JPS6155176A - Binder for glass fiber - Google Patents

Abstract

PURPOSE:To reduce the quantity of a volatile component which is evaporated and lost during curing with heating, by blending hexamethylenetetramine with a binder for glass fiber, which is mainly composed of a resol type (modified) phenolic resin. CONSTITUTION:A resol type phenolic resin and/or a resol type modified phenolic resin (A) (e.g. amino compd.-modified phenolic resin or polyhydric alcohol- modified phenolic resin), 0.5-25wt% (based on the quantity of component A) hexamethylenetetramine (B), water (C) and pref. not more than 50wt% (based on the quantity of component A) urea (D) are mixed together to obtain the desired binder for glass fiber. The binder is suitable for use as a binder which is used in molding short glass fiber into a mat or pipe.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to pine goo for glass fibers, in particular short glass fibers. More specifically, the present invention relates to a binder for glass fibers that has a small amount of volatile components that evaporate during heating and curing.

BACKGROUND OF THE INVENTION Matte fibers made of short glass fibers are widely used as heat-insulating and sound-absorbing materials for buildings, etc. Generally, short glass fiber mats are made by discharging molten glass through pores, blowing it away using centrifugal force, flame, high pressure air, steam, etc. to make short fibers, spraying the formed short fibers with a binder for glass fibers, and then heating them in a heating furnace. It is manufactured by curing the binder by heating it inside.

Conventionally, as a binder, for example, an aqueous binder whose main components are resol type phenol, formaldehyde resin and urea, or a water-based binder whose main component is a resol type amino compound modified phenol-formaldehyde resin modified with an amino compound such as urea has been used. It's here.

However, when this type of binder is heated and cured in a heating furnace, there is a large amount of volatile components that evaporate. Therefore, the yield of the binder, that is, the solid content derived from the binder remaining in the cured glass fiber mat relative to the solid content in the binder, is high. The disadvantage is that the proportion of

As one solution to overcome these drawbacks,
For example, increasing the degree of polymerization of phenolic resin and thereby reducing the amount of volatile components is considered, but in this case, the water solubility of phenolic resin decreases, resulting in a new deterioration of storage stability of phenolic resin. occurs, making it difficult to put it into practical use.

On the other hand, in Japanese Patent Publication No. 45-35.825, 97-3
A bonding composition for matted mineral fibers consisting of % by weight of resol resin, 3 to 97 M of novolac resin, and hexamethylenetetramine of 8 to 16 parts i-1 to the novolak resin has been opened.

This bonding composition is characterized by the fact that the mixture of novolac resin and resol resin exhibits good fluidity before curing, so that it flows up to the joints of the fibers and penetrates into the crevices of the material to be treated, while after curing it is strong. It has the feature of forming a bond (% Publication No. 45-35825, column 3, 10-
See lines 14 and 26-33, etc. Since the novolak resin contained in this bonding composition does not cure by itself even when heated, the composition contains hexamethylenetetramine as a curing agent for the novolac resin at a weight ratio of 8 to 16% by weight relative to the novolac resin. Contains by weight.

9 Problems to be Solved by the Invention The present inventor has solved the drawbacks of conventional binders for glass fibers, which have a large amount of volatile components and low yields, and has developed a new binder that has a completely different composition from conventional binders for glass fibers. As a result of extensive research in order to provide a binder for glass fibers, we surprisingly found that when we mixed hextemethylene tetone with a resol-type phenolic resin that cures simply by heating and does not require a curing agent for curing. It was discovered that a binder for glass fibers with a small amount of volatile components during heating and a high yield can be obtained, and the present invention was developed.

Means and Effects for Solving the Problems According to the present invention, as the broadest concept of the present invention, there is provided a binder for glass fibers containing a resol-type phenolic resin or a resol-type modified phenolic resin and hexamethylenetetramine.

For resol type phenolic resin, for example, formaldehyde sources such as formaldehyde and paraformaldehyde are mixed in a range of 1.5 to 1.5 to 1 mole of phenol in terms of formaldehyde.
3.0 mol, and heating these at a temperature of about 40 to 60° C. in the presence of a basic catalyst for about 5 to 15 hours.

The resol-type modified phenolic resin can be, for example, a resol-type phenolic resin modified with a modifier such as an amino compound, a polyhydric alcohol, or a mixture thereof. Resol-type modified phenolic resins are called, for example, amino compound-modified phenol resins, polyhydric alcohol phenol resins, or amino compound/polyhydric alcohol-modified phenolic resins, depending on the type of modifier.

The amino compound-modified phenol resin can be obtained by using an amino compound such as urea, melamine, or dicyandiamide in place of a part of the phenol used in producing the resol type phenol resin. Similarly, polyhydric alcohol-modified phenolic resins include polyhydric alcohols such as ethylene glycol, globylene glycol, diethylene gelcol, polyethylene glycol, polypropylene glycol, propane triol, trinotyrolpropane, and pentaerythritol to produce resol type phenolic resins. It can be obtained by replacing part of the phenol used in the production. Amino compound/polyhydric alcohol-modified phenolic resin can be produced by replacing part of the phenol in I[ with an amino compound and a polyhydric alcohol.

In either case, the amount of amino compound-containing polyhydric alcohol is less than 50% by weight relative to the total amount of phenol and amino compound and/or polyhydric alcohol, preferably 5 to 40% by weight. Weight In the present invention, a resol type phenol resin and a tresol type modified phenol resin can be used in combination, and two or more types of resol type modified phenol/L/resins can also be used in combination.

The binder for glass fibers of the present invention is advantageously provided in the form of an aqueous binder. The resin concentration is preferably 1 to 3.
It is 0% by weight. Further, hexamethylenetetramine is preferably used at 0.0% relative to the resin content. It is contained in a ratio of 5 to 25 weight i=1.

According to the research of the present inventor, the binder of the present invention can further contain urea in addition to the resol type phenolic resin, the resol type modified phenolic resin, and hexamethylenetetramine, and in that case, V is particularly suitable for the binder of the present invention. It became clear that the yield rate was significantly lower. Urea is preferably used in an amount of up to 50% by weight of the resin, particularly preferably up to 40% by weight.

The binder according to the invention in this case preferably contains hexamethylenetetramine in an amount of up to 50 weight φ, particularly preferably in an amount of l-t2 to 40x, relative to the urea contained. When the amount of hexamethylenetetraban is less than the lower limit, it is difficult to achieve the effect of adding it, and when it is more than the upper limit, the effect of adding more than that is small and the cost is high, which is not preferable.

The binder of the present invention can contain additives commonly used in binders for glass fibers of this type. Such additives are, for example, colorants such as ammonium sulfate, coupling agents such as aminosilanes, or fiber lubricants such as mineral oil.

The binder of the present invention can be used in the same manner as conventional binders for glass fibers.

For example, when molten glass is blown into short fibers by a known manufacturing method such as centrifugation, flame blowing, compressed air blowing, or steam blowing, and then accumulated on a mesh conveyor, The binder of the invention is sprayed onto the short fibers before they fall onto the conveyor. The short glass fibers to which the binder is attached are moved on a conveyor, subjected to drying, heat-pressure treatment, etc. as necessary, and formed into a mat, board, or dog-like shape.

The binder of the present invention is preferably 0% based on the total amount of glass fibers and resin content in the binder with respect to glass fibers.
．． It is applied by means such as spraying at a weight of 5 to 30 weight, preferably 2 to 20 weight.

Hereinafter, the present invention will be explained in further detail with reference to Examples.

The present invention is not limited in any way by these Examples.

Examples 1 to 5 and Comparative Example 1 A resol type phenolic resin, urea and hexamethylenetetramine were mixed in the proportions shown in Table 1, and further water and commonly used additives such as ammonium sulfate and aminosilane were added. By mixing, an aqueous binder having a solid content of 45% by weight including hexamethylenetetramine was prepared. Each binder 101 was placed in a dish with a bottom diameter of 5α and placed in a hot air circulation dryer set at 200°C for 1 hour.
After standing, the weight was measured to determine the nonvolatile content [(resin weight after drying/binder weight before drying flO) x 100]. Solid content of binder using this value (45% by weight)
The binder yield (chi) was calculated by dividing the binder yield (ch). The measurement results are shown in Table 1, and it can be seen that the yield of the binder of the present invention containing hexamethylenetetramine is high.

Examples 6-10 Comparative Example 2 Ethylene Dalicol Modified Phenol Tree JI! + Modification ratio: 15% by weight), urea and hexamethylenetetramine in the proportions shown in Table 2, and then water and commonly used additives such as ammonium sulfate and aminosilane were added and mixed until the solid concentration was reduced. A 45% by weight aqueous binder was prepared.

Thereafter, the same operations as in Example 1 were performed to obtain the binder yield results shown in Table 2.

Examples 11 to 14 and Comparative Example 3 Urea-modified phenol resin (modification ratio 20% by weight) and hexamethylenetetraban were mixed in the proportions shown in Table 3, and water and commonly used ammonium sulfate and aba Additives such as fusilane were added and mixed to prepare an aqueous Ingu with a solids concentration of 45 parts i-1 including hexamethylenetetramine.

Thereafter, the same operations as in Example 1 were performed to obtain the binder yield results shown in Table 3.

Examples 15 to 16 and Comparative Example 4 80 parts by weight of resol type phenolic resin (resin content equivalent),
20 parts by weight of urea, water, and commonly used additives such as ammonium sulfate and aminosilane are mixed, and further hexamethylenetetramine is mixed in the parts by weight listed in Table 4 to obtain a resin solid content of 8 parts by weight. An aqueous binder was prepared. For comparison, a conventional binder (resin solid content concentration: 8% by weight) without hexamethylenetetramine was prepared in the same manner as above. Then, the glass melted in the melting furnace is made to flow 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 from the direction of Next, the glass fibers that have been sprayed with the binder are collected on a belt conveyor having a mesh that moves in a direction perpendicular to the direction of the binder, and heated in a heating furnace at 250°C for 2 minutes to form a glass fiber mat. Manufactured.

The binder yield during the production of this mat is also shown in Table 4. It is clear that when the binder of the present invention is used, the binder yield is improved.

Table 4 Note that the water dilutability of the binder of the present invention and the restorability of glass fiber mats obtained by using the binder were the same as those of the conventional binder. Using the binder of the present invention, glass fiber at could be produced without any problems under the same production conditions as in the conventional method.

Examples 17-18 and Comparative Example 5 75 parts by weight of ethylene glycol-modified phenol resin, 25 parts by weight of urea, water, and commonly used additives such as ammonium sulfate and aminosilane were mixed, and hexamethylenetetramine was further added to the mixture. By mixing the parts by weight listed in Table 5, an aqueous binder having a resin solid content concentration of 8% by weight was prepared. For comparison, a conventional binder C (resin solid content concentration: 8% by weight) without hexamethylenetetramine was prepared in the same manner as above. A glass fiber mat was then produced in the same manner as described in Example 15. The binder yield during the production of this mat is also listed in Table 5.

Table 5 Effects of the Invention The binder for glass fibers of the present invention has a small amount of volatile matter during heating and therefore provides a high yield. On the other hand, due to these properties, the burden of the step of recovering volatile matter is reduced, and it is easy to prevent the occurrence of pollution due to volatile matter, which is extremely advantageous industrially.

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Claims (1)

[Scope of Claims] 1. A binder for glass fibers, characterized in that it contains a resol type phenolic resin and/or a resol type modified phenolic resin and hexamethylenetetramine. 2. The binder according to claim 1, which contains a resol type phenolic resin and hexamethylenetetramine. 3. The binder according to claim 1, which contains a resol-type modified phenolic resin and hexamethylenetetramine. 4. Resol type modified phenol resin is amino compound modified phenol resin, polyhydric alcohol modified phenol resin,
The binder according to claim 1 or 3, which is selected from amino compounds, polyhydric alcohol-modified phenolic resins, and mixtures thereof. 5. The binder according to any one of claims 1 to 4, wherein the binder is an aqueous binder having a resin concentration of 1 to 30% by weight. 6. Hexamethylenetetramine at a ratio of 0.5 to resin content
The binder according to any one of claims 1 to 5, containing 25% by weight. 7. The binder according to any one of claims 1 to 6, wherein the binder further contains urea. 8. The binder according to claim 7, which contains urea in an amount of 50% by weight or less based on the resin content.