JPH06136180A - Glass filler for thermosetting resin molding - Google Patents

Abstract

PURPOSE:To obtain an artificial marble made of a thermosetting resin, having good resistance to hot water and free from whitening and blistering. CONSTITUTION:The filler has a glass composition consisting of 55-65wt.% SiO2, 10-20wt.% Al2O3, 20-30wt.% (CaO+MO) (wherein M is an alkali metal or Zn), and at most 1.0wt.% (Na2O+R2O) (wherein R is an alkali metal).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a filler for a thermosetting resin molded product such as artificial marble, and more particularly, to a thermosetting resin product which is excellent in transparency without fear of whitening or swelling. Glass filler for obtaining.

[0002]

2. Description of the Related Art Artificial marble with a matrix of thermosetting resin such as unsaturated polyester resin, epoxy resin, acrylic resin, allyl resin, etc. is a molded product with transparency and weight, and is used as a bathtub, kitchen counter, washbasin. It is often used as a stand. However, with the spread of these artificial marble products, the performance required for the products has also become strict, and in particular, water resistance and hot water resistance must satisfy extremely severe performance with the advent of full-time buses. It is in.

As a filler for such artificial marble, glass powder has been conventionally used because it is thermally stable. However, with ordinary glass powder, it is not possible to prevent whitening and swelling of artificial marble products due to hot water, and there is a demand for the development of glass fillers that give better hot water resistance to the products.

The cause of whitening and swelling of artificial marble products due to hot water, that is, the cause of deterioration in hot water resistance, is caused by N in the glass component.
It has been found to be related to the amount of alkali metal oxides such as a ₂ O. That is, thermosetting resins such as unsaturated polyester resin, epoxy resin, acrylic resin, and allyl resin that form the matrix for artificial marble are
It is known that each has an ester bond in the structure, and the hydrolysis (saponification) of the ester occurs due to the elution of alkali metal ions in the glass accompanying the infiltration of hot water, which induces whitening and blistering. There is.

Therefore, as a main method for improving the hot water resistance, it has been considered to reduce the content of alkali metal oxides in the glass component. However, if the amount of alkali metal oxide is reduced, the meltability during glass production deteriorates,
Instead of this, B ₂ O ₃ must be contained within a certain range to improve the meltability, and in order to adjust the refractive index of the glass to obtain a transparent feeling with the matrix resin, B ₂ O 3
₃ was considered to be an essential component (Japanese Patent Laid-Open No. 1-22).
No. 61252, Japanese Examined Patent Publication No. 4-9176).

In view of the above points, the present invention has an object to provide a glass filler for thermosetting resin artificial marble having good hot water resistance.

[0007]

The present invention has been devised in order to achieve the above-mentioned object, and an amount which is acceptable as an impurity (1% by weight or less) without introducing B ₂ O _3. In an oxide composition containing only the alkali metal oxide of, for example, a SiO ₂ —Al ₂ O ₃ —CaO system, a glass having very excellent hot water resistance can be obtained, and the refractive index thereof is transparent to the matrix. Showing 1.53 ~
It was completed after finding that it could be adjusted to 1.58.

That is, the glass filler according to the present invention has an oxide composition of SiO ₂ 55 to 65% by weight Al ₂ O ₃ 10 to 20% by weight MO 20 to 30% by weight (M is an alkaline earth metal element and zinc). means at least one element selected from the group consisting of elemental) TiO ₂ 0 wt% ZrO ₂ 0 wt% unavoidable contamination oxide becomes than 1.0 wt% or less, the total amount of the oxide is 100 It is the% by weight.

As the compound MO, MgO, BaO, Z
nO and the like are exemplified, and these may be used alone or in combination of two or more.

The proportion of each component of the glass composition is such that transparency can be ensured even when a thermosetting resin matrix such as unsaturated polyester resin, epoxy resin, acrylic resin, allyl resin is filled with the glass filler. , The refractive index of the glass filler is 1.53 to 1.58
It is a value limited to almost match with.

The glass filler according to the present invention has the above-mentioned glass composition, and the amount of the alkali metal oxide which induces whitening or swelling due to hydrolysis of the ester of the thermosetting resin is 1.0% by weight or less. It is only included in the range.

The glass filler according to the present invention is preferably a glass powder surface-treated with a silane coupling agent. The glass powder surface-treated with the silane coupling agent imparts a transparent marble-like appearance to the molded product, and improves the adhesiveness at the interface with the resin and the hot water resistance of the molded product.

The average particle size of the glass powder is preferably 5 to 3
It is in the range of 00 μm.

As the silane coupling agent, silanes having an ethylenically unsaturated double bond and a hydrolyzable group in the molecule are preferably used, and suitable examples thereof include vinyltriethoxysilane and Vinyl Tris-β-
Examples thereof include methoxyethoxysilane and γ-methacryloxypropyltrimethoxysilane. The amount of these silane coupling agents used is usually in the range of 0.01 to 2 parts by weight per 100 parts by weight of glass powder.

The thermosetting resin compound for artificial marble containing the glass filler according to the present invention is preferably glass-filled with 100 parts of the thermosetting resin such as unsaturated polyester resin, epoxy resin, acrylic resin or allyl resin. It contains 100 to 400 parts of material and a catalytic amount of a curing agent.

If the amount of the glass filler is less than 100 parts with respect to 100 parts of the thermosetting resin, the weight and texture of the molded product will be poor, a transparent marble-like texture will not be obtained, and cracks will occur during molding. Occasionally, a molded product having excellent heat resistance may not be obtained. On the other hand, when the glass filler exceeds 400 parts, the fluidity required for molding cannot be obtained, the machinability also deteriorates, and both the moldability and the mechanical properties of the molded product may deteriorate.

In addition to the above-mentioned essential components, the thermosetting resin compound for artificial marble may optionally contain other compounding components used in this type of thermosetting resin compound. Examples of such a compounding agent include a fiber reinforcing agent, a coloring agent, an internal release agent, and a thickening agent. As the fiber reinforcing agent, the fiber length is 0.5 to 5
Glass fibers in the range of 0 mm, aramid fibers, vinylon fibers, polyester fibers, etc. are used. As the colorant, an organic or inorganic pigment or a toner using the same is used. Zinc stearate as an internal release agent,
Metal soaps such as calcium stearate and phosphate-based ones are generally used. As the thickener, oxides or hydroxides of alkaline earth metals such as magnesium oxide and calcium hydroxide are preferable.

Important curing agents for completing the curing of the thermosetting resin include methyl ethyl ketone peroxide, benzoyl peroxide, parachlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide and acetyl peroxide. Oxide, dicumyl peroxide, 2,5-dimethyl-
Organic peroxides such as 2,5-di (t-butylperoxy) hexane and t-butylperbenzoate are used alone or in combination. The amount of the curing agent used may be a so-called catalytic amount, and is preferably in the range of 0.3 to 2.5% by weight based on the resin.

The resin compound is a liquid or syrup, or SMC and BMC thickened into sheets, rice cakes, columns, pellets, etc., and various molded products such as bathtubs, kitchen counters, vanities, It is used as a material for manufacturing highly transparent molded products such as bathroom panels and table tops. The heat molding method of the resin compound includes a pressure heat molding method. The molding conditions are not particularly limited, but generally 90 to 1
It is preferable to carry out at a temperature of 60 ° C. and a pressure of ^{20 to} 140 kg / cm ² gauge.

[0020]

EXAMPLES Next, the present invention will be described more specifically with reference to examples of the present invention.

Preparation of Filler for Thermosetting Resin First, materials having the compositions shown in Table 1 were mixed, and the compositions were melted into various compositions to produce glass having the refractive index shown in Table 1. The refractive index was measured at 20 ° C. by a polarization microscope immersion method.

Then, silane coupling agent γ-methacryloxypropyltrimethoxysilane (“KBM-50” manufactured by Shin-Etsu Chemical Co., Ltd.) was added to 100 parts by weight of each glass pulverized product.
3 ") was added in an amount of 0.2 part by weight, and then the surface treatment was performed while finely pulverizing the pulverized glass product with a ball mill. The treated finely pulverized product was sieved with 40 mesh, and the passing glass powder was dried at 80 ° C. for 2 hours to obtain a filler for thermosetting resin.

[0023]

[Table 1] Manufacture of artificial marble board Gel coating "NC
-51004P "(manufactured by Nippon Ferro Co., Ltd.) and 100 parts by weight of a curing agent" Permec N "(manufactured by NOF CORPORATION) were added by spray coating to a thickness of 0.3 mm. This coating film was cured at 60 ° C. for 2 hours, and another glass plate coated with a release agent was placed on the gel coat side of this glass plate,
A silicone rubber having a thickness of 10 mm was sandwiched between these two glass plates as a gasket to create a plate-shaped molding die. Then, a resin compound having the following composition was degassed in vacuum and then injected between two glass plates of a molding die.

The resin compound is as follows.

Unsaturated polyester resin, 6424 (manufactured by Nippon Yupica) 100 parts by weight Curing agent "Perkadox 16" (manufactured by Kayaku Akzo) 1 part by weight Filler (glass powder treated with the silane coupling agent) 200 parts by weight This compound was cured at 60 ° C. for 2 hours to prepare a 100 × 100 × 10 mm artificial marble plate having a gel coat on one surface for a hot water resistance test.

Hot Water Test Next, each test plate was placed in a batch type hot water tester, the gel coat surface of the test plate was exposed to hot water of 95 ± 1 ° C., and a hot water test was conducted. After hours and 90
The state of whitening and blistering after 0 hours was observed.

The results are shown in Table 2.

[0028]

[Table 2] As is clear from Table 2, it is recognized that each of the molded products of the examples has superior hot water resistance as compared with the comparative examples.

[0029]

The glass filler according to the present invention has the above glass composition, and the amount of the alkali metal oxide which induces whitening or swelling due to hydrolysis of the ester of the thermosetting resin is 1.0% by weight. It is only included in the following range.

Therefore, according to the glass filler of the present invention, it is possible to obtain a thermosetting resin artificial marble which has good hot water resistance, is free from whitening and swelling, and is excellent in transparency.

Claims (3)

[Claims] 1. An oxide composition having an oxide composition of SiO ₂ 55 to 65% by weight Al ₂ O ₃ 10 to 20% by weight MO 20 to 30% by weight (M is at least selected from the group consisting of alkaline earth metal elements and zinc elements. (Means one element) TiO ₂ 0 to 10% by weight ZrO ₂ 0 to 10% by weight Inevitably mixed oxides 1.0% by weight or less, the total amount of oxides being 100% by weight, thermosetting Glass filler for resin molded products. 2. The glass filler according to claim 1, which has a refractive index of 1.53 to 1.58. 3. The glass filler according to claim 2, which is a glass powder surface-treated with a silane coupling agent.