JP2003238699A - Binder for inorganic fiber and inorganic-fiber-heat- insulated sound-absorbing material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a binder for an inorganic fiber having sufficient water repellency and excellent adhesion to a skinning material or the like and to provide an inorganic-fiber-heat-insulated sound-absorbing material. <P>SOLUTION: The binder for an inorganic fiber contains an aldehyde- condensible thermosetting resin precursor and a polyfluoroalkyl-containing fluorine compound. It is desirable that the fluorine compound has a functional group reactive with the aldehyde-condensible thermosetting resin precursor or the inorganic fiber. The inorganic-fiber-heat-insulated sound-absorbing material is obtained by applying the binder to a fresh inorganic fiber, collecting the inorganic fiber to which the binder has been adhered, and molding the collected fiber by thermal curing. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a binder for an inorganic fiber used as a heat insulating material or a sound absorbing material for a house, a soundproof wall, etc. The present invention relates to a binder for heat insulation and an inorganic fiber heat insulating sound absorbing material using the same.

[0002]

2. Description of the Related Art Conventionally, an aggregate of inorganic fibers has a high porosity and is divided into fine spaces by the single fibers, which makes it difficult for the air contained in the aggregate to move. Widely used as a heat insulating material or sound absorbing material for sound barriers, cooling towers, equipment installed outdoors, and the like.

However, when rainwater or water due to dew condensation is absorbed by the aggregate of inorganic fibers, not only the performance of heat insulation and sound absorption is deteriorated, but also the generation of mold and the metal portion in contact with the aggregate of inorganic fibers. May cause corrosion. Therefore, in the aggregate of inorganic fibers that may come into contact with water, it is required to have as low water absorption as possible and high water repellency.

In response to these requirements, for example, Japanese Patent No. 28
Japanese Patent No. 63585 discloses that various organopolysiloxanes are used as a treating agent for improving the water repellency of inorganic fibers.

Further, Japanese Patent Laid-Open No. 5-330861 discloses a resin composition for hydrophobizing glass fibers for a heat insulating material, which contains metal soap as an active ingredient.

[0006]

However, in the water repellents used in the above-mentioned conventional techniques, organopolysiloxanes and metal soaps, the water repellent is insufficient, so that the water repellent is not used. It is necessary to use a large amount.

However, when a large amount of organopolysiloxanes is contained, stickiness is liable to occur, workability during construction becomes poor, and the cost becomes high, which is not preferable. On the other hand, when the metal soap is contained in a large amount, the adhesiveness between the inorganic fibers is deteriorated and the function as a binder is deteriorated.

Further, in the case of using a binder using an organopolysiloxane or a metal soap as a water repellent, a part of the water repellent may be washed away from the surface of the inorganic fiber with the passage of time, which causes the water repellent to repel over time. There was also a problem that the water content was reduced.

Further, the inorganic fiber heat-insulating sound absorbing material may have a film for moisture-proofing and dust-proofing, or a skin material such as a design material, which is directly attached to the surface of the inorganic fiber heat-insulating sound absorbing material by an adhesive agent depending on the place of construction. . However, when organopolysiloxanes or metal soaps are used as water repellents,
The water repellent agent bleeds out on the surface of the inorganic fibers, reducing the adhesiveness between the inorganic fiber heat insulating and sound absorbing material and the adhesive, and the films do not adhere to each other, or the adhesive force decreases with time and the film peels off. There are cases.

Therefore, an object of the present invention is to provide an inorganic fiber binder which can impart excellent water repellency for a long period of time and is also excellent in adhesiveness to a skin material and the like, and an inorganic fiber heat insulation using the same. It is to provide a sound absorbing material.

[0011]

In order to achieve the above object, the binder for inorganic fibers of the present invention comprises an aldehyde-condensable thermosetting resin precursor and a fluorine-based compound having a polyfluoroalkyl group (hereinafter, referred to as If there is no explanation,
(Abbreviated as "fluorine compound").

According to the above invention, since the fluorine-based compound has a high water-repellent effect, a sufficient water-repellent effect can be obtained even with a small amount of treatment, and further, the function as a binder such as adhesiveness may be impaired. Absent.

In the binder for inorganic fibers of the present invention, it is preferable that the fluorine-based compound has a functional group capable of reacting with the aldehyde-condensable thermosetting resin precursor or the inorganic fibers.

According to this, when the binder is applied to the inorganic fibers and cured by heating, the fluorine-based compound reacts with the aldehyde-condensable thermosetting resin precursor or the inorganic fibers which is the main component of the binder. Adhesion between the fluorine-based compound and the thermosetting resin and / or the inorganic fiber is good, and the water repellency of the inorganic fiber does not decrease with time.
Moreover, since the water repellent is fixed in the binder, the water repellent unlike the silicone water repellent does not flow out to the surface of the inorganic fiber.

In the binder for inorganic fibers of the present invention, the aldehyde-condensable thermosetting resin precursor and the fluorine-based compound are used in terms of solid content with respect to 100 parts by mass of the aldehyde-condensing thermosetting resin precursor. It is preferable that the fluorine-based compound is contained in an amount of 0.1 to 10 parts by mass.

By setting the amount ratio of the fluorine-based compound to the aldehyde-condensable thermosetting resin precursor within the above-mentioned preferred range, it is possible to impart sufficient water repellency to the inorganic fiber heat-insulating sound absorbing material, and further There is no loss of stability.

Further, the fluorine-based compound preferably has a molecular weight or a number average molecular weight of 500 or more.

According to this, when the binder is heat-cured, the low molecular weight fluorine compound does not evaporate due to abrupt heating, so that the water-repellent performance can be effectively exhibited even when a small amount is applied. .

Further, it is preferable that the binder for inorganic fibers further contains a silane coupling agent. According to this, the adhesiveness between the binder and the inorganic fibers can be enhanced, and the water repellency effect can be prevented from decreasing with time.

On the other hand, the inorganic fiber heat-insulating sound absorbing material of the present invention is obtained by applying the binder for inorganic fibers to the inorganic fibers immediately after fiberization, collecting the inorganic fibers to which the binder for inorganic fibers is adhered, and then heat curing. It is characterized by being obtained by molding.

According to the above invention, the surface of the inorganic fiber is not sticky, good water repellency can be maintained for a long period of time, and the adhesion workability with dust-proof, moisture-proof or design skin material is good. An inorganic fiber heat insulating sound absorbing material can be obtained.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

The binder for inorganic fibers of the present invention contains an aldehyde-condensable thermosetting resin precursor and a fluorine-based compound having a polyfluoroalkyl group.

First, the aldehyde-condensable thermosetting resin precursor will be described. Examples of the aldehyde-condensable thermosetting resin precursor used in the present invention include precursors of resol-type phenol resin, melamine resin, urea resin, and furan resin. In this case, the precursor may be used alone or in combination of two or more kinds.

Here, in the present invention, the precursor means the original compound that produces a resol-type phenol resin, a melamine resin, a urea resin and a furan resin by a reaction by heating. In this case, the ratio of the monomers and dimers contained in the precursor of each resin, or the number of methylol groups added per monomer is not particularly limited.

The aldehyde-condensable thermosetting resin precursor is
Since it is a high-viscosity liquid or solid, a medium such as water or an organic solvent is required to apply it to the inorganic fibers.
In the process of manufacturing a general inorganic fiber heat insulating and sound absorbing material, 20 minutes after the inorganic raw material for fibers is melted and made into fibers by a centrifugal method or the like,
Since a binder is often applied in an atmosphere of 0 ° C. or higher, the inclusion of a flammable solvent such as an organic solvent may cause a fire or the like. Therefore, the aldehyde-condensable thermosetting resin precursor is preferably dissolved or dispersed in water.

Next, the fluorinated compound having a polyfluoroalkyl group will be described. The fluorine-based compound used in the present invention is a compound having a polyfluoroalkyl group, and includes compounds having a relatively low molecular weight to oligomers, homopolymers or copolymers of monomers having a polyfluoroalkyl group.

Here, the polyfluoroalkyl group is a functional group imparting water repellency, in which two or more hydrogen atoms of the alkyl group are substituted with fluorine atoms. The alkyl group may have a linear structure or a branched structure.

The carbon number of the polyfluoroalkyl group is
4 to 20 are preferable, and among these carbon atoms, the number of carbons to which one or more fluorine atoms are bonded is 2 or more,
The number is preferably 4 to 18, particularly preferably 6 to 16. Further, the ratio of the number of fluorine atoms in the alkyl group is (the number of fluorine atoms in the polyfluoroalkyl group) / (the total number of hydrogen atoms when the hydrocarbon group has the same carbon number as the polyfluoroalkyl group), 60% or more is preferable, especially 80
% Or more is preferable.

Further, it is more preferable that the end portion of the polyfluoroalkyl group is a perfluoroalkyl group because the water repellency is further improved, and it is particularly preferable that the perfluoroalkyl group has a linear structure. Here, the perfluoroalkyl group refers to a polyfluoroalkyl group having a structure in which all hydrogen atoms are substituted with fluorine atoms. As a result, high water repellency can be imparted to the binder even with a small amount of addition.

Further, the fluorine-based compound used in the present invention preferably has a functional group capable of reacting with the aldehyde-condensable thermosetting resin precursor and a functional group capable of reacting with the inorganic fiber. As a result, the fluorine-based compound is firmly bonded to the aldehyde-condensable thermosetting resin that is the main component of the binder and the surface of the inorganic fiber, and the water-repellent performance deteriorates over time. When the sound absorbing material is used, it is possible to prevent the water repellent agent from flowing away due to the repeated condensation of water. Further, even after the binder is cured, the bleed-out observed with silicone oil or the like does not occur, so that the adhesion to the skin material such as dustproof, moistureproof and design material becomes good.

Examples of the functional group capable of reacting with the aldehyde-condensable thermosetting resin precursor include a hydroxyl group, an amino group, an epoxy group, a methylol group, a carboxyl group and an isocyanate group, and a hydroxyl group, an amino group, an epoxy group, a methylol group. Groups are preferred. Of these, the epoxy group and the methylol group are most preferable because they react efficiently with the aldehyde-condensable thermosetting resin precursor in a short time.

As the functional group capable of reacting with the surface of the inorganic fiber, it is preferable to have, for example, chlorosilane, methoxysilane or ethoxysilane which becomes a silanol group by hydrolysis.

The following two types of structures can be mentioned as preferable structures of such a fluorine-based compound having a polyfluoroalkyl group.

(1) A structure shown below, in which a polyfluoroalkyl group and the functional group are present in the main chain.

[0036]

[Chemical 1]

Here, among the above structures, the divalent or higher valent bonding group is not particularly limited, but as described later, it is preferable that the fluorine-based compound has a molecular weight or a number average molecular weight of 500 or more. Examples thereof include polyethylene group, polyester group, polyurethane group, polyether group, and polycarbonate group.

(2) A structure shown below, in which a polyfluoroalkyl group and the above functional group are added to the side chains of the main chain of polyethylene or polyester, for example.

[0039]

[Chemical 2]

As the divalent or higher-valent bonding group, the same groups as the divalent bonding group in the structure (1) are preferably used.

Among the structures of the above (2), a copolymer of a polyfluoroalkyl group-containing monomer and a copolymerizable monomer having a functional group is more preferable, and the polyfluoroalkyl group-containing monomer is a polyfluoroalkyl group having the following structure. Particularly preferred is the radical acrylate or methacrylate.

[0042]

[Chemical 3]

Here, the copolymerizable monomer having a functional group is a monomer having a functional group such as a hydroxyl group, an amino group, an epoxy group and a methylol group, for example, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, glycidyl acrylate, glycidyl methacrylate. , N-methylol acrylamide, N-methylol methacrylamide, acrylamide, methacrylamide,
Diacetone acrylamide, diacetone methacrylamide, methylol diacetone acrylamide and the like are more preferable. Other than this, for example, acrylic acid, methacrylic acid, or the like can be used.

In this case, the ratio of the copolymerization of the acrylate or methacrylate of the polyfluoroalkyl group and the copolymerization monomer having the functional group is 40% by mass of the polyfluoroalkyl group-containing monomer with respect to the total mass of both. Above all, a polymer polymerized at a ratio of 50 to 80% by mass is particularly preferable.

The fluorine compound used in the present invention preferably has a molecular weight or number average molecular weight of 500 or more. Here, the molecular weight or number average molecular weight of 500 or more means that when the fluorine-based compound is composed of a single molecule, the molecular weight is 500 or more, and when it is composed of two or more molecules of oligomer or polymer, Average molecular weight is 500
It means that it is above.

When the molecular weight or the number average molecular weight is less than 500, a low molecular weight compound is vaporized due to a rapid temperature increase in the binder coating in the manufacturing process of the inorganic fiber adiabatic sound absorbing material or in the curing step after the binder coating, The water-repellent performance of the resulting inorganic fiber heat-insulating sound-absorbing material deteriorates, which is not preferable. In addition, an excessive amount of fluorine compound is required to obtain a predetermined water repellency, which is uneconomical, which is not preferable.

In the binder for inorganic fibers of the present invention, the fluorine compound is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the aldehyde-condensable thermosetting resin precursor. 5 parts by mass, particularly preferably 1 to 5 parts by mass.

When the content of the fluorine-based compound is less than 0.1 part by mass, sufficient water repellency cannot be imparted to the obtained inorganic fiber heat insulating sound absorbing material. Further, even if the content of the fluorine-based compound exceeds 10 parts by mass, the water repellency is not improved in proportion to the increase in the content, which is uneconomical, which is not preferable.

In the present invention, the fluorine compound is preferably added to the aldehyde-condensable thermosetting resin precursor after being dispersed in water. As a result, the aldehyde-condensable thermosetting resin precursor, which is also water-dispersed, can be uniformly mixed and the compatibility with the binder is improved. Further, since it is a water-dispersed system, in the process of manufacturing the resin inorganic fiber heat insulating and sound absorbing material, 2
The binder for inorganic fibers can be safely added even in an atmosphere of 00 ° C or higher.

As a method for dispersing in water, various surfactants such as polyethylene glycols, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene glycols, sorbitan fatty acid esters, polyoxysorbitan are added to fluorine compounds. Examples thereof include a method in which a fatty acid ester, a polyoxyethylene fatty acid ester, an ethylene glycol fatty acid ester, a glycerin fatty acid ester, an ether carboxylic acid type surfactant, a sulfosuccinate type surfactant and the like are added and mixed to emulsify.

In particular, when the fluorine compound is a copolymer of a polyfluoroalkyl group-containing monomer and a copolymerizable monomer having a functional group, the polyfluoroalkyl group-containing monomer and the copolymerizable monomer are polymerized by emulsion polymerization. Is preferred. As a result, a fluorinated water repellent directly dispersed in water is obtained, and the obtained emulsion can be blended with a compounding agent as necessary or diluted with water or the like.

In this case, the surfactant, the polymerization initiator and the polymerization initiation source used in the polymerization are not particularly limited, and almost all of the anionic, cationic or nonionic surfactants are used as the surfactant. Can be used, as the polymerization initiator organic peroxides, azo compounds,
Various polymerization initiators such as persulfates can be used.

However, if an excessive amount of a surfactant is used during emulsification, the surfactant tends to attract water and hinders the water repellency of the fluorine compound. Therefore, the amount of the surfactant is 100 parts by mass of the fluorine-based compound,
The amount is preferably 1 to 30 parts by mass, more preferably 5 to 20 parts by mass.

Further, in the binder for inorganic fibers of the present invention, it is preferable to further add a silane coupling agent in order to enhance the adhesiveness between the binder and the inorganic fibers.

The number of functional groups, the kind, the structure, etc. of the silane coupling agent used here are not particularly limited, but because of the good reactivity or compatibility with the aldehyde-condensable thermosetting resin precursor which is the main component of the binder, Preference is given to using aminosilane coupling agents or epoxysilane coupling agents. Examples of the aminosilane coupling agent include γ- (2-aminoethyl) aminopropyltrimethoxysilane and γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, and examples of the epoxysilane coupling agent include γ-glycan. Examples thereof include sidoxypropyltrimethoxysilane and γ-glycidoxypropylmethyldimethoxysilane.

The amount of the silane coupling agent used is 100 parts by mass of the aldehyde condensable thermosetting resin precursor.
It is preferably in the range of 0.01 to 0.5 parts by mass.
When the amount of the silane coupling agent used is less than 0.01 parts by mass, the effect of increasing the adhesive force between the inorganic fiber and the binder is poor, and the resulting heat insulating and sound absorbing material has an environment of high temperature of 60 ° C. or higher and high temperature and high humidity. When exposed to water, the water repellent effect may decrease over time, which is not preferable. Further, even if the amount of the silane coupling agent used exceeds 0.5 parts by mass, the adhesiveness between the inorganic fiber and the binder does not improve in proportion to the amount used,
In addition, the effect of preventing deterioration of the water-repellent effect over time is not improved, which is uneconomical, which is not preferable.

If necessary, a dustproofing agent, a curing accelerator, a flame retardant, a coloring agent and the like may be added to the inorganic fiber binder of the present invention. Examples of the curing accelerator include sodium sulfate, ammonium sulfate, dodecylbenzenesulfonic acid, p-toluenesulfonic acid and the like.

The above-mentioned binder for inorganic fibers is preferably diluted with a solvent containing water as a main component so that the solid content is 5 to 30% by mass. At this time, by using a tank equipped with a stirrer such as a dissolver,
The inorganic fiber binder of the present invention can be obtained.

Next, the inorganic fiber heat insulating and sound absorbing material of the present invention obtained by using the above-mentioned inorganic fiber binder will be described.

In the production of the heat insulating and sound absorbing material for inorganic fibers of the present invention, first, the molten inorganic raw material is made into a fiber by a fiberizing device, and immediately after that, the above-mentioned binder for inorganic fibers is applied to the inorganic fibers. Then, the inorganic fibers to which the binder for inorganic fibers has been added are collected on a conveyor belt to form a bulky inorganic fiber heat-insulating sound absorbing material intermediate body, and a pair of upper and lower spaces are provided so as to have a desired thickness. It is sent to a belt conveyor or the like and heated under a narrow pressure to cure the inorganic fiber binder to form an inorganic fiber heat insulating and sound absorbing material. Then, if necessary, a cover material or the like is covered, and the inorganic fiber heat insulating and sound absorbing material is cut into a desired width and length to obtain a product. Less than,
Each step will be described.

First, the inorganic fiber used in the present invention is not particularly limited, and glass wool, rock wool, etc. which are commonly used for heat insulating and sound absorbing materials can be used. Various methods such as a flame method, a blowing method, and a centrifugal method (also referred to as a rotary method) can be used as the method for fiberizing the inorganic fiber. Especially when the inorganic fiber is glass wool, it is preferable to use the centrifugal method. The desired density of the inorganic fiber heat-insulating sound absorbing material may be the density used for ordinary heat insulating materials and sound absorbing materials, and is preferably in the range of 5 to 300 kg / m ³ .

Next, in order to apply a binder to the inorganic fibers, it is possible to apply and spray them by using a spray device or the like. The amount of the inorganic fiber binder applied can be adjusted in the same manner as in the conventional binder containing no water repellent. The amount of the binder applied varies depending on the density and use of the inorganic fiber heat insulating and sound absorbing material, but is preferably in the range of 0.5 to 15 mass% in terms of solid content, based on the weight of the inorganic fiber heat insulating and sound absorbing material to which the binder is applied. The range of 0.5 to 9 mass% is more preferable.

The binder may be applied to the inorganic fiber sound-absorbing heat insulating material at any time after fiberizing, but it is preferable to apply it immediately after fiberizing in order to efficiently impart it. The fluorinated compound can be added as a binder mixed with the aldehyde condensable thermosetting resin precursor, but the fluorinated compound may be separately added before and after the aldehyde condensable thermosetting resin precursor is applied. .

As described above, by adding the binder for inorganic fibers obtained by the present invention to the inorganic fibers, it is possible to impart sufficient water repellency to the inorganic fiber heat insulating and sound absorbing material.

The inorganic fibers to which the binder has been added by the above steps are collected on a perforated conveyor to form a bulky inorganic fiber intermediate. Here, when collecting the cotton on the conveyor, it is more preferable to suck with a suction device from the opposite side of the conveyor where the inorganic fibers are collected. After that, the inorganic fiber intermediate that continuously moves on the conveyor is fed into a pair of upper and lower belt conveyors provided with an interval so as to have a desired thickness, and at the same time, the binder is contained by heated hot air. After curing the thermosetting resin precursor, after molding the inorganic fiber heat-insulating sound absorbing material into a mat,
Cut into desired width and length.

The temperature for curing the thermosetting resin precursor contained in the binder is not particularly limited, but it can be the same as in the case of applying a binder containing no conventional water repellent, It may be 350 ° C. The heating time depends on the density and thickness of the inorganic fiber heat insulating and sound absorbing material,
The time is appropriately set within the range of 10 seconds to 10 minutes.

The inorganic fiber heat insulating and sound absorbing material of the present invention may be used as it is, or may be used by 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. As the skin material, it is preferable to use a material having low water absorption and water repellency.

The thus-obtained inorganic fiber heat-insulating sound absorbing material of the present invention has no loss of water repellent or bleed-out, and therefore has good workability for adhesion to the skin material.

Further, even when exposed to rainwater or dew condensation water, since moisture does not accumulate in the heat insulating and sound absorbing material, the performance of heat insulation and sound absorption does not deteriorate for a long time, and the generation of mold and the contact of metal parts. It can solve the problems of corrosion and wood decay.

Furthermore, in the manufacturing process, processing process or construction site of the inorganic fiber heat insulating and sound absorbing material, the fluorine-based compound in the binder coats each single fiber of the inorganic fiber to make the fiber difficult to break, or to prevent the broken fiber from breaking. Since it is fixed so as not to fall off, it is possible to suppress the scattering of the inorganic fibers. Further, since the hydrophobic portion of the fluorine-based compound existing on the contact surface between the inorganic fiber heat insulating and sound absorbing material and the conveyor improves the releasability of the inorganic fiber heat insulating and sound absorbing material from the conveyor, troubles during manufacturing are reduced.

[0071]

EXAMPLES The present invention will be described in more detail below with reference to examples. In the following description, “part” and “%” are based on mass unless otherwise specified. [Preparation of Emulsion of Fluorine-based Compound] Preparation 1 50 parts of MIBK was added to 100 parts of a fluorine-containing compound having a molecular weight of 656 represented by the following chemical formula (I) and dissolved at 70 ° C. to obtain a solution. Next, 8 parts of polyethylene glycol monostearate (HLB11.9) and 2 parts of coconut oil fatty acid sorbitan (HLB4.7) were added and heated to 90 ° C. Then, the mixture was emulsified with a high pressure homogenizer. This emulsion is depressurized at 50 ° C. to remove the contained MIBK,
An emulsion having a solid content of 30% (fluorine compound content 27.3%) was obtained.

[0072]

[Chemical 4]

Formulation 2 A fluorine-based compound having a molecular weight of 398 represented by the following chemical formula (II) was emulsified in the same manner as in Formulation 1 to give a solid content of 30%.
An emulsion having a fluorine compound content of 27.3% was obtained.

[0074]

[Chemical 5]

Formulation 3 In a reaction kettle equipped with a stirrer, the following chemical formula (III)
, 120 parts of perfluoroalkylethyl acrylate, 4 parts of N-methylol acrylamide, polyoxyethylene lauryl ether (HLB12.4) 10
Part, dipalmityl dimethyl ammonium chloride 2
Parts, 120 parts of acetone, 350 parts of water, and 1 part of azobisisobutylamidine hydrochloride were added, and nitrogen substitution was carried out for about 15 minutes while stirring, and then the temperature was raised to 60 ° C. to start polymerization. The mixture was heated and stirred at 60 ° C. for 12 hours and then cooled to obtain an emulsion having a solid content of 31% (fluorine compound content: 28.3%).

[0076]

[Chemical 6]

Formulation 4 In a reaction kettle equipped with a stirrer and a monomer dropping tank,
Polyoxyethylene lauryl ether (HLB12.
4) 10 parts, stearyl trimethyl ammonium chloride 2 parts, and water 330 parts were added, and it heated up at 70 degreeC, stirring. On the other hand, the chemical formula (III) used in Formulation 3
120 parts of perfluoroalkylethyl acrylate,
After mixing 10 parts of 2-hydroxyethyl methacrylate and 1 part of azobisisobutylamidine hydrochloride, the mixture was placed in a monomer dropping tank. The dropping flow rate was controlled so that the total amount of the monomer was completed in 3 hours, and the monomer was added dropwise into the reaction vessel. 1 hour after the completion of the dropping, 0.1 part of azobisisobutylamidine hydrochloride and water were added. One part of the mixture was added to the reactants in the reaction kettle. At this time, stirring was continued while maintaining the temperature of the reaction product at 70 ° C. Further, after 2 hours, the same operation was repeated and the heat insulating stirring was continued. After cooling for 3 hours, the solid content is 30% (the content of the fluorine-based compound is 2
7.4%) emulsion was obtained. [Preparation of Aqueous Dispersion of Zinc Stearate] Preparation 5 After 60 parts of zinc stearate was heated to a melting point of 130 ° C. to be melted, 5 parts of polyoxyethylene polyoxypropylene was added with stirring. After mixing, 200 parts of water was added dropwise with stirring to obtain a solid content of 24.5%.
An aqueous dispersion (content of zinc stearate 22.6%) was obtained. [Preparation of Aqueous Dispersion of Dimethylpolysiloxane] Preparation 6 To 60 parts of dimethylpolysiloxane having a molecular weight of about 5,000,
15 parts of polyoxyethylene polyoxypropylene were added. 200 parts of water was added dropwise with stirring to obtain a solid content of 2
7.3% (dimethylpolysiloxane content 21.8
%) Aqueous dispersion.

Example 1 [Preparation of Binder for Inorganic Fiber] Monomer 10% or less, dimer 80% or more, free phenol 1% dispersed in water
The following resole-type phenol resin precursor is 100 parts in terms of solid content, and the emulsion of the fluorine-based compound obtained in Formulation 1 is 3 parts in terms of content, γ- (2-aminoethyl) aminopropyltrimethoxy. 0.2 parts of silane and 450 parts of water were mixed in an open tank equipped with a stirrer,
With sufficient stirring, water was added so that the solid content was 15% to obtain a binder for inorganic fibers. [Production of Insulating Sound Absorbing Material for Inorganic Fibers] The glass fiber that has been made into a fiber by a centrifugal method is spray-coated with the binder so as to give a predetermined amount, and then collected on a perforated conveyor while sucking with a suction device. Cotton to form an intermediate of an inorganic fiber adiabatic sound absorber. The intermediate is heated in hot air at 280 ° C. for 3 minutes to cure the binder, and the density is 32 kg.
/ M ³ , thickness 50 mm, and amount of binder applied 6.0%, to obtain a glass wool as an inorganic fiber heat insulating and sound absorbing material of Example 1.

Examples 2 to 4 Inorganic fiber heat insulation of Examples 2 to 4 was carried out by the same binder compounding method and manufacturing method as in Example 1 except that the fluorine compound emulsions obtained in Formulations 2 to 4 were used. We obtained glass wool as a sound absorbing material.

Example 5 Using 50 parts of the water-dispersed resol-type phenolic resin precursor used in Example 1, 40 parts of a water-soluble urea resin precursor, 10 parts of a water-soluble methylolated melamine resin precursor, and Formulation 4. 0.2 parts of the obtained fluorine-based compound emulsion in terms of content, 0.1 part of γ- (2-aminoethyl) aminopropyltrimethoxysilane, and 450 parts of water were prepared in an open tank equipped with a dissolver. Then, with sufficient stirring, water was added so that the solid content was 15% to obtain a binder for inorganic fibers.

Next, except that this binder for inorganic fibers was used, glass wool as the inorganic fiber heat-insulating sound absorbing material of Example 5 was obtained by the same manufacturing method as in Example 1.

Example 6 100 parts of the water-dispersed resol-type phenolic resin precursor used in Example 1 in terms of solid content, and 9.5 parts in terms of content of the emulsion of the fluorine-based compound obtained in Formulation 3 ,
γ-glycidoxypropyltrimethoxysilane 0.1
And 450 parts of water were mixed in an open tank equipped with a dissolver, and water was added to the solid content of 15% with sufficient stirring to obtain a binder for inorganic fibers.

Next, glass wool, which is the heat insulating and sound absorbing material for inorganic fibers of Example 6, was obtained by the same manufacturing method as in Example 1 except that this binder for inorganic fibers was used.

Example 7 Inorganic fiber heat insulation of Example 7 was prepared in the same manner as in Example 6 except that the content of the fluorine compound emulsion obtained in Preparation 3 was changed to 12.5 parts. We obtained glass wool as a sound absorbing material.

Example 8 Using the water-repellent treated binder of Example 1, the same manufacturing method as in Example 1 was used to obtain a density of 16 kg / m ³ and a thickness of 100.
A glass wool as an inorganic fiber heat insulating and sound absorbing material of Example 8 was obtained under the conditions of mm and a binder application amount of 4.0%.

Example 9 Using the water-repellent treated binder of Example 6, the same production method as in Example 1 was used to obtain a density of 16 kg / m ³ and a thickness of 100.
A glass wool as an inorganic fiber heat insulating and sound absorbing material of Example 9 was obtained under the conditions of mm and binder application amount of 4.0%.

Comparative Example 1 100 parts of the water-dispersed resol-type phenolic resin precursor used in Example 1 in terms of solid content, 0.1 part of γ- (2-aminoethyl) aminopropyltrimethoxysilane,
450 parts of water was mixed with an open tank equipped with a dissolver, and water was added to the solid content of 15% while sufficiently stirring to obtain a binder containing no water repellent.

Further, using this binder and in the same manufacturing method as in Example 1, glass wool to be the inorganic fiber heat insulating and sound absorbing material of Comparative Example 1 was obtained.

Comparative Example 2 100 parts of the water-dispersed resol-type phenolic resin precursor used in Example 1 in terms of solid content and 5 parts of the aqueous dispersion of zinc stearate obtained in Formulation 5 in terms of content. Part, water 4
50 parts were mixed with an open tank equipped with a dissolver, and water was added to the solid content to 15% with sufficient stirring to obtain a binder.

Further, by using this binder and by the same manufacturing method as in Example 1, glass wool as a heat insulating and sound absorbing material for inorganic fiber of Comparative Example 2 was obtained.

Comparative Example 3 100 parts of the water-dispersed resol-type phenolic resin precursor used in Example 1 in terms of solid content, and 5 parts of the aqueous dispersion of dimethylpolysiloxane obtained in Formulation 6 in terms of content.
Parts and 450 parts of water were mixed in an open tank equipped with a dissolver, and water was added thereto while sufficiently stirring so that the solid content was 15% to obtain a binder.

Further, using this binder and in the same manufacturing method as in Example 1, glass wool as a heat insulating and sound absorbing material for inorganic fiber of Comparative Example 2 was obtained.

All the binders used in Examples 1 to 9 and Comparative Examples 1 to 3 had good stability. Further, the emulsion of the fluorine-based compound used in the examples could be uniformly mixed with the aqueous binder and had good compatibility with other binder components.

Test Example [Evaluation of Water Repellency] From the glass wool obtained in Examples 1 to 9 and Comparative Examples 1 to 3, 50 × 100 × 100 mm square test pieces were cut out, and the dimensions of the test pieces were measured and weighed. Then, it was immersed in water having a water temperature of 25 ° C. and 50 mm below the water surface. The test piece was cut out 24 hours after the start of the immersion, and the temperature was set to 25 ° C. at 1
After being left on the wire net for 0 minutes, the test piece was weighed.

The increased amount after immersion was expressed as a percentage with respect to the volume, and this was taken as the volumetric water absorption. Further, the test piece for which the volumetric water absorption rate was calculated was left on a wire net, and the content of water after 6 hours was expressed as a percentage with respect to the volume, and was taken as the volume content rate. [Evaluation of Adhesiveness] The glass wool obtained in Examples 1 to 9 and Comparative Examples 1 to 3 was uniformly coated with an olefinic hot melt adhesive at a rate of 40 g / m ² , and then aluminum kraft paper was used. Width 100 mm, length 3 from the pasted one
A 00 mm test piece was cut out and the peeling strength (peeling strength) of the aluminum kraft paper was measured by a tensile tester. All results are summarized in Table 1.

[0096]

[Table 1]

From Table 1, it can be seen that the test pieces of Examples 1 to 9 have a lower volumetric water absorption rate and a lower volumetric water content after 6 hours from immersion as compared with the test pieces of Comparative Examples 1 to 3. I understand. This indicates that the various fluorinated compounds used in the examples improved the water repellency of glass wool.

Further, from the comparison between Example 6 and Example 7, it can be seen that even if the fluorine compound is added in an amount exceeding the preferred range, the water repellency is not significantly improved.
Further, comparison between Example 1 and Example 2 shows that the water-repellent performance is higher when the fluorine-based compound has the preferable molecular weight.

On the other hand, in Comparative Example 1 containing no water repellent, both the volumetric water absorption rate and the volumetric water content after 6 hours are significantly inferior to the Examples.

Comparative Example 2 in which dimethylpolysiloxane was dispersed in water instead of the fluorine-based compound of Example 1,
And Comparative Example 3 using an aqueous dispersion of zinc stearate
Shows that although the volumetric water absorption is improved, the water repellency is inferior to the examples using the fluorine-based compound.

Regarding the adhesiveness of the aluminum kraft paper as the skin material, the test pieces of Examples 1 to 9 are not significantly inferior to Comparative Example 1 containing no water repellent. on the other hand,
It can be seen that in Comparative Example 2 using dimethylpolysiloxane and Comparative Example 3 using zinc stearate, the adhesiveness with the skin material is significantly reduced.

[0102]

INDUSTRIAL APPLICABILITY As described above, the water-repellent binder for inorganic fibers of the present invention, which contains a fluorine-based compound, can impart sufficient water repellency to the heat insulating and sound absorbing material of inorganic fibers, and can prevent moisture and dust. Alternatively, even if a skin material for design is attached, the adhesion is not damaged. In addition, the water-repellent inorganic fiber heat-insulating sound absorbing material of the present invention using this water-repellent binder,
Even when exposed to rainwater or condensed water, heat insulation and sound absorption performance do not deteriorate for a long period of time, and it is possible to solve the problems of mold generation, corrosion of metal parts in contact with wood, and decay of wood. It can be suitably used as a heat insulating material or sound absorbing material for walls, cooling towers, equipment installed outdoors, and the like.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] April 21, 2003 (2003.4.2)
1)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0049

[Correction method] Change

[Correction content]

In the present invention, the fluorine compound is preferably added to the aldehyde-condensable thermosetting resin precursor after being dispersed in water. As a result, the aldehyde-condensable thermosetting resin precursor, which is also water-dispersed, can be uniformly mixed, and the compatibility with the binder is improved. Further, since it is a water-dispersed system, in the process of manufacturing the inorganic fiber heat-insulating sound absorbing material , the inorganic raw material for fibers is melted into fibers 20
The binder for inorganic fibers can be safely added even in an atmosphere of 0 ° C or higher.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0085

[Correction method] Change

[Correction content]

Example 8 Using the binder for inorganic fibers of Example 1, the same manufacturing method as in Example 1 was used to obtain a density of 16 kg / m ³ and a thickness of 10
A glass wool as an inorganic fiber heat insulating and sound absorbing material of Example 8 was obtained under the conditions of 0 mm and a binder application amount of 4.0%.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0086

[Correction method] Change

[Correction content]

Example 9 Using the binder for inorganic fibers of Example 6, the same production method as in Example 1 was used to obtain a density of 16 kg / m ³ and a thickness of 10.
A glass wool as an inorganic fiber heat insulating and sound absorbing material of Example 9 was obtained under the conditions of 0 mm and a binder application amount of 4.0%.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0092

[Correction method] Change

[Correction content]

Further, using this binder and in the same manufacturing method as in Example 1, glass wool as a heat insulating and sound absorbing material for inorganic fiber of Comparative Example 3 was obtained.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0094

[Correction method] Change

[Correction content]

Test Example [Evaluation of Water Repellency] From the glass wool obtained in Examples 1 to 9 and Comparative Examples 1 to 3, 50 × 100 × 100 mm square test pieces were cut out, and the dimensions of the test pieces were measured and weighed. Then, it was immersed in water having a water temperature of 25 ° C. and 50 mm below the water surface. Eject the start of immersion 24 hours after the test piece, 1 at room temperature 25 ° C.
After being left on the wire net for 0 minutes, the test piece was weighed.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0095

[Correction method] Change

[Correction content]

The increased amount after immersion was expressed as a percentage with respect to the volume, and this was taken as the volumetric water absorption. Further, the test piece for which the volumetric water absorption was calculated was left on a wire mesh, and the content of water after 6 hours was expressed as a percentage with respect to the volume to obtain the volumetric water content . [Evaluation of Adhesiveness] The glass wool obtained in Examples 1 to 9 and Comparative Examples 1 to 3 was uniformly coated with an olefinic hot melt adhesive at a rate of 40 g / m ² , and then aluminum kraft paper was used. Width 100 mm, length 3 from the pasted one
A 00 mm test piece was cut out and the peeling strength (peeling strength) of the aluminum kraft paper was measured by a tensile tester. All results are summarized in Table 1.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0096

[Correction method] Change

[Correction content]

[0096]

[Table 1]

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0102

[Correction method] Change

[Correction content]

[0102]

As described above, the present inventionBinder for inorganic fiber
Sufficient water repellency by containing a fluorine compound
Can be imparted to the inorganic fiber heat insulation sound absorbing material, moisture-proof,
Even if dustproof or a design skin material is attached, the adhesion will not be damaged.
It never happens. Also thisFor inorganic fiberFor binder
Of the present inventionInorganic fiber thermal insulation materialIs exposed to rainwater or condensation
Heat insulation and sound absorption performance will deteriorate over a long period of time.
, Mold generation, corrosion of metal parts in contact with wood and decay of wood
Can solve the problems of houses, buildings, noise barriers,
Insulation or sound-absorbing material for cooling towers and outdoor equipment
Can be suitably used as.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Manabu Iizuka             3-6-3 Kanda Blacksmith Town, Chiyoda-ku, Tokyo               Asahi Fiber Glass Co., Ltd. F-term (reference) 4F072 AB09 AD04 AD16 AD19 AD20                       AD37 AF21 AL17                 4H020 BA12                 4L047 AA01 AA05 BA17 BC03 BC13                       BC14 CB03

Claims (6)

[Claims] 1. An aldehyde-condensable thermosetting resin precursor,
A binder for inorganic fibers, comprising a fluorine-based compound having a polyfluoroalkyl group. 2. The fluorine-based compound having a polyfluoroalkyl group has a functional group capable of reacting with the aldehyde-condensable thermosetting resin precursor or the inorganic fiber.
The binder for inorganic fibers according to. 3. The aldehyde-condensable thermosetting resin precursor and the polyfluoroalkyl group-containing fluorine-based compound are added to 100 parts by mass of the aldehyde-condensable thermosetting resin precursor in terms of solid content. The binder for inorganic fibers according to claim 1, which is contained in an amount of 0.1 to 10 parts by mass of a fluorine-based compound having a polyfluoroalkyl group. 4. The binder for inorganic fibers according to claim 1, wherein the fluorine-based compound having a polyfluoroalkyl group has a molecular weight or a number average molecular weight of 500 or more. 5. The binder for inorganic fibers according to claim 1, wherein the binder for inorganic fibers further contains a silane coupling agent. 6. The inorganic fiber binder according to any one of claims 1 to 5 is applied to the inorganic fiber immediately after fiberization,
An inorganic fiber heat-insulating sound-absorbing material, which is obtained by collecting the inorganic fibers to which the binder for inorganic fibers adheres, and then heat-curing and molding.