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

Binder composition, molded body, production method for molded body, and binder cured object Download PDF

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WO2020246055A1
WO2020246055A1 PCT/JP2019/040652 JP2019040652W WO2020246055A1 WO 2020246055 A1 WO2020246055 A1 WO 2020246055A1 JP 2019040652 W JP2019040652 W JP 2019040652W WO 2020246055 A1 WO2020246055 A1 WO 2020246055A1
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binder composition
binder
molecular weight
inorganic
group
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PCT/JP2019/040652
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French (fr)
Japanese (ja)
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純 及川
悠 浅野
平 吉田
雄太 野中
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ニチアス株式会社
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Priority to JP2019556724A priority Critical patent/JP6701456B1/en
Publication of WO2020246055A1 publication Critical patent/WO2020246055A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
    • C08K5/23—Azo-compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/02—Starch; Degradation products thereof, e.g. dextrin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J105/00—Adhesives based on polysaccharides or on their derivatives, not provided for in groups C09J101/00 or C09J103/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic

Definitions

  • the present invention relates to a binder composition, a molded product, a method for producing a molded product, and a cured binder.
  • phenolic resin-based binders are widely used 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.
  • a binder 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.
  • 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.
  • 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
  • the binder described in Patent Document 1 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.
  • 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.
  • CaSO 4 calcium sulfate
  • Na 2 SO 4 sodium sulfate
  • 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.
  • 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.
  • 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.
  • inorganic acid ions are not used, the application target such as inorganic fibers does not corrode over time.
  • the sugar is at least one reducing sugar selected from the group consisting of glucose, galactose, mannose, fructose, maltose, and lactose.
  • 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.
  • the radical generator is at least one selected from the group consisting of an azo compound and a peroxide.
  • the peroxide is at least one selected from the group consisting of hydrogen peroxide solution and organic peroxide.
  • 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.
  • 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. ..
  • the organic acid compound is at least one selected from the group consisting of citric acid and ammonium citrate.
  • an amine compound such as ammonia
  • the mechanical properties of the molded product containing the cured product of the binder composition become good.
  • 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 Inorganic fiber, wood, one or more objects selected from cast sand, and the like.
  • 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.
  • the saccharide is at least one reducing sugar selected from the group consisting of glucose, galactose, mannose, fructose, maltose, and lactose
  • the radical generator is composed of an azo compound and a peroxide.
  • 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.
  • 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.
  • the problem is solved by carrying out a heating / curing step of cross-linking the binder composition.
  • 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.
  • the radical generator is at least one kind selected from the group consisting of an azo compound and a peroxide
  • 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.
  • 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.
  • 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. ..
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the reducing sugar examples include monosaccharides, oligosaccharides, polysaccharides, and derivatives thereof.
  • 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
  • the polysaccharide is a polysaccharide. Refers to a combination of 11 or more monosaccharides.
  • a monosaccharide or a disaccharide 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 preferably glucose (dextrose)
  • 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.
  • 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.
  • the reducing sugar for example, corn syrup, high fructose corn syrup and the like can also be used.
  • fructose 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.
  • 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.
  • the “non-reducing sugar” refers to a sugar that does not exhibit reducing sugar and is not a reducing sugar.
  • 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.
  • sucrose is a plant-derived natural product component that is made from sugar cane and is used as sugar.
  • trehalose is made from starch and is a natural product component derived from plants.
  • 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.
  • 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.
  • a stereoisomer or an optical isomer of a natural or synthetic reducing sugar can also be used.
  • any one type may be used alone, or two or more types may be used in combination.
  • 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 refers to a compound that generates radicals under mild reaction conditions in order to proceed with a radical reaction.
  • 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.
  • the peroxide examples include an organic peroxide, an inorganic peroxide, and hydrogen peroxide.
  • 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.
  • 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.
  • 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.
  • 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.
  • tricarboxylic acid which is a low molecular weight polycarboxylic acid
  • examples of the tricarboxylic 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.
  • 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 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.
  • the low molecular weight polycarboxylic acid 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.
  • 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.
  • 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 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.
  • a substituent such as a hydrocarbon group or an aromatic atomic group
  • 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.
  • heterocyclic amine examples 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.
  • ammonia the mechanical properties of the molded product containing the cured product of the binder composition are good.
  • 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.
  • 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).
  • SEM-EDS Energy Dispersive X-ray Spectroscopy
  • XRD X-ray diffractometer
  • 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.
  • HPLC high performance liquid chromatograph
  • the detection amount of the inorganic acid ion is equal to or less than the detection lower limit value of the apparatus.
  • 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.
  • the content of the inorganic acid 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).
  • (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. ..
  • 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.
  • 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.
  • 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.
  • 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
  • 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 could't.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 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. ..
  • a thermosetting binder typified by a phenolic resin binder
  • 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.).
  • the inorganic fiber used in the molded body examples 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the binder composition according to the present embodiment is attached to one or more objects selected from inorganic fibers, wood, and foundry sand.
  • 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.
  • step 2 the object to which the binder composition is attached is heated to cause a cross-linking reaction of the binder composition.
  • a binder composition preparation step for preparing the binder composition in advance may be performed.
  • 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.
  • 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.
  • a method for producing the inorganic fiber molded product will be specifically described.
  • 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.
  • the binder composition preparation step 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.
  • 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.
  • 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.
  • the binder composition according to the present embodiment is attached to the inorganic fibers (step S2).
  • 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 ⁇ m. Those within the range are used, but are not limited to this.
  • 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.
  • 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.
  • 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.
  • 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.
  • the binder composition crosslinked in the heating step is cooled (step S6).
  • 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.
  • 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.
  • 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.
  • 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.
  • a glass filter paper manufactured by Whatman, grade GF / A, 120 mm ⁇ 25 mm
  • the glass filter paper to which the binder composition was attached was dried at 100 ° C. for 1 hour.
  • 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.
  • 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.
  • 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, ⁇ 150 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.
  • a glass filter paper manufactured by Whatman, grade GF / A, ⁇ 150 mm
  • 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.
  • 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.
  • 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.
  • a universal material testing machine manufactured by Shimadzu Corporation, Autograph AGS-500NX
  • ⁇ Test Example 4 Measurement of reaction rate>
  • 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.
  • DMA dynamic mechanical analysis
  • 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.
  • SEM scanning electron microscope
  • 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.
  • 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.
  • 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.
  • the fiber corrosiveness was " ⁇ (no corrosion)".
  • Comparative Examples 1 to 6 and 9 the tensile elastic modulus was lower than that in Example 1.
  • 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).
  • FIGS. 3A, 3B and 3C The results of plotting the elastic modulus E'(MPa) as a function of temperature (° C.) are shown in FIGS. 3A, 3B 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.
  • 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.
  • 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.

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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

バインダー組成物、成形体、成形体の製造方法及びバインダー硬化物Binder composition, molded product, manufacturing method of molded product, and cured binder
　本発明は、バインダー組成物、成形体、成形体の製造方法及びバインダー硬化物に関する。 The present invention relates to a binder composition, a molded product, a method for producing a molded product, and a cured binder.
　従来、グラスウール、ロックウール、セラミックファイバー等の無機繊維を用いた断熱材、防音材、木材ボード製品等の成形体の製造に用いられるバインダーとして、機械的強度等の性能に優れ、低コストであることからフェノール樹脂系のバインダーが、汎用されている。 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.
　無機繊維を用いた成形体を製造する際には、無機繊維にバインダーを付着させ、製品の形状とした後に、加熱によりバインダーを硬化させる。バインダーとしては、過去、原料にホルムアルデヒドを使用するフェノール樹脂系のバインダーが広く用いられていたが、近年、原料にホルムアルデヒドを使用していないバインダーが望まれている。 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.
　原料にホルムアルデヒドを使用しない、いわゆるノンホルムアルデヒドタイプのバインダーとしては、糖類をベースとして、ポリカルボン酸や無機酸アンモニウム塩等と組み合わせたバインダーが提案されている。 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.
　特許文献１には、少なくとも１種の非還元糖、少なくとも１種の無機酸アンモニウム塩と添加剤、および水から成る、鉱物繊維用のホルムアルデヒドを含まないサイズ剤組成物が記載されている。 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.
　特許文献２には、ガラスファイバーおよびセルロース繊維からなる群より選択される集合体とバインダーとを含む組成物に関し、バインダーが、シリコーン化合物および脱水反応混合物の架橋結合メラノイジン反応物を含むことが記載されている。脱水反応混合物は、単量体ポリカルボン酸のアンモニウム塩と単糖とからなる。 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.
　特許文献３は、非還元糖と、不飽和モノカルボン酸塩と、無機酸アンモニウム塩とを含むバインダー組成物が記載されている。 Patent Document 3 describes a binder composition containing a non-reducing sugar, an unsaturated monocarboxylic acid salt, and an ammonium inorganic acid salt.
特許第５９３１９０１号公報Japanese Patent No. 5931901 特許第５４５５１６９号公報Japanese Patent No. 5455169 特許第６０６２０９９号公報Japanese Patent No. 6062099
　特許文献１に記載のバインダーを、成形体の製造に用いた場合、熱硬化後の強度や弾性率などの力学的特性が、フェノール樹脂系バインダーと比べて劣っていることがあった。
　また、特許文献２に記載のバインダーは、反応速度が遅く、製造工程において十分に硬化しないことがあった。 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.
　さらに、本発明者らは、特許文献１や特許文献３に記載されているバインダーのように、無機酸アンモニウム塩を用いた場合、触媒量であるにもかかわらず無機酸アンモニウム塩由来の無機酸イオンが無機繊維を腐食させてしまうという課題があることを見出した。 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.
　具体的には、無機酸イオンとして硫酸イオンを含むバインダー組成物を用いた場合、時間が経過するとともにバインダー硬化物が大気中の水分を吸収し、硫酸イオンを含む水が生成し、バインダー組成物中を移動し、繊維を腐食させてしまうことが新たに見出された。無機繊維がロックウールの場合、硫酸カルシウム（ＣａＳＯ４）が生成し、繊維の表面でＣａＳＯ４・２Ｈ２Ｏとなる。また、無機繊維がグラスウールの場合、硫酸ナトリウム（Ｎａ２ＳＯ４）が生成して繊維表面に析出する。 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.
　したがって、原料に無機酸イオンを用いることなく、バインダーを架橋反応させる際の反応速度が十分であり、強度や弾性率などの力学的特性が、フェノール樹脂系バインダーと同程度又は、フェノール樹脂系バインダーよりも優れたノンホルムアルデヒドタイプのバインダーを提供する必要があることを、本発明者らは新たに見出した。 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.
　本発明は、上記の課題に鑑みてなされたものであり、本発明の目的は、原料に無機酸イオンを用いることなく、バインダーを架橋反応させる際の反応速度が十分であり、強度や弾性率などの力学的特性が良好であり、無機繊維などの適用対象を腐食させることがないバインダー組成物、該バインダー組成物を用いた成形体、該バインダー組成物を用いた成形体の製造方法及びバインダー硬化物を提供することを目的とする。 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.
　本発明者らは、鋭意研究した結果、糖類及びラジカル発生剤の反応生成物と、有機酸化合物と、を含み、無機酸を実質的に含まないバインダー組成物が熱を与えられると、無機酸イオンを用いない場合であっても、架橋反応させる際の反応速度が十分であり、熱硬化後に良好な力学的特性を示すこと、無機繊維などの適用対象を腐食させることがないことを見出し、本発明をするに至った。 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.
　したがって、前記課題は、本発明に係るバインダー組成物によれば、糖類及びラジカル発生剤の反応生成物と、有機酸化合物と、を含み、無機酸を実質的に含まないことにより解決される。
　本発明のバインダー組成物は、ホルムアルデヒドを含まないという利点を有し、グラスウール成形体やロックウール成形体などの成形体の製造に用いた場合に、力学的特性がフェノール樹脂系バインダーを用いた場合と同等である。また、従来のノンホルムアルデヒドタイプのバインダー組成物のように、無機酸イオンを用いていないため、時間が経過しても無機繊維などの適用対象を腐食させてしまうことがない。 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.
　このとき、前記糖類が、グルコース、ガラクトース、マンノース、フルクトース、マルトース、及びラクトースからなる群より選択される少なくとも１種以上の還元糖であるとよい。
　特にグルコースやフルクトースは工業的にとうもろこしを原料として製造されており、安価かつ容易に入手できる植物由来の天然物成分であり、人間にも環境にも優しい物質である。
　このとき、前記ラジカル発生剤が、アゾ化合物及び過酸化物からなる群より選択される少なくとも１種以上であるとよい。
　ラジカル発生剤としても、無機酸イオンを含まないアゾ化合物及び過酸化物を用いることで、時間が経過しても無機繊維を腐食させてしまうことがより一層抑制される。 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.
　このとき、前記過酸化物が、過酸化水素水及び有機過酸化物からなる群より選択される少なくとも１種以上であるとよい。
　ラジカル発生剤としても、無機酸イオンを含まない過酸化水素水及び有機過酸化物を用いることで、時間が経過しても無機繊維を腐食させてしまうことがより一層抑制される。 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.
　このとき、前記有機酸化合物が、低分子ポリカルボン酸、低分子ポリカルボン酸塩、高分子ポリカルボン酸、及び高分子ポリカルボン酸塩からなる群より選択される少なくとも１種以上であるとよい。 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. ..
　このとき、前記有機酸化合物が、クエン酸及びクエン酸アンモニウムからなる群より選択される少なくとも１種以上であるとよい。 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.
　このとき、更にアミン化合物を含むとよい。
　アンモニアなどのアミン化合物を含む場合、バインダー組成物の硬化物を含む成形体の力学的特性が良好なものとなる。 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.
　前記課題は、本発明に係る成形体によれば、糖類及びラジカル発生剤の反応生成物と、有機酸化合物と、を含み、無機酸を実質的に含まないことを特徴とするバインダー組成物と、無機繊維、木材、鋳物砂から選択される１種以上の対象物と、を含むことにより解決される。
　このとき、前記無機繊維としてロックウール、ストーンウール、スラグウール、ミネラルウール、グラスウール、及びミネラルグラスウールからなる群より選択される少なくとも１種以上の鉱物繊維を含むとよい。
　このとき、前記糖類が、グルコース、ガラクトース、マンノース、フルクトース、マルトース、及びラクトースからなる群より選択される少なくとも１種以上の還元糖であり、前記ラジカル発生剤が、アゾ化合物及び過酸化物からなる群より選択される少なくとも１種以上であり、前記有機酸化合物が、低分子ポリカルボン酸、低分子ポリカルボン酸塩、高分子ポリカルボン酸、及び高分子ポリカルボン酸塩からなる群より選択される少なくとも１種以上であるとよい。
　本発明のバインダー組成物は、フェノール樹脂系バインダーの代替品として使用可能であり、グラスウール、ロックウールなど無機繊維用のバインダーとして使用する以外に、木質ボードに用いられる木材チップ用の接着剤、鋳型に用いられる鋳物砂用の接着剤としても使用可能である。 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.
　前記課題は、本発明に係る成形体を製造する方法によれば、成形体を製造する方法であって、無機繊維、木材、鋳物砂から選択される１種以上の対象物に糖類及びラジカル発生剤の反応生成物と、有機酸化合物と、を含み、無機酸を実質的に含まないことを特徴とするバインダー組成物を付着させる付着工程と、前記バインダー組成物が付着した前記対象物を加熱し、前記バインダー組成物を架橋反応させる加熱・硬化工程と、を行うことにより解決される。 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.
　このとき、更に前記バインダー組成物を調製するバインダー組成物調製工程を含み、前記バインダー組成物調製工程において、前記糖類が、グルコース、ガラクトース、マンノース、フルクトース、マルトース、及びラクトースからなる群より選択される少なくとも１種以上の還元糖であり、前記ラジカル発生剤が、アゾ化合物及び過酸化物からなる群より選択される少なくとも１種以上であり、前記有機酸化合物が、低分子ポリカルボン酸、低分子ポリカルボン酸塩、高分子ポリカルボン酸、及び高分子ポリカルボン酸塩からなる群より選択される少なくとも１種以上であるとよい。
　このとき、前記加熱・硬化工程の前に前記バインダー組成物が付着した前記対象物を所望の成形体に対応した形状に成形する成形工程を行うとよい。 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.
　前記課題は、本発明に係るバインダー硬化物によれば、無機酸及び無機酸塩を実質的に含まず、水に浸漬して得られる溶出液のｐＨが６以上８．４未満であることにより解決される。
　前記課題は、本発明に係る成形体によれば、上記のバインダー組成物の硬化物と、無機繊維、木材、鋳物砂から選択される１種以上の対象物と、を含むことにより解決される。 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. ..
　本発明によれば、原料に無機酸イオンを用いることなく、バインダーを架橋反応させる際の反応速度が十分であり、強度や弾性率などの力学的特性が良好であるバインダー組成物、該バインダー組成物を用いた成形体、及び該バインダー組成物を用いた成形体の製造方法を提供することができる。
　本発明のバインダー組成物を用いた場合、糖類ベースのバインダーでありながら、無機酸イオンを含まないため、時間が経過しても無機繊維を腐食させてしまうことがない。 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.
本発明の一実施形態に係る成形体の製造方法を示すフロー図である。It is a flow chart which shows the manufacturing method of the molded article which concerns on one Embodiment of this invention. 本発明の一実施形態に係るロックウールマットの製造方法を示す図である。It is a figure which shows the manufacturing method of the rock wool mat which concerns on one Embodiment of this invention. 実施例１及び比較例１～８のバインダー組成物の弾性率Ｅ’（ＭＰａ）を温度（℃）の関数としてプロットしたグラフである。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.). 実施例１及び比較例４及び比較例５のバインダー組成物の弾性率Ｅ’（ＭＰａ）を温度（℃）の関数としてプロットしたグラフである。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.). 実施例１～３及び比較例４のバインダー組成物の弾性率Ｅ’（ＭＰａ）を温度（℃）の関数としてプロットしたグラフである。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.).
　以下、本発明の実施形態について、図１乃至図３Ｃを参照しながら説明する。
　本実施形態は、糖類及びラジカル発生剤の反応生成物と、有機酸化合物と、を含み、無機酸を実質的に含まないバインダー組成物、該バインダー組成物を用いた成形体、及び該バインダー組成物を用いた成形体の製造方法の発明に関するものである。
　本実施形態の成形体は、住宅等の建物において外壁と内壁との間に配置される断熱材や工場等の配管の外側に配置される断熱材に好適に用いられる。 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.
＜バインダー組成物＞
　本実施形態に係るバインダー組成物は、糖類及びラジカル発生剤の反応生成物と、有機酸化合物と、を含み、無機酸を実質的に含まない。以下に、各成分について詳述する。
（糖類）
　本実施形態のバインダー組成物は１種以上の糖類を含み、該糖類としては、還元糖又は非還元糖、それらの誘導体等が挙げられる。 <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.
（還元糖）
　本実施形態のバインダー組成物に用いることができる還元糖としては、単糖、オリゴ糖、多糖、それらの誘導体等が挙げられる。
　本明細書において、還元糖とは、開放鎖形態でアルデヒド基を有するアルドース又はケトン基を有するケトースを意味し、オリゴ糖とは２以上１０以下の単糖が結合したものを指し、多糖とは１１以上の単糖が結合したものを指す。 (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.
　還元糖として、単糖又は二糖を用いることが好ましく、特に３～８個の炭素原子を含む単糖、好ましくはグルコース（ブドウ糖）を用いることが好ましい。グルコースは、とうもろこしを原料としており、植物由来の天然物成分であり、容易に大量のグルコースを、安価に入手することができる。 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.
　また、工業的にグルコースから製造される異性化糖を用いることもできる。ここで、異性化糖とは、特定組成比のＤ－グルコースとＤ－フルクトースを主組成分とする混合糖を意味し、一般的には、でん粉をアミラーゼ等の酵素または酸により加水分解して得られた、主にグルコースからなる糖液を、グルコースイソメラーゼまたはアルカリにより異性化したグルコースおよびフルクトースを主成分とする液状の糖のことを指す。
　還元糖として、例えば、トウモロコシシロップ、高フルクトーストウモロコシシロップ等を使用することも可能である。
　フルクトースは、グルコースよりも開放鎖形態での存在が大きいため、グルコースよりも迅速にメイラード反応の開始反応が起こることが知られており、フルクトースを含有する異性化糖は、本実施形態のバインダー組成物に用いることができる。また、フルクトースは、グルコースと比較し、水への溶解度が高いため、高濃度のバインダー溶液を作製したい場合に好適に用いることができる。 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.
　還元糖として、上記の単糖に限定されることはなく、ガラクトース、マンノース、フルクトース等の単糖を用いることも可能である。 The reducing sugar is not limited to the above-mentioned monosaccharides, and monosaccharides such as galactose, mannose, and fructose can also be used.
　還元糖として用いることができる二糖としては、ラクトース、アラビノース、マルトースなどが挙げられる。 Examples of disaccharides that can be used as reducing sugars include lactose, arabinose, and maltose.
（非還元糖）
　本実施形態のバインダー組成物に用いることができる非還元糖としては、オリゴ糖、多糖、それらの誘導体等が挙げられる。
　本明細書において、「非還元糖」とは、還元性を示さない等であり、還元糖ではない糖を指す。ここで、「還元糖」とは、開放鎖形態でアルデヒド基を有するアルドース又はケトン基を有するケトースを意味し、単糖はすべて還元糖である。
　オリゴ糖とは２以上１０以下の単糖が結合したものを指し、多糖とは１１以上の単糖が結合したものを指す。 (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.
　非還元糖として、２以上１０以下の単糖が結合したオリゴ糖を用いることが好ましく、二糖、三糖、四糖、五糖を用いることがより好ましく、特に好ましくはスクロース又はトレハロース等の二糖を用いることが好ましい。スクロース（ショ糖）は、サトウキビを原料としており、砂糖として用いられている、植物由来の天然物成分である。また、トレハロースは、デンプンを原料としており、植物由来の天然物成分である。
　特にスクロースは、世界中の家庭で広く使用されており、容易に大量に入手可能であり、高い安全性を有し、保存安定性にも優れた化合物であるため、本実施形態のバインダー組成物に好適に用いることができる。 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.
　非還元糖として用いることができる二糖としては、スクロース又はトレハロースに限定されることはなく、イソトレハロース、イソスクロースなどが挙げられる。 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.
　非還元糖として用いることができる三糖としては、メレジトース、ゲンチアノース、ラフィノース、エルロース、ウンベリフェロースなどが挙げられる。
　非還元糖として用いることができる四糖としては、スタキオースなどが挙げられる。
　非還元糖として用いることができる五糖としては、ベルバスコースなどが挙げられる。 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.
　非還元糖として、例えば、サトウキビシロップ、サトウダイコン（テンサイ）シロップ等を使用することも可能である。 As the non-reducing sugar, for example, sugar cane syrup, sugar beet (sugar beet) syrup, etc. can be used.
　糖類（還元糖又は非還元糖）は、例えば、ヒドロキシル基、ハロゲン、アルキル基、アルコキシル基、カルボニル基もしくは他の置換基で置換されていてもよい。
　さらに、バインダー組成物に用いる糖類として、天然および合成の還元糖の立体異性体又は光学異性体も用いることが可能である。
　糖類は、いずれか１種を単独で用いても、２種以上を併用してもよい。 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.
　糖類として、還元糖であるグルコースや、加水分解することで還元糖であるグルコースとフルクトースを生じるスクロースを用いることが加熱したときのバインダー組成物の硬化速度の観点、原料の入手のしやすさの観点から好ましい。 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.
　バインダー組成物中の、糖類の含有量は、糖類とラジカル発生剤、及び有機酸化合物とから構成される混合物の総重量の、５０～９０重量％、好ましくは６０～８５重量％、及び有利には６５～８０重量％であることが好ましい。 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.
（ラジカル発生剤）
　本明細書において、「ラジカル発生剤」とは、ラジカル反応を進めるために穏和な反応条件でラジカルを発生させる化合物をいう。ここで、ラジカルとは、不対電子を持つ原子や分子、あるいはイオンのこと意味し、フリーラジカル又は遊離基と同義である。 (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.
　本実施形態のバインダー組成物に含まれる、ラジカル発生剤としては、無機酸を実質的に含むものでなく、本発明の目的を損なわないものであれば、特に制限されることはなく、例えば、アゾ化合物及び過酸化物が例示される。 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.
　アゾ化合物は、熱及び／又は光によって分解し、炭素ラジカルを発生するアゾ基（Ｒ－Ｎ＝Ｎ－Ｒ’）をもつ化合物である。具体的には、２，２’－アゾビスブチロニトリル（ＡＩＢＮ）が挙げられる。 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).
　過酸化物としては、有機過酸化物、無機過酸化物、過酸化水素などがあるが、本実施形態のバインダー組成物では、有機過酸化物や過酸化水素が用いられる。
　有機過酸化物は、ペルオキシド構造（－Ｏ－Ｏ－）を含む化合物であり、例えば、過酸化ベンゾイルが代表的である。
　過酸化水素は、化学式Ｈ２Ｏ２で表される化合物である。
　水性媒体への溶解性や、糖類との相溶性の観点から、ラジカル発生剤として、無機酸を含まない過酸化物である過酸化水素を用いることが好ましい。 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.
　バインダー組成物に含まれる、ラジカル発生剤の割合は、糖類のモル比を１としたときに、ラジカル発生剤のモル比が０．０１～０．１であることが好ましく、０．０２～０．０８であることが特に好ましい。 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.
（糖類及びラジカル発生剤の反応生成物）
　本実施形態のバインダー組成物に含まれる、糖類及びラジカル発生剤の反応生成物（変性糖）は、糖類の化学構造がラジカル発生剤によって変化した化合物である。 (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.
　糖類は、ヒドロキシ基とカルボニル基をもつ直鎖構造と、糖類自身のヒドロキシル基を含んで環状アセタール又はケタールの環状構造の２つの構造をとることが知られている。糖類及びラジカル発生剤の反応生成物は、糖類の環状アセタール構造がラジカル発生剤によって開環して直鎖構造に変化し、さらに高分子量化した化合物を含むと推定される。 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.
　バインダー組成物中の、糖類及びラジカル発生剤の反応生成物（変性糖）の含有量は、糖類及びラジカル発生剤の反応生成物と、有機酸化合物とから構成される混合物の総重量の、７０～９９重量％、好ましくは８０～９７重量％、及び有利には８５～９５重量％であることが好ましい。 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.
（有機酸化合物）
　本実施形態のバインダー組成物に含まれる、有機酸化合物としては、例えば、低分子ポリカルボン酸、低分子ポリカルボン酸塩、高分子ポリカルボン酸、及び高分子ポリカルボン酸塩が挙げられるが、これに限定されるものではない。 (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.
　本明細書において、「ポリカルボン酸」とは、ジカルボン酸、トリカルボン酸、テトラカルボン酸、ペンタカルボン酸など、２以上のカルボキシル基を含むカルボン酸を意味する。
　また、ポリカルボン酸としては、低分子ポリカルボン酸（単量体ポリカルボン酸）、その無水物、及びそれらの組み合わせ、並びに高分子ポリカルボン酸、その無水物、その共重合体、及びそれらの組み合わせが例として挙げられる。 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.
（低分子ポリカルボン酸）
　低分子ポリカルボン酸であるジカルボン酸としては、不飽和脂肪族ジカルボン酸、飽和脂肪族ジカルボン酸、芳香族ジカルボン酸、不飽和環状ジカルボン酸、飽和環状ジカルボン酸、それらのヒドロキシ置換誘導体、ハロ置換誘導体、アルキル置換誘導体、アルコキシ置換誘導体等が例示されるが、これらに限定されるものではない。
　具体的な化合物としては、例えば、シュウ酸、マロン酸、琥珀酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、リンゴ酸、酒石酸、タルトロン酸、アスパラギン酸、グルタミン酸、フマル酸、イタコン酸、マレイン酸、トラウマチン酸、樟脳酸、フタル酸及びこれらの誘導体などが例示されるが、これらに限定されるものではない。 (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.
　低分子ポリカルボン酸であるトリカルボン酸としては、不飽和脂肪族トリカルボン酸、飽和脂肪族トリカルボン酸、芳香族トリカルボン酸、不飽和環状トリカルボン酸、飽和環状トリカルボン酸、それらのヒドロキシ置換誘導体、ハロ置換誘導体、アルキル置換誘導体、アルコキシ置換誘導体等が例示されるが、これらに限定されるものではない。
　具体的な化合物としては、例えば、クエン酸、トリカルバリル酸、１，２，４－ブタントリカルバリル酸、アコニット酸、へミメリト酸、トリメリト酸及び甜菜リメシン酸及びこれらの誘導体などが例示されるが、これらに限定されるものではない。 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.
（高分子ポリカルボン酸）
　高分子ポリカルボン酸としては、例えば、ポリアクリル酸、ポリメタクリル酸、ポリマレイン酸等の酸、ならびに同様の高分子ポリカルボン酸、それらの共重合体、それらの無水物、およびそれらの混合物であってもよい。 (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.
　低分子ポリカルボン酸、低分子ポリカルボン酸塩、高分子ポリカルボン酸、及び高分子ポリカルボン酸塩は、いずれか１種を単独で用いても、２種以上を併用してもよい。 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.
　有機酸化合物は、好ましくは低分子ポリカルボン酸及び低分子ポリカルボン酸塩から選択され、より好ましくは、クエン酸又はクエン酸塩である。
　特に、有機酸化合物として、ポリカルボン酸塩、例えば、クエン酸塩であるクエン酸トリアンモニウムを用いることが好ましい。 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.
　バインダー組成物に含まれる、有機酸化合物の割合は、糖類（糖類及びラジカル発生剤の反応生成物：変性糖）のモル比を１としたときに、有機酸化合物のモル比が０．０５～１．０であることが好ましく、０．１～０．５であることがより好ましく、０．１～０．２であることがより一層好ましい。
　糖類のモル比を１としたときに、有機酸化合物のモル比が０．０５以上のバインダー組成物を用いると、所定の温度及び時間で硬化を完了させることが可能となる。 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.
（アミン化合物）
　本明細書において、「アミン化合物」とは、アンモニア及びアミンを含む総称を意味する。
　アンモニアは、分子式ＮＨ３で表される無機化合物であり、常温常圧で無色の気体である。 (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.
　アミンは、アンモニアの水素原子が炭化水素基及び芳香族原子団等の置換基で置換された化合物であり、置換された水素の数が１つであれば第一級アミン、２つであれば第二級アミン、３つであれば第三級アミンと呼ばれる。更に置換基が第三級アミンに結合した場合、第四級アンモニウムカチオンとなる。 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.
　本実施形態において用いることができるアミンとしては、脂肪族アミン、芳香族アミン、複素環式アミンが例として挙げられる。
　脂肪族アミンの例としては、メチルアミン、ジメチルアミン、トリメチルアミン、エチルアミン、ジエチルアミン、トリエチルアミン、エチレンジアミン、トリエタノールアミン、ヘキサメチレンジアミン等が挙げられる。
　また、芳香族アミンとしては、アニリン、フェネチルアミン、トルイジン、カテコールアミン等が挙げられる。
　さらに、複素環式アミンとしては、ピロリジン、ピペラジン、ピペリジン、モルホリン、ピロール、ピラゾール、イミダゾール、ピリジン、ピリダジン、ピリミジン、オキサゾール、チアゾール等が挙げられる。 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.
　本実施形態のバインダー組成物では、アミン化合物として、アンモニアを含むことが好ましい。アンモニアを用いる場合、バインダー組成物の硬化物を含む成形体の力学的特性が良好なものとなる。アミン化合物を用いると糖類及びラジカル発生剤の反応生成物（変性糖）は、アミン化合物に由来する構造を有することになる。 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.
　本実施形態のバインダー組成物は、無機酸を実質的に含まない。ここで、バインダー組成物が無機酸を実質的に含まないとは、無機酸の含有量がバインダー組成物を付着させる対象を腐食させない程度であることを言う。例えば、無機繊維に対してバインダー組成物を適用して成形体を製造したときに、酸に弱いグラスウールやロックウールが腐食していないことを言う。 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.
　なお、無機繊維の腐食は、例えば、成形体を走査型電子顕微鏡（ＳＥＭ）で観察したときに、繊維上に無機酸由来の析出物による凸凹が確認できるか否かで評価をすることが可能である。具体的には、成形体を作製して所定期間経過後（例えば２３．５℃、５０ＲＨ％の環境下で３週間経過後）に、成形体をＳＥＭで観察したときに、繊維上に無機酸の塩が析出している場合に腐食があると評価できる。このとき、析出物が無機酸の塩であることはＳＥＭ－ＥＤＳ（ＥＤＳ：Ｅｎｅｒｇｙ　Ｄｉｓｐｅｒｓｉｖｅ　Ｘ－ｒａｙ　Ｓｐｅｃｔｒｏｓｃｏｐｙ）およびＸ線回折装置（ＸＲＤ）を用いて確認することが可能である。 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).
　また、バインダー組成物が無機酸を実質的に含まないことを定量的に確認するには、バインダー組成物を無機繊維などの対象物に付着させ、架橋反応させて硬化物としたときに、水に浸漬して得られる溶出液中に無機酸イオンが含まれていないことを確認すればよい。例えば、バインダー組成物を架橋反応させて硬化物としたときに、水に浸漬して得られる溶出液を、高速液体クロマトグラフ（ＨＰＬＣ、高速液体クロマトグラフィーを行うための装置）で分析したときに、無機酸イオンの検出量が装置の検出下限値以下であることを確認すればよい。 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.
　また、以下に示す実施例（表２）に基づくと、無機酸を実質的に含まないとは、糖として単糖（グルコース）を用いた場合には、無機酸イオン（例えば、硫酸イオン）の含有量が、単糖１ｍｏｌあたり（つまり、変性糖（変性糖１）１ｍｏｌ）あたりに換算して、０．１７ｍｏｌ未満であればよく、好ましくは０．１０ｍｏｌ未満、より好ましくは０．０５ｍｏｌ未満、更に好ましくは０．０１ｍｏｌ未満であることを意味する。 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.
　また、糖として二糖（スクロース）を用いた場合には、無機酸を実質的に含まないとは、無機酸イオン（例えば、硫酸イオン）の含有量が、二糖１ｍｏｌあたり（つまり、変性糖（変性糖２）１ｍｏｌ）あたりに換算して、０．１０ｍｏｌ未満であればよく、好ましくは０．０８ｍｏｌ未満、より好ましくは０．０５ｍｏｌ未満、更に好ましくは０．０１ｍｏｌ未満であることを意味する。 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. ..
（その他成分）
　本実施形態に係るバインダー組成物は、本発明の効果を阻害しない範囲で必要により、密着性向上剤、粘度調整剤、酸化防止剤、紫外線吸収剤、安定剤、可塑剤、ワックス、顔料若しくは染料、帯電防止剤、抗菌剤、防かび剤、香料、難燃剤、分散剤、造膜助剤及び湿潤剤からなる群から選ばれる１種又は２種以上のその他の添加剤を併用してもよい。
　バインダー組成物中のこれら添加物の含有量は、硬化後のバインダー組成物の力学的特性に影響を与えない範囲である必要があり、糖類とラジカル発生剤、及び有機酸化合物とから構成される混合物の総重量の５重量％以下、好ましくは２重量％以下であるとよい。 (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.
　また、無機繊維としてロックウールやグラスウールを用いる場合、バインダー組成物は、アミノシランなどのシラン、オイル、グリセロール、シリコーン、増量剤など、従来公知の添加剤を含むことができる。 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.
　シランは、繊維とバインダー組成物との間のカップリング剤であると共に、アンチエージング剤としても働く。オイルは、防塵性及び疎水性の観点から添加される。グリセロールは、可塑剤として働き、バインダー溶液のプレゲルを防ぐ。シリコーンは、成形体による水の吸収を低減させる役割を有する疎水性物質である。増量剤は、有機又は無機のフィラーであり、バインダー組成物中に可溶か又は分散可能であり、特に、バインダー組成物のコストを低下させる。 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.
（バインダー組成物の水溶液のｐＨ）
　本実施形態のバインダー組成物は、バインダー水溶液とした際のｐＨが６以上９以下の中性から弱アルカリ性であることを特徴とする。バインダー組成物のｐＨが、ｐＨが６以上８以下であることがより好ましく、特に、６以上７以下であることが好ましい。なお、本明細書において、酸性とはｐＨが１以上６未満、中性とは６以上８以下、アルカリ性とは８より大きく１２以下であると定義する。 (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.
　無機繊維系断熱材として、一般的に、グラスウールやロックウールが用いられている。ロックウールはグラスウールと比較して融点が高く耐熱性に優れるが、グラスウールよりも酸に弱い。従来のノンホルムアルデヒドタイプのバインダー水溶液は、ｐＨが６．０未満と、酸性のものも存在し、ロックウールに用いると、ロックウールが溶解し、製品として要求される水準の成形体を得ることができないこともあった。
　一方、本実施形態のバインダー組成物は、水溶液とした際のｐＨが６以上９以下の中性～弱アルカリ性領域にあるため、ロックウールが溶解せず、ロックウールを用いた成形体の製造にも好適に使用できる。
　また、従来のノンホルムアルデヒドタイプのバインダーは、ロックウール以外の酸による損傷を受け易い鉱物繊維、例えば、ストーンウール、スラグウール、ミネラルウールにも使用することが困難であったが、本実施形態のバインダー組成物は、水溶液とした際のｐＨが６以上９以下の中性～弱アルカリ性領域にあるため、酸による損傷を受け易い鉱物繊維にも好適に適用できる。 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.
　酸性のバインダー溶液に、過剰なアンモニアを添加することで、ｐＨを中性～アルカリ性領域にすることも可能であるが、過剰なアンモニアがバインダー溶液から揮発することにより作業環境が悪化してしまうことがあった。
　また、酸性のバインダー溶液に、過剰な水酸化ナトリウムを加えることにより、ｐＨを中性～アルカリ性領域にすることも可能であるが、ナトリウムが残ることにより、バインダーを塗付した材料の表面が、強アルカリ性になってしまうことがあった。
　本実施形態のバインダー組成物は、水溶液とした際のｐＨが６以上９以下の中性～弱アルカリ性領域にあるため、過剰なアンモニアや水酸化ナトリウムを添加することなく用いることが可能である。 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.
　さらに、フェノール樹脂系バインダーはｐＨが７～９で中性～弱アルカリ性であったため、従来の成形体の製造装置には鋼材が用いられている。従って、バインダー水溶液が酸性であると、当該バインダーを用いて成形体を製造する際に、製造装置に使用されている鋼材、特にＳ５０Ｃなどの炭素鋼材が錆びてしまう。従って、バインダー組成物が酸性であると、バインダー組成物を塗付する際に使用する設備に鋼材が使うことができない。酸性のバインダー水溶液を用いるために、成形体の製造装置をステンレス化するなどの対策を行う場合、莫大な費用が必要となってしまうが、本実施形態のバインダー組成物は、水溶液とした際のｐＨが６以上９以下程度の中性～弱アルカリ性領域にあるので、従来の成形体の製造装置を、そのまま用いることが可能である。 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.
　また、本実施形態のバインダー組成物は、従来のフェノール樹脂系バインダーと同様に中性～弱アルカリ性であり、酸性ではないため、ロックウール等の鉱物繊維に限定されることなく、それ以外の酸に弱い材料に対しても使用可能であり、フェノール樹脂系バインダーの代替品として幅広い用途に用いることができる。 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.
（バインダー硬化物の溶出液のｐＨ）
　本実施形態のバインダー組成物は、架橋反応させて硬化物としたときに、水に浸漬して得られる溶出液のｐＨが６以上７以下であることを特徴とする。バインダー組成物を架橋反応させて硬化物としたときに、水に浸漬して得られる溶出液のｐＨが６以上６．８以下であることがより好ましく、特に、６以上６．６以下であることが好ましい。 (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.
　従来のノンホルムアルデヒドタイプのバインダー組成物は、無機酸や無機酸塩（例えば、硫酸アンモニウム）を使用しているため、架橋反応させて硬化物としたときに、水に浸漬して得られる溶出液のｐＨが３．５未満と低く、酸性である。したがって、無機酸や無機酸塩を含有する従来のノンホルムアルデヒドタイプのバインダーをグラスウールやロックウールに用いると、時間が経過するとともにバインダー硬化物が大気中の水分を吸収し、グラスウールやロックウールが溶解し、製品として要求される水準を維持可能な成形体を得ることができなかった。 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.
　一方、本実施形態のバインダー組成物は、無機酸を実質的に含まないため、架橋反応させて硬化物としたときに、水に浸漬して得られる溶出液のｐＨが６以上７以下である中性領域にあるため、グラスウールやロックウールが溶解せず、グラスウールやロックウールなどの酸に影響を受ける無機繊維を用いた成形体の製造にも好適に使用できる。 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.
　また、従来のノンホルムアルデヒドタイプのバインダーは、ロックウール以外の酸による損傷を受け易い鉱物繊維、例えば、ストーンウール、スラグウール、ミネラルウールにも使用した場合、時間の経過とともに繊維が劣化してしまう可能性があったが、本実施形態のバインダー組成物は、架橋反応させて硬化物としたときに、水に浸漬して得られる溶出液のｐＨが６以上７以下の中性領域にあるため、酸による損傷を受け易い鉱物繊維にも好適に適用できる。 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.
＜バインダー組成物を用いた成形体＞
　本実施形態に係るバインダー組成物を用い、グラスウール、ロックウール、セラミックファイバー等の無機繊維を用いた断熱材、防音材などの成形体を製造することができるが、これに限定されるものではない。例えば、フェノール樹脂系バインダーに代表される熱硬化性バインダーが用いられる各種用途、例えば鋳造用、摩擦材用、砥石用、ろ紙用、成形材料用、合板加工用、化粧板用、積層板用に使用することが可能である。 <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.
　本実施形態に係る成形体は、本実施形態のバインダー組成物を用いて、無機繊維等を成形してなるものであり、例えば断熱材、吸音材、木材ボード製品（チップボード、配向性ストランドボード、パーティクルボード、ファイバーボード等）、その他各種成形体（自動車の屋根、ボンネットのライナー等）として利用できる。 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.).
　成形体に用いられる無機繊維としては、例えばロックウール、ストーンウール、スラグウール、ミネラルウール、グラスウール、ミネラルグラスウール等が挙げられるがこれらに限定されるものではない。これら無機繊維を、いずれか１種を単独で用いても２種以上を組み合わせて用いてもよい。汎用性、断熱性、防音性等の観点から、無機繊維として、グラスウール又はロックウールを用いることが好ましい。
　本実施形態に係る成形体は、例えば梱包のための表皮材等の、該成形体以外の他の部材をさらに備えるものであってもよい。 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.
　また、無機繊維以外にも、木材（木材チップ、木材繊維等）、鋳物砂等の対象物を、本実施形態に係るバインダー組成物を用いて成形することで、木材ボード製品、鋳型等の成形体を提供することができる。本明細書において、対象物とは、無機繊維、木材、鋳物砂などのバインダー組成物の適用対象を意味する。なお、バインダー組成物を適用する際の対象物の状態は、無機繊維、木材、鋳物砂が集積していない状態であっても良く、無機繊維、木材、鋳物砂が集積した状態であっても良い。 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.
＜バインダー組成物を用いた成形体の製造方法＞
　本実施形態に係る成形体は、バインダーとして、本実施形態に係るバインダー組成物を用いる以外は、従来、成形体の製造に用いられている公知の方法を利用することができる。 <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.
　例えば、本実施形態に係る成形体を製造する方法は、無機繊維、木材、鋳物砂から選択される１種以上の対象物に糖類及びラジカル発生剤の反応生成物と、有機酸化合物と、を含み、無機酸を実質的に含まないことを特徴とするバインダー組成物を付着させる付着工程（ステップ１）と、前記バインダー組成物が付着した前記対象物を加熱し、前記バインダー組成物を架橋反応させる加熱・硬化工程（ステップ２）と、を行うことを特徴とする。 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.
　付着工程（ステップ１）では、無機繊維、木材、鋳物砂から選択される１種以上の対象物に本実施形態に係るバインダー組成物を付着させる。対象物にバインダー組成物を付着させる方法としては、例えば、対象物に対し、スプレー装置等を用いてバインダーを吹き付ける方法、集積体をバインダー溶液に含浸させる方法等が挙げられ、いずれの方法を用いてもよい。 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.
　加熱・硬化工程（ステップ２）では、バインダー組成物が付着した対象物を加熱し、バインダー組成物を架橋反応させる。 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.
　また、事前にバインダー組成物を調製するバインダー組成物調製工程（ステップ０）を行っても良く、バインダー組成物調製工程では、糖類が、グルコース、ガラクトース、マンノース、フルクトース、マルトース、及びラクトースからなる群より選択される少なくとも１種以上の還元糖であり、ラジカル発生剤が、アゾ化合物及び過酸化物からなる群より選択される少なくとも１種以上であり、有機酸化合物が、低分子ポリカルボン酸、低分子ポリカルボン酸塩、高分子ポリカルボン酸、及び高分子ポリカルボン酸塩からなる群より選択される少なくとも１種以上であるとよい。 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.
　また、付着工程（ステップ１）を行った後、加熱・硬化工程（ステップ２）を行う前に、バインダー組成物が付着した集積体を所望の成形体に対応した形状に成形する成形工程（ステップ１Ａ）を行ってもよい。 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.
（無機繊維成形体の製造方法）
　以下、無機繊維成形体の製造方法について具体的に説明を行う。
　本実施形態に係る無機繊維成形体の製造方法は、バインダーとして、本実施形態に係るバインダー組成物を用いる以外は、従来、無機繊維成形体の製造に用いられている公知の方法を利用することができる。
　例えば、本実施形態に係る、糖類及びラジカル発生剤の反応生成物と、有機酸化合物と、を含み、無機酸を実質的に含まないバインダー組成物を調製する工程（以下、バインダー組成物調製工程）と、無機繊維に本実施形態に係るバインダー組成物を付着させる工程（以下、付着工程）と、前記バインダー組成物が付着した無機繊維を集積し、集積体とする工程（以下、集積工程）と、前記集積体を、所望の無機繊維成形体に対応した形状に成形する工程（以下、成形工程）と、前記成形された集積体を加熱し、バインダー組成物を架橋反応させる工程（以下、加熱・硬化工程）と、前記加熱工程で架橋したバインダー組成物を冷却する工程（以下、冷却工程）と、を順次行う方法が挙げられる。
　以下、各工程について図１を参照して詳細に説明する。 (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.
（バインダー組成物調製工程）
　バインダー組成物調製工程では、本実施形態に係る、糖類及びラジカル発生剤の反応生成物と、有機酸化合物と、を含み、無機酸を実質的に含まないバインダー組成物を調製する（ステップＳ１）。
　この時、バインダー組成物を、水、アルコール等の溶媒を用いてバインダー溶液として調製する。 (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.
（付着工程）
　付着工程では、無機繊維に本実施形態に係るバインダー組成物を付着させる（ステップＳ２）。
　無機繊維としては、グラスウール、ロックウール、セラミックファイバー等を用いることができ、無機繊維の繊維長や繊維径は、無機繊維成形体に応じて選択すればよく、通常、繊維径が３～１０μｍの範囲内のものが用いられるが、これに限定されるものではない。
　無機繊維は、市販のものを用いてもよく、公知の方法により製造したものをそのまま用いてもよい。無機繊維は、一般的には、溶融した原料（ガラス、玄武岩等の鉱物、鉄炉スラグなど）を繊維化することにより製造され、繊維化方法としては、火炎法、遠心法等が挙げられる。 (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.
　無機繊維にバインダー組成物を付着させる方法としては、例えば、無機繊維に対し、スプレー装置等を用いてバインダーを吹き付ける方法、無機繊維をバインダーに含浸させる方法等が挙げられ、いずれの方法を用いてもよい。
　無機繊維に付着させるバインダー組成物の量は、特に限定されないが、無機繊維を１００質量％としたときに、バインダー組成物の固形成分が、０．５～２０質量％の範囲内であるとよい。バインダー組成物の量は、無機繊維成形体の性質に影響し、バインダー組成物の量が多いほど、無機繊維成形体の機械的強度が強くなる。 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.
（集積工程）
　集積工程では、前記付着工程において、バインダー組成物が付着した無機繊維を集積し、集積体とする（ステップＳ３）。
　集積工程は、公知の方法により実施することができる。バインダー組成物が付着した無機繊維を回転するベルトに堆積させ、フリースを形成させるなどして、集積体とすればよい。 (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.
（成形工程）
　成形工程では、前記集積体を、所望の無機繊維成形体に対応した形状に成形する（ステップＳ４）。
　成形工程は、公知の方法により実施することができる。無機繊維成形体として板状のものを製造する場合を例に挙げると、コンベア上に集積体を積層させればよい。このとき、積層した集積体を鉛直方向から押圧して圧縮する圧縮工程を行ってもよい。 (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.
（加熱・硬化工程）
　加熱・硬化工程では、成形された集積体を加熱し、前記バインダー組成物を架橋反応させる（ステップＳ５）。
　成形された集積体を硬化炉へと送り、加熱して前記バインダー組成物を反応させることにより、異なる重合物（メラノイジン重合物やカラメル化反応重合物）間がエステル結合で架橋した構造を形成させる。
　加熱・硬化工程における加熱温度は、バインダー組成物が架橋する範囲内であればよく、１１０℃以上３００℃以下の範囲内であることが好ましい。１１０℃未満の場合、バインダー組成物の架橋が不充分となり、機械的強度が不足する可能性がある。３００℃を超えると、バインダー組成物が分解し、機械的強度が低下する可能性がある。 (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.
　加熱・硬化工程における加熱時間は、バインダー組成物が架橋する範囲内であればよく、集積体のサイズ、加熱温度等によって適宜調整され、特に限定されないが、３０秒～３０分であればよい。 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.
（冷却工程）
　冷却工程では、前記加熱工程で架橋した、前記バインダー組成物を冷却する（ステップＳ６）。
　具体的には、硬化炉から送出される無機繊維成形体を室温まで冷却する。なお、冷却には、送風等を行い積極的に冷却することや、送風などを行わずに自然乾燥にて冷却することも含まれる。
　得られた無機繊維成形体は、そのまま製品としてもよく、必要に応じてさらに、切断する切断工程や、表皮材による梱包等を施す梱包工程を行ってもよい。 (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.
（ロックウールマットの製造方法）
　本実施形態に係るバインダー組成物を用いた成形体の製造方法の具体例として、ロックウールマットの製造方法を説明する。図２は、本発明の一実施形態にかかるロックウールマットの製造方法を示す図である。
　本実施形態のロックウールマットは、ロックウールの積層体からなるマットであり、ロックウールは硬化したバインダーにより互いに付着している。
　溶融した原料１を、高速で回転するロール１１に垂らす。原料１が周囲に伝わって流れるロール１１に、エアーと共にバインダーを吹きかけ、原料１を繊維化して、スチールベルト（第１のベルト）１３に吹き飛ばす。スチールベルト１３上に繊維が堆積してフリース３が形成される。このフリース３はスチールベルト１３の移動と共に移動し、所定の位置でペンジュラム（第２のベルト）１５に移る。その後、フリース３はさらに移動して、所定の位置でコンベア（第３のベルト）１７上に移る。コンベア１７上でフリースを重ねて積層体５とする。この積層体５を硬化炉１９に通して、バインダーを硬化させ、ロックウールマット７が得られる。 (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.
　以下、具体的実施例に基づいて本発明を具体的に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be specifically described based on specific examples, but the present invention is not limited thereto.
＜変性糖溶液の作製＞
　以下の手順に従い、表１に記載の配合量で変性糖溶液を作製した。
１）水、糖、アンモニア水を混合した溶液を９０℃に加熱した。
２）この混合溶液にラジカル発生剤を４時間かけて滴下した。
３）その後１時間９０℃にて攪拌した。
４）室温まで冷却をして、変性糖５０質量％の変性糖溶液を得た。 <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.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
＜バインダー水溶液の調製＞
　表２に記載の配合量にて、水に各成分を攪拌しながら加え、実施例１～３及び比較例１～７、９のバインダー水溶液（濃度５０質量％）を得た。なお、表２において、糖１ｍｏｌから生成する変性糖（糖類及びラジカル発生剤の反応生成物）を１ｍｏｌとして表記している。
　また、バインダー性能の指標として、市販のレゾールタイプのフェノール樹脂系バインダー（レヂトップ、群栄化学工業社製、無機繊維製品用）を、比較例８のバインダーとした。 <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.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　得られたバインダー水溶液を用いて、以下の手順で成形体の作製及び各種特性の測定を行った。 Using the obtained aqueous binder solution, a molded product was prepared and various characteristics were measured by the following procedure.
＜試験例１：成形体の作製及び引張強度の測定＞
　以下の手順に従い、成形体の作製及び引張強度の測定を行った。
１）ガラス濾紙（ワットマン社製、グレードＧＦ／Ａ、１２０ｍｍ×２５ｍｍ）をバインダー水溶液に含浸させた。
２）バインダー組成物が付着したガラス濾紙を１００℃で１時間乾燥した。
３）バインダー組成物を硬化温度（２００℃）で３０分硬化させ、バインダー硬化物が付着したガラス濾紙を得た。
４）バインダー硬化物が付着したガラス濾紙の重量を１００重量％としたときに、バインダー硬化物重量が７０重量％となるようにした。
５）試験を行うガラス濾紙を、荷重フルスケール２００Ｎ、引張り速度２５．４ｍｍ／分の条件で、万能材料試験機（オリエンテック社製、ＲＴＣ－１１５０Ａ）を用いて、引張試験を行い、引張強度及び引張弾性率を得た。
　なお、ガラス濾紙は、評価を簡便に行うために無機繊維の代替品として使用したものであり、グラスウール等の無機繊維を用いた場合の結果と同様の傾向を示すと推定される。 <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.
＜試験例２：バインダー硬化物の水溶出率及び水溶出ｐＨの測定＞
　以下の手順に従い、硬化物からの溶出物量，溶出液のｐＨ測定を行った。
１）ガラス濾紙（ワットマン社製、グレードＧＦ／Ａ、φ１５０ｍｍ）をバインダー液に含浸させた。
２）バインダー組成物が付着したガラス濾紙を１００℃で１時間乾燥した。
３）バインダー組成物を硬化温度（２００℃）で３０分硬化させ、バインダー硬化物が付着したガラス濾紙を得た。
４）バインダー硬化物が付着したガラス濾紙の重量を１００重量％としたときに、バインダー硬化物重量が７０重量％となるようにした。
５）バインダー硬化物が付着したガラス濾紙の重量を測定し、浸漬前重量とした。
６）バインダー硬化物が付着したガラス濾紙をイオン交換水中に浸漬した。バインダー硬化物１ｇに対し，３５０ｇのイオン交換水を用いた。
７）１２時間浸漬後、溶液のｐＨを測定した。
８）ｐＨ測定後、バインダー硬化物が付着したガラス濾紙を取り出し、１００℃で１２時間乾燥した。
９）バインダー硬化物が付着したガラス濾紙の乾燥後の重量を測定し、乾燥後重量とした。
１０）（浸漬前重量－乾燥後重量）÷（浸漬前重量）×１００の計算式より、水溶出率を算出した。 <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.
＜試験例３：成形体の作製及び曲げ強度の測定＞
　以下の手順に従い、成形体の作製及び曲げ強度の測定を行った。
１）ブラスティング用ガラスビーズ（ポッターズ・バロティーニ株式会社製、グレードＪ－７０）にバインダー液を加え、攪拌した。
２）バインダー水溶液の付着したガラスビーズを金型に入れ、２０５℃、３０分間でプレス成形を行い、幅１５ｍｍ×長さ８０ｍｍ×厚み６ｍｍの曲げ試験体を得た。
３）バインダー硬化物が付着したガラスビーズの重量を１００重量％としたときに、バインダー硬化物重量が３重量％となるようにした。
４）試験体を、荷重フルスケール５００Ｎ、引張り速度５０ｍｍ／分、支点間距離４０ｍｍの条件で、万能材料試験機（島津製作所社製、オートグラフＡＧＳ－５００ＮＸ）を用いて、曲げ試験を行い、曲げ強度を測定した。 <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.
＜試験例４：反応速度の測定＞
　以下の手順に従い、バインダーの硬化特性を明らかにするため、動的機械分析（ＤＭＡ）法による架橋開始温度と架橋終了温度を求めた。動的機械分析装置としては、ＴＡインスツルメント社製動的粘弾性スペクトロメーターＲＳＡIIIを用いた。
１）ろ紙（パルプ製，１２．５ｍｍ×４５ｍｍにバインダー５０質量％溶液を１滴（約５０ｍｇ）滴下して測定用の試料を作製した。
２）試料を装置の２つのチャック間に水平に固定した。なおチャック間距離は２０ｍｍにした。
３）試料を４℃／分の速度で３０℃から２５０℃まで温度に加熱し、弾性率Ｅ’の変化曲線を取得した。
４）この際、振動数を１ｒａｄ／秒，歪０．１％とした。 <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%.
＜試験例５：繊維腐食性の評価＞
　繊維腐食性は、成形体を走査型電子顕微鏡（ＳＥＭ）で観察したときに、繊維上に無機酸由来の析出物による凸凹が確認できるか否かで評価をした。具体的には、成形体を作製して所定期間経過後（例えば２３．５℃、５０ＲＨ％の環境下で３週間経過後又は４０℃８５％ＲＨの高温・高湿度の加速条件で５日経過後）に、成形体をＳＥＭで観察したときに、繊維上に無機酸の塩が析出していない場合に「〇（腐食無）」とし、無機酸の塩が析出している場合に「×（腐食）」とした。なお、析出物が無機酸の塩であることはＳＥＭ－ＥＤＳおよびＸ線回折装置（ＸＲＤ）を用いて確認した。 <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.
＜試験例１～５の結果＞
　試験例１～５で得られた各種特性の測定結果を、バインダー水溶液のｐＨと共に、以下の表３に示す。 <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.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
（比較例８の結果）
　表３に示すように、フェノール樹脂系バインダー（比較例８）を用いた場合の引張強度及び引張弾性率の値を、バインダー性能を判断する際の指標とした。ｐＨは７．５であった。 (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.
（実施例１～３の結果）
　表３に示すように、実施例１のバインダー組成物を用いた場合、引張強度が８．９ＭＰａ、引張弾性率が１００２ＭＰａであり、適切な力学的特性を示していた。
　また、バインダー水溶液のｐＨは６．８であり、中性領域であった。更に、硬化物の水溶出液のｐＨも６．３と中性領域であった。
　さらに、繊維腐食性が「〇（腐食無）」となっていた。 (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)".
　同様に、実施例２、３のバインダー組成物を用いた場合、引張強度が８．５～８．７ＭＰａ、引張弾性率が９７６～９８８ＭＰａであり、適切な力学特性を示していた。
　また、バインダー水溶液のｐＨは６．６～６．７であり、中性領域であった。更に、硬化物の水溶液もｐＨ８．２～８．３（つまり８．４未満）であり、弱アルカリ性領域であった。
　さらに繊維腐食性が「○（腐食無）」となっていた。 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)".
（比較例１～７、９の結果）
　表３に示すように、無機酸アンモニウムとして硫酸アンモニウムを用いた比較例１～３、５～７やリン酸水素２アンモニウムを用いた比較例９では、バインダー硬化物の溶出率が２．４～３．９質量％と高く、溶出液のｐＨも２．９～３．４と酸性が強いものとなっていた。これに起因して、繊維腐食性が「×（腐食）」となっていた。 (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)".
　比較例１～６、９では、実施例１よりも引張弾性率が低かった。また、引張強度について、実施例１が比較例２～６、９、フェノール樹脂（比較例８）よりも大きくなっていた。 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).
　以上の結果から、実施例１～３のバインダー組成物を用いた場合、原料に無機酸を用いていないことから、無機繊維の腐食がなく、力学特性もフェノール樹脂よりも優れていた。 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.
＜試験例４の結果＞
　弾性率Ｅ’（ＭＰａ）を温度（℃）の関数としてプロットした結果を図３Ａ、図３Ｂ及び図３Ｃに示す。
　図３Ａ及び図３Ｃに示すように、実施例１のバインダー組成物の反応速度は、硫酸アンモニウム等の無機酸を用いないバインダーの中では最高の反応速度であった。実施例１のバインダー組成物の反応速度は、糖とクエン酸アンモニウムを組み合わせた比較例４のバインダー組成物よりも早く、従来の製造工程を用いても、十分に硬化することができることが示された。 <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.
＜試験のまとめ＞
　以上の結果から、本実施形態に係るバインダー組成物について、原料に無機酸イオンを用いていないのにもかかわらず、バインダーを架橋反応させる際の反応速度が十分であり、強度や弾性率などの力学的特性が良好であることが示された。
　本実施形態に係るバインダー組成物を用いた場合、糖類ベースのバインダーでありながら、無機酸イオンを含まないため、時間が経過しても無機繊維を腐食させてしまうことがない。 <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　溶融した原料
３　フリース
５　積層体
７　ロックウールマット
１１　ロール
１３　スチールベルト（第１のベルト）
１５　ペンジュラム（第２のベルト）
１７　コンベア（第３のベルト）
１９　硬化炉 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. 　糖類及びラジカル発生剤の反応生成物と、
    　有機酸化合物と、を含み、
    　無機酸を実質的に含まないことを特徴とするバインダー組成物。     Reaction products of sugars and radical generators,
    Contains organic acid compounds,
    A binder composition characterized by substantially containing no inorganic acid.
  2. 　前記糖類が、グルコース、ガラクトース、マンノース、フルクトース、マルトース、及びラクトースからなる群より選択される少なくとも１種以上の還元糖であることを特徴とする請求項１に記載のバインダー組成物。 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. 　前記ラジカル発生剤が、アゾ化合物及び過酸化物からなる群より選択される少なくとも１種以上であることを特徴とする請求項１又は２に記載のバインダー組成物。 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. 　前記過酸化物が、過酸化水素水及び有機過酸化物からなる群より選択される少なくとも１種以上であることを特徴とする請求項３に記載のバインダー組成物。 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. 　前記有機酸化合物が、低分子ポリカルボン酸、低分子ポリカルボン酸塩、高分子ポリカルボン酸、及び高分子ポリカルボン酸塩からなる群より選択される少なくとも１種以上であることを特徴とする請求項１乃至３いずれか１項に記載のバインダー組成物。 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. 　前記有機酸化合物が、クエン酸及びクエン酸アンモニウムからなる群より選択される少なくとも１種以上であることを特徴とする請求項１乃至４いずれか１項に記載のバインダー組成物。 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. 　更にアミン化合物を含むことを特徴とする請求項１乃至５いずれか１項に記載のバインダー組成物。 The binder composition according to any one of claims 1 to 5, further comprising an amine compound.
  8. 　糖類及びラジカル発生剤の反応生成物と、有機酸化合物と、を含み、無機酸を実質的に含まないことを特徴とするバインダー組成物と、
    　無機繊維、木材、鋳物砂から選択される１種以上の対象物と、
    を含むことを特徴とする成形体。     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. 　前記無機繊維としてロックウール、ストーンウール、スラグウール、ミネラルウール、グラスウール、及びミネラルグラスウールからなる群より選択される少なくとも１種以上の鉱物繊維を含むことを特徴とする請求項８に記載の成形体。 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. 　前記糖類が、グルコース、ガラクトース、マンノース、フルクトース、マルトース、及びラクトースからなる群より選択される少なくとも１種以上の還元糖であり、
    　前記ラジカル発生剤が、アゾ化合物及び過酸化物からなる群より選択される少なくとも１種以上であり、
    　前記有機酸化合物が、低分子ポリカルボン酸、低分子ポリカルボン酸塩、高分子ポリカルボン酸、及び高分子ポリカルボン酸塩からなる群より選択される少なくとも１種以上であることを特徴とする請求項８又は９に記載の成形体。     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. 　成形体を製造する方法であって、
    　無機繊維、木材、鋳物砂から選択される１種以上の対象物に糖類及びラジカル発生剤の反応生成物と、有機酸化合物と、を含み、無機酸を実質的に含まないことを特徴とするバインダー組成物を付着させる付着工程と、
    　前記バインダー組成物が付着した前記対象物を加熱し、前記バインダー組成物を架橋反応させる加熱・硬化工程と、
    　を行うことを特徴とする成形体の製造方法。     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. 　更に前記バインダー組成物を調製するバインダー組成物調製工程を含み、
    　前記バインダー組成物調製工程において、
    　前記糖類が、グルコース、ガラクトース、マンノース、フルクトース、マルトース、及びラクトースからなる群より選択される少なくとも１種以上の還元糖であり、
    　前記ラジカル発生剤が、アゾ化合物及び過酸化物からなる群より選択される少なくとも１種以上であり、
    　前記有機酸化合物が、低分子ポリカルボン酸、低分子ポリカルボン酸塩、高分子ポリカルボン酸、及び高分子ポリカルボン酸塩からなる群より選択される少なくとも１種以上であることを特徴とする請求項１１に記載の成形体の製造方法。     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. 　前記加熱・硬化工程の前に前記バインダー組成物が付着した前記対象物を所望の成形体に対応した形状に成形する成形工程を行うことを特徴とする請求項１２に記載の成形体の製造方法。 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. 　無機酸及び無機酸塩を実質的に含まず、
    　水に浸漬して得られる溶出液のｐＨが６以上８．４未満であることを特徴とするバインダー硬化物。     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. 　請求項１４記載のバインダー組成物の硬化物と、
    　無機繊維、木材、鋳物砂から選択される１種以上の対象物と、を含むことを特徴とする成形体。     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.
PCT/JP2019/040652 2019-06-03 2019-10-16 Binder composition, molded body, production method for molded body, and binder cured object WO2020246055A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005171466A (en) * 2003-12-10 2005-06-30 Fuso Kogyo Kk Lightweight heat insulating material formed by using artificial mineral fiber and method for manufacturing the same
JP2011506781A (en) * 2007-12-05 2011-03-03 サン−ゴバン・イソベール Sizing composition for mineral wool containing monosaccharide and / or polysaccharide and organic polycarboxylic acid, and heat insulation product obtained
JP6062099B1 (en) * 2016-09-30 2017-01-18 ニチアス株式会社 Binder composition, molded body, and method for producing molded body
JP2018199793A (en) * 2017-05-29 2018-12-20 ヘンケルジャパン株式会社 Aqueous adhesive composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005171466A (en) * 2003-12-10 2005-06-30 Fuso Kogyo Kk Lightweight heat insulating material formed by using artificial mineral fiber and method for manufacturing the same
JP2011506781A (en) * 2007-12-05 2011-03-03 サン−ゴバン・イソベール Sizing composition for mineral wool containing monosaccharide and / or polysaccharide and organic polycarboxylic acid, and heat insulation product obtained
JP6062099B1 (en) * 2016-09-30 2017-01-18 ニチアス株式会社 Binder composition, molded body, and method for producing molded body
JP2018199793A (en) * 2017-05-29 2018-12-20 ヘンケルジャパン株式会社 Aqueous adhesive composition

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