JP3979546B2 - Glass filler for resin filling - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an improvement of a glass filler which is dispersed and filled in a synthetic resin and used as a material such as artificial marble. In particular, the present invention relates to a resin-filled glass filler suitable for filling a synthetic resin having a refractive index nD in the range of 1.465 to 1.515.
[0002]
[Prior art]
Conventionally, a composite material in which a glass filler made of a certain kind of glass powder is dispersed and filled in a synthetic resin such as unsaturated polyester or vinyl ester has been widely used suitably as a material for so-called artificial marble. These artificial marbles are used for household or commercial furniture materials, such as bathtub bodies, toilet cabinet baseplates or sink sinkballs, system kitchen tables, dressing tables or wall materials, etc. The characteristics of glass fillers are the composite and composite functions of filler and resin, and the function of improving the dimensional stability, chemical durability, mechanical strength, etc. of the composite material. By approximating the refractive index nD of the resin to 1.54 to 1.58, the composite material has favorable transparency, and the combination of subtle refracted light and reflected light gives a rich texture similar to marble. There was where to bring.
[0003]
As a glass material of the glass filler for such a purpose, conventionally, for example, an oxide composition as disclosed in JP-A-5-178646, SiO ₂ : 50 to 65% (% by weight, hereinafter the _{same), Al 2 O 3: 10~20} %, CaO: 20~30%, B 2 O 3: 0.1% or _less, R 2 O: 3% or less (R: alkali metal a is K, Na and The component composition of Li) is known. The feature of this glass filler is that the mixing ratio of a boric acid component and an alkali component that are easily eluted in hot water or hot water is reduced as much as possible to improve durability against hot water or the like.
[0004]
By the way, in recent years, filtration and circulation devices equipped with an automatic temperature control function have been developed as household bath facilities, and as baths that can be bathed for 24 hours have become widespread, hot water stays in the bathtub for an extremely long time, unlike conventional baths. Therefore, durability over a long period of time with respect to the hot water of the bathtub material is required, and further improvement in the performance of the synthetic resin-glass filler composite material that is the material of the bathtub body has been expected.
[0005]
In response to such demands, acrylic resins or polypropylene resins that are resistant to aging and have high durability have been newly used as synthetic resins. However, since these synthetic resins have a refractive index nD of about 1.50, there is a problem in that preferable transparency and texture cannot be obtained with a glass filler having a conventional composition and composition. The refractive index nD indicates the refractive index with respect to the sodium D line (wavelength 589.3 nm).
[0006]
Moreover, based on the chemical composition of conventional glass, there is a method of increasing the SiO ₂ content and reducing the CaO content in order to reduce the refractive index and improve its compatibility. Since the melting temperature of the steel rises to about 2000 ° C., there arises a problem that the manufacturing cost is remarkably increased. Moreover, in order to make a glass that melts at a temperature of about 1500 ° C., which is a conventional melting temperature, the amount of B ₂ O ₃ and the alkali metal oxide must be increased. Therefore, a glass composition that can be practically used for the above applications could not be obtained.
[0007]
[Problems to be solved by the invention]
The present invention has been made in order to solve the above-described problems, and is used by filling a synthetic resin having a refractive index nD in the range of 1.465 to 1.515 to obtain a composite material having good transparency. A glass filler with good hot water resistance is provided while at the same time providing a glass filler that can be manufactured, while enabling vitrification at as low a temperature as possible.
[0008]
[Means for Solving the Problems]
The glass filler for resin filling that can solve the above-mentioned problem includes a silicic acid component, an alumina component, a calcium oxide component, and a fluorine component as essential components, and has a refractive index nD in a range of 1.465 to 1.515. A glass filler for resin filling comprising glass particles surface-treated with an organic substance having a functional group that reacts with glass, wherein the glass particles comprise particles having an average particle diameter of 5 to 35 μm, and in the chemical composition, SiO ₂ to 55 to 80% (% by weight, the same applies hereinafter), Al ₂ O ₃ to 10 to 25%, and the total amount of SiO ₂ and Al ₂ O _{3 to be} in the range of 67 to 83%, B ₂ O ₃ to 0 to 10 %, CaO to 10 to 20%, R ₂ O to 0 to 1% (R represents an alkali metal), fluorine to 0.3 to 7%, and B ₂ O ₃ , CaO, R ₂ O, fluorine The total amount is within the range of 13 to 28%, ZnO is 0 to 3%, Sb ₂ O ₃ is 0 to 3%, ZrO is 0 to 5%, and the total content of ZnO, Sb ₂ O ₃ and ZrO ₂ is included. It is a glass whose amount is in the range of 0 to 5%, and has a viscosity at the time of melting at 1500 ° C. of 500 Ps or less.
[0009]
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Next, an embodiment of the present invention will be described.
The glass filler for resin filling of the present invention is a glass filler because it is used as a filler of a synthetic resin having a refractive index nD in the range of 1.465 to 1.515, for example, an acrylic resin or a polypropylene resin, An organic substance having a functional group that reacts with glass, containing 0.3 to 7% of fluorine as an essential component and having a refractive index nD in the range of 1.465 to 1.515 It consists of glass particles that have been surface-treated.
[0011]
Moreover, it is preferable that the glass particle is adjusted to the range of an average particle diameter of 5-35 micrometers. When the average particle size is less than 5 μm, the contact area with the resin becomes too large and the hot water resistance tends to decrease, and a special pulverizer is required. Moreover, when exceeding 35 micrometers, the kneading | mixing blade of the kneading machine with resin becomes easy to wear out, and the malfunction that a metal impurity mixes arises. From such a viewpoint, the average particle diameter is optimally in the range of 15 to 25 μm.
[0012]
Furthermore, as the chemical composition of the glass which is the material of the glass filler of the present invention, the essential components include 0 part of fluorine content in addition to silicic acid part, alumina part and calcium oxide part . Those containing 3-7% but, as the glass-forming components of the whole, a SiO ₂ 55 to 80% (wt%, hereinafter the same), the _Al 2 _{O 3} 10 _~25%, the SiO ₂ and _Al 2 _{O 3} The total amount is in the range of 67 to 83%, B ₂ O ₃ is 0 to 10 %, CaO is 10 to 20%, and R ₂ O (total amount of K ₂ O, Na ₂ O and Li ₂ O) is 0. -1% and fluorine content of 0.3-7% as described above, and the total content of B ₂ O ₃ , CaO, R ₂ O, fluorine is within the range of 13-28%, and others It contains 0 to 3% of ZnO, 0 to 3% of Sb ₂ O ₃ and 0 to 5% of ZrO _2, and the total amount of ZnO, Sb ₂ O ₃ and ZrO ₂ is within the range of 0 to 5%. Is.
[0013]
In the present invention, SiO ₂ is 55 to 80%. If it is less than 55%, B ₂ O ₃ must be increased in order to obtain the desired refractive index. If the glass melt exceeds 80%, the melting temperature becomes too high. For example, a glass melt having a viscosity of 500 Ps or less cannot be obtained at 1500 ° C., which is not practical.
[0014]
The reason why Al ₂ O _{3 is set} to 0 to 25% is that Al ₂ O ₃ is a component that improves the durability of the glass, so it is preferably included to some extent, but if it exceeds 25%, the melting temperature is high. Thus, for example, a glass melt having a viscosity of 500 Ps or less cannot be obtained at 1500 ° C. A more preferable range is 10 to 25%, and further 13 to 20% is particularly preferable.
[0015]
It is appropriate that the total amount of SiO ₂ and Al ₂ O ₃ is 67 to 83%, and if it exceeds 83%, the melting temperature becomes high, for example, the viscosity of glass at 1500 ° C. is high, and the melting operation is high. If it is less than 67%, the melting operation is easy, but the hot water resistance is deteriorated, which is not practical.
[0016]
Further, the B ₂ O ₃ content of 0 to 10% is selected from the balance between the merit of reducing the melting temperature of the B ₂ O ₃ minutes and the demerit of degrading the hot water resistance. Is preferably 10%, more preferably the upper limit is 5%, and the upper limit is particularly 1%.
[0017]
Further, the CaO content of 10 to 20% is selected from the balance of the merit that the CaO content considerably reduces the melting temperature and the demerit that slightly deteriorates the hot water resistance. In the present invention, the CaO content exceeds 20%. Since the target refractive index cannot be obtained, the upper limit is set to 20%, and the preferable range is 10 to 20%, and further 13 to 18% is particularly preferable.
[0018]
Furthermore, the reason why the total amount of the alkali metal oxides R ₂ O of K ₂ O, Na ₂ O and Li ₂ O is 1% or less is that the R ₂ O greatly reduces the melting temperature and the hot water resistance. This is because it has a demerit to deteriorate, and the upper limit is set to 1% in the present invention.
[0019]
Next, in the present invention, the fluorine content in the glass functions as a strong melting agent and is found to have the effect of lowering the refractive index and has an advantage, and the preferred content range is 0. 3-7%. If the content is less than 0.3%, the effect on the melting action or refractive index cannot be obtained. On the other hand, if it exceeds 7%, the ratio of evaporation from the melt at the time of melting and scattering to the outside increases, which is not effective, and there is a need for deterioration of acid resistance and alkali resistance.
The B ₂ O ₃ , CaO, R ₂ O and fluorine are appropriately combined in an amount of 13 to 28%. If it is less than 13%, the melting temperature rises and the melting operation becomes difficult. Exceeding this is not preferable because the hot water resistance is remarkably deteriorated.
[0020]
Also, ZnO is 0 to 3%, Sb ₂ O ₃ is 0 to 3%, and ZrO ₂ is 0 to 5%. The presence of appropriate amounts of these components adjusts the balance of hot water resistance, refractive index, and melting temperature. Although the effect of stabilizing the glass is recognized, such as when it exceeds the predetermined amount, the refractive index will deviate from the target value, or the glass will become milky and it becomes difficult to obtain a transparent composite material, so the upper limit of the total amount Is preferably 5%.
[0021]
When manufacturing the glass having the component composition described above in a melting furnace, it is necessary to melt the mixed raw material at a high temperature and to flow out of the melting furnace when the glass melt is formed. It is preferable that the glass melt has a low viscosity. Therefore, from the viewpoint of the long-term use temperature of a glass melting furnace in practical use or the difficulty in handling the glass melt, it is preferable that the glass has a viscosity of 500 Ps or less at at least 1500 ° C.
The viscosity of the glass at such a high temperature can be measured by a so-called platinum ball pulling method that measures the flow resistance when passing the platinum ball while maintaining the target glass in a molten state at a predetermined temperature. it can.
[0022]
In the present invention, the above-described chemical components are included in respective contents, but metal oxides other than those described above may be included within a range that does not impair the functions and effects of the present invention. For example, Ti, Ba, S This applies to colored pigments or unavoidable impurities such as Fe, Mo, Mn, Cr, Ni, Co, and Cu.
[0023]
In addition, the present invention can be embodied in an embodiment in which the surface is treated with an organic substance having a functional group that reacts with glass. Examples of such an organic substance include alkoxysilanes such as tetramethoxysilane and methyltrimethoxysilane. Or metal alkoxides such as tetraisoproxy titanium and tetraisopropoxy zinc, or organic substances having a functional group that reacts with both glass and resin, such as gamma-glycidoxypropyltrimethoxysilane Organic substances collectively referred to as silane coupling agents are suitable, and it is suitable to perform surface treatment by adhering one or a plurality of them in a mixed or layered manner.
[0024]
【Example】
Next, the present invention will be described in detail based on the examples shown in Table 1 and the comparative examples shown in Table 2.
[Table 1]
[0025]
[Table 2]
[0026]
The glass of the example is formulated with silica sand, aluminum hydroxide, boric acid, lime, zinc white, antimony oxide, zirconia, aluminum fluoride or calcium fluoride as raw materials so that the chemical composition shown in Table 1 can be obtained. After being melted in a melting furnace and cooled, it was pulverized to have a volume average diameter of 10 μm. The same applies to the comparative example.
In addition, about the refractive index of these glass and the viscosity in 1500 degreeC, it measured by the normal method and described in the column of the refractive index (nD) of Table 1, 2, and a viscosity (Ps).
[0027]
The glass powder thus obtained was subjected to a surface treatment with 1 part by weight of γ-methacryloxypropyltrimethoxysilane to obtain a glass filler. Subsequently, 200 g of these glass fillers, 100 g of acrylic syrup, and 1 g of a curing agent were kneaded and defoamed under vacuum to obtain a compound. 200 g of this compound was poured into an injection mold having an internal volume of 120 × 120 × 10 mm made of a mirror-finished stainless steel plate and a polyurethane foam tape having a thickness of 10 mm, covered with an iron plate and 0.05 N / cm ² . Curing was performed at 50 ° C. for 2 hours under pressure, and further curing was continued for 2 hours at a pressure of 0.3 N / cm ^{2 and a} temperature of 80 ° C.
[0028]
As a result of the above, for the obtained composite material of glass filler and acrylic resin, the degree of whitening of whether or not it turns white when immersed in heated water at 80 ° C. for 1000 hours is visually compared, and the results are shown in Table 1. It was shown in 2.
For the transparency in Tables 1 and 2, 100 wt. Of a reference refractive index mixed solution prepared by mixing ethyl alcohol and ethyl cinnamate and adjusting the refractive index nD to be 1.49, 1.50, 1.51. 10 parts by weight of the glass powder is dispersed in the part, and the turbidity is shown.
[0029]
According to the results shown in Tables 1 and 2, the examples are excellent in hot water resistance, and the refractive index of the glass has a value in the range of 1.465 to 1.515. , 1.49, 1.50, 1.51, it can be seen that good transparency can be obtained in a dispersion medium in which the refractive index nD is adjusted. Further, in this example, the viscosity at 1500 ° C. is 500 Ps or less and shows a preferable molten state, so that glass can be practically produced.
[0030]
On the other hand, Comparative Examples 11 and 14 have a melting point that is too high to obtain glass at a melting temperature of 1500 ° C. Since Comparative Examples 12, 13, and 17 have a large amount of B ₂ O ₃ and Comparative Example 17 has a larger amount of alkali, it can be seen that although the transparency is appropriate, the hot water resistance is remarkably inferior. Comparative Example 15 has a problem of transparency because the refractive index is too high, and Comparative Example 16 is white turbid and similarly inferior in transparency.
[0031]
【The invention's effect】
Since the glass filler for resin filling of the present invention is configured as described above, excellent marble-like transparency and texture can be obtained by dispersing and filling in a highly durable acrylic resin or the like. A resin-glass composite having good hot water resistance is obtained. Moreover, since the glass for glass filler for resin filling of this invention can be manufactured at a comparatively low temperature, it has the outstanding effect that manufacturing cost can be held down. Therefore, the present invention has an extremely large industrial value as a glass filler for resin filling which has solved the conventional problems.

Claims (1)

It contains silicic acid, alumina, calcium oxide and fluorine as essential components , has a refractive index nD in the range of 1.465 to 1.515, and is surface-treated with an organic substance having a functional group that reacts with glass. A glass filler for resin filling made of glass particles, wherein the glass particles are particles having an average particle diameter of 5 to 35 μm, and in the chemical composition, SiO ₂ is 55 to 80% (wt%, the same applies hereinafter), Al ₂ O ₃ along with containing from 10 to 25%, the total amount of SiO ₂ and _Al 2 _{O 3} was in the range of sixty-seven to _{eighty-three%} B 2 _{O 3} 0-10% 10-20% a CaO, _{R 2} 0 to 1% of O (R represents an alkali metal), 0.3 to 7% of fluorine, and the total amount of B ₂ O ₃ , CaO, R ₂ O and fluorine is in the range of 13 to 28% ZnO is 0 to 3%, Sb ₂ A glass containing 0 to 3% of O ₃ and 0 to 5% of ZrO and having the total amount of ZnO, Sb ₂ O ₃ and ZrO ₂ in the range of 0 to 5%, when melted at 1500 ° C. The glass filler for resin filling characterized by having a viscosity of 500 Ps or less.