WO2020246055A1 - Binder composition, molded body, production method for molded body, and binder cured object - Google Patents

Abstract

Provided is a binder composition that does not use inorganic acid ions in the raw material therefor, has sufficient reaction speed when causing a crosslinking reaction in the binder, has good dynamic characteristics such as strength and elastic modulus, and does not cause corrosion of application targets such as inorganic fibers.　The binder composition includes an organic acid compound and a reaction product of sugar and a radical generator and does not substantially include an inorganic acid. Also provided are a molded body using the binder composition and a production method for the molded body using the binder composition. For example, the sugar is a reducing sugar such as glucose, galactose, mannose, fructose, maltose, or lactose. The radical generator is an azo compound or a peroxide (hydrogen peroxide water or an organic peroxide). The organic acid compound is at least one type selected from the group consisting of a low molecular weight polycarboxylic acid, a low molecular weight polycarboxylic acid salt, a high molecular weight polycarboxylic acid, and a high molecular weight polycarboxylic acid salt.

Description

Binder composition, molded product, manufacturing method of molded product, and cured binder

The present invention relates to a binder composition, a molded product, a method for producing a molded product, and a cured binder.

Conventionally, as a binder used for manufacturing molded products such as heat insulating materials, soundproofing materials, and wood board products using inorganic fibers such as glass wool, rock wool, and ceramic fiber, it has excellent mechanical strength and other performance and is low cost. Therefore, phenolic resin-based binders are widely used.

When manufacturing a molded product using inorganic fibers, a binder is attached to the inorganic fibers to form a product shape, and then the binder is cured by heating. In the past, phenolic resin-based binders that use formaldehyde as a raw material have been widely used as binders, but in recent years, binders that do not use formaldehyde as a raw material have been desired.

As a so-called non-formaldehyde type binder that does not use formaldehyde as a raw material, a binder based on saccharides and combined with a polycarboxylic acid, an ammonium inorganic acid salt, or the like has been proposed.

Patent Document 1 describes a formaldehyde-free sizing agent composition for mineral fibers, which comprises at least one non-reducing sugar, at least one inorganic acid ammonium salt and an additive, and water.

Patent Document 2 describes a composition containing an aggregate selected from the group consisting of glass fibers and cellulose fibers and a binder, wherein the binder contains a crosslinked melanoidin reaction product of a silicone compound and a dehydration reaction mixture. ing. The dehydration reaction mixture consists of an ammonium salt of a monomeric polycarboxylic acid and a monosaccharide.

Patent Document 3 describes a binder composition containing a non-reducing sugar, an unsaturated monocarboxylic acid salt, and an ammonium inorganic acid salt.

Japanese Patent No. 5931901 Japanese Patent No. 5455169 Japanese Patent No. 6062099

When the binder described in Patent Document 1 was used in the production of a molded product, its mechanical properties such as strength and elastic modulus after thermosetting were sometimes inferior to those of a phenol resin-based binder.
In addition, the binder described in Patent Document 2 has a slow reaction rate and may not be sufficiently cured in the manufacturing process.

Furthermore, when an inorganic acid ammonium salt is used as in the binders described in Patent Document 1 and Patent Document 3, the present inventors have an inorganic acid derived from the inorganic acid ammonium salt despite the catalytic amount. We have found that there is a problem that ions corrode inorganic fibers.

Specifically, when a binder composition containing sulfate ion is used as the inorganic acid ion, the cured binder absorbs water in the atmosphere with the passage of time, and water containing sulfate ion is generated, resulting in the binder composition. It was newly discovered that it moves inside and corrodes the fibers. If the inorganic fibers of rock wool, produces calcium sulfate (CaSO _4), a CaSO ₄ · 2H ₂ O in the surface of the fibers. When the inorganic fiber is glass wool, sodium sulfate (Na ₂ SO ₄ ) is generated and precipitated on the fiber surface.

Therefore, the reaction rate when the binder is crosslinked without using inorganic acid ions as a raw material is sufficient, and the mechanical properties such as strength and elasticity are about the same as those of the phenol resin binder or the phenol resin binder. The present inventors have newly found that it is necessary to provide a better non-formaldehyde type binder.

The present invention has been made in view of the above problems, and an object of the present invention is that the reaction rate when the binder is crosslinked without using inorganic acid ions as a raw material is sufficient, and the strength and elastic modulus are sufficient. Binder composition that has good mechanical properties such as, and does not corrode the object to be applied such as inorganic fibers, a molded product using the binder composition, a method for producing a molded product using the binder composition, and a binder. The purpose is to provide a cured product.

As a result of diligent research, the present inventors have conducted an intensive study, and when a binder composition containing a reaction product of a saccharide and a radical generator and an organic acid compound and substantially containing no inorganic acid is heated, the inorganic acid It was found that even when ions are not used, the reaction rate during the cross-linking reaction is sufficient, good mechanical properties are exhibited after thermosetting, and the application target such as inorganic fibers is not corroded. The present invention has been made.

Therefore, according to the binder composition according to the present invention, the above-mentioned problem is solved by containing a reaction product of a saccharide and a radical generator, an organic acid compound, and substantially no inorganic acid.
The binder composition of the present invention has an advantage that it does not contain formaldehyde, and when it is used for producing a molded product such as a glass wool molded product or a rock wool molded product, when a phenol resin-based binder is used because of its mechanical properties. Is equivalent to. Further, unlike the conventional non-formaldehyde type binder composition, since inorganic acid ions are not used, the application target such as inorganic fibers does not corrode over time.

At this time, it is preferable that the sugar is at least one reducing sugar selected from the group consisting of glucose, galactose, mannose, fructose, maltose, and lactose.
In particular, glucose and fructose are industrially produced from corn as raw materials, and are inexpensive and easily available plant-derived natural product components that are friendly to both humans and the environment.
At this time, it is preferable that the radical generator is at least one selected from the group consisting of an azo compound and a peroxide.
By using an azo compound and a peroxide that do not contain inorganic acid ions as the radical generator, it is further suppressed that the inorganic fibers are corroded over time.

At this time, it is preferable that the peroxide is at least one selected from the group consisting of hydrogen peroxide solution and organic peroxide.
By using a hydrogen peroxide solution containing no inorganic acid ion and an organic peroxide as the radical generator, it is further suppressed that the inorganic fibers are corroded over time.

At this time, the organic acid compound is preferably at least one selected from the group consisting of low molecular weight polycarboxylic acids, low molecular weight polycarboxylic acids, high molecular weight polycarboxylic acids, and high molecular weight polycarboxylic acids. ..

At this time, it is preferable that the organic acid compound is at least one selected from the group consisting of citric acid and ammonium citrate.

At this time, it is preferable to further contain an amine compound.
When an amine compound such as ammonia is contained, the mechanical properties of the molded product containing the cured product of the binder composition become good.

According to the molded product according to the present invention, the subject is a binder composition containing a reaction product of a saccharide and a radical generator, an organic acid compound, and substantially no inorganic acid. , Inorganic fiber, wood, one or more objects selected from cast sand, and the like.
At this time, it is preferable that the inorganic fiber contains at least one kind of mineral fiber selected from the group consisting of rock wool, stone wool, slag wool, mineral wool, glass wool, and mineral glass wool.
At this time, the saccharide is at least one reducing sugar selected from the group consisting of glucose, galactose, mannose, fructose, maltose, and lactose, and the radical generator is composed of an azo compound and a peroxide. At least one selected from the group, and the organic acid compound is selected from the group consisting of low molecular weight polycarboxylic acid, low molecular weight polycarboxylic acid, high molecular weight polycarboxylic acid, and high molecular weight polycarboxylic acid. It is preferable that there is at least one kind.
The binder composition of the present invention can be used as a substitute for a phenolic resin-based binder, and in addition to being used as a binder for inorganic fibers such as glass wool and rock wool, an adhesive and a mold for wood chips used for wood boards. It can also be used as an adhesive for casting sand used in.

According to the method for producing a molded product according to the present invention, the subject is a method for producing a molded product, in which sugars and radicals are generated in one or more objects selected from inorganic fibers, wood, and cast sand. A bonding step of attaching a binder composition containing a reaction product of an agent and an organic acid compound and substantially free of an inorganic acid, and heating of the object to which the binder composition is attached. The problem is solved by carrying out a heating / curing step of cross-linking the binder composition.

At this time, the binder composition preparation step of preparing the binder composition is further included, and in the binder composition preparation step, the saccharide is selected from the group consisting of glucose, galactose, mannose, fructose, maltose, and lactose. At least one kind of reducing sugar, the radical generator is at least one kind selected from the group consisting of an azo compound and a peroxide, and the organic acid compound is a low molecular weight polycarboxylic acid and a low molecular weight. At least one selected from the group consisting of polycarboxylic acids, high molecular weight polycarboxylic acids, and high molecular weight polycarboxylic acids is preferable.
At this time, it is preferable to perform a molding step of molding the object to which the binder composition is attached into a shape corresponding to a desired molded body before the heating / curing step.

The problem is that, according to the cured binder product according to the present invention, the pH of the eluate obtained by immersing in water is 6 or more and less than 8.4, which does not substantially contain inorganic acids and inorganic acid salts. It will be resolved.
According to the molded article according to the present invention, the problem is solved by including a cured product of the binder composition and one or more objects selected from inorganic fibers, wood, and cast sand. ..

According to the present invention, a binder composition having a sufficient reaction rate when the binder is crosslinked without using inorganic acid ions as a raw material and having good mechanical properties such as strength and elastic modulus, the binder composition. It is possible to provide a molded product using a product and a method for producing a molded product using the binder composition.
When the binder composition of the present invention is used, although it is a saccharide-based binder, it does not contain inorganic acid ions, so that the inorganic fibers do not corrode over time.

It is a flow chart which shows the manufacturing method of the molded article which concerns on one Embodiment of this invention. It is a figure which shows the manufacturing method of the rock wool mat which concerns on one Embodiment of this invention. 6 is a graph in which the elastic modulus E'(MPa) of the binder compositions of Examples 1 and Comparative Examples 1 to 8 is plotted as a function of temperature (° C.). It is a graph which plotted the elastic modulus E'(MPa) of the binder composition of Example 1, Comparative Example 4 and Comparative Example 5 as a function of temperature (° C.). 6 is a graph in which the elastic modulus E'(MPa) of the binder compositions of Examples 1 to 3 and Comparative Example 4 is plotted as a function of temperature (° C.).

Hereinafter, embodiments of the present invention will be described with reference to FIGS. 1 to 3C.
In this embodiment, a binder composition containing a reaction product of a saccharide and a radical generator, an organic acid compound, and substantially no inorganic acid, a molded product using the binder composition, and the binder composition. The present invention relates to an invention of a method for producing a molded product using a product.
The molded product of the present embodiment is suitably used as a heat insulating material arranged between an outer wall and an inner wall in a building such as a house, or a heat insulating material arranged outside a pipe such as a factory.

<Binder composition>
The binder composition according to the present embodiment contains a reaction product of a saccharide and a radical generator, an organic acid compound, and substantially no inorganic acid. Each component will be described in detail below.
(Sugar)
The binder composition of the present embodiment contains one or more kinds of saccharides, and examples of the saccharides include reducing sugars or non-reducing sugars, derivatives thereof and the like.

(Reducing sugar)
Examples of the reducing sugar that can be used in the binder composition of the present embodiment include monosaccharides, oligosaccharides, polysaccharides, and derivatives thereof.
In the present specification, the reducing sugar means an aldose having an aldehyde group or a ketose having a ketone group in an open chain form, the oligosaccharide means a monosaccharide having 2 or more and 10 or less bound, and the polysaccharide is a polysaccharide. Refers to a combination of 11 or more monosaccharides.

As the reducing sugar, it is preferable to use a monosaccharide or a disaccharide, and in particular, a monosaccharide containing 3 to 8 carbon atoms, preferably glucose (dextrose) is preferably used. Glucose is made from corn and is a natural product component derived from plants, and a large amount of glucose can be easily obtained at low cost.

It is also possible to use high fructose corn syrup industrially produced from glucose. Here, the isomerized sugar means a mixed sugar having a specific composition ratio of D-glucose and D-fructose as a main composition, and generally, starch is hydrolyzed by an enzyme such as amylase or an acid. It refers to a liquid sugar containing glucose and fructose as main components, which is obtained by isomerizing the obtained sugar solution mainly composed of glucose with glucose isomerase or alkali.
As the reducing sugar, for example, corn syrup, high fructose corn syrup and the like can also be used.
Since fructose is present in the open chain form more than glucose, it is known that the Maillard reaction initiation reaction occurs more rapidly than glucose, and the fructose-containing isomerized sugar has the binder composition of the present embodiment. Can be used for things. In addition, fructose has a higher solubility in water than glucose, and therefore can be suitably used when a high-concentration binder solution is desired to be prepared.

The reducing sugar is not limited to the above-mentioned monosaccharides, and monosaccharides such as galactose, mannose, and fructose can also be used.

Examples of disaccharides that can be used as reducing sugars include lactose, arabinose, and maltose.

(Non-reducing sugar)
Examples of non-reducing sugars that can be used in the binder composition of the present embodiment include oligosaccharides, polysaccharides, and derivatives thereof.
In the present specification, the “non-reducing sugar” refers to a sugar that does not exhibit reducing sugar and is not a reducing sugar. Here, the "reducing sugar" means an aldose having an aldehyde group or a ketose having a ketone group in an open chain form, and all monosaccharides are reducing sugars.
Oligosaccharides refer to those to which 2 or more and 10 or less monosaccharides are bound, and polysaccharides refer to those to which 11 or more monosaccharides are bound.

As the non-reducing sugar, it is preferable to use an oligosaccharide to which a monosaccharide of 2 or more and 10 or less is bound, and it is more preferable to use a disaccharide, a trisaccharide, a tetrasaccharide or a pentasaccharide, and particularly preferably a disaccharide such as sucrose or trehalose. It is preferable to use sugar. Sucrose (sucrose) is a plant-derived natural product component that is made from sugar cane and is used as sugar. In addition, trehalose is made from starch and is a natural product component derived from plants.
In particular, sucrose is a compound that is widely used in households all over the world, is easily available in large quantities, has high safety, and has excellent storage stability. Therefore, the binder composition of the present embodiment. Can be suitably used for.

The disaccharide that can be used as a non-reducing sugar is not limited to sucrose or trehalose, and examples thereof include isotorehalose and isosculose.

Examples of the trisaccharide that can be used as a non-reducing sugar include melezitose, gentianose, raffinose, erulose, and umbelliferose.
Examples of the tetrasaccharide that can be used as a non-reducing sugar include stachyose and the like.
Examples of pentasaccharides that can be used as non-reducing sugars include velva course.

As the non-reducing sugar, for example, sugar cane syrup, sugar beet (sugar beet) syrup, etc. can be used.

The saccharide (reducing sugar or non-reducing sugar) may be substituted with, for example, a hydroxyl group, a halogen, an alkyl group, an alkoxyl group, a carbonyl group or another substituent.
Further, as the saccharide used in the binder composition, a stereoisomer or an optical isomer of a natural or synthetic reducing sugar can also be used.
As the saccharide, any one type may be used alone, or two or more types may be used in combination.

Using glucose, which is a reducing sugar, or sucrose, which produces fructose and glucose, which is a reducing sugar, as saccharides, from the viewpoint of the curing rate of the binder composition when heated, and the availability of raw materials. Preferred from the point of view.

The content of saccharides in the binder composition is 50-90% by weight, preferably 60-85% by weight, and advantageously, of the total weight of the mixture composed of saccharides, radical generators, and organic acid compounds. Is preferably 65 to 80% by weight.

(Radical generator)
As used herein, the term "radical generator" refers to a compound that generates radicals under mild reaction conditions in order to proceed with a radical reaction. Here, the radical means an atom, a molecule, or an ion having an unpaired electron, and is synonymous with a free radical or a free group.

The radical generator contained in the binder composition of the present embodiment is not particularly limited as long as it does not substantially contain an inorganic acid and does not impair the object of the present invention. Azo compounds and peroxides are exemplified.

An azo compound is a compound having an azo group (RN = N-R') that is decomposed by heat and / or light to generate carbon radicals. Specific examples thereof include 2,2'-azobisisobutyronitrile (AIBN).

Examples of the peroxide include an organic peroxide, an inorganic peroxide, and hydrogen peroxide. In the binder composition of the present embodiment, the organic peroxide and hydrogen peroxide are used.
The organic peroxide is a compound containing a peroxide structure (—O—O—), and for example, benzoyl peroxide is typical.
Hydrogen peroxide is a compound represented by the chemical formula H ₂ O ₂ .
From the viewpoint of solubility in an aqueous medium and compatibility with saccharides, it is preferable to use hydrogen peroxide, which is a peroxide containing no inorganic acid, as a radical generator.

The ratio of the radical generator contained in the binder composition is preferably 0.01 to 0.1, preferably 0.02 to 0, when the molar ratio of the saccharide is 1. It is particularly preferably .08.

(Reaction products of sugars and radical generators)
The reaction product (modified sugar) of the saccharide and the radical generator contained in the binder composition of the present embodiment is a compound in which the chemical structure of the saccharide is changed by the radical generator.

It is known that saccharides have two structures, a linear structure having a hydroxy group and a carbonyl group, and a cyclic acetal or ketal cyclic structure containing the hydroxyl group of the saccharide itself. It is presumed that the reaction product of the saccharide and the radical generator contains a compound in which the cyclic acetal structure of the saccharide is ring-opened by the radical generator to change to a linear structure and further increased in molecular weight.

The content of the reaction product (modified sugar) of the saccharide and the radical generator in the binder composition is 70, which is the total weight of the mixture composed of the reaction product of the saccharide and the radical generator and the organic acid compound. It is preferably from 99% by weight, preferably 80 to 97% by weight, and preferably 85 to 95% by weight.

(Organic acid compound)
Examples of the organic acid compound contained in the binder composition of the present embodiment include low molecular weight polycarboxylic acid, low molecular weight polycarboxylic acid, high molecular weight polycarboxylic acid, and high molecular weight polycarboxylic acid. It is not limited to this.

As used herein, the term "polycarboxylic acid" means a carboxylic acid containing two or more carboxyl groups, such as a dicarboxylic acid, a tricarboxylic acid, a tetracarboxylic acid, and a pentacarboxylic acid.
Examples of the polycarboxylic acid include a low molecular weight polycarboxylic acid (monomeric polycarboxylic acid), an anhydride thereof, and a combination thereof, and a high molecular weight polycarboxylic acid, an anhydride thereof, a copolymer thereof, and their copolymers. A combination is given as an example.

(Low molecular weight polycarboxylic acid)
Examples of the dicarboxylic acid which is a low molecular weight polycarboxylic acid include unsaturated aliphatic dicarboxylic acid, saturated aliphatic dicarboxylic acid, aromatic dicarboxylic acid, unsaturated cyclic dicarboxylic acid, saturated cyclic dicarboxylic acid, their hydroxy-substituted derivatives, and halo-substituted derivative. , Alkyl-substituted derivatives, alkoxy-substituted derivatives and the like are exemplified, but the present invention is not limited thereto.
Specific compounds include, for example, oxalic acid, malonic acid, amber acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, malic acid, tartaric acid, tartronic acid, aspartic acid, glutamate, fumal. Examples include, but are not limited to, acids, itaconic acid, malonic acid, traumatic acid, suberic acid, phthalic acid and derivatives thereof.

Examples of the tricarboxylic acid, which is a low molecular weight polycarboxylic acid, include unsaturated aliphatic tricarboxylic acids, saturated aliphatic tricarboxylic acids, aromatic tricarboxylic acids, unsaturated cyclic tricarboxylic acids, saturated cyclic tricarboxylic acids, their hydroxy-substituted derivatives, and halo-substituted derivatives. , Alkyl-substituted derivatives, alkoxy-substituted derivatives and the like are exemplified, but the present invention is not limited thereto.
Specific examples of the compounds include citric acid, tricarbaryl acid, 1,2,4-butanetricarballylic acid, aconitic acid, hemimeric acid, trimellitic acid, citrus lymesic acid and derivatives thereof. , Not limited to these.

(High molecular weight polycarboxylic acid)
High molecular weight polycarboxylic acids include, for example, acids such as polyacrylic acid, polymethacrylic acid, and polymaleic acid, as well as similar high molecular weight polycarboxylic acids, their copolymers, their anhydrides, and mixtures thereof. You may.

As the low molecular weight polycarboxylic acid, the low molecular weight polycarboxylic acid, the high molecular weight polycarboxylic acid, and the high molecular weight polycarboxylic acid, any one of them may be used alone or two or more thereof may be used in combination.

The organic acid compound is preferably selected from low molecular weight polycarboxylic acids and low molecular weight polycarboxylic acid salts, and more preferably citric acid or citrate salts.
In particular, it is preferable to use a polycarboxylic acid salt, for example, triammonium citrate, which is a citrate, as the organic acid compound.

The ratio of the organic acid compound contained in the binder composition is such that the molar ratio of the organic acid compound is 0.05 to 1 when the molar ratio of the saccharide (reaction product of the saccharide and the radical generator: modified sugar) is 1. It is preferably 1.0, more preferably 0.1 to 0.5, and even more preferably 0.1 to 0.2.
When the molar ratio of saccharides is 1, and a binder composition having a molar ratio of organic acid compounds of 0.05 or more is used, curing can be completed at a predetermined temperature and time.

(Amine compound)
As used herein, the term "amine compound" means a generic term containing ammonia and amines.
Ammonia is an inorganic compound represented by the molecular formula NH ₃ , and is a colorless gas at normal temperature and pressure.

Amine is a compound in which a hydrogen atom of ammonia is substituted with a substituent such as a hydrocarbon group or an aromatic atomic group, and if the number of substituted hydrogens is one, it is a primary amine, and if it is two, it is a primary amine. If there are three secondary amines, they are called tertiary amines. Further, when the substituent is bonded to the tertiary amine, it becomes a quaternary ammonium cation.

Examples of amines that can be used in this embodiment include aliphatic amines, aromatic amines, and heterocyclic amines.
Examples of aliphatic amines include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, triethanolamine, hexamethylenediamine and the like.
Examples of aromatic amines include aniline, phenethylamine, toluidine, and catecholamines.
Further, examples of the heterocyclic amine include pyrrolidine, piperidine, piperidine, morpholine, pyrrole, pyrazole, imidazole, pyridine, pyridazine, pyrimidine, oxazole, thiazole and the like.

The binder composition of the present embodiment preferably contains ammonia as the amine compound. When ammonia is used, the mechanical properties of the molded product containing the cured product of the binder composition are good. When an amine compound is used, the reaction product (modified sugar) of the saccharide and the radical generator will have a structure derived from the amine compound.

The binder composition of the present embodiment substantially does not contain an inorganic acid. Here, the fact that the binder composition does not substantially contain an inorganic acid means that the content of the inorganic acid does not corrode the object to which the binder composition is attached. For example, it means that glass wool and rock wool, which are sensitive to acid, are not corroded when a molded product is manufactured by applying a binder composition to inorganic fibers.

Corrosion of inorganic fibers can be evaluated by, for example, whether or not unevenness due to mineral acid-derived precipitates can be confirmed on the fibers when the molded body is observed with a scanning electron microscope (SEM). Is. Specifically, when the molded product was prepared and after a lapse of a predetermined period (for example, after 3 weeks in an environment of 23.5 ° C. and 50 RH%), when the molded product was observed by SEM, an inorganic acid was formed on the fiber. It can be evaluated that there is corrosion when the salt of the above is precipitated. At this time, it is possible to confirm that the precipitate is a salt of an inorganic acid by using an SEM-EDS (EDS: Energy Dispersive X-ray Spectroscopy) and an X-ray diffractometer (XRD).

Further, in order to quantitatively confirm that the binder composition does not substantially contain an inorganic acid, water is obtained when the binder composition is attached to an object such as an inorganic fiber and crosslinked to form a cured product. It suffices to confirm that the eluent obtained by immersing in the solution does not contain inorganic acid ions. For example, when the binder composition is crosslinked to form a cured product, and the eluate obtained by immersing it in water is analyzed by a high performance liquid chromatograph (HPLC, a device for performing high performance liquid chromatography). , It suffices to confirm that the detection amount of the inorganic acid ion is equal to or less than the detection lower limit value of the apparatus.

Further, based on the examples shown below (Table 2), it is said that the substance does not substantially contain an inorganic acid, which means that when a monosaccharide (glucose) is used as the sugar, the inorganic acid ion (for example, sulfate ion) is used. The content may be less than 0.17 mol, preferably less than 0.10 mol, more preferably less than 0.05 mol, in terms of per 1 mol of monosaccharide (that is, 1 mol of denatured sugar (modified sugar 1)). More preferably, it means that it is less than 0.01 mol.

Further, when disaccharide (sucrose) is used as the sugar, the content of the inorganic acid ion (for example, sulfate ion) is such that the content of the inorganic acid ion (for example, sulfate ion) is per 1 mol of the disaccharide (that is, the denatured sugar). In terms of (modified sugar 2) 1 mol), it may be less than 0.10 mol, preferably less than 0.08 mol, more preferably less than 0.05 mol, still more preferably less than 0.01 mol. ..

(Other ingredients)
The binder composition according to the present embodiment is, if necessary, an adhesion improver, a viscosity modifier, an antioxidant, an ultraviolet absorber, a stabilizer, a plasticizer, a wax, a pigment or a dye, as long as the effect of the present invention is not impaired. , Antistatic agents, antibacterial agents, fungicides, fragrances, flame retardants, dispersants, film-forming aids and wetting agents may be used in combination with one or more other additives selected from the group. ..
The content of these additives in the binder composition must be within a range that does not affect the mechanical properties of the binder composition after curing, and is composed of a saccharide, a radical generator, and an organic acid compound. It is preferably 5% by weight or less, preferably 2% by weight or less, based on the total weight of the mixture.

When rock wool or glass wool is used as the inorganic fiber, the binder composition can contain conventionally known additives such as silane such as aminosilane, oil, glycerol, silicone, and bulking agent.

Silane is a coupling agent between the fiber and the binder composition, and also acts as an anti-aging agent. The oil is added from the viewpoint of dust resistance and hydrophobicity. Glycerol acts as a plasticizer and prevents pregelling of the binder solution. Silicone is a hydrophobic substance that has a role of reducing the absorption of water by the molded product. The bulking agent is an organic or inorganic filler that is soluble or dispersible in the binder composition, especially reducing the cost of the binder composition.

(PH of aqueous solution of binder composition)
The binder composition of the present embodiment is characterized in that the pH of the aqueous binder solution is 6 or more and 9 or less, which is neutral to weakly alkaline. The pH of the binder composition is more preferably 6 or more and 8 or less, and particularly preferably 6 or more and 7 or less. In this specification, acidic is defined as having a pH of 1 or more and less than 6, neutral is defined as 6 or more and 8 or less, and alkaline is defined as being greater than 8 and 12 or less.

Glass wool and rock wool are generally used as the inorganic fiber-based heat insulating material. Rock wool has a higher melting point and better heat resistance than glass wool, but is more sensitive to acids than glass wool. Some conventional non-formaldehyde type binder aqueous solutions are acidic with a pH of less than 6.0, and when used for rock wool, the rock wool can be dissolved to obtain a molded product at the level required for the product. Sometimes I couldn't.
On the other hand, since the binder composition of the present embodiment has a pH of 6 or more and 9 or less in a neutral to weakly alkaline region when it is made into an aqueous solution, rock wool does not dissolve, and it is suitable for producing a molded product using rock wool. Can also be preferably used.
Further, the conventional non-formaldehyde type binder has been difficult to use for mineral fibers other than rock wool, which are easily damaged by acids, such as stone wool, slag wool, and mineral wool. Since the binder composition has a pH of 6 or more and 9 or less in a neutral to weakly alkaline region when made into an aqueous solution, it can be suitably applied to mineral fibers that are easily damaged by acid.

It is possible to set the pH to the neutral to alkaline range by adding excess ammonia to the acidic binder solution, but the excess ammonia volatilizes from the binder solution, which deteriorates the working environment. was there.
It is also possible to make the pH in the neutral to alkaline range by adding excess sodium hydroxide to the acidic binder solution, but the residual sodium causes the surface of the binder-coated material to become It sometimes became strongly alkaline.
Since the binder composition of the present embodiment has a pH of 6 or more and 9 or less in a neutral to weakly alkaline region when made into an aqueous solution, it can be used without adding excess ammonia or sodium hydroxide.

Furthermore, since the phenolic resin binder has a pH of 7 to 9 and is neutral to weakly alkaline, a steel material is used in the conventional molding equipment. Therefore, if the aqueous binder solution is acidic, the steel material used in the manufacturing apparatus, particularly the carbon steel material such as S50C, will rust when the molded product is manufactured using the binder. Therefore, if the binder composition is acidic, the steel material cannot be used in the equipment used when applying the binder composition. In order to use an acidic binder aqueous solution, enormous costs are required when taking measures such as making the molded product manufacturing apparatus stainless, but the binder composition of the present embodiment is an aqueous solution. Since the pH is in the neutral to weakly alkaline region of about 6 or more and 9 or less, it is possible to use the conventional manufacturing apparatus for the molded product as it is.

Further, the binder composition of the present embodiment is neutral to weakly alkaline like the conventional phenolic resin-based binder and is not acidic, so that the binder composition is not limited to mineral fibers such as rock wool, and other acids are used. It can be used for materials that are sensitive to minerals, and can be used in a wide range of applications as a substitute for phenolic resin binders.

(PH of eluate of cured binder)
The binder composition of the present embodiment is characterized in that the pH of the eluate obtained by immersing it in water is 6 or more and 7 or less when it is crosslinked to form a cured product. When the binder composition is crosslinked to form a cured product, the pH of the eluate obtained by immersing it in water is more preferably 6 or more and 6.8 or less, and particularly 6 or more and 6.6 or less. Is preferable.

Since the conventional non-formaldehyde type binder composition uses an inorganic acid or an inorganic acid salt (for example, ammonium sulfate), the eluate obtained by immersing it in water when it is crosslinked to form a cured product. The pH is as low as less than 3.5 and it is acidic. Therefore, when a conventional non-formaldehyde type binder containing an inorganic acid or an inorganic acid salt is used for glass wool or rock wool, the cured binder absorbs moisture in the air over time, and the glass wool or rock wool dissolves. However, it was not possible to obtain a molded product capable of maintaining the level required for the product.

On the other hand, since the binder composition of the present embodiment does not substantially contain an inorganic acid, the pH of the eluate obtained by immersing it in water when it is crosslinked to form a cured product is 6 or more and 7 or less. Since it is in the neutral region, glass wool and rock wool do not dissolve, and it can be suitably used for producing a molded product using inorganic fibers that are affected by acids such as glass wool and rock wool.

In addition, when the conventional non-formaldehyde type binder is also used for mineral fibers that are easily damaged by acids other than rock wool, such as stone wool, slag wool, and mineral wool, the fibers deteriorate over time. Although there was a possibility, the binder composition of the present embodiment has a pH of 6 or more and 7 or less in the neutral region of the eluate obtained by immersing it in water when it is crosslinked to form a cured product. It can also be suitably applied to mineral fibers that are easily damaged by acid.

<Molded product using binder composition>
Using the binder composition according to the present embodiment, molded articles such as heat insulating materials and soundproofing materials using inorganic fibers such as glass wool, rock wool and ceramic fibers can be produced, but the present invention is not limited thereto. .. For example, for various applications in which a thermosetting binder typified by a phenolic resin binder is used, for example, for casting, friction material, grindstone, filter paper, molding material, plywood processing, decorative board, laminated board. It is possible to use.

The molded product according to the present embodiment is formed by molding inorganic fibers or the like using the binder composition of the present embodiment, and is, for example, a heat insulating material, a sound absorbing material, or a wood board product (chip board, oriented strand board). , Particle board, fiber board, etc.), and various other molded products (automobile roof, bonnet liner, etc.).

Examples of the inorganic fiber used in the molded body include, but are not limited to, rock wool, stone wool, slag wool, mineral wool, glass wool, and mineral glass wool. Any one of these inorganic fibers may be used alone or in combination of two or more. From the viewpoint of versatility, heat insulation, soundproofing, etc., it is preferable to use glass wool or rock wool as the inorganic fiber.
The molded product according to the present embodiment may further include members other than the molded product, such as a skin material for packing.

In addition to inorganic fibers, objects such as wood (wood chips, wood fibers, etc.), casting sand, etc. are molded using the binder composition according to the present embodiment to form wood board products, molds, etc. Can provide a body. In the present specification, the object means an application target of a binder composition such as inorganic fiber, wood, and foundry sand. The state of the object when the binder composition is applied may be a state in which inorganic fibers, wood, and casting sand are not accumulated, or a state in which inorganic fibers, wood, and casting sand are accumulated. good.

<Method of manufacturing a molded product using a binder composition>
As the molded product according to the present embodiment, a known method conventionally used for producing a molded product can be used except that the binder composition according to the present embodiment is used as the binder.

For example, in the method for producing a molded product according to the present embodiment, a reaction product of a saccharide and a radical generator and an organic acid compound are added to one or more objects selected from inorganic fibers, wood, and cast sand. A bonding step (step 1) of adhering a binder composition containing substantially no inorganic acid, and a cross-linking reaction of the binder composition by heating the object to which the binder composition is attached. It is characterized in that the heating / curing step (step 2) is performed.

In the attachment step (step 1), the binder composition according to the present embodiment is attached to one or more objects selected from inorganic fibers, wood, and foundry sand. Examples of the method for adhering the binder composition to the object include a method of spraying the binder on the object using a spray device and the like, a method of impregnating the aggregate in the binder solution, and the like. You may.

In the heating / curing step (step 2), the object to which the binder composition is attached is heated to cause a cross-linking reaction of the binder composition.

In addition, a binder composition preparation step (step 0) for preparing the binder composition in advance may be performed. In the binder composition preparation step, the saccharide is a group consisting of glucose, galactose, mannose, fructose, maltose, and lactose. At least one reducing sugar selected from the above, the radical generator is at least one selected from the group consisting of azo compounds and peroxides, and the organic acid compound is a low molecular weight polycarboxylic acid. It is preferable that at least one selected from the group consisting of low molecular weight polycarboxylic acid salts, high molecular weight polycarboxylic acids, and high molecular weight polycarboxylic acids.

Further, after performing the bonding step (step 1) and before performing the heating / curing step (step 2), a molding step (step) of molding the aggregate to which the binder composition is adhered into a shape corresponding to a desired molded body. 1A) may be performed.

(Manufacturing method of inorganic fiber molded product)
Hereinafter, a method for producing the inorganic fiber molded product will be specifically described.
As the method for producing the inorganic fiber molded body according to the present embodiment, a known method conventionally used for producing the inorganic fiber molded body is used except that the binder composition according to the present embodiment is used as the binder. Can be done.
For example, a step of preparing a binder composition containing a reaction product of a saccharide and a radical generator and an organic acid compound according to the present embodiment and substantially free of an inorganic acid (hereinafter referred to as a binder composition preparation step). ), A step of adhering the binder composition according to the present embodiment to the inorganic fibers (hereinafter, attachment step), and a step of accumulating the inorganic fibers to which the binder composition is attached to form an aggregate (hereinafter, integration step). A step of molding the aggregate into a shape corresponding to a desired inorganic fiber molded body (hereinafter, molding step) and a step of heating the molded aggregate to cause a cross-linking reaction of the binder composition (hereinafter, hereinafter). A method of sequentially performing a step (heating / curing step) and a step of cooling the binder composition crosslinked in the heating step (hereinafter referred to as a cooling step) can be mentioned.
Hereinafter, each step will be described in detail with reference to FIG.

(Binder composition preparation step)
In the binder composition preparation step, a binder composition containing a reaction product of a saccharide and a radical generator and an organic acid compound according to the present embodiment and substantially free of an inorganic acid is prepared (step S1). ..
At this time, the binder composition is prepared as a binder solution using a solvent such as water or alcohol.

(Adhesion process)
In the attachment step, the binder composition according to the present embodiment is attached to the inorganic fibers (step S2).
As the inorganic fiber, glass wool, rock wool, ceramic fiber or the like can be used, and the fiber length and fiber diameter of the inorganic fiber may be selected according to the inorganic fiber molded body, and the fiber diameter is usually 3 to 10 μm. Those within the range are used, but are not limited to this.
As the inorganic fiber, a commercially available one may be used, or one produced by a known method may be used as it is. Inorganic fibers are generally produced by fiberizing molten raw materials (glass, minerals such as basalt, iron furnace slag, etc.), and examples of the fiberization method include a flame method and a centrifugation method.

Examples of the method of adhering the binder composition to the inorganic fiber include a method of spraying the binder on the inorganic fiber using a spray device and the like, a method of impregnating the binder with the inorganic fiber, and the like. May be good.
The amount of the binder composition attached to the inorganic fiber is not particularly limited, but it is preferable that the solid component of the binder composition is in the range of 0.5 to 20% by mass when the inorganic fiber is 100% by mass. .. The amount of the binder composition affects the properties of the inorganic fiber molded body, and the larger the amount of the binder composition, the stronger the mechanical strength of the inorganic fiber molded body.

(Integration process)
In the accumulation step, the inorganic fibers to which the binder composition is attached are accumulated in the adhesion step to form an aggregate (step S3).
The integration step can be carried out by a known method. Inorganic fibers to which the binder composition is attached may be deposited on a rotating belt to form a fleece to form an aggregate.

(Molding process)
In the molding step, the aggregate is molded into a shape corresponding to a desired inorganic fiber molded body (step S4).
The molding step can be carried out by a known method. Taking the case of producing a plate-shaped inorganic fiber molded product as an example, the aggregates may be laminated on a conveyor. At this time, a compression step may be performed in which the stacked aggregates are pressed from the vertical direction to be compressed.

(Heating / curing process)
In the heating / curing step, the molded aggregate is heated and the binder composition is crosslinked (step S5).
The molded aggregate is sent to a curing furnace and heated to react the binder composition, thereby forming a structure in which different polymers (melanoidin polymer and caramelized reaction polymer) are crosslinked by an ester bond. ..
The heating temperature in the heating / curing step may be within the range in which the binder composition is crosslinked, and is preferably in the range of 110 ° C. or higher and 300 ° C. or lower. If the temperature is lower than 110 ° C., the binder composition may be insufficiently crosslinked and the mechanical strength may be insufficient. If it exceeds 300 ° C., the binder composition may be decomposed and the mechanical strength may be lowered.

The heating time in the heating / curing step may be within the range in which the binder composition is crosslinked, and may be appropriately adjusted depending on the size of the aggregate, the heating temperature, etc., and is not particularly limited, but may be 30 seconds to 30 minutes.

(Cooling process)
In the cooling step, the binder composition crosslinked in the heating step is cooled (step S6).
Specifically, the inorganic fiber molded product delivered from the curing furnace is cooled to room temperature. The cooling includes positive cooling by blowing air and the like, and cooling by natural drying without blowing air and the like.
The obtained inorganic fiber molded product may be used as it is as a product, or may be further subjected to a cutting step of cutting, a packing step of packing with a skin material, or the like, if necessary.

(Manufacturing method of rock wool mat)
As a specific example of the method for producing a molded product using the binder composition according to the present embodiment, a method for producing a rock wool mat will be described. FIG. 2 is a diagram showing a method for producing a rock wool mat according to an embodiment of the present invention.
The rock wool mat of the present embodiment is a mat made of a laminated body of rock wool, and the rock wool is attached to each other by a cured binder.
The molten raw material 1 is dropped on a roll 11 that rotates at high speed. A binder is sprayed together with air on the roll 11 through which the raw material 1 is transmitted to the surroundings, the raw material 1 is made into fibers, and the raw material 1 is blown off to the steel belt (first belt) 13. Fibers are deposited on the steel belt 13 to form the fleece 3. The fleece 3 moves with the movement of the steel belt 13 and moves to the pendulum (second belt) 15 at a predetermined position. After that, the fleece 3 moves further and moves onto the conveyor (third belt) 17 at a predetermined position. The fleeces are stacked on the conveyor 17 to form the laminated body 5. The laminate 5 is passed through a curing furnace 19 to cure the binder, and a rock wool mat 7 is obtained.

Hereinafter, the present invention will be specifically described based on specific examples, but the present invention is not limited thereto.

<Preparation of denatured sugar solution>
According to the following procedure, a modified sugar solution was prepared in the blending amounts shown in Table 1.
1) A mixed solution of water, sugar and aqueous ammonia was heated to 90 ° C.
2) A radical generator was added dropwise to this mixed solution over 4 hours.
3) After that, the mixture was stirred at 90 ° C. for 1 hour.
4) The mixture was cooled to room temperature to obtain a modified sugar solution having a modified sugar content of 50% by mass.

<Preparation of aqueous binder solution>
Each component was added to water with stirring at the blending amounts shown in Table 2 to obtain aqueous binder solutions (concentration: 50% by mass) of Examples 1 to 3 and Comparative Examples 1 to 7 and 9. In Table 2, denatured sugars (reaction products of sugars and radical generators) produced from 1 mol of sugars are represented as 1 mol.
Further, as an index of binder performance, a commercially available resole-type phenolic resin-based binder (Resitop, manufactured by Gun Ei Chemical Industry Co., Ltd., for inorganic fiber products) was used as the binder of Comparative Example 8.

Using the obtained aqueous binder solution, a molded product was prepared and various characteristics were measured by the following procedure.

<Test Example 1: Preparation of molded product and measurement of tensile strength>
According to the following procedure, the molded product was prepared and the tensile strength was measured.
1) A glass filter paper (manufactured by Whatman, grade GF / A, 120 mm × 25 mm) was impregnated into the binder aqueous solution.
2) The glass filter paper to which the binder composition was attached was dried at 100 ° C. for 1 hour.
3) The binder composition was cured at a curing temperature (200 ° C.) for 30 minutes to obtain a glass filter paper to which the cured binder composition was attached.
4) When the weight of the glass filter paper to which the cured binder was attached was 100% by weight, the weight of the cured binder was 70% by weight.
5) The glass filter paper to be tested is subjected to a tensile test under the conditions of a load full scale of 200 N and a tensile speed of 25.4 mm / min using a universal material testing machine (RTC-1150A, manufactured by Orientec), and the tensile strength is obtained. And the tensile modulus.
The glass filter paper was used as a substitute for the inorganic fiber for easy evaluation, and it is presumed that the glass filter paper shows the same tendency as the result when the inorganic fiber such as glass wool is used.

<Test Example 2: Measurement of water elution rate and water elution pH of cured binder>
The amount of eluate from the cured product and the pH of the eluate were measured according to the following procedure.
1) A glass filter paper (manufactured by Whatman, grade GF / A, φ150 mm) was impregnated into the binder solution.
2) The glass filter paper to which the binder composition was attached was dried at 100 ° C. for 1 hour.
3) The binder composition was cured at a curing temperature (200 ° C.) for 30 minutes to obtain a glass filter paper to which the cured binder composition was attached.
4) When the weight of the glass filter paper to which the cured binder was attached was 100% by weight, the weight of the cured binder was 70% by weight.
5) The weight of the glass filter paper to which the cured binder was attached was measured and used as the weight before immersion.
6) The glass filter paper to which the cured binder was attached was immersed in ion-exchanged water. 350 g of ion-exchanged water was used with respect to 1 g of the cured binder.
7) After soaking for 12 hours, the pH of the solution was measured.
8) After measuring the pH, the glass filter paper to which the cured binder was attached was taken out and dried at 100 ° C. for 12 hours.
9) The weight of the glass filter paper to which the cured binder was attached after drying was measured and used as the weight after drying.
10) The water elution rate was calculated from the formula of (weight before immersion-weight after drying) ÷ (weight before immersion) × 100.

<Test Example 3: Preparation of molded product and measurement of bending strength>
According to the following procedure, the molded product was prepared and the bending strength was measured.
1) A binder solution was added to glass beads for blasting (Potters Barotini Co., Ltd., grade J-70), and the mixture was stirred.
2) Glass beads to which the binder aqueous solution was attached were placed in a mold and press-molded at 205 ° C. for 30 minutes to obtain a bending test piece having a width of 15 mm, a length of 80 mm and a thickness of 6 mm.
3) When the weight of the glass beads to which the cured binder is attached is 100% by weight, the weight of the cured binder is 3% by weight.
4) The test piece was subjected to a bending test using a universal material testing machine (manufactured by Shimadzu Corporation, Autograph AGS-500NX) under the conditions of a load full scale of 500 N, a tensile speed of 50 mm / min, and a distance between fulcrums of 40 mm. The bending strength was measured.

<Test Example 4: Measurement of reaction rate>
According to the following procedure, the cross-linking start temperature and the cross-linking end temperature were determined by the dynamic mechanical analysis (DMA) method in order to clarify the curing characteristics of the binder. As a dynamic mechanical analyzer, a dynamic viscoelastic spectrometer RSAIII manufactured by TA Instruments was used.
1) A sample for measurement was prepared by dropping one drop (about 50 mg) of a binder 50% by mass solution onto a filter paper (made of pulp, 12.5 mm × 45 mm).
2) The sample was fixed horizontally between the two chucks of the device. The distance between the chucks was set to 20 mm.
3) The sample was heated to a temperature from 30 ° C. to 250 ° C. at a rate of 4 ° C./min, and a change curve of elastic modulus E'was obtained.
4) At this time, the frequency was set to 1 rad / sec and the strain was set to 0.1%.

<Test Example 5: Evaluation of fiber corrosiveness>
The fiber corrosiveness was evaluated by whether or not unevenness due to the precipitate derived from the inorganic acid could be confirmed on the fiber when the molded product was observed with a scanning electron microscope (SEM). Specifically, after a predetermined period of time has passed since the molded product was produced (for example, after 3 weeks have passed in an environment of 23.5 ° C. and 50 RH%, or after 5 days have passed under high temperature and high humidity acceleration conditions of 40 ° C. and 85% RH). ), When the molded product is observed by SEM, "○ (no corrosion)" is given when the mineral acid salt is not precipitated on the fiber, and "x (x)" when the inorganic acid salt is precipitated. Corrosion) ”. It was confirmed by using SEM-EDS and an X-ray diffractometer (XRD) that the precipitate was a salt of an inorganic acid.

<Results of Test Examples 1 to 5>
The measurement results of various characteristics obtained in Test Examples 1 to 5 are shown in Table 3 below together with the pH of the aqueous binder solution.

(Result of Comparative Example 8)
As shown in Table 3, the values of tensile strength and tensile elastic modulus when a phenolic resin-based binder (Comparative Example 8) was used were used as indexes for determining the binder performance. The pH was 7.5.

(Results of Examples 1 to 3)
As shown in Table 3, when the binder composition of Example 1 was used, the tensile strength was 8.9 MPa and the tensile elastic modulus was 1002 MPa, showing appropriate mechanical properties.
The pH of the aqueous binder solution was 6.8, which was in the neutral region. Further, the pH of the water eluate of the cured product was 6.3, which was in the neutral range.
Furthermore, the fiber corrosiveness was "○ (no corrosion)".

Similarly, when the binder compositions of Examples 2 and 3 were used, the tensile strength was 8.5 to 8.7 MPa and the tensile elastic modulus was 976 to 988 MPa, showing appropriate mechanical properties.
The pH of the aqueous binder solution was 6.6 to 6.7, which was in the neutral region. Further, the aqueous solution of the cured product also had a pH of 8.2 to 8.3 (that is, less than 8.4), which was in a weak alkaline region.
Furthermore, the fiber corrosiveness was "○ (no corrosion)".

(Results of Comparative Examples 1 to 7 and 9)
As shown in Table 3, in Comparative Examples 1 to 3, 5 to 7 in which ammonium sulfate was used as the inorganic ammonium acid and Comparative Example 9 in which diammonium hydrogen phosphate was used, the elution rate of the cured binder was 2.4 to 3. It was as high as 9.9% by mass, and the pH of the eluate was 2.9 to 3.4, which was strongly acidic. Due to this, the fiber corrosiveness was "x (corrosion)".

In Comparative Examples 1 to 6 and 9, the tensile elastic modulus was lower than that in Example 1. In addition, the tensile strength of Example 1 was larger than that of Comparative Examples 2 to 6 and 9 and the phenol resin (Comparative Example 8).

From the above results, when the binder compositions of Examples 1 to 3 were used, since no inorganic acid was used as a raw material, the inorganic fibers were not corroded and the mechanical properties were superior to those of the phenol resin.

<Result of Test Example 4>
The results of plotting the elastic modulus E'(MPa) as a function of temperature (° C.) are shown in FIGS. 3A, 3B and 3C.
As shown in FIGS. 3A and 3C, the reaction rate of the binder composition of Example 1 was the highest reaction rate among the binders that did not use an inorganic acid such as ammonium sulfate. The reaction rate of the binder composition of Example 1 was faster than that of the binder composition of Comparative Example 4 in which sugar and ammonium citrate were combined, and it was shown that the binder composition could be sufficiently cured even by using a conventional production process. It was.

<Summary of test>
From the above results, the binder composition according to the present embodiment has a sufficient reaction rate when the binder is crosslinked, such as strength and elastic modulus, even though inorganic acid ions are not used as a raw material. It was shown that the mechanical properties were good.
When the binder composition according to the present embodiment is used, although it is a saccharide-based binder, it does not contain inorganic acid ions, so that the inorganic fibers do not corrode over time.

1 Melted raw material 3 Fleece 5 Laminated body 7 Rock wool mat 11 Roll 13 Steel belt (first belt)
15 Pendulum (second belt)
17 Conveyor (third belt)
19 Curing furnace

Claims (15)

1. Reaction products of sugars and radical generators,
   Contains organic acid compounds,
   A binder composition characterized by substantially containing no inorganic acid.
2. The binder composition according to claim 1, wherein the saccharide is at least one reducing sugar selected from the group consisting of glucose, galactose, mannose, fructose, maltose, and lactose.
3. The binder composition according to claim 1 or 2, wherein the radical generator is at least one selected from the group consisting of an azo compound and a peroxide.
4. The binder composition according to claim 3, wherein the peroxide is at least one selected from the group consisting of hydrogen peroxide solution and an organic peroxide.
5. The organic acid compound is at least one selected from the group consisting of low molecular weight polycarboxylic acids, low molecular weight polycarboxylic acids, high molecular weight polycarboxylic acids, and high molecular weight polycarboxylic acids. The binder composition according to any one of claims 1 to 3.
6. The binder composition according to any one of claims 1 to 4, wherein the organic acid compound is at least one selected from the group consisting of citric acid and ammonium citrate.
7. The binder composition according to any one of claims 1 to 5, further comprising an amine compound.
8. A binder composition comprising a reaction product of a saccharide and a radical generator, an organic acid compound, and substantially no inorganic acid.
   One or more objects selected from inorganic fibers, wood, and foundry sand,
   A molded product comprising.
9. The molded product according to claim 8, wherein the inorganic fiber contains at least one mineral fiber selected from the group consisting of rock wool, stone wool, slag wool, mineral wool, glass wool, and mineral glass wool. ..
10. The sugar is at least one reducing sugar selected from the group consisting of glucose, galactose, mannose, fructose, maltose, and lactose.
    The radical generator is at least one selected from the group consisting of azo compounds and peroxides.
    The organic acid compound is at least one selected from the group consisting of low molecular weight polycarboxylic acids, low molecular weight polycarboxylic acids, high molecular weight polycarboxylic acids, and high molecular weight polycarboxylic acids. The molded product according to claim 8 or 9.
11. It is a method of manufacturing a molded product.
    One or more objects selected from inorganic fibers, wood, and cast sand contain reaction products of sugars and radical generators and organic acid compounds, and are characterized in that they are substantially free of inorganic acids. Adhesion process for adhering the binder composition and
    A heating / curing step of heating the object to which the binder composition is attached and causing a cross-linking reaction of the binder composition, and
    A method for producing a molded product, which comprises the above.
12. Further, the binder composition preparation step of preparing the binder composition is included.
    In the binder composition preparation step
    The sugar is at least one reducing sugar selected from the group consisting of glucose, galactose, mannose, fructose, maltose, and lactose.
    The radical generator is at least one selected from the group consisting of azo compounds and peroxides.
    The organic acid compound is at least one selected from the group consisting of low molecular weight polycarboxylic acids, low molecular weight polycarboxylic acids, high molecular weight polycarboxylic acids, and high molecular weight polycarboxylic acids. The method for producing a molded product according to claim 11.
13. The method for producing a molded product according to claim 12, wherein a molding step of molding the object to which the binder composition is attached into a shape corresponding to a desired molded body is performed before the heating / curing step. ..
14. Substantially free of inorganic acids and acid salts
    A binder cured product characterized in that the pH of the eluate obtained by immersing it in water is 6 or more and less than 8.4.
15. A cured product of the binder composition according to claim 14, and
    A molded product comprising one or more objects selected from inorganic fibers, wood, and cast sand.

Images