JPS5913556B2 - Cured resin composition for glass fiber - Google Patents

Description

[Detailed description of the invention] The present invention relates to a cured resin composition for glass fibers.

. Specifically, the present invention relates to a cured resin composition in which a specific water repellent is added to an aqueous glass fiber cured resin solution, and the... of the aqueous solution is adjusted to a value within a specific range. Conventionally, laminated glass fibers have been widely used as heat insulating materials, etc., but in recent years, noise pollution has come under close scrutiny, and glass fibers are increasingly being used outdoors as noise materials.

Along with this, the water repellency of glass fiber laminates has become a problem, and various methods have been proposed. For example, Tokuko Sho 43-423
For No. 3, glass fiber laminate (glass fiber mat)
Modify the thermosetting resin binder with silicone resin,
Once the resin 5 has been cured, it has been shown that a two-stage coating with a silicone resin formulation, ie, a water repellent treatment, imparts water repellency to the glass fiber product. However, in this method, it is necessary to treat the water repellent in two stages, which increases the number of steps for producing the glass fiber laminate by at least 10 steps per step, which is very disadvantageous. . The present inventors have conducted various studies with the aim of imparting water repellency to glass fiber laminates during the normal manufacturing process. As a result, the water repellency of the glass fiber laminates obtained differs depending on the type of water repellent agent15, and this tendency becomes noticeable when used with a cured resin for glass fibers, and is influenced by the pH of the aqueous solution containing these agents. The inventors discovered that this was extremely large, leading to the completion of the present invention. The present invention provides SinOnR2n-mH for 100 parts by weight of phenolic resin or urea resin.
Contains 0.1 to 10 parts by weight of polysiloxane represented by m (where R is alkyl or phenyl, n is a natural number, m is 0 or a natural number, 2n>m), and 0.1 to 1 parts by weight based on the resin.
This is a cured resin composition for glass fibers consisting of an aqueous solution having a concentration of 0% by weight and a pH of 7.5 to 10.5.

The glass fiber cured resin used in the present invention is a phenol resin or a urea resin. Further, the concentration of the cured resin may be a concentration conventionally generally used, and specifically, 90 is used as an aqueous solution having a concentration of about 0.1 to 10% by weight, which varies depending on the type of resin, molecular weight, etc. The water repellent used in the present invention for imparting water repellency is SlnOnR2n
-mHm (where R is alkyl or phenyl, n is a natural number, m is o or a natural number, 2■5n>m), and is a mixture of organopolysiloxane compounds represented by the above formula. It may be.

Further, as long as it is expressed by the above formula, the structure is not limited to a chain structure, and the ladder structure may be a cage structure. In addition, from the viewpoint of water repellency, it is generally preferable to use a material in a range that satisfies 5m>2n. Specific examples of typical water repellents include methylhydrodiene polysiloxane, ethylhydrodiene polysiloxane, phenylhydrodiene polysiloxane, a mixture of methylhydrodiene polysiloxane and dimethylpolysiloxane, and phenylhydrodiene polysiloxane. A mixture of siloxane and diphenylpolysiloxane, etc. For example, when using a mixture of methylhydrodienepolysiloxane and dimethylpolysiloxane, the amount of dimethylpolysiloxane added may be about 60% or less in order to satisfy the above-mentioned 5m>2n. Furthermore, in general, when imparting water repellency to organic fibers, cloth, etc., it has conventionally been carried out by treating a water repellent in the presence of an inorganic or organic metal salt catalyst and then heating. However, the present invention does not necessarily require a catalyst such as those used in these known processes. The water repellent may be simply added to the cured resin aqueous solution as it is or in the form of an emulsion. The amount of water repellent used is 10 parts of the cured resin.
The amount may be in the range of 0.1 to 10 parts by weight relative to 0 parts by weight and may be determined in advance as appropriate. As mentioned above, the effect of the present invention is not sufficient simply by adding a water repellent to the glass fiber cured resin aqueous solution.

That is, in the present invention, ... of the aqueous solution is 7.5 to 10.5.
As such, it is essential to make adjustments. The pH is 7.
If it is less than 5, the cured resin itself becomes colloidal, and the water repellent has poor dispersibility, making it impossible to uniformly impart water repellency to the glass fibers. If the value exceeds 10.5, there will be no problem with the function of the cured resin, the uniform distribution of the water repellent, etc., but the moisture absorption rate of the resulting glass fiber laminate will increase and the product value will be lost. The method of pH adjustment in the present invention is not particularly limited, and any known adjusting agent may be used. Generally, ammonia water and the like are well used. As mentioned above, it is necessary to add a specific water repellent to the cured resin composition for glass fibers in the present invention and adjust the pH to a specific range. There is no problem with adding agents, etc.

In addition, especially when a long-lasting water repellent effect is required, a silane coupling agent for the glass fiber laminate may be added to the cured resin composition for glass fibers.
The mixture may be mixed so that 0.1% or more of the resin adheres.

Generally, it is sufficient to add 0.2 parts or more to 100 parts by weight of the cured resin. As the silane coupling agent, water-soluble ones such as methoxysilane and cellosolve ester silane are generally convenient to use, but aminopropyltrimethoxysilane, ethylene diaminobu, propyltrimethoxysilane and the like can also be used satisfactorily. EXAMPLES In order to explain the present invention more specifically, the present invention will be described below with reference to Examples, but the present invention is not limited to these Examples.

The water repellency and hygroscopicity of the glass fiber laminates in the following Examples were measured using the following method and used as a determination guideline.

Water repellency: 50× from the obtained glass fiber laminate with a thickness of 40 m/m
Make two samples cut to a size of 50 m/m.

A container with an internal volume of 10Z was filled with water at 20°C, and one of the samples was placed on the water surface so that the layered surface was parallel to the water surface and the other sample was placed on the water surface so that the layered surface was perpendicular to the water surface.
The glass fiber laminate was left at room temperature (°C), and the water repellency was expressed as the number of days it took for the glass fiber laminate to get wet, absorb water, and sink under water, or the percentage of the area that sank into the water. Moisture absorption rate: 50 x 50 m/m from glass fiber laminate with a thickness of 40 m/m
Make two m-sized samples.

After thoroughly drying this sample at a temperature of 100°C,
Measure the weight of each. Next, a 10% by weight aqueous sulfuric acid solution was poured into the bottom of the desiccator, and the dried sample was placed in the top of the desiccator, which was designed to maintain a relative humidity of 96%, and the lid was placed at a room temperature of 20°C. After leaving it for 72 hours, take it out and measure its weight. The moisture absorption rate was expressed as the ratio of the weight increase in the above measurement to the sample weight when drying. Example 1 A cured resin composition for glass fibers having the composition shown in Table 1 was almost uniformly sprayed onto a glass fiber laminate having a density of 32 kg/wl.

The cured resin was then cured under pressure at a temperature of 200°C. The water repellency of the obtained glass fiber laminate remained for 30 days or more. On the other hand, the water repellency of the resin compositions shown in Table 1 without the addition of methylhydrodiene polysiloxane was 1 minute or less. Example 2 Same as Example 1 except that the methylhydrodiene polysiloxane used in Table 1 of Example 1 was replaced with a mixture of methylhydrodiene polysiloxane and dimethylpolysiloxane containing 3% by weight of dimethylpolysiloxane. The same procedure was carried out.

The resulting glass fiber laminate had water repellency for 30 days or more. Example 3 The same procedure as Example 2 was carried out except that the amount of water repellent added in Example 2 was changed as shown in Table 2.

The results were as shown in Table 2. The amount of the water repellent added is in parts by weight based on 100 parts by weight of the glass fiber resin. Example 4 The same procedure as in Example 1 was carried out except that the pH in Table 1 in Example 1 was changed as shown in Table 3.

The results were as shown in Table 3. Example 5 The same procedure as in Example 1 was carried out except that Toray Silicone SH6O2O (trade name: manufactured by Toray Silicone Co., Ltd.) was added as a silane coupling agent to the composition in Table 1 in Example 1.

The result was water repellency of 30 days or more. Example 6 30TfL of a 30% sulfuric acid aqueous solution was placed in a 1000ml beaker, and while stirring with a magnetic stirrer, 40d of a 10% aqueous solution of No. 3 sodium silicate was added dropwise over 30 minutes.
Immediately after the dropwise addition, 300 ml of isopropanol is added, and then, while stirring, salt is added until saturation is achieved.

When this solution is allowed to stand, it separates into an isopropanol solution of siloxysilanol and an aqueous phase. The isopropanol phase is further dried with anhydrous sodium sulfate. Trimethylchlorosilane (TMCS) was added to this to give a TMCS/siloxysilanol odor of 11 to cause a reaction, and then the solvent was distilled off to obtain an organosilane compound.

This substance is soluble in organic substances such as petroleum benzine. It was confirmed that the above organosilane compound had a composition of approximately Si2O3(CH3)2.

1.5 parts by weight of this compound was dissolved in 5 parts of petroleum benzine,
Binder 100 for glass fiber made of phenolic resin
Parts by weight, 1.5 methylhydrodiene polysiloxane,
It is suspended in an aqueous solution containing 5,000 parts by weight of water and adjusted to pH 9 to form a water-repellent emulsion.

This was sprayed onto glass fibers according to Example 1, and
Those subjected to heat treatment under pressure at 0C had water repellency for 30 days or more. Example 7 The same procedure as in Example 1 was carried out except that a urea resin was used in place of the phenol resin used in Table 1 of Example 1.

Claims (1)

[Claims] 1 100 parts by weight of phenolic resin or urea resin and general formula, Si_nO_nR_2_n_-_mH_m (however,
R is an alkyl group or a phenyl group, n is a natural number, m is 0 or a natural number, and polysiloxane 0.
A cured resin composition for glass fibers comprising an aqueous solution containing 1 to 10 parts by weight, a concentration of 0.1 to 10% by weight based on the resin, and a pH of 7.5 to 10.5.