JPS5983988A - Inorganic fiber product - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to inorganic fiber products, inorganic long fiber woven fabrics, and other products that are mainly used as thermal insulation and sound absorption in buildings, etc. A special binder composition for the purpose of producing inorganic fiber products.

Inorganic staple fiber products used as insulation and sound absorbing materials are short inorganic fibers such as short glass fibers and rock wool, combined with thermosetting + 1° resin liquid or an aqueous colloid of bolic acid (called a binder). f'J' H, then 'l (
7) Produced by adding inorganic short fibers containing an inder and curing them with a single binder.

1. In the following, glass fiber will be explained as an example of inorganic taAll, but the application of the present invention is limited to glass fiber.
F.

Conventionally, glass fiber product binders have been used, for example, in the form of phenol-monomaldehyde condensates (referred to as resol-type phenolic resins). Used as short fiber matte insulation material for houses1
After manufacturing the glass fiber cloak, the volume of the heat insulating material is reduced to 1/3 to 1/ of the original volume in order to reduce Nli shipping costs.

It is packed and transported in a compressed state, and when it is unpacked at
There is a necessary force t to exhibit a predetermined heat insulation performance. However, +7
The short glass fiber mat using a conventional inder had poor recovery properties, and was unable to meet the requirements for 11 minutes.

Furthermore, when using Glass Knowledge Mt in a glass wool heat-insulating tube, install the heat-insulating tube at the elbow, etc.
Ho 1? 1A There was some technique required to bend the tube, but conventional moisturizing tubes had problems such as breaking or cracking during bending.

The present inventor has developed a binder that improves the drawbacks described in 1.
It is mentioned earlier in the special application 1981-1955-Getsu-g-3.5V
A thermal binder containing at least one of a plastic resin and a synthetic rubber and a thermosetting resin was devised.

However, although short glass fiber mats and heat-insulating tubes manufactured using the binder described in 1' show improvement in resilience and bending immediately after manufacture, if left in hot and humid conditions for a long period of time, the binder described above It has been found that there is a problem in that the bonding points made of the cured product deteriorate and the effectiveness decreases.

Regarding the above-mentioned points (-), as a result of further research, the present inventor found that (1) the use of a binder whose main component is a specially modified resol type phenolic resin improves the resiliency. In addition, it was found that a glass fiber product with no breakage or cracking was obtained, and that the above-mentioned effects were maintained even if the fibers were left in hot and humid conditions for a long time.

1) That is, the present invention is a mixture containing a resol type fer/fer resin and a polyhydric alcohol and/or a precondensate. It is an inorganic fiber product.

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. It consists of the sound of rain.

Examples of this composition are as follows.

1. Mixture of resol-type phenolic resin and polyhydric alcohol 2. Mixture of resol-type phenolic resin, polyhydric alcohol and urea 3. Precondensate of resol-type phenolic resin and polyhydric alcohol 4. Resol-type phenolic resin and F-combined product 5 of polyhydric alcohol and urine, a mixture 6 in which polyhydric alcohol is added to a precondensate of resol type phenol skin fat and urine, 7 a mixture of the precondensate of 3 above and urea, A mixture 8 of the r precondensate of 3 above and a resol type phenol resin, a mixture 9 of the pre6tN condensate of 3 above and a polyhydric alcohol, a mixture 9 of the precondensate of 4 above and (a polyhydric alcohol or urea or a resol type phenol) The pre-MII condensate (polyhydric alcohol-modified phenolic resin Tomoshi-5) of resol type 7-chonort MI fat and polyhydric alcohol used as the composition which is the main component of the aqueous binder in the present invention is For example, it can be obtained by heating phenol, pormaltehyde, and alcohol. This precondensate is a water-soluble condensate,
An unresolved mixture of 1/sol type fugonol resin and polyhydric alcohol may remain in it.

The phenol and the polyaldehyde used in the production of the precondensate are preferably reacted in a molar ratio of s to 3.0.

In addition, a presynthesized product of resol-type phenolic resin, polyhydric alcohol, and urea (referred to as urea, polyhydric alcohol-modified phenol resin) is, for example, phenol, formaldehyde, urea, and seven or more types of polyhydric alcohols combined with an alkaline catalyst. This precondensate obtained by heating in the presence of a water-soluble condensate is a water-soluble condensate, and an unreacted mixture of the resol type phenol resin, polyhydric alcohol, and urea may remain therein. In the production of this precondensate, the molar ratio of phenol (P), urea (U), and formaldehyde (A) is /1.2.
It is preferable to react at a ratio of ~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 cloak decreases, and the polyhydric alcohol component that does not participate in the crosslinking reaction remains in the cured resin and has a hygroscopic effect. The resilience of the inorganic fiber mat decreases,
Alternatively, dimensions such as the outer diameter and inner diameter of an inorganic molded product such as a glass wool heat-insulating cylinder may change, which is undesirable. Therefore, the denaturation ratio of polyhydric alcohol is (phenol + urea) as raw material 7
00 parts by weight of the polyhydric alcohol, preferably 5 to SO parts by weight. The modification ratio of urea is 750 parts by weight or less, preferably 700 parts by weight or less, based on 700 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, but an aqueous binder containing a resol type phenolic resin and a polyhydric alcohol may be used. Alternatively, an aqueous binder containing a resol type phenolic resin, a polyhydric alcohol, and urea can also be used. For example, the resol type phenolic resin preferably contains phenol and formaldehyde in a molar ratio/pair (
/, j~3.0) by heating in the presence of an alkaline catalyst. This resin is a water-soluble condensate,
Resol type phenolic resin in water-based binder (JIS
The ratio of polyhydric alcohol and urea is 5 to 1, 5% by weight, preferably IO to 30% by weight, based on the total of 700%. be.

The reason is the same as in the case of polyhydric alcohol-modified phenol resin.

Furthermore, an aqueous binder containing a resol type phenolic resin (1) and a polyhydric alcohol-modified phenolic resin (Il) 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 (I) and resin (]II by mixing them, so the polyhydric alcohol content can be changed. It is extremely useful industrially because it does not require the preparation of several different types of resins (II).In addition, a composition consisting of a mixture containing a polyhydric alcohol-modified phenolic resin and a polyhydric alcohol or a urea polyhydric alcohol It is possible to use an aqueous binder whose main component is a composition consisting of a mixture containing a modified phenolic resin and a polyhydric alcohol. The total amount of polyhydric alcohol in the polyhydric alcohol-modified phenol resin (or urea-polyhydric alcohol-modified phenol resin) is the same as the total amount of the polyhydric alcohol to be added. The range is preferably such that the amount is % by weight.

Further, as the main component composition of the aqueous binder, a mixture of a resol type phenol resin, a precondensate of urea (referred to as urea-modified phenol 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 /v(/,!i~3.0),
Up to 750 parts by weight of urea is added to 100 parts by weight of phenol, preferably up to 750 parts by weight, preferably up to 1 part by weight. The mixing ratio of urea-modified phenol resin and polyhydric alcohol is 31 to 3 to 1.
3% by weight, preferably 10-30% by weight.

Furthermore, an aqueous binder whose main component is a composition consisting of a mixture containing a urea polyhydric alcohol-modified phenol resin and urea, or a composition consisting of a mixture containing a polyhydric alcohol-modified phenol resin and urea can also be used. urea·
Polyhydric alcohol-modified phenolic resin [Urea reacts with the resol type phenol resin and binds together, so the proportion of urea in 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 allowable amount of urea added to urea polyhydric alcohol-modified phenolic resin (or polyhydric alcohol-modified phenolic resin) is the total amount of urea in the urea/polyhydric alcohol-modified phenolic resin and post-added urea. The maximum content is 60% by weight. Addition (or modification) of urea is advantageous for reducing the cost of the binder. It is also possible to mix conventional resol type phenol horse chestnut resin with urea polyalcohol modified phenol resin, and use it by mixing urea polyalcohol modified phenol resin with different types of polyhydric alcohol! It is also possible to use a mixture of urea/polyhydric alcohol-modified phenol resins of the following types.

The polyhydric alcohol in the present invention has 2 to q alcoholic hydroxyl groups, and at least one of the compounds listed below can be used, for example. Namely, ethylene glycol, propanedimer, butanediol, hexandiol, hebutanediol, mectanediol, dotecandimer, dielene glycol, dipropylene glycol, triethylene glycol, l-
Librobylene glycol, neopentyl glycol, molecular kick 100~. 20000, preferably 200~go
Diols such as polyethylene glycol and polypropylene glycol, general formula HOCnH2nOH (n
= 7 to 10) at one or both ends of the diol
, preferably 7 to 7 ethylene ogicide chains.

Globylene t = t- (examples of alkylene oxide chains such as J-ide chains), triglycerols such as propanetriol, butanetriol, l-rimethylolpropane, and tetraols such as hentaerythritol. , pentites such as atonite, hexants such as sorbitol, mannitol, and other polyhydric alcohols obtained by reduction of carcinoses, probanto-ruatrimethylolpropane, pentaerythritol, adonisotho, sorbitol, ionto・A component represented by the general formula % formula % integer) is added to the hydroxyl group of the polyhydric alcohol of Lehaku. (independently an integer of 0 to 7, at least two of which are integers of 7 or more, and m represents an integer of 3 to 9), preferably a polyhydric alcohol represented by the above formula, where l is 1! n1~
Compounds in which nll+ is / to 3' can be used, and these compounds can be used alone or as a mixture.

Urea may be added to the aqueous binder medium of 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 content in the aqueous binder is 7-30% by weight.
It is.

The inorganic fiber product of the present invention can be obtained by spraying the aqueous binder described in 14 onto inorganic short fibers produced by, for example, the flame method + +g right heart method, and heating the inorganic short fibers to harden the resin. When the composition contained in the aqueous bindu is heated, a condensation reaction progresses and the resin solid content contained in the inorganic fiber product (resol type phenol) changes into a resin solid with a high degree of condensation. Resin and polyhydric alcohol or those derived from these precondensates, or resol type phenol (fats, polyhydric alcohols, urea, or those derived from these precondensates) are 2 to 23% by weight.

The inorganic fiber products of the present invention, such as short glass fiber mantle 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 to be as follows.

//3~//10 Strong stress occurs in the glass fibers that make up the compressed short glass fiber mat, but since conventional binder resins have high hardness, the glass fibers are bonded 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, polyhydric alcohol-modified phenolic resin (
By using glass fiber mats (or urea polyhydric alcohol modified phenolic resins), even if stress occurs during compression, the cured binder has flexibility, so stress does not concentrate near the bonding points and the stress is reduced. It is thought that because the glass is dispersed in a uniform manner, the glass is less likely to break and has excellent restoring properties when unpacked.

Also, regarding the heating tube made of short glass fibers of the present invention, when an external bending force is applied to it, stress concentration near the bonding point does not occur and the glass fibers are less likely to break.
This prevents cracking and cracking.

Another example of the inorganic fiber product of the present invention is Binder N glass cloth, which is impregnated with an aqueous binder containing the above composition as a main component and then cured. When compared with a glass cloth with a binder, it was found that the glass cloth with a binder 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.''--These results demonstrate that the Nokuingu used in the present invention is excellent as a binder for glass fibers. It shows.

The remarkable effects 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 bond with inorganic fibers can also be achieved. Adhesive properties can provide many advantages, such as preventing the product from folding 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 / Formalde A hit' (37%) /7.2 per 1000 grams of phenol! ; Crumb, 2000 grams of ethylene glycol at a rate of 2! Add 10 grams of % sodium hydroxide aqueous solution and mix with stirring.
Parts by weight of ethylene glycol-modified resol type phenolic resin (converted to non-volatile content) obtained by heating at 'C for an hour.
urea,! 0 parts by weight, water, and commonly used mlJ components such as ammonium sulfate and aminosilane were mixed to prepare an aqueous binder having a resin solid content concentration of g%.

Next, the glass melted in the melting furnace is flowed down in the form of a filament from a nozzle, and a flame is injected from the side to blow the molten glass into fibers. The binder was sprayed and the glass fibers were then molded without moving in a direction perpendicular to the direction of travel thereof. Further, the m-silk collected on the belt conveyor was wound into a core frame shape, and this was passed through a heating furnace to be formed into a heat-retaining cylinder.

The results of measuring the restorability of the mats and heat retaining tubes manufactured in this way, the breakage of the heat retaining tubes immediately after manufacture, and the breakage of the heat retaining tubes after being left in hot and humid conditions for a long period of time are as shown in the table. The amount of ethylene glycol-modified resol type phenolic resin contained in the mat and heat insulation cylinder is
Approximately 1% by weight for the heat-insulating cylinder.

For comparison, we also used a conventional phenolic resin binder (containing urea at 0% of the total resin) and a conventional binder with polyacrylic acid ester as a thermoplastic resin.
．． A similar test was conducted on a sample prepared using an aqueous binder added at 2 weights, and the results are also shown in the table.

In addition, the test results for resiliency (/n) are longitudinal, examiner, 2 oam
.

Compress a sample with a thickness of 20 grams and a weight of 20 grams to a thickness of 5 mm! The thickness is measured by releasing the compression after holding it for a week and placing a 100 gram plastic plate on top of it. Also, the resilience (,?) is vertical.

The thickness of the sample was measured by holding it in a constant humidity chamber for 3 weeks, releasing the compression, and placing a SO Gram plastic plate on it.

In addition, the test result for quality failure (1) was that the inner diameter was 311 mm.
.

A heat-insulating tube with a wall thickness of 2Q mm and a density of s s Kg/m3 + length of 7 m was made into a heat-insulating cylinder, held in both hands and bent at a right angle, and the results were judged according to the criteria listed above.

◎・・・・・・・・・No cracks required○・・・・・・
・・・There is a small crack △・・・・・・For the broken insulation tube (2) where there is a large crack, we made the same insulation tube as above and heated it to 3゛0℃2...95% relative humidity. After keeping it in a constant temperature and humidity chamber for 2 weeks, hold both ends and bend them at right angles.
The results were judged according to the same criteria as in the test for thermal insulation tube bending (1).

Example 7000 grams of nophenol, formaldehyde (37%
)2/3! 23% hydroxide in the proportion of 700 grams of goubutanediol) IJum aqueous solution 10
Add grams and heat at 0°C for 17 hours while stirring/mixing/41! - A butanediol-modified resol type phenolic fat was obtained.

In addition to the kneading, 7000 grams of phenol, 900 grams of formaldehyde (37%), and diethylene glycol
) L,, 60 g of 2S% sodium hydroxide aqueous solution was added at a ratio of 230 g, and while stirring and mixing, the mixture was heated to θ°C,
The mixture was heated for an hour to obtain a diethylene glycol-modified resol type phenol resin.

Next, the thus obtained / l-butanedimer-modified ZoA type phenolic resin lI0 parts by weight (in terms of non-volatile content)
, diethylene glycol-modified resol type phenolic resin tI0 parts by weight (in terms of non-volatile content), urea,! 0 parts by weight and the subcomponents described in Examples were mixed to prepare a binder with a concentration of g%, 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 the table.

Example 3 Formaldehyde (3
7%) /72! ; grams, ethylene glycol 700
grams, diethylene glycol at the rate of 700 grams 2
Add 60 grams of IJum aqueous solution (S% hydroxide) and mix while stirring! A resol-type phenolic resin modified with ethylene glycol and diethylene glycol was obtained by heating for a certain period of time. Parts by weight of this resin (converted to non-volatile content)
An aqueous binder having a concentration of g% was prepared by mixing urea, 20 parts by weight, and the subcomponents described in Examples. After shaping and crinkling a glass fiber cloak 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 the table.

Example Type and denaturation ratio of polyhydric alcohol (by mixing the subcomponents listed in Table 4 and Actual example), the concentration is j%.
After preparing the aqueous binder and forming 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 the table.

Example 7 Formaldehyde (37%) per 1000 grams of phenol /72! ; Add 2S% sodium hydroxide aqueous solution go dulam in a ratio of 200 grams, ethylene glycol, and stir, mix and gradually raise the temperature until the liquid temperature reaches 4j'C, then lower the liquid temperature to 60°C. Then, 1 Ioo g of urea was added thereto, followed by heating and stirring to obtain a urea ethylene glycol modified resol type phenol resin. 95 parts by weight of this resin (nonvolatile fraction n), 3 parts by weight of urea, and the subcomponents described in Examples/are mixed to form a binder with a concentration of g%! I arranged it. After forming a glass fiber mat and a heat-retaining cylinder using this binder, the restorability and bending of the heat-retaining cylinder were measured.

The results were as shown in Table 6.

Adding the two ingredients shown in Table 7, Further, the subcomponents described in the urine memo and Examples were mixed to prepare a binder of 9%.

After forming a lIt''J string mat and a heat-insulating cylinder using this binder, the culm origin property and the bending of the retaining cylinder were measured;
! Shita.

Old! 1! should also be written on the O table.

As is clear from the test results shown in Table 1, the 1.11 zihong (manto) of Mokkomei was compared with the 1118 zihong fiber made using the binder of J. 31. τ-(U original 1'k K Excellent, the heat insulating tube can be bent and folded.
There will be no thick or thick cracks.

Furthermore, Bogansho S! Compared to glass fiber mats and heat-retaining cylinders manufactured using a binder containing a thermoplastic resin as described in Section 3, recovery performance when left in particularly hot and humid conditions, 4J −? A remarkable improvement effect was observed in terms of the difficulty of leaking.

Example 9 Three types of multi-4■1 alcohol-denatured resol type phenolic fats and conventional resol 2 (
11 phenol (using momme fat and adding the subcomponents described in Example/) to make a concentrated IJL3j weight% water 11 binder!<
1j'4 I fixed it. The aqueous binder is coated with glass cloth ([1 glass fiber microglass cloth El/Za])
The glass cloth was uniformly impregnated with glass cloth and heat-cured for 1j minutes at 200°C. Complete set? The results of measurements 1-7 of the hard and soft J using a soft J↓L testing machine (manufactured by Toyo Ni? 1 Co., Ltd.) are shown in the table below.

Table 2.
The bending resistance of the test piece formed from a water-based binder using RJ resin with Qphenol resin was higher than that of conventional resol type phenol resin.
It was clearly smaller than when a glass resin was used, and from this fact it was found that this resin and the glass cloth to which it was applied had deformed flexibility.

Test Example Using the polyhydric alcohol-modified resol type phenol resin of 3-non-Φ type described in Example/Ω, and adding the subcomponents described in Example/? A 3'0% aqueous binder was prepared. The thickness of the aqueous binder was 3 mm.

IIJ 2. ．． 8'C+n, coated on a 100m long ordinary glass plate by dipping method and heated to 200m in a hot air circulation dryer.
The binder was cured by heating at 15°C for 15 minutes to give a homogeneous coating approximately 6 microns thick.

This coating film (J glass plate was boiled for 11 minutes with KZi blue in water, taken out after a predetermined period of time, dried at room temperature for 211 FIils, and then parallel lines of wood were drawn on the surface of the coating film vertically and horizontally at mm intervals. After applying cellophane adhesive tape to 700 squares [1', l-Cross Horned Shisono'], peel off the tape and remove the coating film of 100 squares [1', 7
), the adhesion ff was evaluated by 8 degrees by indicating the number of pieces without weak parts.

The results were as shown in Fang Jiu table.

For comparison, a sample made using a conventional binder (containing urea at 20% of the total resin content) had similar results! I did a negative test and recorded the results on the Fangji table.

As is clear from the graph, the coating coated with the binder of the present invention retained strong adhesion even after boiling at 1°C.

Claims (1)

[Scope of Claims] (Co) An aqueous binder whose main component is a composition consisting of a mixture and/or precondensate containing a resol type phenol resin, a polyhydric alcohol, and (6) is applied to inorganic fibers and cured. Inorganic fiber products.
(W) (2) The composition is a mixture containing a resol-type phenolic resin, a polyhydric alcohol, and urea and/or a predetermined composition.
? The inorganic fiber product (3) according to claim 1 comprising a precondensate, wherein the precondensate contains a polyhydric alcohol (
The inorganic fiber product (4) according to claim 1 or 2, which is obtained by adding 7 to 10 parts by weight to 700 parts by weight of phenol + urea). The inorganic material according to claim 1 or 2, wherein the polyhydric alcohol is contained in an amount of j-4'j% by weight based on the total of fat-breaking polyhydric alcohol + urea). Textile product The number of alcoholic hydroxyl groups in the polyhydric alcohol is 2 to 9.
The inorganic fiber product according to claims 1 to q, wherein the composition has a solid content of 2.
Claims 1 to j containing ~25% nail amount
The inorganic fiber product described in Claims δ′ [the inorganic fiber product described in Claims 1 to 2], wherein the inorganic fiber is glass fiber