JP2017190531A - Anti-fraying treatment for glass fiber substrate - Google Patents

Abstract

An object of the present invention is to prevent fraying of glass fiber products, and without using an organic solvent, and is composed only of carbon, oxygen, and hydrogen, is safe during heat deoiling, and prevents a decrease in strength of glass fiber products after heat deoiling. An anti-fraying treatment agent for a glass fiber substrate is provided. A low thermal decomposable polyether polymer which is composed only of carbon, oxygen and hydrogen and does not contain an ester bond in the molecular structure and which can be removed by a heat treatment at 400 ° C. or lower. did. [Selection figure] None

Description

  The present invention relates to a fraying prevention agent for a glass fiber substrate.

  Since glass cloth is excellent in heat resistance, it is used for impurity filtration of heat insulating materials and molten metal (liquid metal), rectification of molten metal, and the like. When used for these applications, organic substances on the surface of the glass cloth cause gas generation. Therefore, it is desirable to use a heat-deoiled cloth at the time of use. However, the heat-deoiled cloth has a problem that it is difficult to handle due to fraying or fluffing when it is cut into various shapes. In particular, in the case of quartz glass fiber, it is remarkable due to poor flexibility.

  In order to prevent this, a method may be considered in which a part or the whole of the glass cloth is subjected to a surface treatment with a fraying preventive agent, then cut into a desired shape, and finally the fraying preventive agent is burned off. For example, an epoxy resin described in Patent Document 1 may be used as a fraying prevention treatment agent, but this is not good for the environment because an organic solvent is used. Moreover, since the polyester resin described in Patent Document 2 and the epoxy ester resin described in Patent Document 3 have an ester bond in the molecular structure, they react with water and are partly decomposed into carboxylic acids or alcohols. Is unstable. In addition, since the water-based urethane resins described in Patent Documents 4 to 5 contain nitrogen in the molecular structure, there is a possibility that nitride oxide or cyanide may be generated at the time of combustion. . Active energy ray-curable resin described in Patent Document 6, polyether imide resin described in Patent Document 7, polyolefin resin described in Patent Document 8, other common nylon 6, vinyl acetate, ethylene-vinyl alcohol, co-polymer There are also anti-fraying treatment agents such as polymerized polyamide, but these all require heating above 400 ° C. in order to completely remove them, and as described in Patent Document 9, the strength of the glass cloth is reduced after heat deoiling. There is a problem that it is greatly reduced. This is particularly true for glass cloth such as quartz glass cloth.

JP-A-8-13343 JP 2001-81671 A JP-A-8-260340 JP-A-6-240578 JP 2006-342445 A Japanese Patent Laid-Open No. 9-279481 JP-A-63-288272 JP 2001-140143 A JP-A-3-218948

  This invention solves the said problem seen in the fraying prevention processing agent of the conventional glass fiber product. That is, it suppresses fraying of the glass fiber product, is made of only carbon, oxygen and hydrogen without using an organic solvent, and is safe at the time of heat deoiling and can prevent the strength reduction of the glass fiber product after the heat deoiling. It aims at providing the fraying prevention processing agent of a glass fiber base material.

  The fraying preventive treatment agent for glass fiber base material of the present invention is made to solve the above-mentioned problems, and is composed only of carbon, oxygen and hydrogen, and does not contain an ester bond in the molecular structure, and is 400 ° C. It contains a low thermal decomposable polyether polymer that can be removed by the following heat treatment.

  The low heat decomposable polyether polymer is preferably at least one selected from the group consisting of polyalkylene glycol and polyalkylene oxide.

  The glass fiber product of the present invention is a glass fiber product to which the fraying prevention agent of the present invention is applied.

  The method for producing a glass fiber product of the present invention includes a step of applying the fraying prevention treatment agent of the present invention to a glass fiber substrate, and a step of cutting the glass fiber substrate coated with the fraying prevention treatment agent into a predetermined shape. And a step of heat-treating the cut glass fiber substrate at 400 ° C. or less to remove the low-heat decomposable polyether polymer.

  According to the present invention, fraying of glass fibers is suppressed, organic solvents are not used, and only carbon, oxygen, and hydrogen are used, so that it is safe during heat deoiling and prevents strength reduction of glass fiber products even after heat deoiling. It is possible to provide a fraying prevention treatment agent that can be provided.

  Embodiments of the present invention will be described below, but these are exemplarily shown, and it goes without saying that various modifications are possible without departing from the technical idea of the present invention.

  The fraying prevention treatment agent for glass fiber base material of the present invention comprises a low-heat-decomposable polyether polymer composed only of carbon, oxygen and hydrogen, and does not contain an ester bond in the molecular structure. . The low-heat-decomposable polyether polymer is a polyether polymer that can be decomposed and removed by a heat treatment at 400 ° C. or lower, and the decomposition temperature is preferably 100 ° C. to 400 ° C., preferably 100 ° C. More preferably, it is -350 degreeC.

As the low heat decomposable polyether polymer, polyalkylene glycol or polyalkylene oxide is preferably used.
The polyalkylene glycol is not particularly limited as long as it is in a solid state at room temperature, specifically, the freezing point is 30 ° C. or higher. For example, PEG # 1000 (manufactured by NOF Corporation), PEG # 1500 (NOF PEG # 2000 (manufactured by NOF Corporation), PEG # 4000 (manufactured by NOF Corporation), PEG # 6000 (manufactured by NOF Corporation), PEG # 11000 (NOF Corporation) )), PEG # 20000 (manufactured by NOF Corporation), Pronon (registered trademark) # 208 (manufactured by NOF Corporation), Unilube (registered trademark) 70DP-600B (manufactured by NOF Corporation), Unilube (Registered trademark) 70DP-950B (manufactured by NOF Corporation), UNIOX (registered trademark) M-1000 (manufactured by NOF Corporation), which is a polyalkylene glycol derivative, UNIOX (registered trademark) M-2000 ( NOF Corporation) Such as UNIOX (registered trademark) M-4000 (manufactured by NOF Co., Ltd.) are commercially available. These polyalkylene glycols can be used alone or in combination of two or more.

  The blending ratio of the polyalkylene glycol in the anti-fraying treatment agent is not particularly limited, but is preferably 0.05 to 50% by mass, more preferably 0.1% with respect to 100% by mass of the total anti-fraying treatment agent. -20% by mass, more preferably 0.1-10% by mass. If the blending ratio exceeds 50% by mass, the viscosity of the fraying preventive treatment agent will increase, and the glass fiber substrate will be bent, and if it is less than 0.05% by mass, the fraying prevention effect may be reduced.

  The polyalkylene oxide is not particularly limited as long as it is in a solid state at room temperature, specifically, the freezing point is 30 ° C. or higher. For example, PEO (registered trademark) -1 (manufactured by Sumitomo Seika Co., Ltd.), PEO (Registered trademark) -2 (manufactured by Sumitomo Seika Co., Ltd.), PEO (registered trademark) -3 (manufactured by Sumitomo Seika Co., Ltd.), PEO (registered trademark) -4 (manufactured by Sumitomo Seika Co., Ltd.), PEO (registered trademark) -8 (manufactured by Sumitomo Seika Co., Ltd.), PEO (registered trademark) -15 (manufactured by Sumitomo Seika Co., Ltd.), PEO (registered trademark) -18 (manufactured by Sumitomo Seika Co., Ltd.) PEO (registered trademark) -27 (manufactured by Sumitomo Seika Co., Ltd.), PEO (registered trademark) -29 (manufactured by Sumitomo Seika Co., Ltd.) and the like are commercially available. These polyalkylene oxides can be used alone or in combination of two or more.

  The blending ratio of the polyalkylene oxide in the anti-fray treatment agent is not particularly limited, but is preferably 0.05 to 50% by mass, more preferably 0.1 to 100% by mass of the total fray prevention agent. -20% by mass, more preferably 0.1-10% by mass. If the blending ratio exceeds 50% by mass, the viscosity of the fraying preventive treatment agent will increase, and the glass fiber substrate will be bent, and if it is less than 0.05% by mass, the fraying prevention effect may be reduced.

  The above polyalkylene glycol and polyalkylene oxide can be used alone or in combination of two or more.

  The fraying prevention treatment agent of the present invention preferably uses water as a solvent.

  As long as the fray prevention treatment agent of the present invention does not impair the effects of the present invention, components other than the polyether polymer described above can be added. Examples of other components include surfactants that can be removed by heat treatment at 400 ° C. or lower.

  Although it does not specifically limit as glass material which comprises glass fiber, E glass, D glass, quartz glass, etc. are mentioned. Among them, quartz glass is particularly effective because it is poor in flexibility and easily frayed on a glass fiber substrate after heat deoiling.

  As the glass fiber substrate to which the fraying prevention treatment agent of the present invention is applied, a glass substrate that has been heat-deoiled after weaving is desirable, but a surface treatment that has been subjected to a surface treatment such as a silane coupling agent after heat-deoiling. You may carry out with a glass base material. Moreover, about the glass fiber base material with which the glass fiber sizing agent which does not require heat deoiling was apply | coated, a fraying prevention process can be performed with respect to the glass fiber base material surface, without performing heat deoiling.

  The fraying preventive treatment agent of the present invention is used to prevent fraying during cutting of the glass fiber substrate. Since the fraying prevention treatment agent of the present invention can be completely removed by heating and deoiling at 400 ° C. or less, the fraying prevention treatment agent is applied, cut into a predetermined shape, and then heated and deoiled at 400 ° C. or less. By doing so, the glass fiber base material of the target shape can be obtained.

  The fraying preventive treatment agent of the present invention is composed of only carbon, oxygen, and hydrogen in a solvent such as water, and has low thermal decomposition that can be removed by heat treatment at 400 ° C. or less that does not contain an ester bond in the molecular structure. It can be produced by adding a predetermined amount of a conductive polyether polymer and stirring.

  Examples of the method for applying the fraying preventive treatment agent of the present invention to a glass fiber substrate include an immersion method and a spray method.

  The fraying preventive treatment agent of the present invention can be dried at room temperature after being applied to a glass fiber substrate, but it is desirable to heat and dry.

  After cutting the glass fiber substrate coated with the fraying preventive agent into a predetermined shape, the cut glass fiber substrate is heat-treated at 400 ° C. or lower to remove the low thermal decomposable polyether polymer. The glass fiber product of the present invention can be produced by heat deoiling. The heat deoiling treatment temperature may be 400 ° C. or lower and above the temperature at which the low thermal decomposable polyether polymer in the fraying prevention treatment agent is decomposed, but preferably 100 ° C. to 400 ° C., preferably 150 ° C. to 400 ° C. ° C is more preferred.

  The glass fiber product of the present invention is suitable for applications such as heat insulation, impurity filtration of molten metal (liquid metal), and glass cloth for rectification of molten metal.

  The present invention will be described more specifically with reference to the following examples. However, it is needless to say that these examples are shown by way of illustration and should not be construed in a limited manner.

  Measurement and evaluation in the following experimental examples and comparative examples were performed by the following methods.

1. Fraying at the time of cutting the glass cloth A part of the glass cloth that had been treated to prevent fraying was cut, and the cross section was visually confirmed.

2. Fraying prevention treatment agent disappearing temperature A part of the fraying prevention treated glass cloth was cut, and deoiling property was confirmed using TG-DTA7300 manufactured by Hitachi High-Tech Science Co., Ltd. The temperature at which the decrease in the TG curve stopped and became constant was defined as the fraying prevention treatment agent disappearing temperature. The atmosphere was air, and the heating rate was 10 ° C./min.

3. Tensile strength of glass cloth The glass cloth that had been subjected to the fraying prevention treatment was subjected to a heat treatment under the conditions of the disappearance temperature of the fraying prevention treatment × 2 hours, and then measured according to JIS R 3420 2013 7.4.2. For comparison, the same method was used to measure the untreated glass cloth before the fraying prevention treatment.

Example 1
950 g of water was taken in a glass beaker, and 50 g of PEG # 4000 (manufactured by NOF Corporation) was added thereto as a polyalkylene glycol and stirred until completely dissolved to obtain a fraying prevention treatment agent. Next, an untreated 2116 type quartz glass cloth (filament number: 7 μm × 200, warp density: 65 pieces / 25 mm, weft density: 62 pieces / 25 mm) is immersed in a fraying prevention treatment agent for 10 minutes, After pulling up, it was dried under heating conditions of 100 ° C. × 10 minutes. Various evaluations were performed using the flaw-prevented quartz glass cloth. The results are shown in Table 1.

(Example 2)
950 g of water was taken in a glass beaker, and 50 g of PEO (registered trademark) -1 (manufactured by Sumitomo Seika Co., Ltd.) was added as a polyalkylene oxide to the glass beaker, followed by stirring until completely dissolved to obtain a fraying prevention treatment agent. Otherwise, the same operation as in Example 1 was performed. The results are shown in Table 1.

(Example 3)
Into a glass beaker, 990 g of water was added, 10 g of PEG # 11000 (manufactured by NOF Corporation) was added as polyalkylene glycol, and the mixture was stirred until completely dissolved to obtain a fraying prevention treatment agent. Otherwise, the same operation as in Example 1 was performed. The results are shown in Table 1.

Example 4
Into a glass beaker, 999 g of water was added, and 1 g of PEG # 20000 (manufactured by NOF Corporation) was added thereto as a polyalkylene glycol and stirred until completely dissolved to obtain a fraying prevention treatment agent. Otherwise, the same operation as in Example 1 was performed. The results are shown in Table 1.

(Example 5)
Into a glass beaker, 850 g of water was added, 150 g of PEG # 1000 (manufactured by NOF Corporation) was added as polyalkylene glycol and stirred until completely dissolved to obtain a fraying prevention treatment agent. Otherwise, the same operation as in Example 1 was performed. The results are shown in Table 1.

(Example 6)
600 g of water was taken in a glass beaker, 400 g of PEG # 1000 (manufactured by NOF Corporation) was added as polyalkylene glycol, and the mixture was stirred until completely dissolved to obtain a fraying prevention treatment agent. Otherwise, the same operation as in Example 1 was performed. The results are shown in Table 1.

(Comparative Example 1)
950 g of water was taken in a glass beaker, and 50 g of Viniblanc (registered trademark) 1002 (manufactured by Nissin Chemical Industry Co., Ltd.) was added as a vinyl acetate emulsion to the glass beaker and stirred until completely dissolved to obtain a fraying prevention treatment agent. Otherwise, the same operation as in Example 1 was performed. The results are shown in Table 2.

(Comparative Example 2)
The same operation as in Example 1 was performed except that an epoxy resin jER (registered trademark) 828 (manufactured by Mitsubishi Chemical Corporation) was used as a fraying prevention treatment agent. The results are shown in Table 2.

(Comparative Example 3)
In a method described in Patent Document 7, 940 g of methylene chloride is taken into a glass beaker, and 60 g of ULTEM (registered trademark) 1000 (manufactured by SABIC Innovative Plastics) is added thereto as a polyetherimide resin and completely dissolved. To obtain a fraying preventive. Otherwise, the same operation as in Example 1 was performed. The results are shown in Table 2.

As shown in Table 1, Examples 1 to 6 are composed of only carbon, oxygen, and hydrogen, and do not contain an ester bond in the molecular structure, and can be removed by a heat treatment at 400 ° C. or lower. Since the glass fiber base fraying prevention treatment agent characterized by containing an ether polymer was used, fraying was suppressed, and heat deoiling was possible at a low temperature. No decrease in tensile strength was observed.
On the other hand, as shown in Table 2, since Comparative Examples 1 to 3 used vinyl acetate, epoxy resin, and polyetherimide resin, the anti-fraying agent disappearing temperature increased, and the tensile strength of the quartz glass cloth decreased after heat treatment. It was.

Claims (4)

  Glass comprising a low-heat-decomposable polyether polymer composed only of carbon, oxygen, and hydrogen and having no ester bond in the molecular structure and capable of being removed by heat treatment at 400 ° C. or lower. An anti-fraying treatment for fiber substrates.   2. The fraying prevention agent for glass fiber base material according to claim 1, wherein the low thermal decomposable polyether polymer is at least one selected from the group consisting of polyalkylene glycol and polyalkylene oxide.   A glass fiber product to which the fraying preventive agent according to claim 1 or 2 is applied. Applying the fraying preventive agent according to claim 1 or 2 to a glass fiber substrate;
Cutting the glass fiber substrate coated with the fraying preventive agent into a predetermined shape;
Heat-treating the cut glass fiber substrate at 400 ° C. or less, and removing the low thermal decomposable polyether polymer;
A method for producing a glass fiber product.