JPH04295031A - Glass balloon product and its composition - Google Patents

Abstract

PURPOSE:To improve desruptive strength of glass balloon products by treating the surface of glass balloons having specified compsn. with a surface treating agent and then coating the balloons with a resin. CONSTITUTION:Glass balloons whose surface is treated with a surface treating agent (e.g. silane) are put into an emulsion or latex having the resin (e.g. olefinic resin) concn. preliminarily controlled, stirred, separated and dried. This glass balloon has the compsn. (by wt.%) 60-80 SiO2, 2-12.5 Na2O, 0-3 K2O, 0-3 Li2O, 5-15 CaO, 0-3 MgO, 6-15 B2O3, 0-3 ZnO, 0-3 Al2O3, 0-3 P2O5, 0-1 Sb2O3, 0-3 As2O3, and 0.05-1 SO2, and has 1.2-3.5 B2O3/ Na2O (weight ratio) and small alkali elution. The proportion of the coating resin is 3-200wt.%. The matrix into which the resin-coated glass balloons are to be compounded is not limited, but the compounding ratio is preferably 10-50wt.%.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to glass balloon products and compositions thereof, and more particularly to glass balloon products and compositions thereof having improved breaking strength.

0002

2. Description of the Related Art Various proposals have been made and implemented to incorporate glass balloons into resins for the purpose of reducing the weight of the resins. In the field of injection molding materials, most resins other than polyethylene are blended with glass balloons and a small amount of polyethylene is blended with this to reduce weight (see Japanese Patent Application Laid-open No. 1-168742). It has been proposed to mix glass balloons with resin and further mix glass fibers in order to reduce weight and improve mechanical strength.

[0003] However, in the field of injection molding, adding a glass balloon to a resin causes compressive stress and frictional force to be applied, so a material with considerably high strength is required. In fact, according to the inventor's study, 20 to 30% of the cases in the above-mentioned Japanese Patent Application Laid-open No. 1-168742 were broken, and 50 to 60% of the cases in which glass fiber was added were broken. . This is thought to be because the glass balloon is violently rubbed against the glass fibers during mixing and injection molding, resulting in numerous scratches on the surface of the glass balloon.

[0004] In this way, even if glass balloons were inserted with the aim of reducing weight, nearly half of them were destroyed.
Not only will the objective of weight reduction not be fully achieved, but the broken glass balloons may also be mixed into the resin and adversely affect the properties of the resin.

On the other hand, a method of increasing the thickness of the glass has been proposed in order to prevent the destruction of the glass balloon.
If this means is adopted, there is a drawback that the original purpose of weight reduction is lost, and the destruction of the glass balloon cannot be suppressed very effectively.

[0006]

[Problems to be Solved by the Invention] The present invention eliminates all of the drawbacks that conventional glass balloons have, and makes it possible to achieve virtually no problem even when the wall thickness is relatively thin or when mixed with glass fiber. The purpose of this study is to find a glass balloon that can be effectively prevented from breaking.

[0007]

[Means for Solving the Problems] The present invention provides a method for treating a glass balloon with a surface treatment agent and then using a resin to
The gist is to cover 200% by weight.

According to the present invention, even if the resin is directly coated on the surface of the glass balloon, it is not compatible with the glass balloon.
Easy to peel off. In order to improve this, the surface of the glass balloon is treated with a surface treatment agent to improve its compatibility with the resin, and then the resin is coated to a predetermined thickness.

Considering the history of scratches that occur on the surface of glass balloons, the most preferable coating with a surface treatment agent is that the frit powder in the areas where the scratches are sharply pointed passes through a reducing flame. , immediately after being inflated, but there is no problem even if the balloon is already on the market as a glass balloon.

[0010] The glass balloon used in the present invention may be any suitable one, but for example, one with a low alkali elution degree is preferred so as not to produce unnecessary coloration when mixed with a large amount of injection resin. preferable.

[0011] For this reason, it is preferable that the glass balloon has the following composition in weight percent, and the B2 O3 /Na2 O weight ratio is in the range of 1.2 to 3.5. SiO2 60
~80Na2O
2~12.5K2O
0~3Li2O
0-3 total alkali metal oxides 2-12.5CaO
5-15MgO
0-3 Total alkaline earth metal oxides 5-15B2 O3
6-15 ZnO
0-3
Al2O3
0~3P2 O5
0~3Sb2O3
0~1As2O3
0~1SO2
0.05 to 1 The glass balloon has an alkali elution amount of 0.08 meq/g, especially 0.06
It is low, less than milliequivalent/g.

Further, according to the studies of the present inventors, among the above glass balloons, the glass balloons have the following compositions in weight percent, and the B2 O3 /Na2 O weight ratio is 1.35 to 3.
A glass balloon having a value of 0 has a low alkali elution degree and is particularly preferable. SiO2 65
~75Na2O
3~6K2 O
0.5-1.5Li2O
0.5-1.2 total alkali metal oxides
3-8CaO
8-13MgO
0-3 Total alkaline earth metal oxides 5-15B2 O3
7-12 ZnO
1~2.5Al2
O3 0.5-1.5P
2 O5 1.1~
2.0Sb2O3
0~1As2O3
0~1SO3
0.05~1

The surface treatment agent for treating the surface of the glass balloon is not particularly limited, but includes, for example, silane, titanium, aluminum, zirconium, and the like. The amount of the surface treatment agent used is not particularly limited, but is preferably 0.3 to 3% by weight. The treatment method for applying the surface treatment agent to the surface of the glass balloon is not particularly limited, and a spraying method using a diluted solution, a dipping method in a diluted solution, or the like may be adopted.

The premise is that the resin to be coated is softer than the glass balloon. From this point of view, most resins are applicable. More preferably olefin resins, fluorine resins, silicone resins, urethane or urea resins, epoxy resins, saturated or unsaturated polyester resins, rubber resins, acrylic resins, vinyl acetate resins, polyamide resins, These include vinyl ester resins, and at least one type of these can be used as appropriate.

[0015] There are no particular limitations on the coating method; for example, a glass balloon is placed in an emulsion, latex, or organic solution whose resin concentration has been adjusted in advance to form a slurry, the liquid is stirred at a low speed, and then the liquid is separate,
A drying method, or a method of putting a glass balloon into a V-type mixer, spraying a solution, emulsion, or latex at a predetermined concentration while rotating it, and drying it is employed.

[0016] The amount of resin coated on the surface-treated glass balloon is generally 3 to 3% by weight relative to the glass balloon.
It is appropriate to employ 200% by weight, preferably 10 to 50% by weight, but strictly speaking it is determined by the type of resin to be coated, the method, etc.

The matrix into which the resin-coated glass balloon is mixed after surface treatment is not limited in any way, and can be applied to a wide range of applications. Specifically, they include inorganic materials such as concrete and plaster, and thermoplastic or thermosetting resins.

More specifically, thermoplastic resins include polyethylene resin, polypropylene resin, polystyrene resin, ABS resin, AS resin, acrylic resin, vinyl chloride resin, various polyamide resins, polyoxymethylene resin,
Polycarbonate resin, modified polyphenylene ether resin, polyethylene terephthalate resin, polybutylene terephthalate resin, ultra-high molecular weight polyethylene resin, polyvinyl acetate resin, polyvinylidene chloride resin, polysulfone resin, polyether sulfone resin, polyphenylene sulfide resin, polyarylate resin, Polyamideimide resin, polyetherimide resin, polyimide resin, polyetheretherketone resin, various liquid crystal resins, tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer resin, polychlorotrifluoroethylene resin, polyvinylidene fluoride resin, polyvinyl fluoride resin, ethylene/tetrafluoroethylene copolymer,
These include ethylene/chlorotrifluoroethylene copolymer resin.

Examples of thermosetting resins include epoxy resins, silicone resins, BT resins, phenol resins, unsaturated polyester resins, and diallyl phthalate resins.

The present invention reduces the breakage rate of glass balloons to efficiently reduce their weight, and also facilitates quality control, which has been difficult due to large variations in specific gravity from production lot to production lot. Other effects obtained when glass balloons are blended include stabilization against sink marks and warpage, reduction of shrinkage rate, heat insulation effect, improvement of rigidity and other physical properties, and improvement of electrical properties such as dielectric constant and dielectric loss tangent.

[0021] The blending ratio of the glass balloon to the matrix is not particularly limited, and the necessary amount to be blended is determined by taking into account the above-mentioned expected improved properties and resin viscosity.
Generally, 5 to 50% by weight, preferably 10 to 40% by weight is suitable.

As an application for resin-coated glass balloons, the two-component glass balloon/matrix system is further combined with fibrous reinforcements, fillers, additives, stabilizers, and flame retardants, either singly or in combination. It is possible to form More specifically, the fibrous reinforcing material includes fibers made of glass, carbon, potassium titanate, asbestos, silicon carbide, silicon nitride, calcium metasilicate, etc., and organic fibers such as aramid fibers.

[0023] As a filler, titanium oxide, antimony trioxide, clay, bentonite, sericite, zeolite,
Gypsum, talc, mica, kaolin, carbon black,
Molybdenum disulfide, quartz powder, glass beads, glass flakes or zinc, aluminum, copper, magnesium,
These include powders of metals such as calcium and iron, and their oxides, carbonates, and hydroxides. Additives include brominated flame retardants, heat stabilizers, antioxidants, and ultraviolet absorbers. The composition can also be constructed by adding other dispersants, colorants, etc.

[0024]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited thereto.

[Example 1] Glass balloon (S in weight %)
iO2 70.5, B2 O3 7.8, Na2 O
4.9, CaO 11.1, K2 O 0.8,
ZnO 1.0, Al2 O3 0.8, P2 O5
1.4, SO3 0.3, Li2 O 0
．． 86, B2 O3 /Na2O 1.59, alkaline elution amount 0.049 meq/g) was put into a 20 liter ribbon mixer, and while stirring at low speed, a glycidyl silane surface treatment agent (Nippon Unicar, A-
A solution prepared by diluting 1.9 g of 187) with 8 g of ethanol was applied. Thereafter, the temperature of the ribbon mixer was raised to 120° C., and heat treatment was performed for 2 hours.

[0026] Thereafter, after cooling this ribbon mixer to room temperature, while stirring the mixer at low speed, 333g
of acrylic ester (solid content 30% by weight) in water
A solution diluted to 7 g was sprinkled onto the mixture and stirred. Thereafter, the temperature of the ribbon mixer was raised to 120° C. again and the material was dried for 2 hours. As a result of thermal analysis, it was found that the total amount of the surface treatment agent and coating resin was 5% by weight based on the glass balloon.

A feeder was installed and the resin-coated glass balloons were individually introduced into a hopper of a kneading machine so that the amount of the glass balloons was 30 parts by weight based on 70 parts by weight of the polybutylene terephthalate resin. 280 in advance
The mixture was kneaded using a co-directional twin-screw kneader set at ℃, and the extruded strand was cooled with water and then cut using a pelletizer to obtain a molding material. After drying the pellets at 120°C for 5 hours, they were placed in the hopper of a molding machine set at 280°C, and a test piece for specific gravity measurement was molded at a holding pressure of 800 kg/cm2. Specific gravity was measured using the underwater displacement method. The destruction rate of the glass balloon in the molded product was calculated from the specific gravity of the molded product. These results are shown in Table 1.
Shown below.

[Example 2] Using the resin-coated glass balloons of Example 1, feeders were installed individually so that the ratio of resin/glass fiber (GF)/glass balloon was 50/20/30 (parts by weight). It was introduced into the hopper of the kneading machine. Thereafter, the mixture was kneaded and molded in the same manner as in Example 1 to obtain test pieces, and the specific gravity was measured. The results are shown in Table 1.

[Example 3] 1.9 kg of the bare glass balloon used in Example 1 was put into a 20 liter ribbon mixer, and while stirring at low speed, a methacrylic silane surface treatment agent (Nippon Unicar, A- 174) A solution prepared by diluting 1.9 g with 8 g of ethanol was applied. Thereafter, the temperature of the ribbon mixer was raised to 120° C., and heat treatment was performed for 2 hours. Thereafter, the ribbon mixer was cooled to room temperature, and a solution prepared by diluting 182 g of acrylic acid ester (solid content: 55% by weight) in 4,818 g of water was sprinkled and stirred while stirring the mixer at low speed. Then use the ribbon mixer again at 120
The temperature was raised to ℃ and dried for 2 hours. As a result of thermal analysis, it was found that the total amount of the surface treatment agent and the coating resin was 5% by weight based on the glass balloon.

A feeder was installed and the resin-coated glass balloons were individually introduced into the hopper of a kneading machine so that the amount of the glass balloons was 30 parts by weight based on 70 parts by weight of the polybutylene terephthalate resin. 280 in advance
The mixture was kneaded using a co-directional twin-screw kneader set at ℃, and the extruded strand was cooled with water and then cut using a pelletizer to obtain a molding material. After drying the pellets at 120°C for 5 hours, they were placed in the hopper of a molding machine set at 280°C, and a test piece for specific gravity measurement was molded at a holding pressure of 800 kg/cm2. Specific gravity was measured using the underwater displacement method. The destruction rate of the glass balloon in the molded product was calculated from the specific gravity of the molded product. These results are shown in Table 1.
Shown below.

[0031]

[Table 1]

[Example 4] 1.9 kg of the bare glass balloon used in Example 1 was put into a 20 liter ribbon mixer, and while stirring at low speed, a glycidyl silane surface treatment agent (Nippon Unicar, A-187) was added to the ribbon mixer. ) was diluted with 8 g of ethanol and applied. The amount of the coupling agent applied was 0.1% by weight based on the glass balloon. Thereafter, the temperature of the ribbon mixer was raised to 120° C., and heat treatment was performed for 2 hours.

After cooling the ribbon mixer to room temperature, while stirring the mixer at low speed, 500 g of fluororesin emulsion (Asahi Mont Co., Ltd., Technoflon) adjusted to 20% by weight was spray applied. The ribbon mixer was heated to 120° C. to dry the surface-treated and resin-coated glass balloon. As a result of thermal analysis of this glass balloon, it was found that the total amount of the surface treatment agent and the coating resin was 5% by weight based on the glass balloon.

The treated glass balloons were mixed into 3 glass balloons per 70 parts by weight of polyamide resin.
A feeder was installed individually so that the amount was 0 parts by weight, and the mixture was introduced into the hopper of the kneading machine. The strands were kneaded in a co-directional twin-screw kneader preset at 270°C, and the extruded strands were cooled with water and then cut with a pelletizer to obtain a molding material.

After drying the pellets at 120°C for 5 hours, they were placed in the hopper of a molding machine set at 270°C, and a test piece for specific gravity measurement was molded at a holding pressure of 850 kg/cm2. Specific gravity was measured using the underwater displacement method. The destruction rate of the glass balloon in the molded product was calculated from the specific gravity of the molded product. These results are shown in Table 2.

[Example 5] Using the resin-coated glass balloons of Example 4, feeders were installed individually so that the ratio of resin/glass fiber/glass balloon was 50/20/30 (weight ratio). introduced into the hopper. Thereafter, the mixture was kneaded and molded in the same manner as in Example 1 to obtain test pieces, and the specific gravity was measured. The results are shown in Table 2.

[Example 6] 6600 g of silicon dioxide, 1220 g of soda ash, 1650 g of lime, 2520 g of boric acid,
Raw materials of 100 g of zinc oxide, 50 g of aluminum oxide, 400 g of dicalcium phosphate, 250 g of lithium carbonate, 150 g of potassium carbonate, and 120 g of sodium sulfate were mixed and melted in a crucible at a surface temperature of 1350° C. to obtain a glass frit. The resulting frit was ground in a ball mill. Next, this powder was continuously fed into the foaming furnace at a rate of 25 g/min and a premixed combustion gas of air and LPG at 600 liters/min, and the glass balloons produced were immediately collected by a collection equipment.

[0038] Immediately after collection, 1.9 kg of glass balloons were
Add glycidylsilane surface treatment agent (Nippon Unicar,
A solution obtained by diluting 1.9 g of A-187) with 8 g of ethanol was applied. The amount of the coupling agent applied was 0.1% by weight based on the glass balloon.

[0039] Thereafter, the ribbon mixer was heated to 120°C and heat treated for 2 hours. After that, after cooling this ribbon mixer to room temperature, while stirring the mixer at low speed,
After spraying 500 g of a fluororesin emulsion (Asahimont Co., Ltd., Technoflon) adjusted to 20 wt%, the ribbon mixer was heated to 120° C. to dry the resin-coated glass balloon. Thermal analysis of this glass balloon revealed that the total amount of the surface treatment agent and coating resin was 5% by weight.

The treated glass balloons were mixed into 3 glass balloons per 70 parts by weight of polyamide resin.
A feeder was installed individually so that the amount was 0 parts by weight, and the mixture was introduced into the hopper of the kneading machine. The strands were kneaded in a co-directional twin-screw kneader preset at 270°C, and the extruded strands were cooled with water and then cut with a pelletizer to obtain a molding material. After drying this pellet at 120°C for 5 hours,
The sample was placed in a hopper of a molding machine set at 70°C, and a test piece for specific gravity measurement was molded at a holding pressure of 850 kg/cm2. Specific gravity was measured using the underwater displacement method. The destruction rate of the glass balloon in the molded product was calculated from the specific gravity of the molded product. These results are shown in Table 2.

[0041]

[Table 2]

[Example 7] A feeder was installed individually so that 70 parts by weight of the polypropylene resin and 30 parts by weight of the resin-coated glass balloon of Example 4 were introduced into the hopper of a kneading machine. The strands were kneaded in a co-directional twin-screw kneader set in advance at 220°C, and the extruded strands were cooled with water and then cut with a pelletizer to obtain a molding material.

After drying the pellets at 120° C. for 5 hours, they were placed in the hopper of a molding machine set at 230° C. and molded into test pieces for specific gravity measurement at a holding pressure of 700 kg/cm 2 . Specific gravity was measured using the underwater displacement method. The destruction rate of the glass balloon in the molded product was calculated from the specific gravity of the molded product. These results are shown in Table 3.

[Example 8] A feeder was installed so that 70 parts by weight of the ABS resin and 30 parts by weight of the resin-coated glass balloon of Example 3 were introduced into the hopper of a kneading machine. The strands were kneaded in a co-directional twin-screw kneader set in advance at 230°C, and the extruded strands were cooled with water and then cut with a pelletizer to obtain a molding material.

After drying the pellets at 120° C. for 5 hours, they were placed in the hopper of a molding machine set at 240° C. and molded into test pieces for specific gravity measurement at a holding pressure of 750 kg/cm 2 . Specific gravity was measured using the underwater displacement method. The destruction rate of the glass balloon in the molded product was calculated from the specific gravity of the molded product. These results are shown in Table 3.

[Example 9] Individual feeders were installed so that 70 parts by weight of fluororesin (Asahi Glass, Aflon PFA P-62) and 30 parts by weight of the resin-coated glass balloons of Example 4 were placed in the hopper of the kneading machine. It was introduced in The strands were kneaded using a co-directional twin-screw kneader set in advance at 360° C., and the extruded strands were cooled with water and then cut with a pelletizer to obtain a molding material.

After drying the pellets at 120° C. for 5 hours, the pellets were placed in the hopper of a molding machine set at 390° C. and molded into test pieces for specific gravity measurement at a holding pressure of 800 kg/cm 2 . Specific gravity was measured using the underwater displacement method. The destruction rate of the glass balloon in the molded product was calculated from the specific gravity of the molded product. These results are shown in Table 3.

[0048]

[Table 3]

[0049]

Effects of the Invention: The composition of the present invention suppresses the destruction of glass balloons used as a weight-reducing material, efficiently reduces their weight, and improves the quality of glass balloons whose specific gravity fluctuates widely from production lot to lot, making it difficult to control their quality. In addition to reducing weight, the glass balloon also exhibits effects such as eliminating sink marks and warpage, reducing mold shrinkage, and improving heat insulation. This material can be used to bring about beneficial effects in the fields of building materials, automobiles, electricity, electronics, and mechanical parts.

Claims (6)

[Claims] Claims: 1. A glass balloon product comprising a glass balloon surface-treated with a surface treatment agent and further coated with 3 to 200% by weight of resin. 2. The glass balloon product according to claim 1, wherein the glass balloon has just been manufactured by passing frit powder through a reducing flame to form a resin. [Claim 3] A glass balloon whose surface is treated with a surface treatment agent has the following composition in weight percent, and contains B2 O3 /
The glass balloon product according to claim 1, which has a low alkali elution degree and has a Na2O weight ratio of 1.2 to 3.5. SiO2 60
~80Na2O
2~12.5K2 O
0~3Li2O
0-3 total alkali metal oxides 2-12.5CaO
5-15MgO
0-3 Total alkaline earth metal oxides 5-15B2 O3
6-15 ZnO
0-3
Al2O3
0~3P2 O5
0~3Sb2O3
0~1As2O3
0~3SO2
0.05~1 4. The glass balloon product according to claim 1, wherein the surface treatment agent is at least one selected from silane, titanium, aluminum, and zirconium. 5. The resin is an olefin resin, a fluorine resin,
silicone resin, urethane or urea resin, epoxy resin, saturated or unsaturated polyester resin,
The glass balloon product according to claim 1 or 3, wherein the glass balloon product is at least one resin selected from rubber resin, acrylic resin, vinyl acetate resin, polyamide resin, and vinyl ester resin. 6. A resin composition for injection molding, which contains the glass balloon product according to any one of claims 1 to 5.