JP2003089953A - Heat-resistant glass fiber mat and method of producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat-resistant glass fiber mat that can retain the resistance to heat for a long period of time and solves the problems, for example, the rust caused by acid and environmental pollution by increasing the resistance to heat of the heat-resistant glass fiber mat inexpensively. SOLUTION: A glass filament 1 is impregnated with a mixed liquid 4 of a ceramic sol 2 and an organic resin 3 having a pH of 6-8 and dried whereby the glass filaments 1 are surface-coated individually. Then, the glass filaments 1 are loosened to a mixed cotton-like fabric and needle-punched to form the mat.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-resistant glass fiber mat used as a heat-resistant sound-absorbing material which is a material for a silencer, an engine cover and the like, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
The following are known as methods for improving the heat resistance of this type of heat-resistant glass fiber mat, but all of them have problems. The inexpensive E-glass long fibers are treated with acid such as hydrochloric acid, nitric acid, sulfuric acid, etc. to elute the acid-soluble components other than silica (SiO ₂ ) on the fiber surface to increase the silica content on the fiber surface and improve heat resistance. Method (JP-A-5-14797)
No. 5, JP-A-7-172876, and JP-A-9-
169548, etc.). In this method, the E-glass long fibers are usually washed with water after the acid treatment and dried, but the acid that has entered between the fibers does not fall off even after washing with water, and remains easily.
Therefore, the residual acid in the mat made of this fiber induces rust of the contact metal and environmental pollution of the surroundings during use.

A method in which E glass long fibers are mixed with ceramic fibers (mainly silica fibers) in a blended form to form a composite.
In the case of this method, the E glass long fibers are thermally deteriorated at the ratio in which they are mixed, so that they have a short life.

A method in which fibers such as T glass fibers and ceramic fibers themselves are manufactured from only raw materials having heat resistance. This method makes the mat expensive.

The object of the present invention is to solve the above-mentioned problems, improve heat resistance and maintain it for a long period of time, have no problems of rust due to acid and environmental pollution, and realize these effects at low cost. A heat-resistant glass fiber mat and a method for producing the same are provided.

[0006]

[Means for Solving the Problems] In order to solve the above problems, the following means were adopted. (1) A heat resistance obtained by subjecting the surface of each glass long fiber to a surface coating treatment in which ceramic fine particles and an organic resin are adhered, and the glass long fiber is formed into a mat shape by a needle punch method. Fiberglass mat.

The term "long glass fiber" as used herein includes cut glass long fibers. The material of the long glass fiber is not particularly limited, but E glass and C glass can be exemplified, and if strong, the most common and low cost E glass fiber is preferable. The fiber diameter of the long glass fiber is also not particularly limited, but is preferably 3 to 20 μm, more preferably 5 to 10 μm, and particularly preferably an average fiber diameter of about 9 μm because of its versatility. The fiber length of the glass long fibers (cut length for cut products) is also not particularly limited, but is 30 to 200.
mm is preferable, and 50-100 mm is more preferable.

The "ceramic fine particles" are not particularly limited, but silica fine particles, alumina fine particles, zirconia fine particles, titania fine particles and the like can be exemplified, and one kind or a combination of two or more kinds selected from these can be exemplified.
From the balance of heat resistance and price, silica fine particles are preferable.

In particular, when the glass long fibers are E glass long fibers and the ceramic fine particles are silica fine particles,
The heat-resistant glass fiber mat preferably has a SiO ₂ component content of 59% by weight or more. E Glass long fiber SiO
While the _{two-component} content of about 57 wt%, an amount corresponding to the silica fine particles are deposited, in which a SiO ₂ component content increased by 59% or more by weight (an increase of more than 2 wt%).

The "organic resin" is not particularly limited, but it is an ionomer resin, EEA resin, EVA resin, vinyl chloride resin, vinylidene chloride resin, chlorinated polyethylene resin, fluorinated resin, polyamide resin, polyether ether ketone resin, Polysulfone resin, polyethylene resin, polycarbonate resin, polybutadiene resin, polypropylene resin, polystyrene resin, polyacrylate resin, polyurethane resin, polyethylene terephthalate resin, polybutylene terephthalate resin, unsaturated polyester resin, ABS resin, polyacetal resin, polymethylbenten resin, Polyphenyl ether resin, polyimide resin, polyetherimide resin, polyphenylene sulfide resin, aramid resin, cellophane, cellulose modified product, gelatin , Chitosan, polyvinyl alcohol, polyethylene oxide, can be exemplified sodium polyacrylate, it can be exemplified adoption of one or more combinations selected from these. These organic resins are preferably those that are easily dispersed in water from the viewpoint of being uniformly mixed with the ceramic sol. Above all, a flexible acrylic resin is preferable in terms of price.

(2) Each glass long fiber is subjected to a surface coating treatment by impregnating the glass long fiber with a mixed solution of a ceramic sol and an organic resin, and then drying the mixture. A method for producing a heat-resistant glass fiber mat, which comprises forming a mat-like material by needle-punching, after unraveling it into a mixed cotton shape.

As for "glass long fibers", paragraph 000
As described in 7 above. The “organic resin” is also as described above in paragraph 0010. "Ceramic sol"
Is not particularly limited, silica sol, alumina sol,
Examples thereof include zirconia sol and titania sol, and examples thereof include the use of one kind or a combination of two or more kinds selected from these. From the balance of heat resistance and price, silica sol is preferable.

The mixing ratio of the ceramic sol and the organic resin depends on the solid content and is not particularly limited, but it is preferable that the organic resin is 5 to 15 parts with respect to 50 to 100 parts of the ceramic sol.

Commercially available ceramic sols may be acidic, neutral or alkaline. However, even if an acidic or alkaline ceramic sol becomes a mixed solution with an organic resin, its acidic or alkaline strength is weakened and approaches neutral. In some cases (for example, when the pH of the mixed solution is less than 6 or more than 8), some PH may be added to bring the mixed solution closer to neutrality.
A regulator may be added. When the pH of the mixed solution is adjusted to be in the range of 6 to 8 (substantially neutral), the molded article made of the glass fiber mat also becomes neutral, and it is possible to prevent rust of the contact metal and environmental pollution of the surroundings, which is preferable.

In addition to the above-mentioned pH adjuster, the mixed solution contains a dispersant for increasing the dispersibility of the ceramic fine particles or the organic resin, a penetrant for increasing the permeability of the long glass fiber, and the like. May be added.

When molding a three-dimensional molded body from a glass fiber mat or manufacturing a rigid flat molded body, silica sol is applied to the surface of the glass fiber mat and dried, It is a well-known fact that it plays a part in maintaining the shape of the molded body and improves the heat resistance of the surface of the molded body. However, these are improvements in the surface of the molded article, and are not aimed at the overall modification of each glass fiber as in the present invention.

Even if silica sol is attached to each of the glass fibers, it will almost fall off during the mat manufacturing process. Further, if each glass fiber is provided with an organic substance, the fibers stick to each other, and it is difficult to produce a mat having an appropriate shape. The present invention improves on these points.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION A heat-resistant glass fiber mat according to an embodiment of the present invention and a method for producing the same will be described below in the order of steps with reference to the drawings. First, Fig. 1
As shown in (a), the mixed solution 4 is prepared by mixing the ceramic sol 2 and the organic resin 3 in a ratio of 50 to 100 parts by weight of the former and 5 to 15 parts by weight of the latter. P of mixture 4
H is adjusted to a neutral level of 6 to 8, and when it is difficult to prepare H alone, a pH adjustor is added. In addition, a dispersant and a penetrant are added if necessary. This mixture 4
Dip mixed long glass fiber 1 into
The mixed solution 4 is permeated so as to spread over each of the above.

The long glass fiber 1 after immersion is taken out from the mixed solution 4, and is dehydrated at about 1000 to 5000 rpm in a centrifugal dehydrator 5 as shown in FIG. 1 (b), to 10 parts by weight of the long glass fiber 1. , The adhering amount of the mixed liquid 4 is approximately 5 to
Squeeze until it reaches 7 parts by weight.

The long glass fiber 1 after dehydration is taken out from the centrifugal dehydrator 5 and, as shown in FIG. 2 (a), the temperature at which the organic resin is cured by the dryer 6 (for example, in the case of acrylic, it is generally 140 to 160 ° C.). To dry. FIG. 2 (c) is an enlarged view of the fiber level of the long glass fiber 1 after drying, in which one surface of each long glass fiber 1 is provided with the ceramic fine particles 2a, which are the solid content of the ceramic sol 2, and the organic material after drying. A surface coating treatment is performed to which the resin 3 is attached.

After the dried long glass fibers 1 are loosened into a mixed cotton shape, the adhesive of the long glass fibers 1 by the organic resin 3 is appropriately peeled off and left appropriately, and then, as shown in FIG. 2 (b).
As shown in FIG. 3, the heat-resistant glass fiber mat 10 is completed by forming it into a mat shape by a general needle punching method. The ceramic fine particles 2a remain almost without falling off,
The attached state of FIG. 2C is maintained. The density and thickness of the mat 10 are not particularly limited, but the solid content of the ceramic sol (ceramic fine particles 2a) is generally increased as compared with a normal mat.

According to the heat resistant glass fiber mat and the method for manufacturing the same according to this embodiment, the following effects can be obtained. Since the ceramic fine particles 2a are strongly adhered to the fiber surface by the organic resin 3, the ceramic fine particles 2a are hardly removed even during the step of the needle punching method, and the heat resistance of the mat 10 is improved. For example, when the ceramic fine particles 2a are silica fine particles, the content of the SiO ₂ component in the mat 10 is increased by the amount of the silica fine particles attached, and the heat resistance is improved. Since the ceramic fine particles 2a carry out the overall modification of each glass long fiber 1, there is no uneven heat deterioration,
It has a long life. When only the organic resin is adhered, it is difficult to manufacture a mat having an appropriate shape because the fibers are adhered to each other too much. However, in the present embodiment, since the ceramic fine particles 2a are adhered together with the organic resin 3, As described above, the adhesion of the long glass fibers 1 to each other by the organic resin 3 can be appropriately peeled off and appropriately left, so that the mat can be easily loosened and a mat having an appropriate shape can be manufactured. Even if it is an acidic or alkaline ceramic sol,
Since the pH of the mixed solution is adjusted to be in the range of 6 to 8 (substantially neutral), the molded product made of the mat 10 does not induce rust of the contact metal or environmental pollution of the surroundings during use. Since the inexpensive long glass fiber 1 can be used as a base, the mat 10 can be inexpensive.

[Test Example] In order to confirm the effect of this embodiment, the following test examples 1 to 3 were tested. As a ceramic sol, a silica sol (trade name: Snowtex ST20) manufactured by Nissan Chemical Industry Co., Ltd., an acrylic resin (trade name: soft acrylic 3H-90) manufactured by Shinba Co., Ltd. as an organic resin, and a Takamatsu Yushi Co., Ltd. as a penetrant. A penetrant (trade name: synthol) and citric acid as a PH adjusting agent were used, and as shown in Table 1 below, mixed in different proportions in Test Examples 1 to 3 to prepare mixed solutions. Table 1 also shows the PH of the mixed solutions of the respective test examples.

E-glass long fibers (a long-fiber cut product having an average fiber diameter of 9 μm) manufactured by Nitto Boseki Co., Ltd. was dipped in the above-mentioned mixed liquid, and the mixed liquid was spread so as to spread over each E-glass long fiber. Permeated. Then, as in the above embodiment, the E glass long fibers after immersion were dehydrated to squeeze the mixed liquid. Table 1 also shows the squeezing conditions of the respective test examples. Subsequently, similarly to the above-described embodiment, the E-glass long fibers after dehydration are dried (surface coating treatment), the E-glass long fibers after drying are loosened into a mixed cotton shape, and then the mat-like shape is formed by a needle punch method. And a heat-resistant glass mat was completed. Table 1 also shows the areal weight, thickness and PH of the mats of the respective test examples. In addition, as a comparative example, Table 1 also shows the data of the E glass long fibers without the surface coating treatment. As for the PH of the mat, the sample obtained by opening the mat in a beaker is put into
100 parts by weight of distilled water was added, and the mixture was stirred at room temperature for 1 hour and then measured with a PH meter (model number H-7VP) manufactured by Horiba Ltd.

Table 1 also shows the results of the test / analysis results of the heat shrinkage rate, chemical composition, and heat resistance of the mats of the respective test examples to comparative examples. The chemical composition was analyzed by a fluorescent X-ray elemental analyzer after crushing the sample. Heat shrinkage is JAS
It was measured by OM405-87 at 720 ° C. for 1 hour. For heat resistance, place the sample on a heat resistant plate and
It was heated at 20 ° C. for 1 hour, the change of the fiber was observed, and the heat resistance was judged according to the following criteria. ◎ The suppleness of the fibers is maintained. ○ The suppleness of the fiber is half lost. △ The shape of the fiber remains, but the flexibility is almost lost. ▲ The fibers are fused and deformed. × The fibers are fused and deformed. All were fused and the whole sample became one lump.

[0026]

[Table 1]

As is apparent from Table 1, the mat of Comparative Example has a SiO ₂ component content of 57% by weight and a heat resistance of ◯ to ∘.
On the other hand, the mats of each of Test Examples 1 to 4 had a SiO ₂ component content of 59% by weight or more (further 60% by weight or more) due to the adhesion of the silica sol, and the mats of Test Examples 1 to 4 had excellent heat resistance.
It was a judgment of.

The present invention is not limited to the above-described embodiment, but may be embodied with appropriate modifications within the scope not departing from the spirit of the invention, for example, as follows. (1) The method of infiltrating the mixed solution into the long glass fibers is not limited to the above dipping, and for example, the mixed solution may be made to flow through the long glass fibers or sprayed at high speed. (2) The method of squeezing the mixed liquid from the E-glass long fibers after the immersion is not limited to dehydration by the centrifugal dehydrator, but may be, for example, squeezing by pressing a roller.

[0029]

As described in detail above, according to the heat resistant glass fiber mat and the method for producing the same according to the present invention, the heat resistance can be improved and maintained for a long period of time, and the problems of rust due to acid and environmental pollution. In addition, these effects can be realized at low cost.

[Brief description of drawings]

FIG. 1 shows a method for producing a heat-resistant glass fiber mat according to an embodiment of the present invention, (a) is a schematic view of immersing long glass fibers in a mixed solution, and (b) is a dewatering process of long glass fibers. FIG.

FIG. 2A is a schematic view of drying long glass fibers, and FIG. 2B is a cross-sectional view of a heat-resistant glass mat.
(C) is an enlarged view of the fiber level of the mat.

[Explanation of symbols]

1 glass filament 2 Ceramic sol 2a Ceramic fine particles 3 organic resin 4 mixed liquid 5 Centrifugal dehydrator 6 dryer 10 Heat-resistant glass fiber mat

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) F01N 1/24 F02B 77/13 A 7/18 D06M 101: 00 F02B 77/13 11/06 // D06M 101 : 00 F term (reference) 3D023 BA02 BA05 BB16 BB29 BC01 BD21 BE04 BE31 3G004 CA13 DA06 DA15 FA01 FA07 4L031 AA07 AB34 BA09 BA19 BA20 BA23 DA00 DA17 4L047 AA05 BA03 CB03 CB05 DA00

Claims (4)

[Claims] 1. A surface coating treatment in which fine ceramic particles and an organic resin are adhered to the surface of each long glass fiber, and the long glass fiber is formed into a mat by a needle punch method. A heat resistant glass fiber mat. 2. The heat-resistant glass according to claim 1, wherein the glass long fibers are E-glass long fibers, the ceramic fine particles are silica fine particles, and the SiO ₂ component content of the heat-resistant glass fiber mat is 59% by weight or more. Fiberglass mat. 3. A glass long fiber is impregnated with a mixed solution of a ceramic sol and an organic resin and then dried to subject each glass long fiber to a surface coating treatment, and then the glass long fiber is treated. A method for producing a heat-resistant glass fiber mat, which comprises unraveling into a mixed cotton shape and then forming into a mat-like shape by a needle punch method. 4. The method for producing a heat-resistant glass fiber mat according to claim 3, wherein the pH of the mixed solution is in the range of 6-8.