JP6085501B2 - Thermosetting binder, inorganic fiber product using the same - Google Patents

Description

  The present invention relates to a thermosetting binder 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 a binder are used for heat insulating materials, sound absorbing materials, and other various molded products (automobile roofs, bonnet liners, etc.). ing.
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. One of the causes 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. Under the revised Building Standard Law, the amount of formaldehyde emitted 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) has been proposed.

European Patent Application No. 0044614 Special table 2010-535864 Special table 2011-506781 gazette

However, although the binder as proposed in Patent Documents 1 to 3 does not use formaldehyde as a raw material, there is a problem that the performance as a binder (for example, normal strength after thermosetting) is inferior to a phenol resin binder.
Therefore, even a non-formaldehyde type binder is required that can exhibit excellent binder performance equal to or higher than that of a phenol resin binder.

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a thermosetting binder that exhibits good binder performance without using formaldehyde as a raw material, and an inorganic fiber product using the same. To do.

As a result of intensive studies, the present inventors have found that binder performance can be improved by further adding phenols to a combination of a saccharide and an ammonium salt, and have completed the present invention.
The present invention for solving the above problems has the following aspects.

[1] Contains a saccharide, an ammonium salt, and phenols ,
The carbohydrate is at least one selected from the group consisting of glucose, fructose, sucrose, maltose, isomerized sugar and chickenpox;
The ammonium salt is at least one selected from the group consisting of ammonium sulfate, ammonium phosphate, ammonium borate, ammonium oxalate and ammonium citrate;
The phenol is at least one selected from the group consisting of resorcinol, tannin, hydroquinone and phloroglucinol,
The ratio of the phenols to the total of the carbohydrates and the phenols is 1 to 25% by mass,
Ratio of the ammonium salt to the total of the phenol and the saccharide is 20% by mass Ru thermosetting binder.
[2] The thermosetting binder according to [1], in which formaldehyde and a raw material containing formaldehyde are not blended .
[3 ] An inorganic fiber product comprising a molded body formed by molding inorganic fibers using the thermosetting binder according to [1] or [ 2] .
[ 4 ] The inorganic fiber product according to [ 3 ], wherein the inorganic fiber is glass wool or rock wool.

  ADVANTAGE OF THE INVENTION According to this invention, the thermosetting binder which exhibits favorable binder performance, without using formaldehyde as a raw material, and an inorganic fiber product using the same can be provided.

6 is a graph showing the results of Test Example 2. 10 is a graph showing the results of Test Example 3. 10 is a graph showing the results of Test Example 4. 10 is a graph showing the results of Test Example 5. 10 is a graph showing the results of Test Example 6.

  The thermosetting binder according to the first aspect of the present invention (hereinafter also simply referred to as a binder) contains a saccharide, an ammonium salt, and a phenol.

[Sugar]
Examples of the saccharide include monosaccharides, oligosaccharides, polysaccharides, and derivatives thereof.
In the present invention, the “oligosaccharide” is a combination of 2 to 10 monosaccharides, and the “polysaccharide” is a combination of 11 or more monosaccharides.
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 starch 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.
Any one of these carbohydrates may be used alone, or two or more thereof may be used in combination. Among the above, monosaccharide is preferable.

In the present invention, from the viewpoint of excellent effects of the present invention, the saccharide is at least one saccharide selected from the group consisting of glucose, fructose, mannose, sucrose and maltose (hereinafter also referred to as a specific saccharide). It is preferable to contain. Any one of these specific carbohydrates may be used alone, or two or more thereof may be used in combination.
As the specific carbohydrate, at least one selected from the group consisting of glucose and fructose is particularly preferable since monosaccharides are excellent in the effects of the present invention.
The proportion of the specific carbohydrate in the carbohydrate 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 more preferably 65% by mass or more, 70 mass% or more is more preferable, 75 mass% or more is more preferable, 80 mass% or more is more preferable, 85 mass% or more is more preferable, 90 mass% or more is more preferable, and 95 mass% or more is more preferable. An upper limit is not specifically limited, 100 mass% may be sufficient. That is, the saccharide may be composed only of the specific saccharide.
When using 2 or more types as saccharide together, each saccharide may be mix | blended at the time of preparation of a binder, and the raw material containing 2 or more types of saccharides may be used. Examples of the raw material containing two or more sugars include isomerized sugar (containing glucose, fructose, etc.), starch syrup (containing glucose, maltose, etc.), and the like.

[Ammonium salt]
Examples of ammonium salts include inorganic ammonium salts and organic ammonium salts.
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 hydrogen carbonate, and the like. .
Examples of the organic ammonium salt include ammonium acetate, ammonium oxalate, and ammonium citrate.
These ammonium salts may be used alone or in combination of two or more. Among these, inorganic ammonium salts are preferable.

  In the present invention, the ammonium salt contains at least one ammonium salt selected from the group consisting of ammonium sulfate, ammonium phosphate, ammonium borate, ammonium oxalate, and ammonium citrate from the viewpoint of excellent effects of the present invention. It is preferable. Among these, at least one selected from the group consisting of ammonium sulfate and ammonium phosphate is particularly preferable because the inorganic ammonium salt is excellent in the effects of the present invention.

The content of the ammonium salt in the binder is such that the ratio of the ammonium salt to the total (100% by mass) of the saccharide and phenol in the binder (hereinafter also referred to as the ammonium salt addition rate) is in the range of 1 to 20% by mass. An amount that is within is preferred. The addition rate of ammonium salt is more preferably 2.5 to 15% by mass, further preferably 5 to 10% by mass.
Although the curing reaction of the binder will be described in detail later, the ammonium salt is a source of ammonia that reacts with the saccharide in the curing reaction of the binder, and the subsequent reaction (the reaction product of the saccharide and ammonia, It functions as a supply source of an acidic substance that functions as a catalyst in reaction with phenols and reaction between the reaction products).
When the ammonium salt addition rate is 1% by mass or more, when molding inorganic fibers using the binder, curing is completed within the predetermined molding conditions (temperature, time), and the required performance is achieved. Easy to make. When the ammonium salt addition rate is 20% by mass or less, the binder performance is good, and the possibility that the performance such as the water resistance strength of the molded article obtained using the binder is deteriorated can be reduced.

[Phenols]
Examples of phenols include plant material-derived phenols and fossil fuel-based phenols.
Examples of plant-derived phenols include flavonoid tannins, catechins, anthocyanins, rutin, isoflavones, phenolic chlorogenic acids, and other polyphenols such as ellagic acid, lignan, curcumin, coumarin, and lignin, cardanol, cashew nut shell Liquid etc. are mentioned.
Examples of the 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 the water-soluble phenols include tannin, phenol, cresol, catechol, resorcinol, hydroquinone, pyrogallol, phloroglucinol and the like.

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.
The polyhydric phenol is preferably at least one selected from the group consisting of tannin, catechol, resorcinol, hydroquinone, pyrogallol and phloroglucinol, and particularly preferably at least one selected from the group consisting of tannin and resorcinol.

Phenols are components that form a skeleton of a cured product together with carbohydrates. The binder performance can be improved by further adding phenols to the combination of the saccharide and the ammonium salt. As a result of extensive studies by the present inventors, the following knowledge was obtained.
The effect of improving the binder performance by blending phenols is affected by the ratio of phenols to the total of sugars and phenols (hereinafter also referred to as phenol addition rate). Increasing the phenol addition rate stepwise from 0 improves the binder performance to a certain extent and increases the strength (normal strength, water resistance, etc.) of the resulting molded product. If the ratio of phenols starts to decrease and the phenol addition rate becomes too high, the binder performance tends to be lower than when no phenols are blended.
A suitable range of the phenol addition ratio that can achieve the binder performance improving effect is generally in the range of 0.1 to 50% by mass, but there is a difference depending on the type of sugar or phenol used.
Below, the preferable embodiment example of the binder of this aspect is shown. However, the present invention is not limited to these embodiments. For example, the combination of saccharides and phenols is not limited to the combination shown in the following embodiment. The suitable range of the phenol addition rate in other combinations can be appropriately set by conducting a preliminary test.

First embodiment: The sugar is glucose, the phenol is resorcinol, and the phenol addition rate is 0.1 to 25% by mass (preferably 5 to 20%, more preferably 10 to 15% by mass). And the ammonium salt addition rate is 1 to 20% by mass.
Second Embodiment: The carbohydrate is fructose, the phenol is resorcinol, and the phenol addition rate is 0.1 to 25% by mass (preferably 5 to 20%, more preferably 10 to 15% by mass). And the ammonium salt addition rate is 1 to 20% by mass.
Third Embodiment: The carbohydrate is glucose, the phenol is tannin, and the phenol addition rate is 0.1 to 50% by mass (preferably 5 to 40%, more preferably 10 to 30% by mass). And the ammonium salt addition rate is 1 to 20% by mass.
Fourth Embodiment: The carbohydrate is an isomerized sugar, the phenol is resorcinol, and the phenol addition rate is 0.1 to 20% by mass (preferably 2.5 to 17.5%, more preferably Is 5 to 15% by mass), and the ammonium salt addition rate is 1 to 20% by mass.
In these embodiments, if the phenol addition rate is within the above range, curing within predetermined molding conditions (temperature, time) is completed, and the resulting molded article has good normal strength, water resistance strength, and the like. The required performance of inorganic fiber products can be expressed.
The preferred range of the ammonium salt addition rate in these embodiments is the same as described above.

The binder of this aspect may contain other components other than saccharides, ammonium salts, and phenols as long as they do not impair the effects of the present invention.
As said other component, it can select and use suitably from what is well-known as a component which can be mix | blended with the thermosetting binder used for manufacture of inorganic fiber products etc., for example, urea, melamine, furfural, furfuryl alcohol, Ammonia, silane coupling agents, known water repellents, dust-preventing oil, water and the like can be mentioned. These may be used alone or in combination of two or more.

For example, among the above components, at least one selected from the group consisting of urea, melamine, furfural, furfuryl alcohol and ammonia may be added to the binder of this embodiment for the purpose of promoting curing.
The blending amount of at least one selected from the group consisting of urea, melamine, furfural, furfuryl alcohol and ammonia is preferably 0 to 30% by mass with respect to the nonvolatile content of the binder.
In the present invention, the “nonvolatile content” refers to a value measured according to 5.6 of JIS K6910.

The silane coupling agent is not particularly limited, and examples thereof include aminosilane compounds such as N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane or 3-aminopropyltriethoxysilane.
The blending amount of the silane coupling agent is preferably 0 to 0.5% by mass with respect to the nonvolatile content of the binder (excluding the silane coupling agent).

Examples of the water repellent include a silicone water repellent or a fluorine water repellent.
Examples of the dust-preventing oil include mineral oil-based oil emulsions.

In order to adjust the concentration (nonvolatile content) as appropriate, water (adjusted water) may be added to the binder of this embodiment.
The binder of this embodiment is preferably an aqueous solution in which saccharides, ammonium salts, and phenols are dissolved in water because they are easily attached to inorganic fibers and the like.

The binder of this embodiment can exhibit good binder performance without using formaldehyde as a raw material. Therefore, preferred embodiments of the binder of this aspect include embodiments that are substantially free of formaldehyde.
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 preparing the binder. .

  The binder of this embodiment can be prepared by mixing a saccharide, an ammonium salt, a phenol, and other components as necessary.

The binder of this embodiment has thermosetting properties that are cured by heating.
As a thermosetting mechanism of the binder of this embodiment, a mechanism similar to caramelization can be considered.
When the binder of this embodiment 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-deoxy- with ring opening. 2-Ketose is formed. 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 also 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 structure in which a skeleton of phenols is introduced into a caramel-like structure.

It is thought that only water is produced as a by-product in the above reaction. Therefore, when the binder of this embodiment is used in the production process of an inorganic fiber product, the gas generated when the binder is cured is considered to be generally only water vapor. Proper selection and blending of saccharides, ammonium salts and phenols constituting the binder of this embodiment can reduce the production cost of inorganic fiber products and the like.
The binder of this embodiment is useful for the production of inorganic fiber products. However, the use of the binder of this embodiment is not limited to this, and can be used for various uses in which thermosetting binders such as phenol resin binders are conventionally used. For example, for casting, for friction materials, for grinding wheels , For filter paper, for molding materials, for plywood processing, for decorative plates, laminated plates and the like.

<Inorganic fiber products>
The inorganic fiber product of the second aspect of the present invention comprises a molded body formed by molding inorganic fibers using the binder of the first aspect.
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 this aspect may consist of the said molded object, and may further be provided with other members other than the said molded object. Examples of the other member include a skin material for packaging.
The inorganic fiber product of this embodiment 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 embodiment can use a known method conventionally used in the production of inorganic fiber products, except that the binder of the first embodiment is used as the binder. As an example, a process of attaching the binder of the first aspect to inorganic fibers (hereinafter referred to as an adhesion process), collecting the inorganic fibers to which the binder is adhered, and forming an aggregate having a shape corresponding to the inorganic fiber product to be manufactured. Then, the method of heating the said integration body and hardening the said binder and obtaining a molded object (henceforth a molding process) sequentially is mentioned. 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 to the inorganic fiber include a method of spraying the binder on the inorganic fiber using a spray device or the like, a method of impregnating the inorganic fiber with the binder, and any method may be used. .
The amount of the binder 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 with respect to the inorganic fiber (100% by mass). The amount of the binder affects the physical properties (such as mechanical strength) of the obtained molded body. For example, the greater the binder amount, the higher the mechanical strength of the obtained molded body.

(Molding process)
Next, the inorganic fibers to which the binder is attached 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.
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, 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 in the aggregate is cured, but the heating temperature is preferably in the range of 200 to 270 ° C. If it is lower than 200 ° C., curing may be insufficient and mechanical strength may be insufficient. When it exceeds 270 ° C., the binder may be decomposed, and the yield and the mechanical strength may be lowered. 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 measurement methods of pH, gelation time, normal strength of the molded body, and water resistance strength used in each example described below are shown below.

<PH>
Measurement was performed in accordance with 5.4 of JIS K6910.

<Gelification time>
The measurement was performed at a measurement temperature of 150 ° C. in accordance with the provisions of 5.14.1 (gelation time A method) of JIS K6910.

<Normal strength and water resistance of the molded body>
After uniformly mixing 65 g of shirasu balloon (hollow glassy sphere having an average particle size of 300 μm) and 23 g of binder, it is uniformly filled into a mold having a predetermined size (100 mm × 220 mm × 13 mm), and at 200 ° C. for 30 minutes. A molded body (bulk density: 0.25 g / cm ³ ) was obtained by heating.
Ten test pieces of 100 mm × 20 mm × 13 mm were cut out from the obtained molded body, and normal strength (kgf / cm ² ) was measured using five of them, and water resistance strength (kgf was measured using the remaining five. / Cm ² ) was measured. Specifically, the strength of the five test pieces was measured as it was, and the average value thereof was defined as the normal strength. Moreover, about the remaining 5 test pieces, after performing the immersion process for 2 hours in 60 degreeC warm water, intensity | strength measurement was performed and those average values were made into the water-resistant strength.
The strength measurement (normal strength measurement and water resistance strength measurement) was performed under the conditions of a span of 50 mm and a load speed of 10 mm / min by a three-point bending test method according to the provisions of 5.17 of JIS K6911.
The Shirasu balloon is used as a substitute for inorganic fibers for easy evaluation, and is presumed to show the same tendency as the result when inorganic fibers such as glass wool are used.

<Test Example 1>
The binders of Examples 1-19 were prepared according to the following procedure. Each binder is an aqueous solution having a solid content concentration of 50% containing the components shown in Table 1 in the binder composition shown in Table 1 as a mass mixing ratio. The solid content concentration is a value calculated by 100-water (%).
In addition, as a binder performance index, 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 Example 20. This phenolic binder is an aqueous solution having a non-volatile content of 50%.
The pH and gelation time (150 ° C.) of each binder were measured. Moreover, the normal strength and water resistance strength of the molded body prepared using each binder and shirasu balloon were measured. The measurement results are shown in Table 1.

[Examples 1 to 5]
In the binder composition shown in Table 1, glucose (reagent, manufactured by Kanto Chemical Co., Inc.), ammonium sulfate (reagent, manufactured by Kanto Chemical Co., Ltd.), and resorcinol (reagent, manufactured by Kanto Chemical Co., Inc.) so that the solid concentration is 50% aqueous solution. ) And pure water were mixed to obtain a binder.

[Examples 6 to 8]
Fructose, sucrose or maltose (all reagents, manufactured by Kanto Chemical Co., Inc.), ammonium sulfate (reagent, manufactured by Kanto Chemical Co., Ltd.), and resorcinol so that the solid content concentration is 50% aqueous solution with the binder composition shown in Table 1. (Reagent, manufactured by Kanto Chemical Co., Inc.) and pure water were mixed to obtain a binder.

[Examples 9 to 12]
Glucose (reagent, manufactured by Kanto Chemical Co., Inc.), ammonium phosphate, ammonium borate, ammonium oxalate or ammonium citrate (both reagents) so that the solid content concentration is 50% aqueous solution with the binder composition shown in Table 1. , Manufactured by Kanto Chemical Co., Inc.), resorcinol (reagent, manufactured by Kanto Chemical Co., Ltd.) and pure water were mixed to obtain a binder.

[Examples 13 to 15]
In the binder composition shown in Table 1, glucose (reagent, manufactured by Kanto Chemical Co., Inc.), ammonium sulfate (reagent, manufactured by Kanto Chemical Co., Inc.), tannin (MIMOZA, manufactured in Tanzania), Hydroquinone or phloroglucinol (both reagents, manufactured by Kanto Chemical Co., Inc.) and pure water were mixed to obtain a binder.

[Example 16]
In the binder composition shown in Table 1, syrup (solid content concentration: 75%, specific carbohydrate: 57% (glucose: 1.4%, maltose: 56.0%) so that the solid content concentration is 50% aqueous solution. , Manufactured by Gunei Chemical Industry Co., Ltd., trade name: KM-55), ammonium sulfate (reagent, manufactured by Kanto Chemical Co.), resorcinol (reagent, manufactured by Kanto Chemical Co., Ltd.) and pure water were mixed to obtain a binder. .

[Examples 17 to 19]
Example 17 of European Patent Application Publication No. 0044614 (Patent Document 1), Example 18 of Japanese Translation of PCT International Publication No. 2010-535864 (Patent Document 2), and Japanese Patent Application Laid-Open No. 2011-506781 (Patent Document 3) In accordance with each of Examples 19, binders were prepared according to the formulation shown in Table 1. In the binder compositions of Examples 17 to 19 shown in Table 1, the numerical value described after the component name indicates the blending amount (parts by mass) of the component.

  Examples 1 to 16 in which saccharides, ammonium salts and phenols are blended, Examples 17 to 19 which are non-formaldehyde type binders described in the prior art documents, and phenol resin systems which are currently widely used for inorganic fiber products When compared with Example 20 which is a binder, the normal strengths of the molded bodies obtained from the binders of Examples 1 to 16 were higher than those of Examples 17 to 19, and were almost equal to or higher than Example 20. Moreover, the water resistance strength was also good. From these facts, it was confirmed that the binder performance of the binders of Examples 1 to 16 was excellent as compared with the binder performance of phenolic binders currently used for general purposes.

<Test Example 2>
This test example was carried out in order to evaluate the influence of the blending ratio of resorcinol on the binder performance in the glucose-resorcinol-ammonium salt system.
In Example 1 of Test Example 1, the ratio of the amount of resorcinol (mass part) to the total amount (resorcinol) while the total amount of glucose and resorcinol (100 parts by mass) was kept constant. The binder was prepared by changing the addition ratio to 0, 2, 5, 10, 15, 20, or 25%.
The normal strength and water resistance strength of the molded body prepared using each binder and shirasu balloon were measured. The measurement results are shown in Table 2. From the measurement results, a graph was created with the resorcinol addition rate on the horizontal axis and the strength (kgf / cm ² ) on the vertical axis. The graph is shown in FIG.
As shown in these results, within the range of resorcinol addition rate of 0.1 to 25%, higher strength (normal strength and water resistance strength) than when resorcinol addition rate was 0% (no resorcinol blended) was obtained. .

<Test Example 3>
This test example was performed in order to evaluate the influence which the compounding ratio of resorcinol has on binder performance in a fructose-resorcinol-ammonium salt system.
In Example 6 of Test Example 1, the ratio of the amount of resorcinol (parts by mass) to the total amount (resorcinol) with the total amount of fructose and resorcinol (100 parts by mass) being constant The binder was prepared by changing the addition ratio to 0, 2, 5, 10, 15, 20, or 25%.
The normal strength and water resistance strength of the molded body prepared using each binder and shirasu balloon were measured. Table 3 shows the measurement results. From the measurement results, a graph was created with the resorcinol addition rate on the horizontal axis and the strength (kgf / cm ² ) on the vertical axis. The graph is shown in FIG.
As shown in these results, when the resorcinol addition rate is in the range of 0.1 to 25%, the higher the resorcinol addition rate, the higher the strength (normal strength and water resistance strength) than in the case of 0% (no resorcinol added). It was.

<Test Example 4>
This test example was carried out in order to evaluate the influence of the blending ratio of tannin on the binder performance in the glucose-tannin-ammonium salt system.
In Example 13 of Test Example 1, the blending amount of glucose and tannin was kept constant with the total amount of glucose and tannin (100 parts by mass), and the ratio of tannin blending amount (parts by mass) to the total amount (tannins) The binder was prepared by changing the addition ratio to 0, 2, 5, 10, 15, 20, 40, or 50%.
The normal strength and water resistance strength of the molded body prepared using each binder and shirasu balloon were measured. Table 4 shows the measurement results. From the measurement results, a graph was created with the tannin addition rate as the horizontal axis and the strength (kgf / cm ² ) as the vertical axis. The graph is shown in FIG.
As shown in these results, the strength (normal strength and water resistance strength) higher than the case where the tannin addition rate is in the range of 0.1 to 50% and the tannin addition rate is 0% (without tannin) was obtained. .

<Test Example 5>
This test example was carried out in order to evaluate the influence of the blending ratio of resorcinol on the binder performance in the isomerized sugar-resorcinol-ammonium salt system.
In Example 1 of Test Example 1, an isomerized sugar (manufactured by Gunei Chemical Industry Co., Ltd., trade name: 75FG, glucose / fructose = 58/42 (mass ratio)) was used instead of glucose, and the isomerized sugar and resorcinol While the total amount (100 parts by mass) of isomerized sugar and resorcinol is kept constant, the ratio (resorcinol addition rate) of the amount of resorcinol to the total amount (parts by mass) is 0, 5, 10, The binder was prepared by changing the content to 15 or 20%.
The normal strength and water resistance strength of the molded body prepared using each binder and shirasu balloon were measured. Table 5 shows the measurement results. From the measurement results, a graph was created with the resorcinol addition rate on the horizontal axis and the strength (kgf / cm ² ) on the vertical axis. The graph is shown in FIG.
As shown in these results, the resorcinol addition rate was in the range of 0.1 to 20%, and a higher strength (normal strength and water resistance strength) was obtained than when the resorcinol addition rate was 0% (no resorcinol blended). .

<Test Example 6>
This test example was performed in order to evaluate the influence which the compounding ratio of an ammonium salt has on binder performance in a glucose-resorcinol-ammonium salt system.
In Example 2 of Test Example 1, the ratio (ammonium sulfate addition rate) of ammonium sulfate to the total amount (100 parts by mass) of glucose and resorcinol (ammonium sulfate addition rate) is 1, 2.5, 5, 7.5, 10 Alternatively, the binder was prepared by changing to 20%.
The normal strength and water resistance strength of the molded body prepared using each binder and shirasu balloon were measured. Table 6 shows the measurement results. From the measurement results, a graph was created with the ammonium sulfate addition rate on the horizontal axis and the strength (kgf / cm ² ) on the vertical axis. The graph is shown in FIG.
From these results, it was shown that high strength (normal strength and water resistance strength) can be obtained when the ammonium sulfate addition rate is in the range of 1 to 20%.

Claims (4)

Contains carbohydrates, ammonium salts, and phenols ,
The carbohydrate is at least one selected from the group consisting of glucose, fructose, sucrose, maltose, isomerized sugar and chickenpox;
The ammonium salt is at least one selected from the group consisting of ammonium sulfate, ammonium phosphate, ammonium borate, ammonium oxalate and ammonium citrate;
The phenol is at least one selected from the group consisting of resorcinol, tannin, hydroquinone and phloroglucinol,
The ratio of the phenols to the total of the carbohydrates and the phenols is 1 to 25% by mass,
Ratio of the ammonium salt to the total of the phenol and the saccharide is 20% by mass Ru thermosetting binder. The thermosetting binder according to claim 1, wherein formaldehyde and a raw material containing formaldehyde are not blended . An inorganic fiber product provided with the molded object formed by shape | molding an inorganic fiber using the thermosetting binder of Claim 1 or 2 . The inorganic fiber product according to claim 3 , wherein the inorganic fiber is glass wool or rock wool.

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