JPH01261252A - Thermosetting resin molded article having excellent water-resistance - Google Patents

Abstract

PURPOSE:To improve the water-resistance and coloring flexibility of the subject article, by using a filler produced by the surface-treatment of glass powder containing SiO2, Al2O3, CaO, MgO, B2O3, Na2O, As2O3, Sb2O3 and Fe2O3 at respective specific ranges and containing a specific amount of fluorine. CONSTITUTION:Water-granulated glass containing 0.2-1.6pts.wt. of fluorine based on 100pts.wt. of a composition containing 22-26wt.% CaO+MgO, 51-55wt.% SiO2, 12-15wt.% Al2O3, 20-25wt.% CaO, 0-4wt.% MgO, 4.5-6.5wt.% B2O3, 1.5-4wt.% Na2O, 0-0.2wt.% As2O3, 0-0.2wt.% Sb2O3 and <=0.1wt.% Fe2O3 is prepared beforehand. The prepared glass is added with a silane coupling agent or an organosiloxane (e.g., gamma-methacryloxypropyltri methoxysilane) and crushed in wet state and, at the same time, surface-treated. The product is dehydrated and dried to obtain a filler for a thermosetting resin.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a resin molded product that has transparency and gives a luxurious feel when used for artificial marble, etc., and its purpose is to resist hot water, etc. The objective is to provide a resin molded product with excellent durability.

[Prior Art] Currently, artificial marble made of thermosetting resins such as unsaturated polyester resin and epoxy resin is widely used for bathtubs, washstands, interior panels, and other interior products. Possible fillers include aluminum hydroxide, magnesium hydroxide, glass powder, etc., but as demand for products such as bathtubs that require heat resistance and boiling resistance increases, thermally stable glass powder has become almost monopolistic. began to be used.

Currently, glass powders having compositions disclosed in JP-A-56-148538 and JP-A-58-157835 are commercially available.

[Problems to be Solved by the Invention] However, in the former case, the total amount of one or more monovalent alkali metal oxides is 5 to 20% by weight, and in the latter case, the total amount of Na2O is 8.4 to 16.0% by weight. Because of their large size, the boiling resistance of thermosetting resin molded products using these fillers as fillers was insufficient.

An object of the present invention is to provide a thermosetting resin molded article having excellent water resistance and boiling resistance. Another object of the present invention is to provide a thermosetting resin molded product that has a transparent feel and a luxurious feel by using glass powder having a refractive index similar to that of the thermosetting resin as a filler. It is in.

[Means for Solving the Problems] The present inventors have continued intensive research on durability against hot water, etc., and as a result, the amount of alkaline elution from glass powder has been determined to improve the water resistance and boiling resistance of the resulting thermosetting resin molded product. We found that Na in the glass powder has a large effect on the
We discovered that it was necessary to suppress the amount of 2O to 4.0% by weight or less, and we also continued to conduct intensive research on giving the resulting thermosetting resin molded products a colorless and transparent feel. In addition to using glass powder with a similar refractive index as a filler, F in the glass powder
The present invention was completed based on the discovery that an amount of e2O3 of 0.1% by weight or less is an essential factor for obtaining a colorless thermosetting resin molded article. That is, the present invention has the following composition 5to2 51-0 to 55.0% by weight Al2O312
．． 0~15.0II CaO20, 0~25.0 11 Mg0 O~ 4.0〃 Fe2O3≦0.1// However, CaO+ MgO= 22.0~26.0% by weight
Further, the surface of the glass powder containing 0.2 to 1.6 parts by weight of fluorine per 100 parts by weight of the above composition is treated with a silane coupling agent or organosiloxane, and the glass powder is filled. This is a thermosetting resin molded product with excellent water resistance obtained by using it as a reagent.

Therefore, in order to improve the boiling resistance of a thermosetting resin molded article containing glass powder as a filler, it is important to reduce the amount of alkali eluted from the glass at the interface with the resin. This reduces the amount of Na2O, which is thought to have a large effect on the amount of alkali elution, and
By increasing the amount of 12O3, the amount of alkali elution could be reduced. However, in order to manufacture the glass for the glass powder used in the present invention, in addition to the above-mentioned amount of alkali elution, there are other issues such as meltability and liquidus temperature.

As a result of considering the above-mentioned requirements, the proportion of 5102 in the glass powder composition used in the present invention is determined mainly to maintain appropriate viscosity of the molten glass. If Sio2 is less than 51% by weight, the rate of devitrification increases and the liquidus temperature increases, and if it exceeds 55% by weight, the viscosity increases and the meltability deteriorates. Al2O3 is 12
If the weight % is not negative, the devitrification rate will be high, and if it is 15 weight % or more, the meltability will be poor. If CaO is less than 20% by weight, the meltability will be poor, while if it is more than 25% by weight, the devitrification rate will be high. MgO is added to improve meltability, but up to 2 to 3% by weight it lowers the crystal precipitation temperature, but beyond this it increases the crystallization temperature again, so the upper limit is limited to 4.0% by weight. It will be done.

Regarding the content of CaO + MgO, if it is less than 22.0% by weight, the meltability will be poor;
When the amount increases, heat resistance deteriorates. B2O3 is added to increase the meltability of glass, but if it is less than 4.5% by weight, its effect is weak, while if it is more than 6.5% by weight, the meltability is not improved and it is expensive. The cost of glass powder becomes high. Part of Na2O is 20
However, if it is less than 1.5% by weight, the meltability of the glass deteriorates, while if it is more than 4.0% by weight, the amount of alkali elution increases. As
2O3 is added to improve the defoaming properties of molten glass, but because of its strong toxicity, the amount added is limited to 0.2% by weight or less. Further, 5b203 is added for the same purpose as AS20s, has the same effect as As2O3, and can completely replace As2O3, and although it is less toxic than As2O3, it is expensive, so the upper limit is limited to 0.2% by weight. If Fe2O3 exceeds 0.1% by weight, the glass will be colored green, so
Since it becomes impossible to obtain a thermosetting resin molded article that has transparency and gives a luxurious feel, the amount must be limited to 0.1% by weight or less, as much as possible. Fluorine is a component that improves the meltability of glass, but if it is less than 0.2 parts by weight based on 100 parts by weight of the glass composition used in the present invention, sufficient meltability cannot be obtained; The upper limit is limited to 1.6 parts by weight, since if it exceeds the amount, the amount of volatilization increases and causes deterioration of the working environment and environmental pollution.

The glass powder used in the present invention is prepared by thoroughly mixing raw materials containing oxides and fluorine in the composition ranges stated in the claims in a mixer, and then adding chromium, iron, titanium, and other glass colorants. It is melted in a melting furnace lined with a refractory that does not contain transition elements. Approximately 1900°C
The homogeneous high-temperature molten glass, which is free from defects such as bubbles and striae, is poured through a nozzle at the bottom of the melting furnace into a granulation tank filled with water, where it is rapidly cooled and crushed into granules with a size of 2 to 15 mm. Make coarse glass. This crushed water is sent to a dehydrator together with water, dehydrated, and then stored during fertilization. The separated water is returned to the granulation tank by a circulation pump and reused.

A fixed amount of the crushed glass in the receiving box is fed into the imaging mill via the hopper. Add 100 parts by weight of a 0.25 to 1.5% solution of a silane coupling agent or organosiloxane to 100 parts by weight of coarsely crushed glass in a vibrating mill, and grind to a particle size of approximately 30P using a wet grinding method. . The pulverized and surface-treated slurry is then dehydrated to a moisture content of 5 to 10% using a centrifugal dehydrator, and then dried in a dryer.
Dry at 30°C for about 2 hours, cool to room temperature, crush and remove large blocks that occur during drying, and then dry at 80°C.
Sieve through mesh sieve and use.

The properties of the glass powder obtained in the above process were as follows.

On the other hand, as the thermosetting resin used as the matrix of the present invention, unsaturated polyester resin is generally suitable due to its hot water resistance, chemical resistance, etc., but the type can be selected as long as it has sufficient transparency after curing. Regardless of the purpose, acrylic resin, epoxy resin, etc. whose components are adjusted to have a refractive index of 1.56 can be used.

In addition, the silane coupling agent or organopolysiloxane used for treating the surface of the glass powder in the present invention is 0.01 to 0.0% per 100 parts by weight of glass.
．． It is desirable that the amount is 5 parts by weight, and even if 0.5 parts by weight or more of This is because the boiling resistance is insufficient.

Furthermore, the size of the surface-treated glass powder is preferably 80 mesh to prevent coarse glass particles from protruding on the surface of the molded product and to facilitate mixing into the resin. The addition ratio of surface-treated glass particles to the resin is desirably 20 to 250 parts by weight per 100 parts by weight of the thermosetting resin in view of workability during resin molding and mechanical strength of the molded product.

As described above, the present invention improves transparency and water resistance by adding a filler in which the surface of glass particles having the above-mentioned specific composition is treated with a silane coupling agent or an organopolysiloxane to a thermosetting resin. We succeeded in obtaining an excellent thermosetting resin molded product.

[Example 1] Next, the effectiveness of the present invention will be clarified by comparing the present invention with products produced by conventional methods using specific examples.

Examples 1 to 5 and Comparative Examples 1 to 5 γ-
100 parts by weight of a 1.5% by weight solution of methacryloxypropyltrimethoxysilane was added to reduce the particle size to 30% by weight in a vibrating mill.
Wet grinding was carried out on a 11 m tube, and after dehydration, it was dried at 130° C. for 2 hours, and the material that passed through 80 meshes was collected. The amount of silane coupling attached to the surface of this glass powder was 0.1% by weight. This surface-treated glass powder is used as a filler for thermosetting resin.

The relationship between the glass composition, 103 poise temperature, liquidus temperature, and alkali elution amount is shown in Table 1.
The glass composition of JP-A No. 56-148538, Comparative Example 2
, B correspond to JP-A-58-157835, Comparative Example 5, and glass composition E corresponds to E glass, a so-called alkali-free glass, respectively.

It can be seen from the above coating 1 that the glass composition with a large proportion of Na2O has a large amount of alkali elution.

On the other hand, it can be seen that a glass with a small proportion of Na2O and a large proportion of 8102 has a small amount of alkali elution, but the 103 voice temperature is high and it is difficult to melt, making it uneconomical in terms of thermal energy.

Next, 20 parts by weight of the glass powder of Example 1, Comparative Example 1 or Comparative Example 2 shown in Table 1 was used as a curing accelerator, and an iso-unsaturated polyester containing 10 parts of a cobalt naphthenate 5.2% by weight styrene solution was prepared. Resin [Japanese Yupica strain Nyupika 6514
] or ortho-based unsaturated polyester resin [Inu Nippon Ink Chemical Industry Co., Ltd. (Kikki: DICPS156)] Mix well with 70 weight, and add 150 mm x 150 mm to maintain the shape.
Chopped strand mat of E glass fiber with dimensions [
Nitto Boseki (41: #4501) was poured into a mold while being controlled with a 3 mm thick spacer, left overnight at room temperature, and then cured at 120°C for 1 hour.This molded product Cut with a diamond cutter 5
A test piece measuring 0 mm x 50 mm x 3 mm was cut out and subjected to a hot water resistance test at 100°C for 48 hours to measure changes in light transmittance.

The results are shown in Figure 1. Although the absolute value of the light transmittance itself differs depending on the type of resin, molding using the glass powder of Example 1 of the present invention can be used for thermosetting resin molded products made of either ortho-based or iso-based unsaturated polyester resin. It is clearly shown in FIG. 1 that the decrease in light transmittance of the plate is smaller than that of the molded plates using glass powders of Comparative Examples A and H, which have a large amount of Na2O.

Furthermore, 150 parts by weight of the glass powder of Example 1, Comparative Example 1, or Comparative Example 5 in Table 1 was added as a curing accelerator to methyl ethyl ketone peroxide [manufactured by NOF: trade name Permec 10].
．． 5 parts by weight of iso-based unsaturated polyester resin [Japanese U-Pica (Scooping: U-Pica 6514)] Mix well with 100 ffi parts, and after degassing under reduced pressure for 5 minutes, a diameter of 80 mm and a depth of 15
Pour into a 8mm thick circular mold, 8mm thick.
Cured for 5 hours in a dryer at 0°C. Harden and remove the mold,
As a test piece, a boiling resistance test was conducted for up to 300 hours in boiling water at 100°C, and changes in light transmittance and appearance were measured and observed.

The results are shown in Table 2.

Table 2 A boiling test was conducted in boiling water at 100°C.
The surface of the test piece of the molded plate of Example 1 of the present invention was slightly yellowish even after 300 hours, and the transparency was only slightly reduced. On the other hand, the molded plate obtained by filling glass powder with a large amount of Na2O in Comparative Example 1 and heating and hardening it was
After 4 hours, the surface of the molded plate began to whiten without rapidly losing its transparency, and after 300 hours, the surface became uneven and the surface of the molded plate became completely milky and cloudy. In addition, in the molded plate obtained using the glass powder with a large amount of Fe2O3 in Comparative Example 5, there was no deterioration of the molded plate surface and the decrease in light transmittance was not so large, but the molded plate was colored green. Because of this, it has the disadvantage that it cannot be colored to any desired hue.

[Effects of the Invention] As is clear from the results of the water resistance (boiling resistance) test for the above Examples and q Comparative Examples, the surface of the glass powder having the specific composition of the present invention was coated with a silane coupling agent or organopolysiloxane. The thermosetting resin molded product obtained by using the treated glass powder as a filler is
It exhibits extremely superior water resistance compared to conventional thermosetting resin molded products obtained by using glass powder with a high alkali content as a filler. Furthermore, unlike thermosetting resin molded products obtained by using conventional alkali-free glass powder as a filler, the product does not exhibit green color, so it can be colored in any color. Therefore, it is expected to be widely used in fields where water resistance and decorativeness are required, such as bathtubs, washstands, indoor and outdoor lighting, window frames, etc.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing the relationship between boiling time and light transmittance of a thermosetting resin molded article.

Claims (1)

[Claims] (1) The following composition SiO_251.0-55.0% by weight Al_2O_312.0-15.0〃 CaO20.0-25.0〃 MgO0-4.0〃 B_2O_34.5-6.5〃 Na_2O1.5-4 .0〃 As_2O_30-0.2〃 Sb_2O_30-0.2〃 Fe_2O_3≦0.1〃 However, CaO+MgO=22.0-26.0% by weight, and fluorine is added to 100 parts by weight of the above composition. A glass powder with excellent water resistance obtained by treating the surface of a glass powder containing 0.2 to 1.6 parts by weight with a silane coupling agent or organosiloxane and using the glass powder as a filler. Thermosetting resin molded product.