JPS6228113B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention mainly relates to mats and cylindrical bodies made of inorganic short fibers used as heat insulating materials and sound absorbing materials in buildings, etc., inorganic long fiber woven fabrics, and other products, especially special materials for bonding or covering inorganic fibers. The present invention relates to an inorganic fiber product using a binder composition. Inorganic short fiber products used as heat insulating materials and sound absorbing materials are made by attaching a thermosetting resin liquid or an aqueous colloid of silicic acid (called a binder) to short inorganic fibers such as short glass fibers and rock wool. It is manufactured by heating inorganic short fibers containing a binder to harden the binder. Although glass fiber will be explained below as an example of inorganic fiber, the application of the present invention is not limited to glass fiber. Conventionally, as a binder for glass fibers, for example, a solution or dispersed phenol-formaldehyde condensate (referred to as a resol type phenolic resin) has been used. Generally, when short glass fiber pine is used as a residential insulation material, after the glass fiber pine is manufactured, the volume of the insulation material is
It is packed and transported in a compressed state of 1/3 to 1/10 and unpacked immediately before use, but when used, it must be restored to the specified thickness and exhibit the specified insulation performance. However, the short glass fiber mat using the conventional binder had poor recovery properties, and could not fully satisfy this requirement. In addition, when short glass fibers are formed into glass wool insulation tubes, it is necessary to bend the insulation tubes in order to install the insulation tubes at elbows, etc. However, the conventional insulation tubes break during bending. This caused problems such as cracks and other problems. The present inventor has proposed a binder containing at least one of a thermoplastic resin and synthetic rubber and a thermosetting resin as previously described in Japanese Patent Application No. 56-46853 as a binder that improves the above-mentioned drawbacks. However, although short glass fiber mats and heat-insulating tubes manufactured using the above-mentioned binders show improvement in resilience and bending immediately after manufacture, if they are left in hot and humid conditions for a long period of time, the bonds formed by the hardened products of the above-mentioned binders It was found that there was a problem in that the points deteriorated and the effectiveness decreased. As a result of further research on the above points, the present inventor has found that by using a binder whose main component is a special modified resol type phenolic resin, the resilience is improved and glass fiber products that are less likely to break or crack can be created. The inventors have also found that the above effects are maintained even when left in hot and humid conditions for a long time. That is, the present invention is an inorganic fiber product obtained by applying and curing to inorganic fibers an aqueous binder whose main component is a composition consisting of a mixture and/or precondensate containing a resol type phenolic resin and a polyhydric alcohol. The composition that is the main component of the aqueous binder in the present invention is a mixture containing a resol-type phenolic resin and a polyhydric alcohol, a precondensate containing a resol-type phenolic resin and a polyhydric alcohol, or a precondensate containing these. Consists of both. Examples of this composition are as follows. 1 A mixture of a resol-type phenolic resin and a polyhydric alcohol 2 A mixture of a resol-type phenolic resin, a polyhydric alcohol, and urea 3 A precondensate of a resol-based phenolic resin and a polyhydric alcohol 4 A resol-type phenolic resin and a polyhydric alcohol Precondensate with urea 5 Mixture of precondensate of resol type phenolic resin and urea with polyhydric alcohol added 6 Mixture of precondensate of 3 above and urea 7 Precondensate of 3 above and resol type phenolic resin Mixture 8 of the precondensate of 3 above and polyhydric alcohol 9 Mixture of the precondensate of 4 above and (polyhydric alcohol or urea or resol type phenolic resin) Main component of the aqueous binder in the present invention A precondensate of a resol-type phenolic resin and a polyhydric alcohol (also referred to as a polyhydric alcohol-modified phenolic resin) used as a composition is obtained, for example, by heating phenol, formaldehyde, and a polyhydric alcohol. This precondensate is a water-soluble condensate, and an unreacted mixture of the resol type phenolic resin and the polyhydric alcohol may remain therein. The phenol and formaldehyde used in the production of this precondensate are preferably reacted at a molar ratio of 1:1.5 to 3.0. In addition, a precondensate of resol-type phenolic resin, polyhydric alcohol, and urea (referred to as urea, polyhydric alcohol-modified phenolic resin) is, for example, a precondensate of phenol, formaldehyde, urea, and one or more polyhydric alcohols in an alkaline catalyst. This precondensate obtained by heating in the presence of the precondensate is a water-soluble condensate, and an unreacted mixture of the resol type phenolic resin, polyhydric alcohol, and urea may remain therein. Phenol (P), urea (U), and formaldehyde (A) used in the production of this precondensate have a molar ratio of A/(P+U).
It is preferable to react at a ratio of 1.2 to 3.0. If the proportion of polyhydric alcohol in the polyhydric alcohol-modified phenolic resin or urea-polyhydric alcohol-modified phenolic resin is too small, the restorability of the resulting inorganic fiber mat will decrease; on the other hand, if the proportion of polyhydric alcohol is too high, The tensile strength of the inorganic fiber mat decreases, and the polyhydric alcohol component that does not participate in the crosslinking reaction remains in the cured resin and has a hygroscopic effect, so if left in hot and humid conditions for a long time, the inorganic fiber mat will recover. This is undesirable because the properties of the inorganic molded product such as the glass wool heat-insulating tube may deteriorate, or the dimensions such as the outer diameter and inner diameter of the inorganic molded product such as the glass wool insulation cylinder may change. Therefore, the modification ratio of the polyhydric alcohol is 4 to 60 parts by weight, preferably 5 to 50 parts by weight, per 100 parts by weight of the raw materials (phenol + urea). The modification ratio of urea is 150 parts by weight or less, preferably 100 parts by weight or less, based on 100 parts by weight of phenol as a raw material. In the present invention, it is preferable to use an aqueous binder containing a polyhydric alcohol-modified phenolic resin or a urea-polyhydric alcohol-modified phenolic resin as described above. Aqueous binders containing resins, polyhydric alcohols, and urea can also be used. For example, the resol type phenolic resin contains phenol and formaldehyde, preferably in a molar ratio of 1:1 (1.5 to 1:1).
3.0) by heating in the presence of an alkaline catalyst. This resin is a water-soluble condensate, and the ratio of resol type phenol resin (non-volatile content according to JISK6909), polyhydric alcohol, and urea in the aqueous binder is 100%, and the polyhydric alcohol is 5 to 5%. 45% by weight, preferably 10 to 30% by weight. The reason is the same as in the case of polyhydric alcohol-modified phenolic resin. Furthermore, an aqueous binder containing a resol type phenolic resin and a polyhydric alcohol-modified phenolic resin can also be used. In this case, if you want to change the content of the polyhydric alcohol component in the binder depending on the type of product, you can change the ratio of resin to resin and mix it. It is not necessary to prepare many different types of resin, and it is extremely useful industrially. Furthermore, an aqueous binder whose main component is a composition consisting of a mixture containing a polyhydric alcohol-modified phenolic resin and a polyhydric alcohol, or a composition consisting of a mixture containing a urea polyhydric alcohol-modified phenolic resin and a polyhydric alcohol can be used. In this case, the amount of polyhydric alcohol added is the total amount of this and the polyhydric alcohol content in the polyhydric alcohol-modified phenolic resin (or urea-polyhydric alcohol-modified phenolic resin). The amount is preferably within a range of 545% by weight based on the total amount of the polyhydric alcohol-modified phenolic resin) and the polyhydric alcohol to be added. Further, as the main component composition of the aqueous binder, a mixture of a resol type phenolic resin, a precondensate of urea (referred to as urea-modified phenolic resin), and a polyhydric alcohol can be used. Urea-modified phenolic resin is obtained, for example, by heating phenol, formaldehyde, and urea. At this time, phenol and formaldehyde are reacted at a molar ratio of 1:1 (1.5 to 3.0), and 150 parts by weight or less, preferably 100 parts by weight or less of urea is added to 100 parts by weight of phenol. The mixing ratio of the urea-modified phenolic resin and the polyhydric alcohol is 5 to 45% by weight, preferably 10 to 30% by weight of the total. Furthermore, an aqueous binder whose main component is a composition consisting of a mixture containing a urea-polyhydric alcohol-modified phenolic resin and urea, or a composition consisting of a mixture containing a polyhydric alcohol-modified phenolic resin and urea can also be used. In urea/polyhydric alcohol-modified phenolic resin, the urea reacts with the resol type phenol resin and binds together, so the cured resin product is lower than when the same amount of urea is added later to the resol type phenol resin. It is possible to form a cured resin product with extremely little uneven distribution of urea and a uniform composition. The permissible amount of urea added to urea polyhydric alcohol-modified phenolic resin (or polyhydric alcohol-modified phenolic resin) is that the total amount of urea in the urea/polyhydric alcohol-modified phenolic resin and post-added urea is up to 60% of the total resin. up to % by weight. Addition (or modification) of urea is advantageous for reducing the cost of the binder. It is also possible to mix urea polyhydric alcohol modified phenolic resin with a conventional resol type phenolic resin, or mix two or more types of urea/polyhydric alcohol modified phenolic resin modified with different types of polyhydric alcohols. It is also possible to use The polyhydric alcohol in the present invention has 2 to 9 alcoholic hydroxyl groups, and for example, at least one of the compounds listed below can be used. Namely ethylene glycol, propanediol, butanediol, hexanediol,
Diols such as heptanediol, octanediol, dodecanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, neopentyl glycol, polyethylene glycol and polypropylene glycol with a molecular weight of 100 to 20,000, preferably 200 to 8,000, general formula HOCnH ₂ nOH (n=3
~10) 1 to 10 pieces at one end or both ends of the diol,
Preferably, those having 1 to 7 alkylene oxide chains such as ethylene oxide chains and propylene oxide chains, triols such as propanetriol, butanetriol, and trimethylolpropane, tetraols such as pentaerythritol, and pentites such as adonite. , hexites such as sorbitol, mannite, polyhydric alcohols obtained by reducing other monosaccharides, propanetriol, trimethylolpropane, pentaerythritol, adonite, sorbitol, inositol, etc. The hydroxyl group of polyhydric alcohols has the general formula -(
ClH ₂ lO) - _o (l is an integer of 1 to 6, n is an integer of 1 to 7), and especially the following formula: (In the formula, l is an integer of 1 to 6, n1 to _n are each independently an integer of 0 to 7, and at least two of them are integers of 1 or more, and m is an integer of 3 to 9. ) Among the polyhydric alcohols represented by the above formula, compounds in which 2n1 to n _n is preferably 1 to 5 can be used, and these compounds can be used alone or as a mixture. Urea can also be added to the aqueous binder in the present invention in order to reduce costs.
The amount of urea added is preferably up to 50% by weight of the total resin content. Components that may be added to the aqueous binder in the present invention include ammonium sulfate as a coloring agent, aminosilane as a coupling agent, and mineral oil as a fiber lubricant. The appropriate resin concentration in the aqueous binder is 1 to 30.
Weight%. The inorganic fiber products of the present invention can be produced by, for example, flame method,
It is obtained by spraying the above-mentioned aqueous binder onto inorganic short fibers produced by a centrifugal method or the like, and heating the inorganic short fibers to harden the resin. When the composition contained in the aqueous binder is heated, a condensation reaction proceeds and the resin solids contained in the inorganic fiber product (resol-type phenol resin and polyhydric The amount of alcohol or alcohol derived from a precondensate thereof, or a resol type phenolic resin, polyhydric alcohol, urea, or a precondensate thereof) is 2 to 25% by weight. The inorganic fiber products of the present invention, such as short glass fiber pine products, have excellent recovery properties, and the short glass fiber insulation tubes have the characteristics of being hard to break and crack. These properties will not deteriorate even if left under these conditions for a long time. The reason why such an effect can be obtained by the present invention is considered as follows. Strong stress occurs in the glass fibers that make up short glass fiber mats compressed to 1/3 to 1/10, but because conventional binder resins have high hardness, the glass fibers are bonded together very hard with the resin. It is thought that the glass fibers cannot withstand the stress and break near the bonding point. However, according to the present invention, by using a polyhydric alcohol-modified phenolic resin (or a urea-polyhydric alcohol-modified phenolic resin), the cured binder material of the glass fiber mat remains flexible even when stress is generated during compression. Since stress is not concentrated in the vicinity of the bonding point and stress is evenly distributed, the glass is less likely to break and is considered to have excellent restorability when unpacked. Furthermore, regarding the short glass fiber heat-insulating cylinder of the present invention,
When an external bending force is applied to this, stress concentration near the bonding point does not occur, making it difficult for the glass fiber to break.
Therefore, the heat insulating cylinder is prevented from breaking and cracking. Another example of the inorganic fiber product of the present invention is a glass cloth with a binder impregnated with an aqueous binder containing the above composition as a main component and then cured. When compared with the binder-attached glass cloth, it became clear that the binder-attached glass cloth of the present invention had better flexibility. This excellent flexibility helps improve workability during FRP manufacturing. Furthermore, it was found that the resin coating film on the surface of each fiber of the inorganic fiber product of the present invention exhibited superior boiling resistance compared to conventional ones, as shown in the test examples described below. The role of the binder is to firmly bind the glass fibers at their intersections and to maintain the bond, so the above results demonstrate that the binder used in the present invention is excellent as a binder for glass fibers. . The remarkable effects of the binder of the present invention have been explained using glass fibers as an example, but when applied to inorganic fibers other than glass fibers, such as rock wool and asbestos, the above-mentioned moderate flexibility and strong adhesion with inorganic fibers can also be achieved. Depending on its properties, it can provide many advantages, such as preventing the product from bending or cracking and preventing changes in the dimensions of the molded product over time. Next, the present invention will be further explained with reference to Examples, Test Examples, and Comparative Examples, but the present invention is not limited to these Examples. Example 1 For 1000 grams of phenol, 1725 grams of formaldehyde (37%), 2000 grams of ethylene glycol
80 parts by weight of ethylene glycol-modified resol type phenolic resin (calculated as non-volatile content), 20 parts by weight of urea, and water by adding 60 grams of 25% aqueous sodium hydroxide solution in a proportion of 25% by weight and heating at 60°C for 6 hours while stirring and mixing. Further, commonly used subcomponents such as ammonium sulfate and aminosilane were mixed to prepare an aqueous binder having a resin solid content concentration of 8%. Next, the glass melted in the melting furnace is flowed down from a nozzle in the form of a filament, and a flame is injected from the side to blow the molten glass into fibers. The binder is sprayed, and the glass fibers are then collected on a belt conveyor having a mesh that moves perpendicularly to the direction of movement of the glass fibers.
℃ for 2 minutes to form a mat. Further, the fibers collected on the belt conveyor were wound into a core rod shape, and passed through a heating furnace to form a heat-retaining tube. Table 1 shows the results of measuring the restoration properties of the mats and insulation tubes produced in this way, the breakage of the insulation tubes immediately after manufacture, and the breakage of the insulation tubes after being left in hot and humid conditions for a long period of time. The amount of ethylene glycol-modified resol type phenol resin contained in the mat and the heat-insulating cylinder is about 6% by weight based on the mat and the heat-insulating cylinder. For comparison, samples manufactured using a conventional phenolic resin binder (containing urea at 20% of the total resin) and an aqueous binder in which 22% by weight of polyacrylic acid ester as a thermoplastic resin was added to the conventional binder were also examined. A similar test was conducted and the results are also listed in Table 1.

[Table] The test results for Restorability 1 are 20cm each in length and width.
A sample with a thickness of 8 cm and a weight of 20 grams was compressed to a thickness of 5 mm and held for two weeks, then uncompressed and a sample of 100 g was placed on top of it.
It shows the thickness when measured with a plastic plate of grams placed on it. In addition, resilience 2 is 20% in both vertical and horizontal directions.
A sample of 20g, 8cm thick and 20g was compressed to a thickness of 5mm and kept in a constant temperature and humidity chamber set at 50℃ and 95% relative humidity for 2 weeks, then released from the compression and made into a 50g plastic plate. It shows the thickness when measured by placing it on top. In addition, the test results for thermal insulation cylinder bending 1 were obtained by creating a thermal insulation cylinder with an inner diameter of 34 mm, a wall thickness of 20 mm, a density of 55 kg/m ³ and a length of 1 m, holding both ends in your hands and bending it at a right angle, and then checking the results according to the following criteria. I judged it. ◎……No cracks needed at all. 〇...There is a small crack. △...There is a big crack. Regarding thermal insulation tube bending 2, make the same thermal insulation tube as above, keep it in a constant temperature and humidity chamber set at 50℃ and 95% relative humidity for 2 weeks, then hold both ends in your hands and bend it at right angles, and then fold the thermal insulation tube. Judgment was made using the same criteria as the test for fold 1. Example 2 1000 grams of phenol, formaldehyde (37
%), 100 grams of 1,4-butanediol, and 60 grams of 25% sodium hydroxide aqueous solution were added and heated at 60℃ for 7 hours while stirring to form a 1,4-butanediol-modified resol type phenolic resin. Obtained. Separately, 60 grams of a 25% aqueous sodium hydroxide solution was added in a ratio of 1,000 grams of phenol, 1,900 grams of formaldehyde (37%), and 250 grams of diethylene glycol, and the mixture was stirred and mixed at 60°C.
A diethylene glycol-modified resol type phenol resin was obtained by heating for a period of time. Next, 40 parts by weight of the thus obtained 1,4-butanediol-modified resol type phenolic resin (in terms of non-volatile content), 40 parts by weight of diethylene glycol-modified resol-type phenolic resin (in terms of non-volatile content), 20 parts by weight of urea, and A binder having a concentration of 8% was prepared by mixing the subcomponents described in Example 1, and after molding a glass fiber mat and a heat-insulating tube, the restorability and bending of the heat-insulating tube were measured. The results were as shown in Table 1. Example 3 For 1000 grams of phenol, 1725 grams of formaldehyde (37%), 100 grams of ethylene glycol, and 100 grams of diethylene glycol were added at a ratio of 25
% aqueous sodium hydroxide solution was added and heated to 60° C. for 6 hours while stirring to obtain an ethylene glycol- and diethylene glycol-modified resol type phenolic resin. 80 parts by weight of this resin (in terms of nonvolatile content), 20 parts by weight of urea, and the subcomponents described in Example 1 were mixed to prepare an aqueous binder having a concentration of 8%. After forming a glass fiber mat and a heat-insulating tube using this binder, the restorability and bending of the heat-insulating tube were measured. The results were as shown in Table 2. Example 4 Type of polyhydric alcohol and denaturation ratio (phenol

[Table] The parts by weight of polyhydric alcohol per 100 parts by weight of alcohol are as shown in Table 3. The polyhydric alcohol-modified resol type phenol resin and urea described in the present invention are mixed in the proportions shown in Table 3, Furthermore, Example 1
An aqueous binder having a concentration of 8% was prepared containing the subcomponents described in . After molding a glass fiber mat and a heat-insulating cylinder using the aqueous binder, the restorability and bending of the heat-insulating cylinder were measured, and the results are shown in Table 3. Example 5 A polyhydric alcohol was mixed with the conventionally used phenolic resin and urea in the proportions listed in Table 4, and the subcomponents listed in Example 1 were added to give a concentration of 8.
% of aqueous binder was adjusted.

【table】

[Table] Next, a glass fiber mat and a heat-insulating cylinder were formed in the same manner as in Example 1, and the restorability and bending of the heat-insulating cylinder were measured. The results are shown in Table 4. Example 6 Conventionally used resol type phenolic resin
20 parts by weight (in terms of nonvolatile content), 60 parts by weight of the diethyl glycol-modified resol type phenolic resin described in Example 2 (in terms of nonvolatile content), 20 parts by weight of urea.

[Table] An aqueous binder having a concentration of 8% was prepared by mixing the subcomponents described in Section 1 and Example 1, and after molding a glass fiber mat and a heat-insulating cylinder, the restorability and bending of the heat-insulating cylinder were measured. The results were as shown in Table 5. Example 7 Formaldehy for 1000 grams of phenol

[Table] Do (37%) 1725 grams, ethylene glycol 200
Add 80 grams of 25% sodium hydroxide aqueous solution at a ratio of 1.5 grams, mix with stirring, and gradually raise the temperature until the liquid temperature reaches
After reaching 65℃, lower the liquid temperature to 60℃ and add urea.
400 grams were added, heated and stirred to obtain a urea ethylene glycol modified resol type phenolic resin. 95 parts by weight of this resin (converted to non-volatile content)
5 parts by weight of urea and the subcomponents described in Example 1 were mixed to prepare a binder having a concentration of 8%. After forming a glass fiber mat and a heat-insulating tube using this binder, the restorability and bending of the heat-insulating tube were measured. The results were as shown in Table 6.

[Table] Example 8 The second component shown in Table 7 was added to the urea ethylene glycol modified phenol resin described in Example 7, and the urea and the subcomponents described in Example 1 were further mixed to give a concentration of 8%. Adjusted the binder. After forming a glass fiber mat and a heat-insulating tube using this binder, the restorability and bending of the heat-insulating tube were measured. The results are also listed in Table 1. As is clear from the test results shown in Tables 1 to 7, the glass fiber mat of the present invention has superior resilience compared to the glass fiber mat manufactured using a conventional binder, and the heat insulating tube can be bent easily. broken or large

[Front] There will be no cracks. Furthermore, compared to glass fiber mats and heat insulating tubes manufactured using a binder containing a thermoplastic resin as described in Japanese Patent Application No. 56-46853, the recovery performance when left in high temperature and humid conditions is excellent. A remarkable improvement effect on resistance to breakage is observed. Example 9 An aqueous binder with a concentration of 35% by weight was prepared by using the three types of polyhydric alcohol-modified resol type phenolic resins described in Examples 1 and 2 and the conventional resol type phenolic resin and adding the subcomponents described in Example 1. adjusted. The aqueous binder was uniformly impregnated into a glass cloth (Micro Glass Cloth EH18 manufactured by Nippon Glass Fibers) and heated and cured at 200°C for 5 minutes so that the resin adhesion was 25 ± 1% by weight based on the weight of the glass cloth. Table 8 shows the results of measuring the bending resistance of the test pieces adjusted to

[Table] The bending resistance of the test piece formed from the aqueous binder using the polyhydric alcohol-modified resol type phenolic resin described in Examples 1 and 2 is clearly compared to that when a conventional resol type phenolic resin is used. It was found that this resin and the glass cloth to which it was attached had excellent flexibility. Test Example Example 1 using the three types of polyhydric alcohol-modified resol type phenolic resins described in Examples 1 and 2.
An aqueous binder with a concentration of 50% was prepared by adding the subcomponents described in . The aqueous binder has a thickness of 3
It is coated on an ordinary glass plate with a width of 2.5 cm, a width of 2.5 cm, and a length of 10 cm using the dipping method, and heated in a hot air circulation dryer at 200°C for 15 minutes to harden the binder and obtain a homogeneous coating film with a thickness of approximately 6 microns. Ta. This coated glass plate was immersed in boiling water, taken out after a predetermined period of time, dried at room temperature for 24 hours, and then cut into 100 squares by cutting 11 parallel lines vertically and horizontally at 1 mm intervals on the surface of the coating using a knife. After cross-cutting the eyes and adhering a cellophane adhesive tape thereon, the tape was peeled off and the adhesion was evaluated by indicating the number of coatings that did not peel off among 100 squares of coating film. The results were as shown in Table 9. For comparison, a similar experiment was conducted on a sample made using a conventional binder (containing urea at 20% of the total resin content), and the results are also listed in Table 9.

[Table] As is clear from Table 9, the coating film obtained using the binder of the present invention maintained strong adhesive strength even after boiling.

Claims (1)

[Scope of Claims] 1. A composition comprising a mixture and/or precondensate containing a resol type phenolic resin, an aliphatic polyhydric alcohol, and urea, the mixture comprising:
(Resol type phenolic resin + polyhydric alcohol +
The precondensate contains 5 to 45% by weight of polyhydric alcohol based on the total amount of urea), and the precondensate is prepared by adding 4 to 60 parts by weight of polyhydric alcohol to 100 parts by weight of (phenol + urea). An inorganic fiber product obtained by applying and curing an aqueous binder whose main component is a composition obtained by reacting with inorganic fibers. 2. The inorganic fiber product according to claim 1, wherein the polyhydric alcohol has 2 to 9 alcoholic hydroxyl groups. 3. The inorganic fiber product according to any one of claims 1 to 2, wherein the composition is contained in a solid content of 2 to 25% by weight based on the inorganic fiber product. 4. The inorganic fiber product according to any one of claims 1 to 3, wherein the inorganic fiber is a glass fiber.