JP2016108707A - Water-soluble binder for inorganic fiber containing no formaldehyde and method for producing inorganic fiber heat-insulating and acoustic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-soluble binder for an inorganic fiber that contains no formaldehyde, exhibits physical properties suitable for use in the production process of an inorganic fiber heat-insulating and acoustic material, produces a cured product of the binder having excellent resilience and water resistance by heat treatment and to provide an inorganic fiber heat-insulating and acoustic material using the water-soluble binder for an inorganic fiber.SOLUTION: The water-soluble binder for an inorganic fiber is produced by mixing a water-soluble polymer composed mainly of a polyvinyl alcohol-based resin, a crosslinking agent, an adhesion inhibitor, a silane coupling agent and a mold releasing agent. The inorganic fiber heat-insulating and acoustic material is molded by heat treatment with use of the binder.SELECTED DRAWING: None

Description

  The present invention is a water-soluble binder for inorganic fibers which does not contain formaldehyde and has physical properties suitable for the production process of heat insulating and absorbing materials for inorganic fibers such as glass wool and rock wool, and has excellent elasticity and water resistance in the cured product. And an inorganic fiber heat-absorbing sound-absorbing material using the same.

  Conventionally, phenolic binders mainly composed of water-soluble phenol / formaldehyde resins have been widely used as heat-absorbing and sound-absorbing materials made of inorganic fibers such as glass wool and rock wool, as binders for bonding fibers. The phenolic binder is cured by heating, and a cured product with excellent elasticity and water resistance can be obtained. Therefore, the inorganic fiber heat-insulating sound absorbing material using this has elasticity during compression and long-term use. Excellent dimensional stability.

  However, since the water-soluble phenol resin used in the phenolic binder uses formaldehyde as a cross-linking agent, formaldehyde emission in the production process is a problem. In addition, a large amount of formaldehyde is released during heat-curing and remains inside the inorganic fiber heat-absorbing sound-absorbing material, so that there is a problem that the formaldehyde is gradually released to the outside after being applied to the building.

  In recent years, health damage such as sick house syndrome caused by pollution of indoor air by volatile organic compounds such as formaldehyde has become a problem. For this reason, there is a legal limit on the amount of formaldehyde released into the manufacturing process and indoor air of buildings.

  Since formaldehyde released from an inorganic fiber heat-absorbing sound-absorbing material is a substance contained in a phenolic binder, a solution of the above problem requires a water-soluble binder that does not contain formaldehyde. Has been made.

  For example, in the following Patent Document 1, (A) a water-soluble polymer having a hydroxyl group (more specifically, a water-soluble polymer having a hydroxyl group is polyvinyl alcohol): 100 parts by mass, and (B) a boron-based polymer An inorganic fiber binder characterized by containing 5 parts by mass or more of a compound is disclosed.

  Patent Document 2 below contains an acrylic resin having an acid value of 350 to 850 mg KOH / g, a crosslinking agent containing at least one dialkanolamine, and a curing accelerator, The total number of moles of hydroxyl groups and imino groups in the crosslinking agent is 0.8 to 1.5 in terms of mole ratio with respect to the number of moles of the carboxyl group, and the pH is 6.0 to 6.0 depending on the volatile basic compound. An aqueous binder for inorganic fibers characterized by being adjusted to 8.0 is disclosed.

JP 2011-153395 A JP 2007-56415 A

  The aqueous solution of the polyvinyl alcohol-based resin has a higher aqueous solution viscosity than the aqueous solution of the phenol-based resin, and the adhesiveness is generated in the inorganic fiber heat insulating material intermediate after coating. Usually, inorganic fibers coated with a binder are deposited while being sucked onto a perforated conveyor. When adhesiveness arises in the inorganic fiber heat-insulation material intermediate, the bulky shape does not occur, and the surface smoothness of the inorganic fiber heat-absorption material may be impaired due to insufficient pressurization during heating.

In general, polyvinyl alcohol-based resins, acrylic resins, and the like have water absorbency as compared with phenol-based resins, and the cured product is inferior in water resistance compared to phenol-based resins. Therefore, the inorganic fiber heat-absorbing sound-absorbing material using them is softened due to the humidity in the air, and becomes softer than that immediately after the production, and the thickness may vary.
Moreover, the intermediate body of the inorganic fiber heat-insulation material to which the binder is attached is dried by heat treatment. In general, a water-soluble binder of a polyvinyl alcohol-based resin tends to have a high viscosity and a strong stickiness compared to a water-soluble binder of a phenol-based resin. In the inorganic fiber sprayed with the water-soluble binder, the stickiness of the polyvinyl alcohol-based resin is stronger, and there is a problem of sticking to the inorganic fiber deposition conveyor and sticking to the dryer perforated plate during the heat treatment.
Furthermore, when a precipitate is generated in the water-soluble binder for inorganic fibers, a problem such as clogging occurs in the spray device in a subsequent process, and therefore, the binder is required not to generate a precipitate.

  Accordingly, an object of the present invention is an inorganic material that does not contain formaldehyde, has excellent suitability for the production process of an inorganic fiber heat-absorbing sound-absorbing material, and a cured binder obtained by heat treatment has excellent elasticity and water resistance. It is an object to provide a water-soluble binder for fibers and an inorganic fiber heat insulating sound absorbing material using the same.

  In achieving the above object, the water-soluble binder for inorganic fibers of the present invention includes a water-soluble polymer mainly composed of polyvinyl alcohol resin, a crosslinking agent, an adhesion inhibitor, a release agent, and a silane coupling agent. The aqueous solution after mixing is a water-soluble binder for inorganic fibers that has excellent permeability to inorganic fibers, and is characterized by having excellent elasticity and water resistance in its cured product. (Claim 1).

  In the water-soluble binder for inorganic fibers of the present invention, the crosslinking agent is one type selected from (a) a compound, polymer or copolymer of polycarboxylic acid, (b) a borax compound, and (c) a mixture thereof. The polyvinyl alcohol resin preferably contains 4.0 parts by mass or more in terms of solid content with respect to 100 parts by mass (Claim 2).

In the water-soluble binder for inorganic fibers of the present invention, the adhesion inhibitor is an aqueous solution of a salt compound, and is 3.0 to 20 in terms of solid content with respect to a total of 100 parts by mass of the polyvinyl alcohol resin and the crosslinking agent. It is preferable to contain 0.0 mass part (Claim 3).

  In the water-soluble binder for inorganic fibers of the present invention, the silane coupling agent preferably contains 0.1 to 3.0 parts by mass with respect to 100 parts by mass in total of the polyvinyl alcohol resin and the crosslinking agent. (Claim 4).

  In the water-soluble binder for inorganic fibers of the present invention, the release agent is heavy oil or an aqueous dispersion of a mixture of heavy oil and silicone oil, and a total of 100 of the polyvinyl alcohol-based resin and the crosslinking agent. It is preferable to contain 5.0 to 30.0 parts by mass in terms of solid content with respect to parts by mass (Claim 5).

  The inorganic fiber heat-absorbing sound-absorbing material of the present invention is characterized in that the water-soluble binder for inorganic fibers of the present invention is applied to inorganic fibers and cured by heat treatment (Claim 6).

  The water-soluble binder for inorganic fibers according to claim 1 is made of a polyvinyl alcohol resin and does not contain formaldehyde, so that it can be used without releasing formaldehyde during binder coating or heat treatment.

  And by mixing a polyvinyl alcohol-type resin with a crosslinking agent, it can perform a crosslinking reaction with the hydroxyl group in hydrophilic polyvinyl alcohol, and can provide water resistance. Thereby, depending on the temperature and humidity, the thickness dimensions of the heat insulating sound absorbing material related to the heat insulating sound absorbing performance and the physical properties equivalent to those of conventional phenolic binders are not reduced regardless of the independence during construction, It can be suitably used as a heat insulating sound absorbing material for houses and buildings.

  The polyvinyl alcohol-based resin is a water-soluble polymer, and when cured without adding a crosslinking agent, the cured product is water-soluble and absorbs water and swells. By mixing the cross-linking agent specified in claim 2, it is possible to cause a cross-linking reaction with a hydroxyl group in a water-soluble polymer which is a hydrophilic group, thereby imparting water resistance to the cured product.

  A polyvinyl alcohol-type resin will permeate | transmit an inorganic fiber by melt | dissolving in water, and will express adhesiveness. According to invention of Claim 3, the salt compound used as an adhesion inhibitor crystallizes a polyvinyl alcohol-type resin, and suppresses the melt | dissolution to water. Excessive adhesiveness can be suppressed by adjusting the solubility of the polyvinyl alcohol resin in water.

  According to invention of Claim 4, a silane coupling agent can improve the adhesiveness in the interface of an inorganic fiber and a binder, and improves the elasticity and water resistance of the inorganic fiber heat insulation material obtained. be able to.

According to the fifth aspect of the present invention, the heavy oil and silicone oil used as the release agent can slip the inorganic fibers and reduce sticking to the fiber accumulation conveyor and the dryer perforated plate.
According to invention of Claim 6, the inorganic fiber heat insulation sound-absorbing material which has the outstanding elasticity and water resistance is provided.

  The water-soluble binder for inorganic fibers of the present invention comprises a water-soluble polymer containing a polyvinyl alcohol resin as a main component, a crosslinking agent, an adhesion inhibitor, a release agent, and a silane coupling agent, and an aqueous solution thereof. It is a water-soluble binder for inorganic fibers that does not generate excessive tackiness, and is a composition having excellent elasticity and water resistance in its cured product. In addition, it is said that it has excellent elasticity compared with the inorganic fiber heat insulation sound-absorbing material manufactured using the water-soluble binder which has a phenol-type resin as a main component which is a representative example of a prior art. This means that it has a repulsive force equal to or greater than the repulsive force of an inorganic fiber heat-absorbing sound-absorbing material produced using a water-soluble binder mainly composed of a phenolic resin. The excellent water resistance is, for example, a value that can be recognized as a rate of change in thickness when allowed to stand for 1 hour under saturated water vapor, and means that the rate of change is 10% or less.

  The polyvinyl alcohol resin used for the water-soluble binder for inorganic fibers of the present invention is not particularly limited. Since the degree of polymerization of the polyvinyl alcohol resin directly affects the viscosity of the aqueous solution, it is necessary to select it according to the sprayability of the coating apparatus, and a low viscosity grade having a degree of polymerization of 500 or less is preferable. For example, “JL-05E” manufactured by Nippon Vinegar Poval Co., Ltd. can be mentioned, but the present invention is not limited to this.

The crosslinking agents (a), (b) and (c) used for the water-soluble binder for inorganic fibers of the present invention contain 4.0 parts by mass or more in terms of solid content with respect to 100.0 parts by mass of the polyvinyl alcohol resin. It is preferable. In addition, since the crosslinking agent acts with respect to polyvinyl alcohol, it was made into the mass part with respect to polyvinyl alcohol solid content.
If it is less than 4.0 parts by mass in terms of solid content, the hydroxyl group in the water-soluble polymer which is a hydrophilic group and the crosslinking agent do not sufficiently undergo a crosslinking reaction, and water resistance cannot be imparted to the cured product.
In addition, although the upper limit of a crosslinking agent is not specifically limited, From an economical viewpoint, 100.0 mass parts or less are preferable with respect to 100.0 mass parts of polyvinyl alcohol-type resin.

  The crosslinking agent (a) is a compound, polymer or copolymer of one or more monomers selected from aliphatic carboxylic acid monomers. Examples of the aliphatic carboxylic acid monomer include polymers of aliphatic monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, and copolymers, maleic acid, fumaric acid, and itaconic acid. A compound, polymer, or copolymer of an aliphatic dicarboxylic acid such as Considering the reactivity with the polyvinyl alcohol resin, a maleic acid copolymer having two carboxylic acids in the monomer is more preferable. Preferred examples of the crosslinking agent (a) include “Gantrenz AN-119” (maleic acid copolymer) manufactured by Gokyo Sangyo Co., Ltd. and acrylic resin “Glass Pearl” for inorganic fibers manufactured by Sanyo Chemical Co., Ltd. It is not limited to this.

  Examples of the cross-linking agent (b) include boron compounds such as borax, boric acid, and boric acid complexes. Since the boron-based compound undergoes a crosslinking reaction during mixing and stirring, an excessive increase in viscosity of the aqueous solution may be observed, and it is preferable to add it as a low-concentration aqueous solution. Preferred cross-linking agents (b) include those prepared by adjusting commercially available borax to 4.0% aqueous solution, but the present invention is not limited to this.

  The crosslinking agent (c) is a mixture of the crosslinking agents (a) and (b). The crosslinking agents (a) and (b) can be used in combination depending on the water resistance effect and the viscosity state of the aqueous solution. Conventionally, in the field of film forming, (b) for the purpose of crosslinking and thickening a boron compound with a polyvinyl alcohol resin, (a) crosslinking an aliphatic carboxylic acid compound with a polyvinyl alcohol resin to impart water resistance For this purpose, it is often used in combination and is known as a well-known technique.

  The adhesion inhibitor used in the water-soluble binder for inorganic fibers of the present invention is an aqueous solution of a salt compound, and is 3.0 in terms of solid content with respect to a total of 100.0 parts by mass of the polyvinyl alcohol resin and the crosslinking agent. To 20.0 parts by mass is preferable. If the solid content is less than 3.0 parts by mass, the tackiness cannot be suppressed. If it exceeds 20.0 parts by mass in terms of solid content, the polyvinyl alcohol-based resin may be precipitated and the sprayability at the time of application may be deteriorated. In addition, since an adhesion inhibitor acts on a resin in which a polyvinyl alcohol-based resin and a crosslinking agent have undergone a crosslinking reaction, the amount of the adhesion inhibitor is based on a total of 100 parts by mass of the polyvinyl alcohol-based resin and the crosslinking agent. It was set as the mass part. The same applies to the amounts of the following silane coupling agent and release agent.

  Examples of the adhesion inhibitor include sulfuric acid such as ammonium sulfate, sodium sulfate, sodium hydrochloride, and sodium carbonate, alkali metal salts such as hydrochloric acid, carbonic acid, and acetic acid, or ammonium salts, which can be used alone or in combination of two or more. . Among these, ammonium sulfate is preferable because it is excellent in water solubility and the aqueous solution concentration can be adjusted arbitrarily. Excessive addition may cause polyvinyl alcohol to precipitate and deteriorate sprayability during application.

  Examples of the silane coupling agent used for the water-soluble binder for inorganic fibers of the present invention include aminosilanes such as 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and aminopropyltriethoxysilane. Examples include coupling agents, epoxy silane coupling agents such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and the like. Specifically, aminopropyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd. KBE903 "is included, but the present invention is not limited to this. These can use together 1 type, or 2 or more types, 0.1 to 3.0 mass parts is preferable in conversion of solid content with respect to a total of 100 mass parts of the said polyvinyl alcohol-type resin and the said crosslinking agent. When the solid content is less than 0.1 parts by mass, the interfacial adhesion between the polyvinyl alcohol-based resin and the inorganic fibers is not sufficiently performed. If it exceeds 3.0 parts by mass in terms of solid content, there is no problem in water solubility and reactivity of the polyvinyl alcohol resin, but a significant performance improvement cannot be expected, leading to an increase in cost. The silane coupling agent not only acts on the interfacial adhesion between the polyvinyl alcohol resin and the inorganic fiber, but also acts to fix the silicone additive such as silicone oil on the surface of the inorganic fiber. It is also effective in improving water resistance.

  As described above, generally, a water-soluble binder of a polyvinyl alcohol resin tends to have a high viscosity and a strong stickiness compared to a water-soluble binder of a phenol resin. For inorganic fibers sprayed with a water-soluble binder, the stickiness of the polyvinyl alcohol resin is stronger, and the problem of sticking to the inorganic fiber deposition conveyor and sticking to the perforated plate of the dryer during heat treatment is likely to occur. . By adding a release agent, release properties can be imparted to the polyvinyl alcohol resin, and these problems can be solved.

  The water-soluble binder for inorganic fibers of the present invention is a water dispersion of heavy oil or a mixture of heavy oil and silicone oil as a release agent, and a surfactant can be added to disperse in water. Or those dispersed in water. The content is preferably 5.0 to 30.0 parts by mass, more preferably 5.0 to 20.0 parts by mass with respect to 100 parts by mass in total of the polyvinyl alcohol resin and the crosslinking agent. If it is less than 5.0 parts by mass in terms of solid content, the releasability cannot be sufficiently exhibited. If it exceeds 30.0 parts by mass in terms of solid content, the elasticity and water resistance of the inorganic fiber heat-absorbing sound-absorbing material may be deteriorated due to the influence of the surfactant that disperses the oil.

  As the heavy oil, emulsions based on viscosity grades VG320, VG460, and VG680 are preferable, and specifically, heavy oil emulsion "Dafney Prosolvable PF" manufactured by Idemitsu Kosan Co., Ltd. may be mentioned. The present invention is not limited to this. In grades smaller than VG320, volatilization during heat treatment increases, and the effect as a release agent may be weakened. If the grade is larger than VG680, the viscosity of the inorganic fiber binder is increased, and the permeability to the inorganic fiber may be deteriorated.

  The silicone oil is preferably an emulsion of an organic functional type polysiloxane oil such as dimethyl type, amino-modified, epoxy-modified or hydrogen-modified. In particular, the dimethyl type imparts a strong slip to the polyvinyl alcohol-based resin and has a high releasability effect. Furthermore, the silicone oil is effective in improving the water resistance, and the water resistance can be improved by addition. Specific examples include silicone oil emulsion “Polon MR” manufactured by Shin-Etsu Chemical, but the present invention is not limited to this.

  The water-soluble binder for inorganic fibers of the present invention may be further added with additives such as a dustproof agent, other water repellent, a colorant, and a pH adjuster, if necessary.

  The water-soluble binder for inorganic fibers of the present invention is prepared by mixing the polyvinyl alcohol resin, a crosslinking agent, an adhesion inhibitor, a silane coupling agent, and a release agent using a tank equipped with a stirrer. can do.

  The solid concentration of the coating solution of the water-soluble binder for inorganic fibers of the present invention is preferably 2.0 to 20.0% by mass, more preferably 2.0 to 10.0% by mass. If it exceeds 20.0% by mass, the viscosity of the aqueous solution increases and the permeability to inorganic fibers decreases. If it is less than 2.0% by mass, the amount of water increases, and it takes time for the heat treatment, resulting in a decrease in productivity.

  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 water-soluble binder for inorganic fibers to inorganic fibers and curing it by heat treatment.

  The inorganic fiber heat insulating sound-absorbing material of the present invention can be produced, for example, as follows. First, the molten inorganic raw material is fiberized with a fiberizing apparatus, and immediately after that, the above-mentioned water-soluble binder for inorganic fibers is applied to the inorganic fibers. Next, inorganic fibers to which a water-soluble binder for inorganic fibers has been applied are deposited on a perforated conveyor in a fiber depositing device to form an inorganic fiber heat insulating material intermediate, and the upper and lower sides set to a desired thickness in a drying facility Narrow pressure is applied with a pair of perforated plates or the like, heat treatment is performed, and the aqueous binder for inorganic fibers is cured to form an inorganic fiber heat insulating 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 | variety and length. Hereinafter, each step will be described in more detail.

Although 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 known 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 fiberizing 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 a binder to the inorganic fiber, it is applied and sprayed using a spray device or the like known in this field. The amount of the binder applied can be adjusted by the same method as the conventional binder. The amount of the binder applied varies depending on the density and use of the inorganic fiber heat-absorbing sound absorbing material, but is 0.5 to 15.0% by mass in terms of solid content based on the mass of the inorganic fiber heat-absorbing sound absorbing material to which the binder is applied. The range is preferable, and the range of 0.5 to 9.0% by mass is more preferable.

Inorganic fibers are gradually intertwined between fiberizing and depositing and take a wooly form. As for the timing of applying the binder to the inorganic fiber, it may be any time after fiberization, but because it becomes difficult to adhere to the inside of the wool, in order to efficiently give the binder, the wool form is weak, immediately after fiberization It is preferable to give to.

The inorganic fiber to which the binder has been applied by the above process is deposited on a perforated conveyor in the fiber deposition apparatus, and becomes a bulky inorganic fiber heat insulating material intermediate. The fiber deposition apparatus can efficiently deposit inorganic fibers by suction from the back surface of the perforated conveyor.

  Thereafter, the inorganic fiber heat insulating sound absorbing material intermediate is continuously narrowed by a pair of upper and lower perforated conveyors set to have a desired thickness in a drying facility, and the binder is cured by heated hot air. Then, after the inorganic fiber heat insulating sound absorbing material is formed into a mat shape, it is cut into a desired width and length.

  Although the heat curing temperature of a binder is not specifically limited, 160-250 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, those known in this field can be used. For example, paper, synthetic resin film, metal foil film, nonwoven fabric, woven fabric, or a combination thereof can be used.

The inorganic fiber heat-absorbing sound-absorbing material of the present invention thus obtained does not release formaldehyde when the binder is heat-cured, and therefore has less environmental impact than conventional phenolic binders.

  Hereinafter, the present invention will be described by way of examples. The present invention is not limited to the following examples. In the following description, parts and% represent mass standards.

Example 1
An aqueous solution of polyvinyl alcohol-based resin “JL-05E” manufactured by Nihon Ventures and Poval Co., which has a polymerization degree of 300 and a saponification degree of 88%, is 96.0 parts in terms of solid content and 4 borax as a crosslinking agent. % Aqueous solution 4.0 parts in terms of solids, 24% aqueous solution of ammonium sulfate as an adhesion inhibitor 15.0 parts in terms of solids, Idemitsu Kosan Heavy Oil Emulsion “Daphne Prosolve” PF ”is 15.0 parts in terms of solid content, and silicone oil emulsion“ Polon MR ”made by Shin-Etsu Chemical is 5.0 parts in terms of solid content, and aminopropyltrimethoxysilane“ KBE903 ”manufactured by Shin-Etsu Chemical Co., Ltd. as a silane coupling agent. Was mixed with 1.0 part, and after stirring, it was adjusted with water so that the concentration of the aqueous solution was 4% to obtain a water-soluble binder for inorganic fibers of Example 1.

(Example 2)
92.5 parts of an aqueous solution of polyvinyl alcohol resin “JL-05E” manufactured by Nihon Ventures and Poval Co., which has a polymerization degree of 300 and a saponification degree of 88%, in terms of solid content, and Gokyo Sangyo Co., Ltd. as a crosslinking agent. 7.5 parts of an aqueous solution of maleic acid-based copolymer “Gantrenz AN-119” in terms of solid content, and 3.0 parts of a 24% aqueous solution of ammonium sulfate as an adhesion inhibitor in terms of solid content, as a release agent Idemitsu Kosan Co., Ltd. heavy oil emulsion “Daphne Prosolvable PF” 15.0 parts in terms of solid content and Shin-Etsu Chemical silicone oil emulsion “Polon MR” 5.0 parts in solid content, silane coupling agent As an example, aminopropyltrimethoxysilane “KBE903” manufactured by Shin-Etsu Chemical Co., Ltd. was mixed with 1.0 part, stirred, and adjusted with water so that the concentration of the aqueous solution was 4%. To obtain a machine for fibers a water-soluble binder.

(Example 3)
92.5 parts of an aqueous solution of polyvinyl alcohol resin “JL-05E” manufactured by Nihon Ventures and Poval Co., which has a polymerization degree of 300 and a saponification degree of 88%, in terms of solid content, and Gokyo Sangyo Co., Ltd. as a crosslinking agent. 7.5 parts of an aqueous solution of maleic acid-based copolymer “Gantrenz AN-119” in terms of solid content, and 3.0 parts of a 24% aqueous solution of ammonium sulfate as an adhesion inhibitor in terms of solid content, as a release agent Idemitsu Kosan Co., Ltd. heavy oil emulsion “Daphne Prosolvable PF” is 5.0 parts in terms of solid content, and Shinetsu Chemical Co., Ltd. aminopropyltrimethoxysilane “KBE903” is 1.0 part as a silane coupling agent. After mixing and stirring, the mixture was adjusted with water so that the concentration of the aqueous solution was 4% to obtain a water-soluble binder for inorganic fibers of Example 3.

Example 4
70.0 parts of an aqueous solution of polyvinyl alcohol resin “JL-05E” manufactured by Nippon Vinegar Poval Co., which has a polymerization degree of 300 and a saponification degree of 88%, in terms of solid content, and an acrylic acid polymer as a crosslinking agent 30.0 parts of an aqueous solution of acrylic resin “Glasspearl” for inorganic fibers made by Sanyo Chemical Co., Ltd. in solids, and 3.0 parts of a 24% aqueous solution of ammonium sulfate as an adhesion inhibitor in terms of solids. Idemitsu Kosan Co., Ltd.'s heavy oil emulsion "Daphne Prosolvable PF" in solids equivalent 15.0 parts, Shin-Etsu's silicone oil emulsion "Polon MR" in solids equivalents 5.0 parts, and silane cup Mix 1.0 part of aminopropyltrimethoxysilane “KBE903” manufactured by Shin-Etsu Chemical Co., Ltd. as a ring agent and, after stirring, adjust with water so that the concentration of the aqueous solution becomes 4%. , To obtain an inorganic fiber for a water-soluble binder of Example 4.

(Example 5)
An aqueous solution of polyvinyl alcohol-based resin “JL-05E” manufactured by NIPPON POVAL CO., LTD. Having a polymerization degree of 300 and a saponification degree of 88% is 50.0 parts in terms of solid content, and an acrylic acid polymer as a crosslinking agent. 30.0 parts by weight of an aqueous solution of acrylic resin “Glasspearl” for inorganic fibers made by Sanyo Chemical Co., Ltd., and 3.0 parts by weight of a 24% aqueous solution of ammonium sulfate as an adhesion inhibitor, in terms of solids. Idemitsu Kosan Co., Ltd.'s heavy oil emulsion "Daphne Prosolvable PF" in solids equivalent 15.0 parts, Shin-Etsu's silicone oil emulsion "Polon MR" in solids equivalents 5.0 parts, and silane cup Mix 1.0 part of aminopropyltrimethoxysilane “KBE903” manufactured by Shin-Etsu Chemical Co., Ltd. as a ring agent and, after stirring, adjust with water so that the concentration of the aqueous solution becomes 4%. , To obtain an inorganic fiber for a water-soluble binder of Example 5.

(Comparative Example 1)
96.0 parts of an aqueous solution of polyvinyl alcohol resin “JL-05E” manufactured by Nihon Ventures and Poval Co., which has a polymerization degree of 300 and a saponification degree of 88%, in terms of solid content, and a 4% aqueous solution of borax as a crosslinking agent Is 4.0 parts in terms of solid content, and 15.0 parts in terms of solid content is Daphne Prosolvable PF, a heavy oil emulsion made by Idemitsu Kosan Co., Ltd. as a mold release agent, and “Polon MR” is a silicone oil emulsion made by Shin-Etsu Chemical. Is mixed with 5.0 parts in terms of solid content and 1.0 part of aminopropyltrimethoxysilane “KBE903” manufactured by Shin-Etsu Chemical Co., Ltd. as a silane coupling agent. After stirring, the concentration of the aqueous solution is 4%. Then, a water-soluble binder for inorganic fibers of Comparative Example 1 was obtained by adjusting with water.

(Comparative Example 2)
92.5 parts of an aqueous solution of polyvinyl alcohol resin “JL-05E” manufactured by Nihon Ventures and Poval Co., which has a polymerization degree of 300 and a saponification degree of 88%, in terms of solid content, and Gokyo Sangyo Co., Ltd. as a crosslinking agent. 7.5 parts of an aqueous solution of maleic acid-based copolymer “Gantrenz AN-119” in terms of solids and a heavy oil emulsion “Dafney Prosolvable PF” made by Idemitsu Kosan Co., Ltd. as solids in terms of solids 15.0 parts and 5.0 parts of Shinetsu Chemical's silicone oil emulsion “Polon MR” in terms of solid content, and 1.0 part of Shin-Etsu Chemical's aminopropyltrimethoxysilane “KBE903” as a silane coupling agent After mixing and stirring, the mixture was adjusted with water so that the concentration of the aqueous solution was 4% to obtain a water-soluble binder for inorganic fibers of Comparative Example 2.

(Comparative Example 3)
An aqueous solution of polyvinyl alcohol-based resin “JL-05E” manufactured by Nihon Vitamin Poval Co., which has a polymerization degree of 300 and a saponification degree of 88%, is 97.0 parts in terms of solid content, and a 4% aqueous solution of borax as a crosslinking agent. 3.0 parts in terms of solid content, 15.0 parts in terms of solid content of a 24% aqueous solution of ammonium sulfate as an adhesion inhibitor, and a heavy oil emulsion "Dafney Prosolvable PF" manufactured by Idemitsu Kosan Co., Ltd. as a release agent. 15.0 parts in terms of solid content and 5.0 parts in terms of solid content silicone oil emulsion “Polon MR” and 1 part of aminopropyltrimethoxysilane “KBE903” made by Shin-Etsu Chemical Co., Ltd. as a silane coupling agent. After mixing with 0.0 part, the mixture was stirred and adjusted with water so that the concentration of the aqueous solution was 4%. Thus, a water-soluble binder for inorganic fibers of Comparative Example 3 was obtained.
The comparative example 3 is included in the invention of claim 1 but is not included in the invention of claim 2. Here, paying attention to claim 2, it grasped as “comparative example”.

(Comparative Example 4)
An aqueous solution of polyvinyl alcohol-based resin “JL-05E” manufactured by Nihon Ventures and Poval Co., which has a polymerization degree of 300 and a saponification degree of 88%, is 97.0 parts in terms of solid content and Gokyo Sangyo Co., Ltd. as a crosslinking agent. 3.0 parts by weight of maleic acid copolymer “Gantrenz AN-119” in terms of solids, 3.0 parts by weight of 24% aqueous solution of ammonium sulfate as an adhesion inhibitor, and Idemitsu Kosan as a release agent Shin-Etsu's heavy oil emulsion “Daphne Prosolvable PF” is 15.0 parts in terms of solids and Shinetsu Chemical's silicone oil emulsion “Polon MR” is 5.0 parts in terms of solids, Shinetsu as a silane coupling agent. Aminopropyltrimethoxysilane “KBE903” manufactured by Kagaku Co., Ltd. was mixed with 1.0 part, and after stirring, adjusted with water so that the concentration of the aqueous solution was 4%. It was obtained 維用 water-soluble binder.
The comparative example 4 is included in the invention of claim 1 but is not included in the invention of claim 2. Here, paying attention to claim 2, it grasped as “comparative example”.

(Comparative Example 5)
96.0 parts of an aqueous solution of polyvinyl alcohol resin “JL-05E” manufactured by Nihon Vitamin Poval Co., which has a polymerization degree of 300 and a saponification degree of 88%, in terms of solid content, and 4% of borax as a crosslinking agent Aqueous solution is 4.0 parts in terms of solids, 24% aqueous solution of ammonium sulfate as an adhesion inhibitor is 25.0 parts in terms of solids, and a heavy oil emulsion “Dafney Prosolvable PF” made by Idemitsu Kosan Co., Ltd. as a release agent. "15.0 parts in terms of solid content and 5.0 parts in terms of solid content silicone oil emulsion" Polon MR ", and aminopropyltrimethoxysilane" KBE903 "manufactured by Shin-Etsu Chemical Co., Ltd. as a silane coupling agent. After mixing with 1.0 part and stirring, it adjusted with water so that the density | concentration of aqueous solution might be 4%, and the water-soluble binder for inorganic fibers of the comparative example 5 was obtained.
The comparative example 5 is included in the invention according to claim 1, but is not included in the invention according to claim 3. Here, paying attention to claim 3, it grasped as a comparative example.

(Comparative Example 6)
96.0 parts of an aqueous solution of polyvinyl alcohol resin “JL-05E” manufactured by Nihon Vitamin Poval Co., which has a polymerization degree of 300 and a saponification degree of 88%, in terms of solid content, and 4% of borax as a crosslinking agent Aqueous solution is 4.0 parts in terms of solids, 24% aqueous solution of ammonium sulfate as an adhesion inhibitor is 15.0 parts in terms of solids, and Idemitsu Kosan Heavy Oil Emulsion “Daphne Prosolve PF” as a release agent. 40.0 parts in terms of solid content and 1.0 part of aminopropyltrimethoxysilane “KBE903” manufactured by Shin-Etsu Chemical Co., Ltd. as a silane coupling agent are mixed, and after stirring, the concentration of the aqueous solution becomes 4%. Thus, the water-soluble binder for inorganic fibers of Comparative Example 6 was obtained by adjusting with water.
The comparative example 6 is included in the invention according to claim 1, but is not included in the invention according to claim 5. Here, paying attention to claim 5, it grasped as a comparative example.

(Comparative Example 7)
96.0 parts of an aqueous solution of polyvinyl alcohol resin “JL-05E” manufactured by Nihon Vitamin Poval Co., which has a polymerization degree of 300 and a saponification degree of 88%, in terms of solid content, and 4% of borax as a crosslinking agent Aqueous solution is 4.0 parts in terms of solids, 24% aqueous solution of ammonium sulfate as an adhesion inhibitor is 15.0 parts in terms of solids, and Idemitsu Kosan Heavy Oil Emulsion “Daphne Prosolve PF” as a release agent. "15.0 parts in terms of solid content and 20.0 parts in terms of solid content silicone oil emulsion" Polon MR "and aminopropyltrimethoxysilane" KBE903 "manufactured by Shin-Etsu Chemical Co., Ltd. as a silane coupling agent. 1.0 part was mixed and, after stirring, the mixture was adjusted with water so that the concentration of the aqueous solution was 4% to obtain a water-soluble binder for inorganic fibers of Comparative Example 7.
In addition, although this comparative example 7 is included in the invention which concerns on Claim 1, it is not included in the invention which concerns on Claim 5 (the total amount of solid content conversion of a mold release agent is 35.0 parts) . Here, paying attention to claim 5, it grasped as a comparative example.

(Comparative Example 8)
96.0 parts of an aqueous solution of polyvinyl alcohol resin “JL-05E” manufactured by Nihon Vitamin Poval Co., which has a polymerization degree of 300 and a saponification degree of 88%, in terms of solid content, and 4% of borax as a crosslinking agent 4.0 parts of aqueous solution in terms of solid content, 15.0 parts of 24% aqueous solution of ammonium sulfate as an adhesion inhibitor in terms of solid content, and aminopropyltrimethoxysilane “KBE903” manufactured by Shin-Etsu Chemical Co., Ltd. as a silane coupling agent After mixing with 1.0 part and stirring, it adjusted with water so that the density | concentration of aqueous solution might be 4.0%, and the water-soluble binder for inorganic fibers of the comparative example 8 was obtained.

(Comparative Example 9)
Silane coupling with an aqueous solution of water-soluble phenolic resin “Phenolite” manufactured by DIC, 100.0 parts in terms of solids, and a 24% aqueous solution of ammonium sulfate as a reaction accelerator, 3.0 parts in terms of solids 1.0 parts of aminopropyltrimethoxysilane “KBE903” manufactured by Shin-Etsu Chemical Co., Ltd. as an agent, and 15.0 parts in terms of solid content of heavy oil emulsion “Dafney Prosolvable PF” manufactured by Idemitsu Kosan Co., Ltd. as a release agent The inorganic fiber of Comparative Example 9 was prepared by mixing 5 parts of a silicone oil emulsion “Polon MR” manufactured by Shin-Etsu Chemical Co., Ltd. in solids with water and adjusting with water so that the concentration of the aqueous solution was 4.0%. A water-soluble binder was obtained. The water-soluble phenolic resin “Phenolite” is already mixed with a crosslinking agent (formaldehyde), so no new crosslinking agent is added.
In the case of polyvinyl alcohol resin and phenol resin, the action of ammonium sulfate is different. When the water-soluble polymer is a polyvinyl alcohol resin, ammonium sulfate functions as an adhesion inhibitor because it crystallizes the polyvinyl alcohol resin and suppresses dissolution in water. On the other hand, when the water-soluble polymer is a water-soluble phenol resin, the resin is acidified during the heat treatment and acts as a reaction accelerator.

(Comparative Example 10)
An aqueous solution of “Glass Pearl”, an acrylic resin for inorganic fibers manufactured by Sanyo Chemical Co., Ltd., which is mainly composed of polyacrylic acid, and 50.0% of a 24% aqueous solution of ammonium sulfate as a solid content in terms of solid content. 1.0 part of aminopropyltrimethoxysilane “KBE903” manufactured by Shin-Etsu Chemical Co., Ltd. as a silane coupling agent, and a heavy oil emulsion “Dafney Prosolvable PF” manufactured by Idemitsu Kosan Co., Ltd. as a release agent. 15.0 parts in terms of conversion and 5.0 parts in terms of solid content of silicone oil emulsion “Polon MR” manufactured by Shin-Etsu Chemical Co., Ltd. are mixed and adjusted with water so that the concentration of the aqueous solution becomes 4% after stirring. The water-soluble binder for inorganic fibers of Comparative Example 10 was obtained. In addition, since the acrylic resin for inorganic fibers “Glass Pearl” is already mixed with a crosslinking agent, no new crosslinking agent is added.

  Evaluation was carried out by the method described below using the water-soluble binder for inorganic fibers obtained in Examples 1 to 5 and Comparative Examples 1 to 10.

(Evaluation of liquid stability)
The water-soluble binder for inorganic fibers obtained in Examples 1 to 5 and Comparative Examples 1 to 10 was allowed to stand for 1 hour, and the presence or absence of precipitates in the liquid was confirmed.
In the case where a precipitate is generated, it becomes a standard because it develops into a problem such as clogging in a spray device in a later process.

(Evaluation of adhesiveness)
The inorganic fiber deposition apparatus was coated with a spray device so that 5% of the resin solids adhered to the glass wool fiberized by the centrifugal method using the water-soluble binder for inorganic fibers obtained in Examples 1 to 5 and Comparative Examples 1 to 10. The mixture was deposited on a perforated conveyor while being sucked in, to obtain an inorganic fiber heat insulating material intermediate. The thickness of the resulting inorganic fiber heat-absorbing sound-absorbing material intermediate was measured, and the degree of adhesion was determined by the following mathematical formula.
Adhesiveness = intermediate thickness / molding thickness × 100
* Molding thickness: 20mm
The target value for adhesiveness is preferably 150% or more in consideration of a crushing margin at the time of nipping and pressing in the subsequent process.
Intermediate thickness = Molding thickness 20mm × Adhesiveness 150% or more = 30mm or more

(Evaluation of dryer suitability)
10 minutes at the drying temperature (polyvinyl alcohol-type resin: 190 degreeC, phenol-type resin: 240 degreeC, acrylic resin: 260 degreeC) suitable for each resin characteristic for the inorganic fiber heat insulation sound-absorbing material intermediate body obtained above. Then, an inorganic fiber heat insulating sound absorbing material having a density of 64 kg / m ³ , a thickness of 20 mm, and a binder adhesion rate of 5.0% was formed. The state of sticking of the molded product to the dryer plate surface was confirmed during molding.
The sticking is based on the fact that there is no sticking because it causes problems in the manufacturing process.

(Evaluation of elasticity)
Using the universal tester “AG-IS” manufactured by SHIMADZU, the repulsive force when each inorganic fiber heat-absorbing and sound-absorbing material obtained above was compressed to 50% was measured and compared.
The elasticity is based on the repulsive force of the inorganic fiber heat insulating material using the phenolic resin of Comparative Example 9, and has a numerical value larger than the repulsive force of the inorganic fiber heat insulating material using the phenolic resin. It was judged as “good elasticity”.

(Evaluation of water resistance)
The inorganic fiber heat insulating sound absorbing material obtained above was allowed to stand for 1 hour under saturated steam using a pressure humidification tester “HG-50” manufactured by HIRAYAMA, and the thickness change rate after the test was measured. Compared.
Thickness change rate (blowing rate) = (Thickness after test−Thickness before test) / Thickness before test × 100
By leaving the inorganic fiber heat-absorbing sound-absorbing material under saturated water vapor, the heat-insulating sound-absorbing material contains water and increases in thickness as the strength decreases. Therefore, it can be said that the smaller the rate of change in thickness, the smaller the amount of water contained, and the heat insulating sound-absorbing material that is excellent in water resistance without causing strength reduction.

(Evaluation of formaldehyde emission)
The inorganic fiber heat insulating sound absorbing material obtained above was measured for the amount of formaldehyde diffused based on the test standard of JIS A 1901.
Since it is a resin material that does not contain formaldehyde, it was based on undetected.

  The evaluation results of Examples 1 to 5 described above are shown in Table 1, and the evaluation results of Comparative Examples 1 to 10 are shown in Table 2.

  From the above results, a decrease was observed in the values of Comparative Examples 1 and 2 with respect to tackiness. In Comparative Examples 1 and 2, since the adhesion inhibitor was not added, the inorganic fiber intermediate was considered to be sticky and collapsed during suction. In Comparative Examples 1 and 2, since the thickness of the inorganic fiber intermediate was insufficient, there was no sufficient pressurization during subsequent heating, and a tendency to be inferior in surface smoothness was observed. Moreover, sufficient results were obtained for the others in which 3.0 parts or more of an adhesion inhibitor was added.

  From the above results, a precipitate was observed in Comparative Example 5 with respect to the liquid stability. In Comparative Example 5, since ammonium sulfate was added in a large amount of 25.0 parts as an adhesion inhibitor, the solubility of the polyvinyl alcohol resin in water was extremely reduced, and precipitation of the resin component was observed. The generation of precipitates can lead to clogging in the spray device over long periods of use. And since the resin component precipitated and the amount of adhesion decreased, it led to the deterioration of the elasticity and water resistance of the molded product.

  From the above results, sticking to the drying plate was seen in Comparative Example 8 for the suitability of the dryer. In Comparative Example 8, since no release agent was added, the inorganic heat insulating sound-absorbing material had no releasability and sticking occurred. No sticking was observed in other cases where 5.0 parts or more of a release agent was added. In Comparative Example 8, the molded product could not be produced because it adhered to the drying plate, and therefore, tests on elasticity, water resistance, and formaldehyde emission were not conducted.

  From the above results, low values were found in Comparative Examples 3 to 7 for elasticity. In Comparative Examples 3 and 4, it seems that the crosslinking reaction was not sufficiently performed because the amount of the crosslinking agent was as small as 3.0 parts. In Comparative Example 5, it is considered that the resin component was precipitated due to the excessive addition of the adhesion inhibitor, and the adhesion to the inorganic fibers was not sufficiently performed. In Comparative Examples 6 and 7, the surfactant contained in the release agent had an adverse effect on the strength (elasticity) of the inorganic fiber heat insulating material due to the excessive addition of the release agent. Moreover, in the comparison of Example 1 and 2 and Comparative Example 1 and 2, since the big change is not seen in the intensity | strength, it turns out that the adhesion inhibitor does not have a bad influence on reaction of resin.

  From the above results, regarding the water resistance, bad values were seen in Comparative Examples 3 and 4 and Comparative Examples 6 and 7. In Comparative Examples 3 and 4, the amount of the crosslinking agent is as small as 3.0 parts, and it seems that the crosslinking reaction of the resin was not sufficiently performed. In Comparative Examples 6 and 7, the total addition rate of the release agent was as large as 30.0 parts or more, and it seems that water resistance deteriorated due to the influence of the surfactant contained in the release agent.

  From the above results, the amount of formaldehyde emitted was not detected except for Comparative Example 9 using a phenolic resin.

  The water-soluble binder for inorganic fibers of the present invention is a binder that does not contain formaldehyde and exhibits excellent suitability for the production process of an inorganic fiber heat-absorbing sound-absorbing material. Or it can use suitably as a sound-absorbing material.

Claims (6)

  It is a water-soluble binder for inorganic fibers obtained by mixing a water-soluble polymer mainly composed of a polyvinyl alcohol resin, a crosslinking agent, an adhesion inhibitor, a silane coupling agent, and a release agent, A water-soluble binder for inorganic fibers, characterized in that the cured product has excellent elasticity and water resistance.   The cross-linking agent is one selected from (a) a compound of a polycarboxylic acid, a polymer or copolymer, (b) a borax compound, and (c) a mixture thereof. The water-soluble binder for inorganic fibers according to claim 1, which contains 4.0 parts by mass or more in terms of solid content with respect to parts.   The said adhesion inhibitor is the aqueous solution of a salt compound, and contained 3.0 to 20.0 mass parts in conversion of solid content with respect to 100 mass parts in total of the said polyvinyl alcohol-type resin and the said crosslinking agent. 3. The water-soluble binder for inorganic fibers according to any one of 2 above.   The silane coupling agent contains 0.1 to 3.0 parts by mass in terms of solid content with respect to 100 parts by mass in total of the polyvinyl alcohol resin and the crosslinking agent. The water-soluble binder for inorganic fibers according to Item. The release agent is an aqueous dispersion of heavy oil or a mixture of heavy oil and silicone oil, and is from 5.0 to 30 with respect to 100 parts by mass in total of the polyvinyl alcohol resin and the crosslinking agent. The water-soluble binder for inorganic fibers according to any one of claims 1 to 4, which contains 0 part by mass. An inorganic fiber heat-absorbing sound-absorbing material, wherein the water-soluble binder for inorganic fibers according to any one of claims 1 to 5 is applied to inorganic fibers and cured by heat treatment.