JP4166265B2 - Inorganic fiber insulation - Google Patents

Description

The present invention, glass wool, relates rock wool-free machine fiber insulation sound-absorbing material that can be of suitably used for heat insulating acoustic material consisting of inorganic fiber and, more particularly, excellent aqueous binder to the adhesion force between the inorganic fibers The present invention relates to an inorganic fiber heat-absorbing sound absorbing material.

  Conventionally, in heat-absorbing and sound-absorbing materials made of inorganic fibers such as glass wool and rock wool, phenolic resin-based binders mainly composed of phenol / formaldehyde resin (or resol type phenolic resin) have been widely used as binders for bonding fibers together. ing. These phenolic resin binders are heat-cured in a relatively short time to obtain a strong cured product. For this reason, the inorganic fiber heat-insulation material using a phenol resin binder is excellent in shape retention, thickness restoration after opening the compressed package, flex resistance, and the like.

  However, when a phenol resin binder is used, formaldehyde is released during the manufacturing process, particularly when the binder is cured. In particular, in recent years, the amount of formaldehyde emission is required to be restricted by laws and regulations due to the reduction of environmental burden.

  It is known that the phenol resin binder increases the amount of formaldehyde emitted as the amount of binder attached increases. Although it is possible to reduce the amount of formaldehyde emitted by reducing the amount of binder attached, it has the problem that the mechanical strength such as compressive strength and tear peel strength of the resulting inorganic fiber heat-absorbing sound-absorbing material is impaired. Yes.

  In addition, various binders for formaldehyde-free inorganic fiber heat-absorbing and sound-absorbing materials in consideration of the environment have been studied. For example, Patent Document 1 listed below includes (a) at least two carboxylic acid groups, acid anhydride groups, Or a polyacid containing a salt thereof, (b) a polyol containing at least two hydroxyl groups, and (c) a phosphorus-containing accelerator, and the carboxylic acid group, acid anhydride group, The equivalent ratio of the salts: the equivalent ratio of the hydroxyl groups is about 1 / 0.01 to about 1/3, and the carboxylic acid group, acid anhydride group, or salt thereof is about a non-volatile base. A curable aqueous composition is disclosed that is neutralized to the extent of 35% or less.

  However, although the polycarboxylic acid resin binder does not emit formaldehyde, it requires more time to complete the curing or more heating than the phenol resin binder. Depending on the case, the mechanical strength of the inorganic heat insulating sound-absorbing material is impaired, and it is necessary to increase the amount of binder attached.

  On the other hand, silica sol (colloidal silica) and alumina sol (colloidal alumina) are used for the purpose of improving the stain resistance of a cured coating film in the field of paint (see Patent Document 2 below), and a matting agent (Patent Document below). Used as reference 3).

Moreover, the following patent document 4 discloses a mineral fiber product having high temperature heat resistance and biosolubility provided with a coating layer containing colloidal silica and a phosphorus compound.
JP-A-6-184285 JP 2000-136332 A JP 2003-286443 A Special Table 2000-502151

  The addition of silica sol to the thermosetting resin is disclosed in Patent Documents 2 to 4 above. And the said patent document 4 is disclosing the coating agent for mineral fibers containing a silica sol.

  However, there has been no known attempt to improve the adhesiveness between inorganic fibers by using silica sol or alumina sol as a binder for inorganic fibers without impairing the fluidity of the binder and the strength of the binder cured product.

  That is, Patent Document 4 is intended to improve the heat resistance and fire resistance of mineral fibers, and for this reason, for example, as shown in the same Example, a large amount of inorganic filler is blended in the coating agent. is doing. Although it is advantageous in increasing heat resistance and fire resistance by increasing the content of the inorganic filler, embrittlement due to the inorganic filler tends to occur, and adhesion between inorganic fibers is easily impaired.

Accordingly, an object of the present invention is to provide an inorganic fiber heat insulating sound absorbing material using an aqueous binder that can improve adhesion between inorganic fibers without impairing the fluidity of the binder and the strength of the cured binder .

In order to achieve the above object, the first inorganic heat insulating sound absorbing material of the present invention comprises a water-soluble thermosetting resin composition containing at least a resol type phenol resin, an aqueous silica sol and / or an aqueous alumina sol, In terms of minutes, an aqueous binder containing 0.1 to 10 parts by weight of an aqueous silica sol and / or an aqueous alumina sol is added to inorganic fibers with respect to 100 parts by weight of the resin in the water-soluble thermosetting resin composition. It is characterized by being molded by heat curing .
The second of the inorganic fiber heat-absorbing sound-absorbing material of the present invention includes polycarboxylic acids containing two or more carboxyl groups in the molecule and a crosslinking agent, and the number of moles of carboxyl groups in the polycarboxylic acids. On the other hand, the water-soluble thermosetting resin composition in which the number of moles of the functional group capable of reacting with the carboxyl group in the cross-linking agent is 0.7 to 1.5, and the aqueous silica sol and / or the aqueous alumina sol And an aqueous binder containing 0.1 to 10 parts by mass of an aqueous silica sol and / or an aqueous alumina sol with respect to 100 parts by mass of the resin content in the water-soluble thermosetting resin composition in terms of solid content. It is characterized by being imparted to inorganic fibers and heat-cured and molded .

The water-based binder used for the inorganic fiber heat-insulating sound absorbing material of the present invention is 0.1 to 0.1 water-based silica sol and / or water-based alumina sol based on 100 parts by weight of the resin content in the water-soluble thermosetting resin composition in terms of solid content. By containing 10 parts by mass, a cured binder having excellent strength can be obtained without changing the production process of the inorganic fiber heat-absorbing sound-absorbing material such as a binder coating process and a curing process. And the adhesion | attachment of fibers can be strengthened by apply | coating this binder to an inorganic fiber. For this reason, even if the amount of binder used is small, the mechanical strength of the inorganic fiber heat-absorbing sound-absorbing material can be improved, so that the amount of binder used can be reduced during the production of inorganic fiber heat-absorbing sound-absorbing materials and the like. Excellent economy.

In addition, since the aqueous binder used for the second inorganic fiber heat insulating sound absorbing material of the present invention is a formaldehyde-free binder, it does not release formaldehyde at the time of heat curing, and reduces the environmental burden in exhaust gas etc. Can do. And by making the molar number of the functional group which can react with the carboxyl group in a crosslinking agent 0.7-1.5 by molar ratio with respect to the molar number of the carboxyl group in polycarboxylic acids, polycarboxylic acids And the cross-linking agent can be reacted with each other without excess or deficiency, and moisture absorption by the remaining excessive functional groups can be suppressed.

Aqueous binders used for the first inorganic fiber insulation sound-absorbing material of the present invention, water-soluble thermosetting resin composition comprises a resole phenolic resin and urea, the weight ratio of the resole phenolic resin and urea, solid In terms of minutes, it is preferable that phenol resin: urea = 90: 10 to 50:50.
The aqueous binder used for the second inorganic fiber heat-absorbing and sound-absorbing material of the present invention is an acrylic resin-based polycarboxylic acid having an acid value of 500 to 850 mgKOH / g and a weight average molecular weight of 1,000 to 15,000. It is preferable that According to this, fusing of polycarboxylic acids due to rapid heating can be suppressed in the heat curing process of the inorganic fiber heat-absorbing sound-absorbing material, and a high-strength binder cured product can be obtained without losing the binder amount. The binding (adhesive force) of the material becomes stronger.

In the aqueous binder used for the second inorganic fiber heat-absorbing sound-absorbing material of the present invention, the crosslinking agent preferably contains at least one dialkanolamine. According to this, among the functional groups contained in the crosslinking agent, the imino group reacts with the carboxyl group faster than the hydroxyl group, and further, the delay in crosslinking of the binder due to steric hindrance and the incomplete portion are reduced. The curing time can be shortened, and further the productivity and the strength of the cured binder can be improved.

The aqueous binder used for the first and second inorganic fiber heat-absorbing sound-absorbing materials of the present invention preferably has a pH adjusted to 6.0 to 8.0 with a volatile basic compound. According to this, there is no corrosion of the production equipment due to the acid, and maintenance costs, equipment costs, wastewater treatment costs, etc. can be reduced.

As for the 1st and 2nd of the inorganic fiber heat insulation sound-absorbing material of this invention, it is preferable that the said inorganic fiber is glass wool or rock wool. Moreover, it is preferable that a density is 5-300 kg / m < ³ >.

According to the present invention, the aqueous silica sol and / or the aqueous alumina sol is added to 100 parts by mass of the resin content in the water-soluble thermosetting resin composition in terms of solid content in the aqueous binder for heat insulating and sound absorbing material of inorganic fibers. Since 0.1-10 mass parts is contained, the binder hardened | cured material which has the outstanding intensity | strength is obtained, without changing the manufacturing process of an inorganic fiber heat insulation sound-absorbing material, such as a binder application | coating process and a hardening process. And by apply | coating this binder to an inorganic fiber, since adhesion | attachment of fibers can be strengthened, even if the usage-amount of a binder is small, the mechanical strength of the inorganic fiber heat insulation sound-absorbing material obtained can be made favorable.

[Aqueous silica sol and aqueous alumina sol]
In the present invention, the aqueous silica sol (also referred to as colloidal silica) is preferably one in which silica having a particle size of 10 to 500 nm is dispersed in water at a solid content of 1 to 40% by weight. This aqueous silica sol can be produced by a sol-gel method produced from alkoxysilane or a sodium silicate method produced from sodium silicate.

  In the present invention, the aqueous alumina sol (also referred to as colloidal alumina) is preferably one in which alumina having a particle size of 10 to 500 nm is dispersed in water at a solid content of 1 to 40% by weight. This aqueous alumina sol can be produced, for example, by a sol-gel method produced from alkoxyaluminum.

  In the present invention, an aqueous silica sol obtained by a sodium silicate method is particularly preferable from the viewpoint of economy.

[Water-soluble thermosetting resin composition]
In the present invention, the aqueous thermosetting resin composition preferably includes an aldehyde condensable thermosetting resin and a polycarboxylic acid resin composition, and from the viewpoint of environmental considerations, a formaldehyde-free resin composition is preferable, Polycarboxylic acid resin compositions are particularly preferred.

(Aldehyde condensable thermosetting resin)
Examples of the aldehyde condensable thermosetting resin include a resol type phenol resin, a melamine resin, a urea resin, and a furan resin, and a resol type phenol resin is preferable. Among the aldehyde condensable thermosetting resins, the resol type phenolic resin has a relatively small amount of formaldehyde released during curing and is excellent in moisture resistance of the cured product. These resins may be used alone or in combination of two or more.

  Moreover, when an excess formaldehyde is thrown in molar ratio with respect to a phenol nucleus at the time of a synthesis | combination, a resol type phenol resin may contain a lot of free formaldehyde in the obtained resol type phenol resin. In that case, it is preferable to use by modifying urea-phenol resin or phenol-melamine resin in which urea, melamine, or a urea derivative such as ethylene urea is added and freed formaldehyde is consumed. And when adding urea in order to consume free formaldehyde, it is preferable that the mass ratio of a resol type phenol resin and urea exists in the range of phenol resin: urea = 90: 10-50: 50 in conversion of solid content. More preferably, it is in the range of 70:30 to 60:40. When the urea content is less than 10%, formaldehyde in the resol type phenol resin is not sufficiently captured, and formaldehyde is diffused in the heat curing process of the inorganic fiber heat-absorbing sound absorbing material, which causes an environmental problem. There is a case. Moreover, when urea content ratio exceeds 50%, the obtained binder hardened | cured material will be influenced by the hydrolysis by humidity, and the physical-property deterioration of an inorganic fiber heat-insulation sound-absorbing material will become remarkable, and the wall of the heat-insulation sound-absorbing material constructed will be in the wall Due to sedimentation and strength reduction, there may be a problem that desired heat insulation and sound absorption cannot be obtained.

(Polycarboxylic acid resin composition)
As said polycarboxylic acid-type resin composition, what is comprised from the polycarboxylic acid which contains a 2 or more carboxyl group in a molecule | numerator, and a crosslinking agent is preferable.

(Polycarboxylic acids)
Examples of the polycarboxylic acids used in the polycarboxylic acid-based resin composition include polycarboxylic acid monomers, polyester resin-based polycarboxylic acids, amide resin-based polycarboxylic acids, and acrylic resin-based polycarboxylic acids.

  Examples of the polycarboxylic acid monomer include aliphatic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, and tricarballylic acid. Polycarboxylic acids; oxypolycarboxylic acids such as malic acid, tartronic acid, tartaric acid, citric acid; aromatic polycarboxylic acids such as orthophthalic acid, isophthalic acid, terephthalic acid, benzenetricarboxylic acid, trimellitic acid, and pyromellitic acid It is done.

  Examples of the polyester resin-based polycarboxylic acids include 1,2-ethanediol (ethylene glycol), 1,2-propanediol (propylene glycol), 1,3-propanediol, and 2,2-methyl-1,3-propane. Diol, 2-butyl-2-ethyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-2,4-butanediol, 1,5-pentanediol, 3 -Methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 2-ethyl-1,3-hexanediol, 2-hydroxymethyl -2-Methyl-1,3-propanediol, 2-ethyl-2-hydroxymethyl-2-methyl-1,3-propane Aliphatic polyols such as all, 1,2,6-hexanetriol, 2,2-bis (hydroxymethyl) -2,3-propanediol; selected from sugars such as glucose, fructose, mannitol, sorbitol, maltitol What has an acid value obtained by ester-polymerizing polyols and the said polycarboxylic acid monomer is mentioned.

  Examples of the polyamide resin-based polycarboxylic acids include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1, 6-diaminohexane, 3,3'-iminobis (propylamine), 3- (methylamino) propylamine, 3- (dimethylamino) propylamine, 3- (ethylamino) propylamine, 3- (butylamino) propyl Aliphatic polyamines such as amine, N-methyl-3,3'-iminobis (propylamine), polyethyleneimine; phenylenediamine, o-tolidine, m-toluylenediamine, m-xylylenediamine, dianisidine, diaminodiphenyl ether Aromatic polyamines such as 1,4-diaminoanthraquinone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 4,4'-diamino-3,3'-diethyldiphenylmethane Piperazine, 2-methylpiperazine, 1- (2-aminoethyl) piperazine, 2,5-dimethylpiperazine, cis-2,6-dimethylpiperazine, bis (aminopropyl) piperazine, 1,3-di (4- A polyamine selected from heterocyclic amines such as piperidyl) propane, 3-amino-1,2,4-triazole, 1-aminoethyl-2-methylimidazole, and the polycarboxylic acid monomer. And having an acid value obtained.

  Examples of the acrylic resin-based polycarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid, 2-methylmaleic acid, itaconic acid, 2-methylitaconic acid, α-β-methyleneglutaric acid, maleic acid Monoalkyl, monoalkyl fumarate, maleic anhydride, acrylic anhydride, β- (meth) acryloyloxyethylene hydrodiene phthalate, β- (meth) acryloyloxyethylene hydrogen maleate, β- (meth) acryloyloxyethylene hydro Examples thereof include those obtained by polymerizing one or more selected from ethylenically unsaturated carboxylic acid monomers such as diene succinate.

  The acid value of the polycarboxylic acids is preferably 500 to 850 mgKOH / g, more preferably 600 to 750 mgKOH / g. When the acid value of the polycarboxylic acid is less than 500 mgKOH / g, the crosslinked structure of a cured product obtained by heat-curing the aqueous binder becomes rough, and the strength and rigidity of the binder cured product tend to be reduced. Therefore, the thickness restoration property (hereinafter referred to as “restoration property”) of the inorganic fiber heat insulating sound absorbing material obtained after opening the compressed package and the rigidity of the board are lowered, and the heat insulating property, sound absorbing property, or self-supporting property, that is, construction The workability of the time may be impaired. Moreover, when the acid value of polycarboxylic acids exceeds 850 mgKOH / g, the crosslinked structure after binder curing tends to become too dense and brittle, and when used as a binder for an inorganic fiber heat-absorbing sound absorbing material, the desired performance is obtained. Or when unreacted carboxyl groups remain in the cured product even after curing, for example, when moisture is absorbed under high humidity, the bond strength between fibers due to the binder decreases. There is. In addition, the acid value of polycarboxylic acids in the present invention is expressed in milligrams of potassium hydroxide required to neutralize 1 g of polycarboxylic acids.

  The weight average molecular weight of the polycarboxylic acids is preferably 1,000 to 15,000, more preferably 2,000 to 10,000, and particularly preferably 2,000 to 5,000. If the weight average molecular weight of the polycarboxylic acid exceeds 15,000, the viscosity of the binder after the evaporation of water from the binder application is remarkably increased, and the fluidity after application to the inorganic fiber or after application tends to be inferior. On the other hand, it tends to be difficult to uniformly apply the binder. In addition, the adhesiveness of the binder attached to the inorganic fiber tends to increase. If the adhesiveness of the binder attached to the inorganic fiber is high, the fiber to which the binder is attached becomes more likely to adhere to the production equipment, and the production line becomes dirty. In addition, the fibers on the surface of the inorganic heat insulating sound absorbing material may be agglomerated and adhere to manufacturing equipment, resulting in problems such as partial lack of appearance and thickness of the resulting product. On the other hand, when the weight average molecular weight of the polycarboxylic acid is less than 1,000, the binder component is easily volatilized as fume by heating at the time of curing, and the amount of the binder attached to the inorganic fiber is likely to be reduced. Therefore, when it is an inorganic fiber heat insulating sound-absorbing material, various physical properties are reduced, or it is necessary to suppress the degree of polymerization at the time of polymerization of polycarboxylic acids, so that the ethylenically unsaturated monomer tends to remain, There is a risk that odor will be generated and a new environmental load may occur.

If the weight average molecular weight of the polycarboxylic acid is within the above range, it is easy to adjust the viscosity of the aqueous binder for an inorganic fiber heat-absorbing sound-absorbing material , and the fluidity at the time of application to an inorganic fiber or after application can be improved. In addition, it is possible to suppress variation in the amount of binder attached to the inorganic fibers. In the production of an inorganic fiber heat-absorbing sound-absorbing material, the step of applying the binder to the fiber is often performed in a high-temperature atmosphere of about 200 to 350 ° C. immediately after being fiberized by a centrifugal method or the like. Evaporation of moisture can be improved.

  In addition, the weight average molecular weight of the polycarboxylic acids is related not only to the fluidity of the binder but also to the curing speed and the crosslinking density after curing. Even if the polycarboxylic acids having the same acid value have different molecular weights, The curing speed of the resin and the strength of the cured binder vary, and the physical properties of the resulting inorganic fiber heat-absorbing sound-absorbing material also change. For example, as the weight average molecular weight of polycarboxylic acids decreases, the curing rate of the binder increases, but the cured binder tends to become brittle, and depending on the production conditions of the production line, the desired physical properties may not be obtained. is there. When the weight average molecular weight of the polycarboxylic acids is within the above range, the fluidity of the binder and various physical properties of the resulting inorganic fiber heat-absorbing sound absorbing material can be optimized.

  In view of ease of control of the molecular weight of the polycarboxylic acid, etc., an acrylic resin-based polycarboxylic acid using acrylic acid or methacrylic acid as the ethylenically unsaturated carboxylic acid monomer is preferable. When adjusting the acid value of the acrylic resin-based polycarboxylic acid to a high region of 700 mgKOH / g or more, vinyl polymerization-based polycarboxylic acid using maleic acid or fumaric acid as the ethylenically unsaturated carboxylic acid monomer. Is preferred.

  Moreover, in this invention, when adjusting the acid value of polycarboxylic acid, the ethylenically unsaturated monomer which does not contain a carboxyl group can also be used together with the said polycarboxylic acid.

  Examples of the ethylenically unsaturated monomer containing no carboxyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cetyl (meth) acrylate, n-stearyl (meth) acrylate, diethylene glycol ethoxy (meth) acrylate, methyl-3-methoxy (meth) acrylate, ethyl-3-methoxy (meth) acrylate, butyl -3-Methoxy (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl acrylate, 2-hydroxyethyl acrylate, 2- Droxypropyl acrylate, 4-hydroxybutyl acrylate, mono (meth) acrylate of trivalent or higher polyol, aminoalkyl (meth) acrylate, N-alkylaminoalkyl (meth) acrylate, N, N-dialkylaminoalkyl (meth) Acrylic monomers such as acrylates; Vinyl-based compounds such as vinyl alkyl ethers, N-alkyl vinyl amines, N, N-dialkyl vinyl amines, N-vinyl pyridines, N-vinyl imidazoles, N- (alkyl) aminoalkyl vinyl amines Monomer; (meth) acrylamide, N-alkyl (meth) acrylamide, N, N-dialkyl (meth) acrylamide, N, N-dialkylaminoalkyl (meth) acrylamide, diacetone (meth) acrylamide, N-vinylform Amide monomers such as amide, N-vinylacetamide and N-vinylpyrrolidone; Aliphatic unsaturated hydrocarbons such as ethylene, propylene, isobutylene, isoprene and butadiene; styrene, α-methylstyrene, p-methoxystyrene, vinyl Styrene monomers such as toluene, p-hydroxystyrene, p-acetoxystyrene; vinyl ester monomers such as vinyl acetate and vinyl propionate; acrylonitrile, glycidyl (meth) acrylate and the like. These can use together 1 type (s) or 2 or more types. However, it is preferable not to use N-methylol (meth) acrylamide and methyl-N-methylol (meth) acrylamide because they release formaldehyde with the crosslinking reaction when heated.

  In the present invention, the polycarboxylic acids are particularly preferably acrylic resin-based polycarboxylic acids having an acid value of 500 to 850 mgKOH / g and a weight average molecular weight of 1,000 to 15,000. The polycarboxylic acid monomer may sublimate or volatilize as fumes when the binder is heat-cured. Depending on the binder curing conditions, it may not only reduce the amount of the binder applied but also create a new environmental burden. In some cases, it is not preferable. In addition, polyester-based polycarboxylic acids and polyamide-resin-based polycarboxylic acids undergo an exchange reaction simultaneously with crosslinking during the curing reaction with a crosslinking agent, that is, ester bonds and amide bonds in the polycarboxylic acids are cleaved by heat. In some cases, monomers and oligomers are produced, and there is a possibility that the reaction of recombination may occur. Therefore, the curing reaction of the binder may take time or the curing may be insufficient. In polycarboxylic acids, the exchange reaction as described above does not occur at the same time, so that the curing time can be shortened, and further, a sufficiently cured binder cured product can be obtained.

(Crosslinking agent)
The crosslinking agent used in the polycarboxylic acid resin composition is a compound having a functional group capable of reacting with a carboxyl group, and preferably contains at least one dialkanolamine. In the present invention, the “functional group capable of reacting with a carboxyl group” means a hydroxyl group, an amino group, an imino group, and an epoxy group.

  Dialkanolamines are polyols having an imino group and a hydroxyl group. When the reactivity of the imino group and the hydroxyl group with respect to the carboxyl group is compared, the imino group tends to react faster than the hydroxyl group. Therefore, the reactivity with a carboxyl group can be improved by using dialkanolamines as a crosslinking agent.

  Examples of the dialkanolamines include diethanolamine, diisopropanolamine, and the like, and diethanolamine is more preferable because of the speed of reaction with polycarboxylic acids.

  Among the crosslinking agents, compounds other than dialkanolamine include (a) 1,2-ethanediol (ethylene glycol) and its dimer or trimer, 1,2-propanediol (propylene glycol) And dimer or trimer thereof, 1,3-propanediol, 2,2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,3-butane Diol, 1,4-butanediol, 2-methyl-2,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 1 , 6-hexanediol, 1,4-cyclohexanediol, 2-ethyl-1,3-hexanediol, 2-hydroxymethyl-2-methyl-1,3-propane Fats such as all, 2-ethyl-2-hydroxymethyl-2-methyl-1,3-propanediol, 1,2,6-hexanetriol, 2,2-bis (hydroxymethyl) -2,3-propanediol Group polyols; trialkanolamines such as triethanolamine and triisopropanolamine; sugars such as glucose, fructose, mannitol, sorbitol, maltitol, and the above polyols, and polyester polyols such as phthalic acid, adipic acid, and azelaic acid Compounds having a hydroxyl group such as polyethylene glycol, polypropylene glycol, acrylic resin polyol, (b) ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 1, -Diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 3,3'-iminobis (propylamine), 3- (methylamino) propylamine, 3- (dimethylamino ) Aliphatic polyamines such as propylamine, 3- (ethylamino) propylamine, 3- (butylamino) propylamine, N-methyl-3,3′-iminobis (propylamine), polyethyleneimine; -Tolidine, m-toluylenediamine, m-xylylenediamine, dianisidine, diaminodiphenyl ether, 1,4-diaminoanthraquinone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide 4,4'-diamino-3,3'-diethyldiphenylme Aromatic polyamines such as tan; piperazine, 2-methylpiperazine, 1- (2-aminoethyl) piperazine, 2,5-dimethylpiperazine, cis-2,6-dimethylpiperazine, bis (aminopropyl) piperazine, 1, Heterocyclic amines such as 3-di (4-piperidyl) propane, 3-amino-1,2,4-triazole, and 1-aminoethyl-2-methylimidazole, and further, ethylene oxide or Compounds containing amino groups or imino groups such as polyamine polyols with propylene oxide added, (c) propanediol diglycidyl ether, butanediol diglycidyl ether, pentanediol diglycidyl ether, hexanediol diglycidyl ether, neopentyl Glycoldi Ricidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol polyglycidyl ether, polypropylene polyglycidyl ether, cyclohexanediol diglycidyl ether, sorbitol polyglycidyl ether adipic acid diglycidyl ester, azelaic acid diglycidyl ester, tetrahydro Aliphatic epoxies such as phthalic acid diglycidyl ester and hexahydrophthalic acid diglycidyl ester; bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, cresol phenol polyglycidyl ether, novolac phenol polyglycidyl ether, phthalic acid diglycidyl ester, etc. Contains epoxy groups such as aromatic epoxies That compound, and the like. These can use together 1 type (s) or 2 or more types.

Moreover, it is preferable that the said crosslinking agent is a water-soluble compound. If it is a water-insoluble compound, it is necessary to emulsify the aqueous binder for heat insulating sound absorbers of inorganic fibers, but if it is an emulsion or aqueous dispersion binder, it will have the property of forming a film at a relatively low temperature. Therefore, when producing an inorganic fiber heat-absorbing sound-absorbing material, the binder is easily formed into a film before curing. As a result, the compatibility with the polycarboxylic acids decreases, or a phenomenon occurs in which only the surface is first formed into a film and water is trapped inside, and the curing rate of the binder becomes slow, or the obtained binder curing In some cases, the physical properties of the inorganic fiber heat-absorbing sound-absorbing material may be impaired due to a decrease in strength of the object.

  The crosslinking agent is preferably a compound having a molecular weight of 50 to 500. When a crosslinking agent having a relatively high molecular weight is used, the curing rate of the binder tends to be slow. In the production process of an inorganic fiber heat-absorbing sound absorbing material, it takes time for the binder curing step or increases the temperature of the binder curing oven. Productivity and economic efficiency may be impaired.

  And as for the said crosslinking agent, the mole number of the functional group which can react with the carboxyl group in a crosslinking agent becomes 0.7-1.5 by molar ratio with respect to the mole number of the carboxyl group of polycarboxylic acid. The polycarboxylic acid resin composition is preferably contained, more preferably 0.8 to 1.2, and particularly preferably 0.9 to 1.1. When the molar ratio is less than 0.7, the carboxyl group of the polycarboxylic acid remains even after curing, and when it exceeds 1.5, the crosslinking agent remains after curing. Due to environmental factors such as moisture resistance of the material, physical properties tend to decrease, excess polycarboxylic acids or cross-linking agents tend to be produced, and the economy is also inferior. If the number of moles of the functional group capable of reacting with the carboxyl group in the crosslinking agent is within the above range relative to the number of moles of the carboxyl group of the polycarboxylic acid, both the polycarboxylic acid and the crosslinking agent are crosslinked at the time of binder curing without excess or deficiency. Since the structure is formed, the strength of the cured binder is increased, and various properties of the obtained inorganic fiber heat-absorbing sound-absorbing material can be optimized.

(Curing accelerator)
The polycarboxylic acid resin composition preferably further contains a curing accelerator. The curing accelerator accelerates the curing reaction such as amidation reaction, imidation reaction or esterification reaction between the polycarboxylic acid and the crosslinking agent, and acts to shorten the curing time of the binder and the curing temperature.

  Examples of such a curing accelerator include hypophosphites such as sodium hypophosphite, potassium hypophosphite, calcium hypophosphite, magnesium hypophosphite; and organic phosphorus such as tris (3-hydroxypropyl) phosphine. Compounds: Tetraethylphosphonium salt, triethylbenzylphosphonium salt, quaternary phosphonium salt such as tetra-n-butylphosphonium salt, tri-n-butylmethylphosphonium salt; lithium hydrogen sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, magnesium hydrogen sulfite, sulfurous acid Bisulfites such as calcium hydrogen and ammonium bisulfite; Lewis acid compounds such as boron trifluoride amine complex, zinc chloride, aluminum chloride, magnesium chloride; titanium lactate, titanium triethanolamate, zirconyl acetate And the like of the water-soluble organic metal compound. These can use together 1 type (s) or 2 or more types.

And as for content of the hardening accelerator in the aqueous binder for inorganic fiber heat insulation sound-absorbing materials , 0.1-10 mass parts is preferable in conversion of solid content with respect to a total of 100 mass parts of polycarboxylic acids and a crosslinking agent, 0.5-5 mass parts is more preferable. If the amount is less than 0.1 parts by mass, the curing reaction between the polycarboxylic acids and the crosslinking agent cannot be accelerated sufficiently. If the amount exceeds 10 parts by mass, the effect of curing acceleration commensurate with the increase in content is not observed. Since an excessive amount of bisulfite is hydrophilic, the moisture resistance and water resistance of the cured binder may be impaired.

[Aqueous binder for inorganic fiber insulation ]
The aqueous binder for an inorganic fiber heat-absorbing sound absorbing material of the present invention contains the water-soluble thermosetting resin composition and an aqueous silica sol and / or an aqueous alumina sol.

The aqueous binder for an inorganic fiber heat-absorbing sound-absorbing material of the present invention is an aqueous silica sol and / or an aqueous alumina sol, in terms of solid content, in an amount of 0.1 to 100 parts by mass of the resin content in the water-soluble thermosetting resin composition. It contains 10 mass parts, and it is preferable to contain 0.5-5 mass parts. When the content of the aqueous silica sol and / or the aqueous alumina sol is less than 0.1 parts by mass, the effect of improving the strength of the binder cured product is small, and the adhesion between fibers cannot be made sufficient. In addition, when the content of the aqueous silica sol and / or the aqueous alumina sol exceeds 10 parts by mass, the cured binder becomes brittle and, for example, the bonded portion between the inorganic fibers is easily broken by restoration after compression packing or repeated compression. Thus, the mechanical strength of the obtained inorganic fiber heat-absorbing sound-absorbing material may be impaired. And the balance of the strength improvement of binder hardened | cured material and embrittlement suppression becomes optimal because content of aqueous silica sol and / or aqueous alumina sol shall be 0.5-5 mass parts.

Moreover, it is preferable that the pH of the aqueous binder for an inorganic fiber heat-absorbing sound-absorbing material of the present invention is adjusted to 6.0 to 8.0 with a volatile basic compound, and is adjusted to 6.0 to 7.0. It is more preferable that it is adjusted to 6.0 to 6.5. If the pH is less than 6.0, the production equipment is likely to be corroded and deteriorated due to long-term use, and the cost of treating wastewater tends to be required. On the other hand, if the pH exceeds 8.0, the crosslinking reaction in the binder becomes gradual, and curing is not completed, or heating for a long time is required until the curing is completed, and productivity is likely to be impaired. In addition, various physical properties such as restoration property and self-supporting property of the obtained inorganic fiber heat-absorbing sound-absorbing material are likely to be impaired. If the pH of the aqueous binder for an inorganic fiber heat-absorbing and sound-absorbing material is within the above range, the corrosion of the production equipment can be suppressed and the wastewater treatment can be facilitated, so that the maintenance cost can be reduced.

  Examples of the volatile basic compound used for adjusting the pH include ammonia water and amines, and it is preferable to use ammonia water in consideration of an odor generated during curing.

Moreover, a silane coupling agent may be used for the aqueous binder for an inorganic fiber heat-absorbing and sound-absorbing material of the present invention. The silane coupling agent acts at the interface between the inorganic fiber and the binder, and can improve the adhesion of the binder to the inorganic fiber.

  Examples of the silane coupling agent include γ-aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, and γ- (2-aminoethyl) aminopropylmethyldimethoxysilane. Examples thereof include epoxy silane coupling agents such as γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropylmethyldimethoxysilane. These can use together 1 type (s) or 2 or more types.

  And as for content of a silane coupling agent, 0.1-2.0 mass parts is preferable with respect to 100 mass parts of resin parts in a water-soluble thermosetting resin composition in conversion of solid content.

Further, the aqueous binder for an inorganic fiber heat-absorbing sound absorbing material of the present invention may use at least one water dispersion selected from waxes or a mixture of waxes and heavy oils.

In particular, as a water-soluble thermosetting resin composition, an aqueous binder for an inorganic fiber heat-absorbing and sound-absorbing material using polycarboxylic acids as a water-soluble thermosetting resin composition has good adhesion to metal. It is easy to adhere to equipment such as, and at the same time, inorganic fibers may adhere to the production equipment. As a result, irregularities are likely to occur on the surface of the resulting inorganic fiber product, and the appearance of the product may be impaired. Also, in order to remove the lump of inorganic fibers adhered to the manufacturing equipment, complicated work at high temperatures However, by blending the above waxes or a mixture of waxes and heavy oils into the binder, these components can be used as an inorganic fiber heat insulating sound absorbing material. It acts as a mold release agent during production and can solve these problems. At the same time, the waxes or the mixture of waxes and heavy oils can remain in the binder cured product to improve the water repellency of the inorganic fiber heat-absorbing sound-absorbing material.

  The above waxes are not strictly defined, but are solids at room temperature, but when heated to about 40 ° C. or higher, they become liquids with relatively high fluidity, specifically, beeswax, Animal waxes such as lanolin wax and shellac wax, plant waxes such as carnauba wax, wax wax, rice wax and candelilla wax, mineral waxes such as montan wax and ozokerite, petroleum waxes such as paraffin wax and microcrystalline wax. And synthetic waxes such as Fischer-Tropsch wax, polyethylene wax, polypropylene wax, polycarbonate wax, palm oil fatty acid ester, beef tallow fatty acid ester, stearamide, dipeptadecyl ketone and hardened castor oil. These can use together 1 type (s) or 2 or more types. Of these, paraffin wax, polyethylene wax, and polypropylene wax are preferred from the viewpoint of economy.

  As heavy oils, those composed of paraffin or naphthene, which are aliphatic hydrocarbons having approximately 15 to 120 carbon atoms, are used. Heavy oils have a chemical structure relatively similar to waxes and have high fluidity, and therefore act as plasticizers for waxes. Therefore, when heating to cure the aqueous binder, the fluidity of the waxes can be increased, the wax and heavy oil can be applied evenly on the inorganic fibers, and the inorganic fiber heat insulating sound absorbing material can be separated. Variations in moldability and water repellency can be suppressed.

Classification of heavy oils is carried out by the viscosity, there can be used preferably has in the region of 320mm ² / s~680mm ² / s at VG (Viscosity Grade). In heavy oils having a relatively low viscosity, for example, VG of less than 320 mm ² / s, there is a tendency for components having 30 or less carbon atoms, particularly 20 or less carbon atoms to increase, and during heating during binder curing If the viscosity is high and, for example, VG exceeds 680 mm ² / s, mixing with the dispersant during emulsification takes time, and productivity may be impaired.

  When the waxes and the heavy oils are used in combination, the mass ratio of the waxes and the heavy oils is not particularly limited, but waxes: heavy oils = 40: 60 to 95: 5. It is preferable. When the ratio of heavy oils exceeds 60% by mass, the water repellency of the water repellent increases at room temperature, resulting in a decrease in the water repellency of the resulting inorganic fiber heat-absorbing and sound-absorbing material for a long period of time. There is. On the other hand, when the ratio of heavy oils is less than 5% by mass, when using high melting point waxes, the plasticizing effect of the waxes is reduced, and the water repellency of the resulting inorganic fiber heat insulating sound absorbing material varies. May occur. Therefore, it is more preferable that the use ratio of the heavy oils is appropriately adjusted in accordance with the melting point of the waxes used or the desired water repellency.

  Generally, since waxes and heavy oils are hydrophobic materials, when adding waxes or a mixture of waxes and heavy oils to a binder, It is preferably used after being dispersed or emulsified in water.

  There are no particular restrictions on the above-mentioned waxes and dispersants for heavy oils in water, and various surfactants, water-soluble resins, etc. may be mentioned, and the type and amount of the dispersant should be set as appropriate. Is preferred.

  The content of the wax or the mixture of the wax and the heavy oil is 0.1 to 5 parts by mass in terms of solid content with respect to 100 parts by mass of the resin in the water-soluble thermosetting resin composition. Is preferable, 0.5-3 mass parts is more preferable, and 0.5-2 mass parts is especially preferable. When the content is less than 0.1 parts by mass, improvement in releasability and water repellency is hardly observed, and even when the content exceeds 5.0 parts by mass, the water repellency is not improved in proportion to the increase in content. It is not preferable because it is uneconomical.

Moreover, you may add a dustproof agent, a coloring agent, etc. further as needed to the aqueous | water-based binder for heat insulation materials of an inorganic fiber of this invention.

Then, the aqueous binder for an inorganic fiber heat-absorbing sound-absorbing material of the present invention includes the water-soluble thermosetting resin composition and an aqueous silica sol or an aqueous alumina sol, and further, if necessary, a curing accelerator, waxes, or waxes and heavy. One aqueous dispersion selected from a mixture of oils, a silane coupling agent, and the like can be prepared by mixing using a tank equipped with a stirrer such as a dissolver.

  Examples of the aqueous binder include emulsions, colloidal dispersions, and water-soluble compositions. However, emulsions and colloidal dispersions have poor miscibility between the dispersed resin component and water, and are water as a medium. When volatilizes, it has the characteristic that it is easy to form a film. If the resin composition in the binder forms a film before curing, the fluidity of the binder on the fiber surface is liable to be impaired, and not only an inorganic heat-insulating sound-absorbing material with a uniform amount of binder can be obtained, but also fibers. In some cases, there are many portions that are not bonded by the binder, and it is difficult to maintain the shape of the product. In addition, in colloidal dispersions and emulsions, once the medium water is volatilized and a film is formed, it is difficult to return to the aqueous material again. Tend to occur.

On the other hand, when the aqueous binder is a water-soluble composition, since there is no film formation due to volatilization of water, the above problems do not occur. Therefore, it is preferable to prepare the aqueous binder for an inorganic fiber heat-absorbing sound absorbing material of the present invention as a water-soluble composition.

  Here, the emulsion refers to an emulsion emulsified with an emulsifier different from the resin component, for example, a surfactant, and the colloidal dispersion refers to a material dispersed in water by a functional group in the resin component. Both are milky white in appearance. On the other hand, a water-soluble composition refers to a resin component that is completely dissolved in water, and has an appearance that is transparent or nearly transparent.

Moreover, 5-40 mass% is preferable and, as for the solid content of the aqueous | water-based binder for heat insulation materials for inorganic fibers, 10-30 mass% is more preferable. If the solid content is less than 5% by mass, the amount of water increases, and it may take time in the curing process and impair productivity. If it exceeds 40% by mass, the binder is lost during suction in the cotton collection process. However, the loss becomes large, which is not preferable from the viewpoint of economic efficiency, and further, it becomes difficult to control the amount of binder attached.

[Inorganic fiber thermal insulation material]
Next, the inorganic fiber heat insulating sound absorbing material of the present invention will be described.

The inorganic fiber heat insulating sound-absorbing material of the present invention is obtained by applying the above-mentioned aqueous binder for an inorganic fiber heat-absorbing sound absorbing material to inorganic fibers, and heating and curing the binder.

The inorganic fiber heat insulating sound-absorbing material of the present invention can be produced, for example, as follows. That is, first, the melted inorganic raw material is fibrillated with a fiberizing apparatus, and immediately after that, the above-mentioned aqueous binder for an inorganic fiber heat-absorbing sound absorbing material is applied to the inorganic fiber. Next, the inorganic fiber to which the aqueous binder for the inorganic fiber heat-insulating material is added is deposited on the perforated conveyor to form a bulky inorganic fiber heat-absorbing material, and the interval is set to a desired thickness. narrow pressed and heated while by feeding the provided with a pair of upper and lower perforated conveyor such as to cure the inorganic fiber insulation sound absorbing material aqueous binder to form a mineral fiber insulation sound absorbing material. And a skin material etc. are coat | covered as needed, and a product is obtained by cut | disconnecting the inorganic fiber heat insulation sound-absorbing material to the desired width and length. Hereinafter, each step will be described in more detail.

It does not specifically limit as an inorganic fiber used for the inorganic fiber heat insulation sound-absorbing material of this invention, The glass wool, the rock wool, etc. which are used for the normal heat insulation sound absorption material can be used. Various methods such as a flame method, a blow-off method, and a centrifugal method (also referred to as a rotary method) can be used as a method for forming inorganic fibers. In particular, when the inorganic fiber is glass wool, it is preferable to use a centrifugal method. In addition, the density of the target inorganic fiber heat-insulating material may be a density used in ordinary heat-insulating materials and sound-absorbing materials, and is preferably in the range of 5 to 300 kg / m ³ .

  In order to impart the binder to the inorganic fibers, it is applied and sprayed using a spray device or the like. The amount of binder applied varies depending on the density and use of the inorganic fiber heat-absorbing sound-absorbing material, but since the inorganic fiber binder of the present invention can be bonded firmly even with a small amount, the amount of binder attached can be reduced, and the cost From a specific point of view, 0.5 to 12% by mass in terms of solid content is preferable, and 0.5 to 8% by mass is more preferable based on the mass of the inorganic fiber heat-absorbing sound-absorbing material provided with a binder.

  The timing of applying the binder to the inorganic fiber may be any time after fiberization, but in order to efficiently apply the binder, it is preferable to apply it immediately after fiberization.

  The inorganic fiber to which the binder has been applied by the above process is deposited on a perforated conveyor and becomes a bulky inorganic fiber intermediate. Here, when depositing on the perforated conveyor, it is more preferable to suck by the suction device from the opposite side of the perforated conveyor on which the inorganic fibers are deposited.

  After that, the inorganic fiber intermediate that continuously moves on the perforated conveyor is sent to a pair of upper and lower perforated conveyors and the like that are spaced so as to have a desired thickness, and at the same time, the binder is removed by heated hot air. After curing and forming the inorganic fiber heat-absorbing sound-absorbing material into a mat shape, it is cut into a desired width and length.

  Moreover, the inorganic fiber heat insulating sound-absorbing material of the present invention can also be produced by cutting the inorganic fiber intermediate body into a predetermined size and then thermoforming it into a desired shape.

  Although the heat curing temperature of a binder is not specifically limited, 200-350 degreeC is preferable. Further, the heat curing time is appropriately adjusted between 30 seconds and 10 minutes depending on the density and thickness of the inorganic fiber heat-absorbing sound-absorbing material.

  The inorganic fiber heat-absorbing sound-absorbing material of the present invention may be used as it is, or may be used after being covered with a skin material. As the skin material, paper, synthetic resin film, metal foil film, non-woven fabric, woven fabric, or a combination thereof can be used.

  The inorganic fiber heat-absorbing sound-absorbing material of the present invention is excellent in mechanical strength and is not only used in the construction field such as houses and buildings, but also in industrial equipment fields such as mechanical devices and electrical equipment, and in vehicle fields such as automobiles and railway vehicles. It can also be applied to applications.

  Hereinafter, the present invention will be described in more detail by way of examples. In the following description, “part” and “%” are based on mass unless otherwise specified.

(Example 1)
A resin solution (solid content 40%) in which a mixture of a resole-type phenolic resin and a urea resin in a mass ratio of 80:20 is dissolved in water is 100 parts in terms of solid content, and an aqueous silica sol (average particle size 50 nm, solid 2 parts of γ-aminopropyltriethoxysilane, 2 parts of ammonium sulfate, and 2 parts of heavy oil emulsion (VG 380 mm ² / s, solid content 30%) were mixed and stirred, 25 parts After adjusting the pH to 8.0 with% ammonia water, the solid content was diluted with water so that the solid content would be 18%, whereby the aqueous binder for an inorganic fiber heat-absorbing sound absorbing material of Example 1 was obtained.

(Example 2)
In Example 1, an aqueous binder for an inorganic fiber heat-absorbing sound absorbing material of Example 2 was obtained in the same manner as in Example 1 except that the amount of aqueous silica sol added was 10 parts.

(Example 3)
Resin type phenol resin dissolved in water (solid content 35%) 100 parts in terms of solid content, aqueous alumina sol (average particle size 20 nm, solid content 12%) 0.5 part, γ-aminopropyl After mixing and stirring 0.2 part of triethoxysilane, 1 part of ammonium sulfate, and 2 parts of heavy oil emulsion (VG320 mm ² / s, solid content 30%), and adjusting to pH 8.4 with 25% aqueous ammonia, It diluted with water so that solid content might be 18%, and the water-based binder for inorganic fiber heat-insulation sound-absorbing materials of Example 3 was obtained.

Example 4
As a crosslinking agent, 100 parts of a resin solution (solid content 50%) in which an acrylic resin-based polycarboxylic acid made of acrylic acid (acid value 770 mgKOH / g, weight average molecular weight 4,000) is dissolved in water is converted into a solid content. Mix 45.6 parts of diethanolamine and 4.0 parts of calcium hypophosphite as a curing accelerator (total molar amount of imino group and hydroxyl group of crosslinking agent / molar amount of carboxyl group of acrylic resin-based polycarboxylic acid = 0) 95), adjusted to pH 6.5 with 25% aqueous ammonia, and further added 3 parts of aqueous silica sol (average particle size 20 nm, solid content 30%) and 0.3 part of γ-aminopropyltriethoxysilane After mixing and stirring, the mixture was diluted with water so that the solid content was 15% to obtain an aqueous binder for an inorganic fiber heat-absorbing sound absorbing material of Example 4.

(Example 5)
A resin solution (solid content 35%) in which a vinyl polymerized polycarboxylic acid (acid value 720 mgKOH / g, weight average molecular weight 12,000) composed of styrene and maleic acid is dissolved in water is crosslinked with 100 parts in terms of solid content. 35.9 parts of diethanolamine as an agent and 6.0 parts of sodium hypophosphite as a curing accelerator (total molar amount of imino group and hydroxyl group of crosslinking agent / carboxyl group of acrylic resin-based polycarboxylic acid) And adjusted to pH 6.5 with 25% aqueous ammonia, and further 3 parts of an aqueous silica sol (average particle size 20 nm, solid content 30%), and γ-aminopropyltriethoxysilane 0.3%. After adding 3 parts and mixing and stirring, it was diluted with water so that the solid content was 15%, to obtain an aqueous binder for an inorganic fiber heat-absorbing sound absorbing material of Example 5.

(Example 6)
As a crosslinking agent, a resin solution (solid content 50%) in which an acrylic resin-based polycarboxylic acid made of methacrylic acid (acid value 640 mgKOH / g, weight average molecular weight 13,000) is dissolved in water is 100 parts in terms of solid content. 79.3 parts of triethanolamine and 4.0 parts of sodium hydrogen sulfite as a curing accelerator were mixed (total molar amount of hydroxyl group of crosslinking agent / molar amount of carboxyl group of acrylic resin-based polycarboxylic acid = 1. 40) to obtain a water-soluble composition having a pH of 3.3, and further adding 3 parts of an aqueous alumina sol (average particle size 10 nm, solid content 20%) and 0.3 part of γ-aminopropyltriethoxysilane. After mixing and stirring, the mixture was diluted with water so that the solid content was 18%, and the aqueous binder for an inorganic fiber heat-absorbing sound absorbing material of Example 6 was obtained.

(Example 7)
A resin solution (solid content 40%) in which an acrylic resin-based polycarboxylic acid (acid value 500 mgKOH / g, weight average molecular weight 7,800) composed of acrylic acid, methyl acrylate and ethyl acrylate is dissolved in water is 100 in terms of solid content. 31.2 parts of diethanolamine as a crosslinking agent and 4.0 parts of sodium hypophosphite as a curing accelerator (total molar amount of imino group and hydroxyl group of the crosslinking agent / acrylic resin-based polycarboxylic acid) To obtain a water-soluble composition having a pH of 3.2, and further 2 parts of an aqueous silica sol (average particle size 20 nm, solid content 30%) and γ- (2-amino). After adding 0.2 parts of ethyl) aminopropyltrimethoxysilane and mixing and stirring, the mixture was diluted with water to a solid content of 15%, and paraffin wax having a solid content of 40% was obtained. Hex aqueous dispersion 4.0 parts were added, to obtain an inorganic fiber insulation sound absorbing material aqueous binder of Example 7.

(Example 8)
In Example 5, an aqueous binder for an inorganic fiber heat-absorbing sound absorbing material of Example 8 was obtained in the same manner as in Example 5 except that the amount of aqueous silica sol added was 8 parts.

Example 9
A resin solution (solid content 40%) in which an acrylic resin-based polycarboxylic acid (acid value 480 mgKOH / g, weight average molecular weight 10,000) composed of acrylic acid, methyl acrylate and ethyl acrylate is dissolved in water is 100 in terms of solid content. 31.2 parts of diethanolamine as a crosslinking agent and 4.0 parts of sodium hypophosphite as a curing accelerator (total molar amount of imino group and hydroxyl group of the crosslinking agent / acrylic resin-based polycarboxylic acid) To obtain a water-soluble composition having a pH of 3.2, and further 3 parts of an aqueous silica sol (average particle size 20 nm, solid content 30%) and γ- (2-amino). Ethyl) aminopropyltrimethoxysilane (0.2 part) was added and mixed and stirred, then diluted with water to a solid content of 15%, and paraffin having a solid content of 40%. The box aqueous dispersion 4.0 parts were added, to obtain an inorganic fiber insulation sound absorbing material aqueous binder of Example 9.

(Comparative Example 1)
In Example 1, an aqueous binder for an inorganic fiber heat-absorbing sound absorbing material of Comparative Example 1 was obtained in the same manner as in Example 1 except that the aqueous silica sol was not added.

(Comparative Example 2)
In Example 1, an aqueous binder for an inorganic fiber heat-absorbing sound absorbing material of Comparative Example 2 was obtained in the same manner as in Example 1 except that the addition amount of the aqueous silica sol was changed to 15 parts.

(Comparative Example 3)
In Example 4, the aqueous | water-based binder for inorganic fiber heat insulation materials of the comparative example 3 was obtained like Example 4 except not adding aqueous silica sol.

(Comparative Example 4)
In Example 5, an aqueous binder for an inorganic fiber heat-absorbing sound absorbing material of Comparative Example 4 was obtained in the same manner as in Example 5 except that the aqueous silica sol was not added.

(Comparative Example 5)
In Example 6, an aqueous binder for an inorganic fiber heat-absorbing sound absorbing material of Comparative Example 5 was obtained in the same manner as in Example 6 except that the aqueous alumina sol was not added.

(Comparative Example 6)
In Example 5, an aqueous binder for an inorganic fiber heat-absorbing sound absorbing material of Comparative Example 6 was obtained in the same manner as in Example 5 except that the amount of aqueous silica sol added was 12 parts.

About the inorganic fiber heat insulation sound-absorbing material obtained using Examples 1-9 and the aqueous binder for inorganic fiber heat insulation sound-absorbing materials of Comparative Examples 1-6, the 10% compressive strength was evaluated by the following method. The results are summarized in Table 1.

[Restorability evaluation]
After applying the aqueous fiber heat-absorbing material for inorganic fiber heat-absorbing material of Examples 1 to 9 and Comparative Examples 1 to 6 to a predetermined amount by spraying on the glass fiber fiberized by the centrifugal method, suction is performed with a suction device. While being deposited on a perforated conveyor, an intermediate of an inorganic fiber heat-absorbing sound-absorbing material was formed. The intermediate is heated in a hot air oven at 220 ° C. for 3 minutes to cure the binder, and the binder adheres at a density of 16 kg / m ³ , a thickness of 100 mm, a binder adhesion amount of 3.0%, and the same density and the same thickness. An inorganic fiber heat-absorbing and sound-absorbing material (glass wool) having an amount of 2.5% was obtained. Then, the glass wool was compressed until the thickness became 1/8, and the glass wool was inserted into a low density polyethylene bag and left in an environment of a temperature of 40 ° C. and a humidity of 95%. After 1 day, 14 days, and 28 days, the glass wool was opened, the restored thickness of the glass wool was measured, and the comparison with the initial thickness was evaluated.

[Evaluation of peel strength]
After applying the aqueous fiber heat-absorbing material for inorganic fiber heat-absorbing material of Examples 1 to 9 and Comparative Examples 1 to 6 to a predetermined amount by spraying on the glass fiber fiberized by the centrifugal method, suction is performed with a suction device. While being deposited on a perforated conveyor, an intermediate of an inorganic fiber heat-absorbing sound absorbing material was formed. The intermediate is heated in a hot air of 220 ° C. for 5 minutes to cure the binder, and an inorganic fiber heat insulating sound absorption having a density of 32 kg / m ³ , a length of 1350 mm, a width of 430 mm, a thickness of 50 mm, and a binder adhesion of 5.0%. Each material (glass wool board) was obtained. The obtained 32 kg / m ³ glass wool board was sandwiched between chucks of a universal testing machine in the thickness direction, and the peel strength was measured at a speed of 1 m / min.

From the above results, the inorganic fiber heat-absorbing sound-absorbing material using the aqueous binder for inorganic fiber heat-absorbing sound-absorbing materials of Examples 1 to 9 has no practical problem with respect to resilience and peel strength.

On the other hand, the amount of the inorganic fiber heat-absorbing and water- absorbing sound absorbing material of Comparative Example 1 that does not include the aqueous silica sol and the aqueous alumina sol is 100 parts by weight of the water-soluble thermosetting resin composition. In comparison with Examples 1 to 3, the inorganic fiber heat-absorbing and sound-absorbing material using the aqueous binder for inorganic fiber heat-and-absorbing and sound-absorbing material of Comparative Example 2 exceeding 10 parts by mass is likely to have poor recoverability over time and has a peel strength. It was low.

Similarly, the inorganic fiber heat-absorbing sound-absorbing material using the aqueous binder for inorganic fiber heat-absorbing sound-absorbing materials of Comparative Examples 3 to 5 that does not contain an aqueous silica sol and an aqueous alumina sol has a recoverability over time as compared with Examples 4 to 9. It was easy to fall, and also peel strength was low, and it was lacking in practicality. Moreover, the inorganic fiber heat-insulation sound-absorbing material using the aqueous binder for inorganic fiber heat-insulation sound-absorbing material of Comparative Example 6 in which the addition amount of the aqueous silica sol exceeds 10 parts by mass with respect to 100 parts by mass of the water-soluble thermosetting resin composition was carried out. Compared with Examples 4-9, resilience was likely to deteriorate with time, and the peel strength was also low.

Claims (8)

A water-soluble thermosetting resin composition containing at least a resol-type phenolic resin and an aqueous silica sol and / or an aqueous alumina sol, and 100 parts by mass of the resin content in the water-soluble thermosetting resin composition in terms of solid content On the other hand, an inorganic fiber heat-absorbing sound-absorbing material, characterized in that an aqueous binder containing 0.1 to 10 parts by mass of an aqueous silica sol and / or an aqueous alumina sol is applied to inorganic fibers and cured by heating. The water-soluble thermosetting resin composition contains a resol type phenol resin and urea, and a mass ratio of the resol type phenol resin and urea is phenol resin: urea = 90: 10 to 50:50 in terms of solid content. The inorganic fiber heat-insulating sound-absorbing material according to claim 1, wherein A functional group capable of reacting with the carboxyl group in the crosslinking agent with respect to the number of moles of the carboxyl group in the polycarboxylic acid, comprising a polycarboxylic acid containing two or more carboxyl groups in the molecule and a crosslinking agent; The water-soluble thermosetting resin composition comprising a water-soluble thermosetting resin composition having a molar ratio of 0.7 to 1.5 and an aqueous silica sol and / or an aqueous alumina sol in terms of solid content. That an inorganic binder containing an aqueous silica sol and / or an aqueous alumina sol in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin component in the water-soluble resin composition was formed by heating and curing. An inorganic fiber heat-absorbing sound absorbing material. The inorganic fiber heat-insulating sound absorbing material according to claim 3, wherein the polycarboxylic acid is an acrylic resin-based polycarboxylic acid having an acid value of 500 to 850 mgKOH / g and a weight average molecular weight of 1,000 to 15,000 . The inorganic fiber heat-insulating material according to claim 3 or 4, wherein the crosslinking agent contains at least one dialkanolamine . The inorganic fiber heat-absorbing sound-absorbing material according to any one of claims 1 to 5, wherein a pH of the aqueous binder is adjusted to 6.0 to 8.0 with a volatile basic compound . The inorganic fiber heat-insulating material according to any one of claims 1 to 6 , wherein the inorganic fiber is glass wool or rock wool. The inorganic fiber heat insulating sound-absorbing material according to any one of claims 1 to 7 , wherein the density is 5 to 300 kg / m ³ .