, more preferably 85% by mass or more, more preferably 90% by mass or more, and more than 95% by mass. More preferred is 100% by mass. That is, it is most preferable that the saccharide is composed only of a specific saccharide.

When using 2 or more types as saccharide together, each saccharide may be mix | blended in the case of preparation of a binder composition, respectively, and the raw material containing 2 or more types of saccharides may be used. Examples of the raw material containing two or more kinds of carbohydrates include isomerized sugar (containing glucose, fructose, etc.), starch syrup (containing glucose, maltose, etc.), and the like.
In the present specification, a raw material that contains water and saccharide and is in a liquid state is referred to as a liquid saccharide raw material.

[Phenols]
Examples of phenols include plant material-derived phenols and fossil fuel-based phenols.
Examples of plant-derived phenols include flavonoid tannin, catechin, anthocyanin, rutin, isoflavone, phenolic chlorogenic acid, ellagic acid, lignan, curcumin, coumarin, lignin and other polyphenols, cardanol, cashew nut shell liquid, etc. Is mentioned.
Examples of fossil fuel-based phenols include phenol, cresol, xylenol, trimethylphenol, ethylphenol, propylphenol, butylphenol, butylcresol, phenylphenol, cumylphenol, methoxyphenol, bromophenol, bisphenol A, bisphenol F, and bisphenol S. Catechol, resorcinol, hydroquinone, pyrogallol, phloroglucinol and the like.
These phenols may be used alone or in combination of two or more.

Phenols are preferably water-soluble.
Water-soluble phenols refer to phenols having a solubility in water at 20 ° C. of 2 g / 100 mL or more.
Examples of water-soluble phenols include tannin, phenol, cresol, catechol, resorcinol, hydroquinone, pyrogallol, and phloroglucinol.

Among the above, the phenols are preferably polyhydric phenols (phenols having two or more hydroxyl groups) and more preferably water-soluble polyhydric phenols because of the excellent effects of the present invention.
As polyhydric phenols, at least one selected from the group consisting of resorcinol, tannin, catechol, hydroquinone, pyrogallol, phloroglucinol and lignin is preferable, and either or both of resorcinol and tannin are particularly preferable.

[Ammonium salt]
The ammonium salt functions as a supply source of ammonia that reacts with the saccharide in the curing reaction of the binder composition, and a supply source of an acidic substance that functions as a catalyst in the subsequent reaction.
In the present invention, as the ammonium salt, at least one selected from the group consisting of ammonium sulfate, triammonium citrate, diammonium citrate, and ammonium phenolsulfonate is used. These ammonium salts, when combined with silane coupling agents and water repellents, compared to other ammonium salts (eg, ammonium phosphate, ammonium borate, ammonium paratoluenesulfonate, ammonium xylenesulfonate, etc.) Excellent water resistance (strength retention, low water absorption, etc.).
These ammonium salts may be used alone or in combination of two or more.

As the ammonium salt, ammonium sulfate, triammonium citrate, and diammonium citrate are preferable from the viewpoint of water resistance.
When increasing the amount of the ammonium salt in the binder composition in order to increase the curing rate (for example, 15% by mass or more based on the first component), triammonium citrate and diammonium citrate are more preferable. In the case of ammonium sulfate, if the blending amount is increased, the water resistance may be lowered.
Diammonium citrate is particularly preferable in terms of more excellent water absorption characteristics. This is thought to be due to the fact that the triammonium citrate solution is neutral, whereas the diammonium citrate solution is acidic.

[Surfactant]
Examples of the surfactant include an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant.
Examples of the anionic surfactant include linear sodium alkylbenzene sulfonate, sodium alkyl sulfate ester, sodium alkyl ether sulfate, sodium alpha olefin sulfonate, sodium alkyl sulfonate, fatty acid sodium, and fatty acid potassium.
Examples of the cationic surfactant include alkyltrimethylammonium salts and dialkyldimethylammonium salts.
Examples of amphoteric surfactants include sodium alkylamino fatty acids, alkyl betaines, and alkyl amine oxides.
Nonionic surfactants include sucrose fatty acid ester sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid alkanolamide, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, alkyl polyglucoside and the like.
These surfactants may be used alone or in combination of two or more.

As the surfactant, an ionic surfactant such as an anionic surfactant, a cationic surfactant, and an amphoteric surfactant is preferable, and an anionic surfactant is more preferable from the viewpoint of excellent effects of the present invention. Among the anionic surfactants, sodium alkylsulfate ester and sodium linear alkylbenzene sulfonate are preferable.
As the alkyl sulfate sodium, those having 8 to 24 carbon atoms in the alkyl group are preferable, those having 10 to 18 carbon atoms are more preferable, and sodium dodecyl sulfate is particularly preferable.
As the linear alkylbenzene sulfonate, those having 8 to 24 carbon atoms in the linear alkyl group are preferable, those having 10 to 18 carbon atoms are more preferable, and sodium dodecylbenzenesulfonate is particularly preferable.

[Silane coupling agent]
It does not specifically limit as a silane coupling agent, A well-known silane coupling agent can be used. For example, amino group-containing silane coupling agent, epoxy group-containing silane coupling agent, vinyl group-containing silane coupling agent, methacryloyl group-containing silane coupling agent, acryloyl group-containing silane coupling agent, ureido group-containing silane coupling agent, isocyanate Examples thereof include a group-containing silane coupling agent.

  The amino group-containing silane coupling agent hydrolyzes to produce a silanol group, and has an alkoxy group that strengthens the bond with the inorganic component and an amino group that strengthens the bond with the organic component in the same molecule. A general term for silicon carbide compounds such as N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2- Examples include hydrochloride of aminoethyl-3-aminopropyltrimethoxysilane.

  The epoxy group-containing silane coupling agent hydrolyzes to produce a silanol group, and has an alkoxy group that strengthens the bond with the inorganic component and an epoxy group that strengthens the bond with the organic component in the same molecule. A general term for silicon carbide compounds such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl Examples thereof include methyldiethoxysilane and 3-glycidoxypropyltriethoxysilane.

The vinyl group-containing silane coupling agent hydrolyzes to produce a silanol group, and has an alkoxy group that strengthens the bond with the inorganic component and a vinyl group that strengthens the bond with the organic component in the same molecule. A general term for silicon carbide compounds, such as vinyltriethoxysilane.
A methacryloyl group-containing silane coupling agent hydrolyzes to produce a silanol group, and has an alkoxy group that strengthens the bond with the inorganic component and a methacryloyl group that strengthens the bond with the organic component in the same molecule. A generic term for silicon carbide compounds, such as 3-methacryloxypropyltrimethoxysilane.
The acryloyl group-containing silane coupling agent hydrolyzes to produce a silanol group, and has an alkoxy group that strengthens the bond with the inorganic component and an acryloyl group that strengthens the bond with the organic component in the same molecule. A generic term for silicon carbide compounds, such as 3-acryloxypropyltrimethoxysilane.

The ureido group-containing silane coupling agent hydrolyzes to produce a silanol group, and has an alkoxy group that strengthens the bond with the inorganic component and a ureido group that strengthens the bond with the organic component in the same molecule. A generic term for silicon carbide compounds, such as 3-ureidopropyltriethoxysilane.
The isocyanate group-containing silane coupling agent hydrolyzes to produce a silanol group, and has an alkoxy group that strengthens the bond with the inorganic component and an isocyanate group that strengthens the bond with the organic component in the same molecule. A general term for silicon carbide compounds, such as 3-isocyanatopropyltriethoxysilane.

These silane coupling agents may be used alone or in combination of two or more.
Among the above, the silane coupling agent is composed of an amino group-containing silane coupling agent and an epoxy group-containing silane coupling agent in terms of more excellent properties such as normal strength, water resistance strength, strength retention, etc. of the inorganic fiber product. At least one selected from the group is preferred, and an amino group-containing silane coupling agent is more preferred.
As the amino group-containing silane coupling agent, among the above, one or both of 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane are preferable, and 3-aminopropyltriethoxysilane is particularly preferable.
Among the above, the epoxy group-containing silane coupling agent is preferably 3-glycidoxypropyltriethoxysilane.

[Water repellent]
Examples of water repellents include silicone water repellents, fluorine water repellents, and hydrocarbon water repellents. These water repellents may be used alone or in combination of two or more.
Among these, as the water repellent, an aqueous emulsion type silicone water repellent is preferable from the viewpoint of reducing the water absorption rate of the inorganic fiber product.
A water-based emulsion type silicone water repellent contains a surfactant as an emulsifier, and includes a type containing a nonionic surfactant as a surfactant (nonionic emulsion) and a type containing an anionic surfactant (anionic type). Emulsion). From the viewpoint of compatibility with the binder composition, an aqueous emulsion type silicone water repellent containing an anionic surfactant is preferred.

[Other ingredients]
As other components, it can be used by appropriately selecting from various known components as components that can be blended in the thermosetting binder composition used in the production of inorganic fiber products and the like. For example, dust prevention oil, a curing regulator, a curing accelerator, urea, melamine, furfural, furfuryl alcohol, ammonia, water and the like can be mentioned. These may be used alone or in combination of two or more. Typically, at least one selected from the group consisting of dust-preventing oils, curing modifiers, curing accelerators and water is added in an appropriate amount as necessary.

The binder composition of the present invention preferably contains a curing regulator as another component. Thereby, characteristics, such as normal strength, of the inorganic fiber product obtained tend to be more excellent.
As the curing regulator, a water-soluble high-boiling solvent is preferable. For example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, 1,4-butylene glycol, glycerin, diglycerin (also referred to as diglycerol), Polyglycerin etc. are mentioned. These curing regulators may be used alone or in combination of two or more.
Among the above, as the curing modifier, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol having an average molecular weight of 160 to 500, propylene glycol, 1,4- At least one selected from the group consisting of butylene glycol, glycerin and diglycerin is preferred, and glycerin is particularly preferred.
In addition, it is thought that a hardening regulator improves characteristics, such as intensity | strength, by improving the fluidity | liquidity of a binder composition and improving the adhesion efficiency between inorganic fibers. A combination of a silane coupling agent and a curing modifier is unlikely to inhibit each action.

Examples of the dust prevention oil include mineral oil-based oil emulsions.
As the curing accelerator, a phosphoric acid compound is preferable. Examples of the phosphoric acid compound include alkali metal hypophosphites, alkali metal phosphites, alkali metal polyphosphates, alkali metal hydrogen phosphates, and alkyl phosphates. The alkali metal salt is preferably a sodium salt or potassium salt, and examples thereof include sodium hypophosphite and sodium phosphite.

The binder composition of the present invention is preferably in a liquid state when sprayed onto inorganic fibers. In order to make the binder composition liquid, a liquid saccharide raw material may be used, or water may be added to the binder composition in advance.
When water is contained, the solid content concentration of the binder composition of the present invention is preferably 50.0 to 80.0 mass%, more preferably 60.0 to 70.0 mass%.
The solid content in the present invention is the total of components other than moisture. For example, when powdered saccharides are used as a saccharide source, all of them are handled as solids, and when a raw material containing active ingredients and moisture, such as a liquid saccharide raw material, is used, Handle (sugar) and water separately.
The solid content concentration is a value calculated by {(total mass-water mass) / total mass} × 100 (% by mass).

The binder composition of the present invention can exhibit good binder performance without using formaldehyde. Therefore, it is preferable that the binder composition of this invention does not contain formaldehyde substantially. If the binder composition does not contain formaldehyde, odor generation during the production of inorganic fiber products can be further reduced.
Here, “substantially free of formaldehyde” means that formaldehyde or a raw material containing formaldehyde (for example, a phenol resin obtained by reaction of phenols with formaldehyde) is not blended in the preparation of the binder composition. Show.

[composition]
In the binder composition of the present invention, the content of the first component is preferably 70.0 to 97.5% by mass when the total solid content of the binder composition is 100% by mass. The lower limit of the content is more preferably 75.0% by mass or more, further preferably 77.5% by mass or more, and particularly preferably 80.0% by mass or more. The upper limit of the content is more preferably 95.0% by mass or less, and particularly preferably 92.5% by mass or less. The content of the first component is the solid content.
The first component is a component that forms the skeleton of the cured product. When the content of the first component is not less than the lower limit of the above range, the binder performance is efficiently exhibited, and the properties such as normal strength of the resulting inorganic fiber product are good. On the other hand, if the content of the first component is less than or equal to the upper limit of the above range, when molding the inorganic fiber product, curing is completed within predetermined molding conditions (temperature, time), and the required performance is obtained. Easy to express.

When the first component is a mixture of a saccharide and a phenol, the ratio of the phenol to the saccharide (100% by mass) is preferably 0.1 to 30% by mass. The lower limit of the ratio is more preferably 0.5% by mass or more, and particularly preferably 1% by mass or more. The upper limit of the ratio is more preferably 20% by mass or less, and particularly preferably 10% by mass or less. The saccharide content and the phenol content are solid contents.
When the proportion of phenols is at least the lower limit of the above range, the binder performance is more excellent, and the inorganic fiber product obtained has more excellent properties such as normal strength and water resistance. On the other hand, if the proportion of phenols is not more than the upper limit of the above range, the properties such as normal strength and water resistance strength of the inorganic fiber product can be maintained better, and the binder composition and inorganic fiber can be more economically cost-effective. Can produce products.

The proportion of the ammonium salt relative to the first component (100% by mass) is preferably 1 to 30% by mass. The content of ammonium salt is the solid content.
Although the curing reaction of the binder composition will be described in detail later, the ammonium salt is a source of ammonia that reacts with carbohydrates in the curing reaction of the binder composition, and an acidic substance that functions as a catalyst in the subsequent reaction. Functions as a source.
When the proportion of the ammonium salt is equal to or more than the lower limit of the above range, when the inorganic fiber product is molded, the curing is completed within predetermined molding conditions (temperature, time), and the required performance is easily exhibited. On the other hand, if the proportion of the ammonium salt is not more than the upper limit of the above range, the binder performance is efficiently exhibited, and the resulting inorganic fiber product has good properties such as normal strength and water resistance.
The lower limit of the proportion of the ammonium salt relative to the first component is more preferably 2% by mass or more, and particularly preferably 5% by mass or more.
When the ammonium salt is ammonium sulfate, the upper limit of the ratio of the ammonium salt to the first component is more preferably 16% by mass or less, and particularly preferably 12% by mass or less. When the ammonium salt is one or both of triammonium citrate and diammonium citrate, it is more preferably 20% by mass or less, and particularly preferably 16% by mass or less. When the ammonium salt is ammonium phenolsulfonate, it is more preferably 16% by mass or less, and particularly preferably 12% by mass or less.

The ratio of the surfactant to the total (100% by mass) of the first component and the ammonium salt is preferably 0.01 to 1.0% by mass. The lower limit of the ratio is more preferably 0.05% by mass or more, more preferably 0.06% by mass or more, more preferably 0.075% by mass or more, more preferably 0.10% by mass or more, and 0.12% by mass. The above is more preferable, and 0.15% by mass or more is particularly preferable. The upper limit of the ratio is more preferably 0.60% by mass or less, more preferably 0.50% by mass or less, more preferably 0.45% by mass or less, still more preferably 0.35% by mass or less, and 0.30% by mass. % Or less is particularly preferable. The surfactant content is the solid content.
The surfactant has the effect of improving the wettability of the binder composition to the inorganic fibers, improving the adhesion between the inorganic fibers, and improving the physical properties such as the normal strength of the inorganic fiber product.
When the ratio of the surfactant is equal to or higher than the lower limit of the above range, the effect of the surfactant is sufficiently exhibited when the inorganic fiber product is molded, and the required performance is easily exhibited. On the other hand, if the ratio of the surfactant is not more than the upper limit of the above range, the binder performance is efficiently exhibited and the properties such as normal strength of the resulting inorganic fiber product are good.

The content of the silane coupling agent is preferably 0.01 to 5.00% by mass and more preferably 0.02 to 1.00% by mass with respect to the total (100% by mass) of the first component and the ammonium salt. 0.05 to 0.50 mass% is more preferable, and 0.10 to 0.20 mass% is particularly preferable. The content of the silane coupling agent is a solid content.
The silane coupling agent contributes to improvement of the normal strength, water resistance strength, strength retention, etc. of the inorganic fiber product. This is presumably because the silane coupling agent increases the adhesive strength between the inorganic fiber and the binder composition.
If content of a silane coupling agent is more than the lower limit of the said range, characteristics, such as normal strength of the obtained inorganic fiber product, water-proof strength, and strength retention, will be more excellent. If content of a silane coupling agent is below the upper limit of the said range, a binder composition and an inorganic fiber product can be manufactured at more economical cost.

The content of the water repellent is preferably 0.05 to 5.0% by mass with respect to the total (100% by mass) of the first component and the ammonium salt. The content of the water repellent is the amount of active ingredients. An active ingredient shows a non volatile matter.
The water repellent contributes to a reduction in water absorption of the inorganic fiber product.
When the content of the water repellent is not less than the lower limit of the above range, the water absorption of the resulting inorganic fiber product can be sufficiently reduced. If content of a water repellent is below the upper limit of the said range, a binder composition and an inorganic fiber product can be manufactured at more economical cost.
The upper limit of the content of the water repellent is more preferably 4.5% by mass or less, further preferably 4.0% by mass or less, and particularly preferably 3.0% by mass or less.
When the ammonium salt is ammonium sulfate, the lower limit of the content of the water repellent is preferably 0.1% by mass or more, more preferably 0.4% by mass or more based on the total of the first component and the ammonium salt. 0.8 mass% or more is more preferable, and 1.0 mass% or more is particularly preferable. When the ammonium salt is any one or both of triammonium citrate and diammonium citrate, it is preferably 0.1% by mass or more, more preferably 0.15% by mass or more, and 0.2% by mass or more. Particularly preferred. When the ammonium salt is ammonium phenol sulfonate, 1.0% by mass or more is more preferable, and 1.5% by mass or more is particularly preferable.

  When the binder composition of the present invention contains a curing modifier, the content of the curing modifier is 0.50 to 8.00 mass% with respect to the total (100 mass%) of the first component and the ammonium salt. Preferably, 1.50 to 6.50 mass% is more preferable, and 2.50 to 5.00 mass% is particularly preferable. The content of the curing modifier is a solid content. If content of a hardening regulator is in the said range, characteristics, such as normal strength of the inorganic fiber product obtained, will be more excellent.

When the binder composition of the present invention contains a dust prevention oil, the content of the dust prevention oil is 0.05 to 10.0 mass with respect to the total (100 mass%) of the first component and the ammonium salt. % Is preferred.
When the binder composition of the present invention contains a curing accelerator, the content of the curing accelerator is 0.50 to 20.0% by mass with respect to the total (100% by mass) of the first component and the ammonium salt. preferable.

[Method for producing binder composition]
The binder composition of the present invention comprises a first component (sugar, or sugar and phenols), an ammonium salt, a surfactant, a silane coupling agent, a water repellent, and other components as necessary. It can be prepared by mixing the ingredients.

The binder composition of the present invention has curability that is cured by heating.
As the thermosetting mechanism of the binder composition of the present invention, a mechanism similar to caramelization can be considered. When the binder composition of the present invention is heated, a saccharide having a 5- or 6-membered ring structure first reacts with ammonia derived from an ammonium salt to become glucosylamine, and then 1-amino-1- with ring opening. Forms deoxy-2-ketose. This is generally called the Amadori transition. Subsequently, the ring is closed with dehydration under the influence of an acidic substance derived from an ammonium salt and heating to produce hydroxymethylfurfural (hereinafter referred to as HMF). HMF is a thermally unstable compound, and the produced HMF reacts with other HMF and pre-mixed phenols with further dehydration under continuous heating. Curing proceeds with the progress of this reaction and is eventually completed. The resulting cured product is presumed to have a caramel-like structure or a structure in which a phenolic skeleton is introduced into a part thereof.

It is thought that only water is produced as a by-product in the above reaction. Therefore, when the binder composition of the present invention is used in the production process of an inorganic fiber product or the like, the gas generated when the binder composition is cured is generally considered to be only water vapor. If the first component (saccharides, phenols), ammonium salt, surfactant, silane coupling agent, water repellent and other components constituting the binder of the present invention are appropriately selected and blended, inorganic fiber products The manufacturing cost can be reduced.
The binder composition of the present invention is useful for the production of inorganic fiber products. However, the use of the binder composition of the present invention is not limited to this, and can be used for various uses in which a thermosetting binder such as a phenol resin binder has been used. For example, for casting, for friction material, for grindstone, for filter paper, for molding material, for plywood processing, for decorative plate, for laminated plate and the like.

<Inorganic fiber products>
The inorganic fiber product of the present invention includes a molded body in which inorganic fibers are bonded with a binder.
The binder is a cured product of the binder composition of the present invention.
The inorganic fiber is not particularly limited, and examples thereof include glass wool, rock wool, and ceramic fiber. These may be used alone or in combination of two or more. As the inorganic fiber, glass wool or rock wool is preferable in terms of versatility and heat insulating performance.
The inorganic fiber product of the present invention may be composed of the molded body, or may further include other members other than the molded body. Examples of the other member include a skin material for packaging.
The inorganic fiber product of the present invention can be used as, for example, a heat insulating material, a sound absorbing material, and other various molded products (automobile roof, bonnet liner, etc.).

[Production method of inorganic fiber products]
The inorganic fiber product of this invention can be manufactured with the manufacturing method which has a process of shape | molding an inorganic fiber product using the binder composition of this invention, and obtaining a molded object.
For the production of inorganic fiber products, known methods conventionally used for the production of inorganic fiber products can be used except that the binder composition of the present invention is used as a binder.
As an example of the method for producing an inorganic fiber product of the present invention, a process of attaching the binder composition of the present invention to an inorganic fiber (hereinafter referred to as an adhesion process), the inorganic fibers to which the binder composition is adhered are collected and manufactured. An example is a method in which, after forming an aggregate having a shape corresponding to an inorganic fiber product, the aggregate is heated and the binder composition is cured to obtain a molded body (hereinafter, a molding process). Hereinafter, each process will be described in more detail.

(Adhesion process)
Examples of the inorganic fiber used in the attaching step include the same ones as described above.
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.
A commercially available thing may be used for an inorganic fiber, and what was manufactured by the well-known method may be used as it is. Inorganic fibers are generally produced by fiberizing raw materials (waste glass, basalt, iron furnace slag, etc.), and examples of the fiberizing method include a flame method and a centrifugal method. The fiberization by these various methods can be performed using a corresponding fiberizing apparatus.

Examples of the method of attaching the binder composition to the inorganic fiber include a method of spraying the binder composition on the inorganic fiber using a spray device, a method of impregnating the binder composition with the inorganic fiber, and the like. A method may be used.
The amount of the binder 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 nonvolatile content of the binder composition with respect to the inorganic fiber (100% by mass). The amount of the binder composition affects the physical properties (mechanical strength, etc.) of the obtained molded body. For example, as the amount of the binder composition to be adhered increases, the mechanical strength of the obtained molded body tends to increase. .
In the present invention, the “nonvolatile content” refers to a value measured according to 5.6 of JIS K6910.

(Molding process)
Next, the inorganic fibers to which the binder composition is adhered are accumulated to form an aggregate having a shape corresponding to the inorganic fiber product to be manufactured, and then the aggregate is heated to cure the binder composition.
The molding step can be performed by a known method. For example, in the case of producing a plate-like product as an inorganic fiber product, for example, inorganic fibers are deposited on a conveyor, and this deposit is pressed from the up and down direction of the conveyor to be compressed into an aggregate. Is sent to a heating furnace (curing furnace) and heated to cure the binder composition, whereby a plate-like molded body is obtained.
The amount of inorganic fibers used (the amount of inorganic fibers deposited on the conveyor) and the 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 the binder composition in the aggregate is cured, but the heating temperature is preferably in the range of 180 to 270 ° C. If it is lower than 180 ° C., curing may be insufficient and mechanical strength may be insufficient. If it exceeds 270 ° C., the binder composition may be decomposed, and the yield and mechanical strength may be reduced. 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 body 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 as necessary.

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the examples.
In the following examples, “part” and “%” represent “part by mass” and “% by mass”, respectively, unless otherwise specified. The solid content concentration is a value calculated by 100-water (%).
The materials used in each example are shown below.

(First component)
Glucose: manufactured by Sanei Saccharification Co.
Fructose: Reagent, manufactured by Wako Pure Chemical Industries.
75FG: isomerized sugar (containing glucose, fructose, etc.), solid content concentration 75%, glucose 45% and fructose 42% with respect to the entire carbohydrate, manufactured by Gunei Chemical Industry Co., Ltd.
Resorcinol: manufactured by Sumitomo Chemical Co., Ltd.
Tannin: MIMOZA, Tanzania.

(Ammonium salt)
Ammonium sulfate: Ube Chemical Co.
Ammonium phosphate: Reagent, manufactured by Wako Pure Chemical Industries.
Ammonium borate: Reagent, manufactured by Wako Pure Chemical Industries.
Diammonium citrate: Reagent, manufactured by Wako Pure Chemical Industries.
Triammonium citrate: Reagent, manufactured by Wako Pure Chemical Industries.
Ammonium phenolsulfonate: Reagent, manufactured by Wako Pure Chemical Industries.
Ammonium paratoluenesulfonate: Reagent, manufactured by Wako Pure Chemical Industries, Ltd.
Ammonium xylenesulfonate: Reagent, manufactured by Wako Pure Chemical Industries.
Ammonium oxalate: Reagent, manufactured by Wako Pure Chemical Industries.

(Surfactant)
[Anionic surfactant]
Sodium dodecyl sulfate: Reagent, manufactured by Wako Pure Chemical Industries.
Sodium dodecylbenzenesulfonate: Reagent, manufactured by Kanto Chemical Co., Inc.
Potassium stearate: Reagent, manufactured by Kanto Chemical Co., Inc.

[Cationic surfactant]
n-octadecylamine hydrochloride: Reagent, manufactured by Kanto Chemical Co., Inc.
[Amphoteric surfactant]
Lauryldimethylaminoacetic acid betaine: Nissan Anon BL, manufactured by NOF Corporation.

[Nonionic surfactant]
Polyoxyethylene (20) sorbitan monolaurate: Reagent, manufactured by Wako Pure Chemical Industries, Ltd.
Polyoxyethylene (9) lauryl ether: Emulgen 109P, manufactured by Kao Corporation.
Polyoxyethylene (10) octyl phenyl ether: manufactured by ICN Biomedicals.
Decyl glucoside: manufactured by Gunei Chemical Industry Co., Ltd.
The numerical value in parentheses after “polyoxyethylene” indicates the average number of repeating oxyethylene groups.

(Silane coupling agent)
Silane coupling agent 1: KBM-602 (N-2- (aminoethyl) -3-aminopropyltrimethoxysilane), manufactured by Shin-Etsu Chemical Co., Ltd.
Silane coupling agent 2: KBM-903 (3-aminopropyltrimethoxysilane), manufactured by Shin-Etsu Chemical Co., Ltd.
Silane coupling agent 3: KBE-903 (3-aminopropyltriethoxysilane), manufactured by Shin-Etsu Chemical Co., Ltd.
Silane coupling agent 4: KBM-573 (N-phenyl-3-aminopropyltrimethoxysilane), manufactured by Shin-Etsu Chemical Co., Ltd.
Silane coupling agent 5: KBE-1003 (vinyltriethoxysilane), manufactured by Shin-Etsu Chemical Co., Ltd.
Silane coupling agent 6: KBM-503 (3-methacryloxypropyltrimethoxysilane), manufactured by Shin-Etsu Chemical Co., Ltd.
Silane coupling agent 7: KBE-403 (3-glycidoxypropyltriethoxysilane), manufactured by Shin-Etsu Chemical Co., Ltd.
Silane coupling agent 8: KBE-585 (3-ureidopropyltriethoxysilane), manufactured by Shin-Etsu Chemical Co., Ltd.
Silane coupling agent 9: KBE-9007 (3-isocyanatopropyltriethoxysilane), manufactured by Shin-Etsu Chemical Co., Ltd.

(Water repellent)
Water repellent 1: POLON-MF-33A, anionic emulsion of silicone water repellent, 30% active ingredient, manufactured by Shin-Etsu Chemical Co., Ltd.
Water repellent 2: POLON-MR, nonionic emulsion of silicone water repellent, active ingredient 60%, manufactured by Shin-Etsu Chemical Co., Ltd.
Here, the active ingredient indicates a nonvolatile content (105 ° C. × 3 hours, catalog value).

(Other)
Anti-dusting oil: Marlex 69, manufactured by Mobil.
Curing modifier 1: ethylene glycol, reagent, manufactured by Kanto Chemical Co., Inc.
Curing modifier 2: diethylene glycol, reagent, manufactured by Kanto Chemical Co., Inc.
Curing modifier 3: Triethylene glycol, reagent, manufactured by Kanto Chemical Co., Inc.
Curing modifier 4: Polyethylene glycol 200, reagent, manufactured by Kanto Chemical Co., Inc.
Curing modifier 5: Polyethylene glycol 400, reagent, manufactured by Kanto Chemical Co., Inc.
Curing modifier 6: Propylene glycol, reagent, manufactured by Kanto Chemical Co., Inc.
Curing modifier 7: 1,4-butylene glycol, reagent, manufactured by Kanto Chemical Co., Inc.
Curing modifier 8: Glycerin, reagent, manufactured by Kanto Chemical Co., Inc.
Curing modifier 9: Diglycerin (diglycerol), reagent, manufactured by Kanto Chemical Co., Inc.

<Test Example 1>
The effects of components such as surfactants on normal strength were evaluated by the following procedure.
(Preparation of binder composition 1)
Ingredients and blending amounts (parts) shown in Tables 1 to 19, the silane coupling agent 3, the water repellent 1, and the dust-preventing oil were mixed, and Examples 1 to 27 and Comparative Examples 1-19 binder compositions were prepared. Each binder composition is an aqueous solution having a solid concentration of 65%. The amount of the silane coupling agent 3 was 0.15% with respect to the total of the first component and the ammonium salt. The blending amount of the water repellent 1 was 1.1% with respect to the total of the first component and the ammonium salt. The blending amount of the dust-preventing oil was 3.5% with respect to the total of the first component and the ammonium salt.

(Preparation of binder composition 2)
Components having the types and blending amounts (parts) shown in Tables 20 to 24 were mixed to prepare binder compositions of Reference Examples B1 to B45 and Comparative Examples 20 to 24. Each binder composition is an aqueous solution having a solid concentration of 65%.

  Using the obtained binder composition, a molded body was prepared and the tensile strength was measured by the following procedure.

(Production of molded body and measurement of tensile strength)
A glass fiber filter (manufactured by Whatman, grade GF / A, square 460 mm × 570 mm) was cut into 130 mm × 200 mm, and impregnated with a binder solution obtained by adding 90 g of ion-exchanged water to 60 g of the binder composition. After removing the excess binder liquid, it was pre-dried at 90 ° C. for 3 minutes, and further heated at 190 ° C. for 3 minutes to cure the binder composition in the binder liquid to obtain a molded body. When the molded body was 100% by mass, the ratio of the cured product of the binder composition was 60% by mass.
Ten test pieces of 25 mm × 100 mm were cut out from the obtained molded product, a tensile test was performed at a fixed gap of 50 mm, a tensile speed of 3 mm / min, and a tensile strength (MPa) was measured. Among the measured values of each of the ten test pieces, the average value of the measured values of the eight test pieces excluding the maximum value and the minimum value was taken as the tensile strength in each example.
The glass fiber filter is used as a substitute for inorganic fiber for simple evaluation, and is presumed to show the same tendency as the result when inorganic fiber such as glass wool is used.

The measurement results of the tensile strength are shown in Tables 1 to 24. Moreover, among the examples in each table, the value of the tensile strength of a comparative example in which the binder composition does not contain a surfactant (for example, Comparative Example 1 in the case of Table 1 and Comparative Example 2 in the case of Table 2) is 100. Tables 1 to 24 show the relative values of the tensile strength of other examples.
In the measurement method described above, there is a slight variation in the measured tensile strength depending on the temperature and humidity at the time of measurement. Therefore, in order to accurately perform the comparison, the examples shown in the same table (for example, Example 1 and Comparative Example 1 in the case of Table 1) were measured at almost the same timing.

(Reference Example A)
As an index of binder performance, a commercially available phenol resin binder for inorganic fiber products (manufactured by Gunei Chemical Industry Co., Ltd., trade name: PL-6757) was prepared and used as the binder of Reference Example A.
Except that this binder was used instead of the binder composition, a molded body was prepared and the tensile strength was measured in the same manner as described above. As a result, the tensile strength was 5.84 MPa.

  In Tables 1 to 24, “surfactant content (%)”, “silane coupling agent content (%)”, and “curing modifier content (%)” are respectively the first component and ammonium. The ratio (%) of each component with respect to the total with salt is shown. Each ratio is a value in solid content.

The tensile strengths in Examples 1 to 27 and Reference Examples B1, B11, B22, B32, and B42 were higher than those of the comparative examples shown in the same table (the same composition except that the surfactant was not included). This is considered to be because the wettability of the binder composition to the glass fibers was improved by the addition of the surfactant, and the adhesion between the glass fibers was improved.
Reference Examples B2-B10, B12-B21, B23-B31, B33-B41, B43-B45 in which any one or both of a silane coupling agent and a curing modifier are added to Reference Examples B1, B11, B22, B32, B42 The tensile strengths in were higher than those in Reference Examples B1, B11, B22, B32, and B42.
Further, the tensile strengths in Examples 1 to 27 and Reference Examples B1 to B45 were excellent as compared with the performance of a phenolic binder currently used for general purposes (Reference Example A).

From the results of Examples 1 to 3 and 5 that differ only in the type of sugar, it was confirmed that the tensile strength was improved by addition of a surfactant even if the sugar was different. Similarly, from the results of Examples 10 to 13, it was confirmed that even when phenols and ammonium salts were different, the tensile strength was improved by adding a surfactant.
From the results of Examples 4 to 8 that differ only in the content of the surfactant, the content of Example 5 in which the ratio of the surfactant to the total of the saccharide and the ammonium salt is 0.10 to 0.50%. The results of ˜7 were particularly excellent. Similarly, from the results of Examples 15 to 19, Examples 16 to 18 in which the content of the surfactant is 0.10 to 0.50% with respect to the total of the sugar, the phenol, and the ammonium salt. The results were particularly excellent.
From the results of Reference Examples B2 to B10, which differ only in the type of silane coupling agent, it was confirmed that the tensile strength improvement effect was excellent when an amino group-containing silane coupling agent was used among the silane coupling agents.
From the results of Reference Examples B23 to B31, which differ only in the type of curing modifier, it was confirmed that the tensile strength improvement effect was excellent when glycerin was used among the curing modifiers.
From the comparison of Reference Examples B43 to B45, it was confirmed that when both of the silane coupling agent and the curing modifier were used in combination, the tensile strength improvement effect was excellent as compared with the case of using either one.

<Examples 28 to 74, Comparative Examples 25 to 42>
(Preparation of binder composition)
Ingredients and blending amounts (parts) shown in Tables 25 to 35 were mixed with dust generation preventing oil to prepare binder compositions of Examples 28 to 74 and Comparative Examples 25 to 42. Each binder composition is an aqueous solution having a solid concentration of 65%. The blending amount of the dust-preventing oil was 3.5% with respect to the total of the first component of the binder composition and the ammonium salt.

  Using the obtained binder composition, a molded body was prepared and the normal bending strength (MPa), water-resistant bending strength (MPa), and water absorption rate (%) were measured by the following procedure.

(Production of molded body and measurement of normal bending strength, water-resistant bending strength and water absorption)
After uniformly mixing 80 g of shirasu balloon (hollow glassy sphere having an average particle size of 300 μm) and 43 g of a binder composition adjusted to a non-volatile content of 33%, 117 g is placed in a mold having a predetermined size (100 mm × 220 mm × 13 mm). The mixture was uniformly filled and heated at 200 ° C. for 30 minutes to obtain a molded body (bulk density: 0.30 g / cm ³ ).
Ten test pieces of 100 mm × 20 mm × 13 mm were cut out from the obtained molded body, normal bending strength (MPa) was measured using five of them, and water absorption (%) was measured using the remaining five. In addition, the water bending strength (MPa) was measured. Specifically, the bending strength of the five test pieces was measured as it was, and the average value thereof was defined as the normal bending strength. For the remaining five test pieces, the mass (g) of the test piece was measured in advance, and after immersion for 2 hours in warm water at 60 ° C., the mass (g) was measured to absorb water. The rate was calculated. Subsequently, the bending strength of the test piece after the immersion treatment and the measurement of the mass was measured, and the average value thereof was defined as the water-resistant bending strength.
The bending strength (normal state, water resistance) was measured by a three-point bending test method, with the distance between supporting points being 50 mm and the crosshead speed being 10 mm / min.
The water absorption was calculated by the following formula. The water absorption is preferably less than 100%, more preferably less than 80%, and particularly preferably less than 60%.
Water absorption rate = (mass after immersion / mass before immersion) × 100-100

Further, the strength retention (%) was calculated from the measured normal bending strength and water-resistant bending strength by the following formula. The strength retention is preferably 70% or more, and more preferably 80% or more.
Strength retention rate = (water resistance bending strength / normal bending strength) × 100

The results are shown in Tables 25-35.
In the measurement method described above, the measured value slightly varies depending on the temperature and humidity at the time of measurement. Therefore, in order to accurately perform the comparison, the examples shown in the same table (for example, Example 31 and Comparative Example 25 in the case of Table 26) were measured at almost the same timing.

<Reference Example C>
As an index of binder performance, a commercially available phenol resin binder for inorganic fiber products (manufactured by Gunei Chemical Industry Co., Ltd., trade name: PL-6757) was prepared and used as the binder of Reference Example C.
Except that this binder was used in place of the binder composition, the molded product was prepared and the normal bending strength, water-resistant bending strength and water absorption were measured, and the strength retention was calculated. As a result, the normal bending strength was 24.5 MPa, the water-resistant bending strength was 22.1 MPa, the water absorption was 51%, and the strength retention was 90.2%.

  In Tables 25 to 35, “surfactant content (%)”, “silane coupling agent content (%)”, “water repellent content (%)”, “curing modifier content ( %) ”Indicates the ratio (%) of each component to the total of the first component and the ammonium salt. Each ratio is a value in solid content.

  The normal bending strength, water resistance strength, strength retention, and water absorption in Examples 28 to 74 were superior to those of phenolic binders currently used for general purposes (Reference Example C). It was.

<Example 75, Comparative Example 43>
Ingredients and amounts (parts) shown in Table 36 were mixed with dust-preventing oil to prepare binder compositions of Example 75 and Comparative Example 43. Each binder composition is an aqueous solution having a solid concentration of 65%. The blending amount of the dust-preventing oil was 3.5% with respect to the total of the first component of the binder composition and the ammonium salt.
For the obtained binder composition, the molded body was prepared and the tensile strength was measured in the same manner as in Test Example 1, and the relative tensile strength of Example 75 when the tensile strength value of Comparative Example 43 was 100 was used. The value was calculated. Separately, for this binder composition, the molded body was prepared and the normal bending strength was measured in the same manner as in Example 28, and the value of the normal bending strength in Comparative Example 43 was set to 100. The relative value of normal bending strength was calculated. The results are shown in Table 36.

  Tensile strength and normal bending strength are both indices of normal strength, and it is known that there is a correlation between these measured values. This point was also confirmed from the above results. The accuracy of the measured value tends to be higher in tensile strength than in normal bending strength.

  In the binder composition of the present invention, excellent normal strength and water resistance can be obtained without using formaldehyde as a raw material. Therefore, the binder composition of the present invention can be used for various applications in which thermosetting binders such as phenol resin binders are conventionally used. For example, for inorganic fiber products, for casting, for friction materials, for grindstones, and filter paper For molding materials, for plywood processing, for decorative boards, for laminated boards and the like, and particularly useful for inorganic fiber products.

Claims (15)

  A first component which is a carbohydrate or a mixture of a carbohydrate and a phenol, and at least one ammonium salt selected from the group consisting of ammonium sulfate, triammonium citrate, diammonium citrate and ammonium phenolsulfonate, and a surface activity Thermosetting binder composition containing an agent, a silane coupling agent, and a water repellent.   The thermosetting binder composition according to claim 1, substantially free of formaldehyde.   The thermosetting binder composition according to claim 1 or 2, wherein the carbohydrate includes at least one selected from the group consisting of glucose, fructose, and sucrose.   The thermosetting binder composition according to any one of claims 1 to 3, wherein the surfactant includes an ionic surfactant.   The thermosetting binder composition according to any one of claims 1 to 4, wherein the surfactant contains one or both of sodium dodecyl sulfate and sodium dodecylbenzenesulfonate. The first component is a mixture of a saccharide and a phenol;
The thermosetting binder composition according to any one of claims 1 to 5, wherein the phenol is a polyhydric phenol.   The thermosetting binder composition according to claim 6, wherein the polyhydric phenol contains at least one selected from the group consisting of resorcinol, tannin, catechol, hydroquinone, pyrogallol, phloroglucinol and lignin.   The thermosetting binder composition according to any one of claims 1 to 7, wherein a ratio of the surfactant to a total of the first component and the ammonium salt is 0.01 to 1.0% by mass. The first component is a mixture of a saccharide and a phenol;
The thermosetting binder composition according to any one of claims 1 to 8, wherein a ratio of the phenols to the saccharide is 0.1 to 30% by mass.   The thermosetting binder according to any one of claims 1 to 9, wherein the silane coupling agent is at least one selected from the group consisting of an amino group-containing silane coupling agent and an epoxy group-containing silane coupling agent. Composition.   The thermosetting binder composition according to any one of claims 1 to 10, wherein the water repellent is a silicone-based water repellent.   The thermosetting binder composition according to any one of claims 1 to 11, further comprising at least one selected from the group consisting of a dust-preventing oil, a curing regulator, a curing accelerator, and water. Contains a curing modifier,
The curing regulator is at least one selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol having an average molecular weight of 160 to 500, propylene glycol, 1,4-butylene glycol, glycerin and diglycerin. Item 13. The thermosetting binder composition according to Item 12. An inorganic fiber product including a molded body in which inorganic fibers are bonded with a binder,
The inorganic fiber product whose said binder is a hardened | cured material of the thermosetting binder composition as described in any one of Claims 1-13.   The inorganic fiber product according to claim 14, wherein the inorganic fiber is glass wool or rock wool.