JPS608338A - Flame-retardant composition - Google Patents

Abstract

PURPOSE:To provide a flame-retardant composition having excellent transparency, sulfide-stain resistance, dispersibility, etc., by coating antimony trioxide with a curable resin. CONSTITUTION:For example, 100pts.wt. of antimony trioxide is mixed with preferably 1-50pts.wt. of a curable resin (e.g. acrylic resin, alkyd resin, etc.), and the resin is cured. The mixture is crushed finely with a crusher to obtain the objective composition having particle size of preferably 5-150mu.

Description

DETAILED DESCRIPTION OF THE INVENTION An object of the present invention is to provide a flame retardant having excellent transparency, sulfur stain resistance, dispersibility, etc.

Antimony trioxide (Sb203) has been widely put into practical use in recent years because it is used in combination with halogen compounds to improve the flame retardancy of synthetic resins. However, since Sb203 is a powder with an average particle size of about 0.1 to 5 microns, when added to a synthetic resin, it has a strong hiding power and becomes a white synthetic resin.

Therefore, it was considered unsuitable for the use of synthetic resins that require transparency.Also, when coloring synthetic resins that have been given flame retardancy with Sb203, it has a strong hiding power. Therefore, the amount of expensive coloring pigments added increases accordingly, resulting in an increase in cost.Furthermore, the addition of Sb203 significantly impairs the sulfurization stain resistance of synthetic resins. When a resin is brought into contact with hydrogen sulfide, the reaction between the two causes the resin to turn yellow, resulting in a significant loss of commercial value.

In order to solve these problems, conventionally, for example, Sb203
A method of increasing the crystal grain size to 5 to 15 microns, and a method of increasing the crystal grain size of S
Attempts have been made to coat the surface of b203 with a silane coating agent, thermoplastic resin, etc. However, in the case of Sb20 having a large crystal grain size, although it showed some effects in terms of transparency and sulfur stain resistance, it significantly reduced the mechanical strength of the synthetic resin. In addition, Sb203 surface-coated with a silane coupling agent or thermoplastic resin has only a slight effect on improving transparency and sulfur stain resistance, especially in the case of 5b2o3 coated with thermoplastic resin.
200'C during molding of synthetic resin to which this is added.

Due to the above temperature and considerable shearing force, the coating phase was softened and destroyed, and the effectiveness of the coating was significantly impaired.

The inventors of the present invention conducted intensive research to solve the problems mentioned above, and as a result, they arrived at the present invention in which 5b2o3 is coated with a curable resin.

The curable resin used in the present invention is a thermosetting resin or an ultraviolet curable resin, and the form of the resin is an aqueous type, an organic solvent type, or a solventless type. The types of resin are generally known, such as acrylic, alkyd, melamine, urethane, epoxy, and phenol, and depending on the required properties, a mixture of two or more of these types may be used. can also be used.

Coating with these resins is performed by a commonly known method. For example, (1) a method of mixing a thermosetting resin and 5b203, then heat-treating the resin under the curing conditions of the used thermosetting resin to harden the resin, and pulverizing it in a pulverizer; (iii) curable resin A method of spraying a mixture of 5b203 in a liquid into a hot air atmosphere, that is, a method of drying and curing by a spray drying method, followed by a method of further curing by heat treatment or ultraviolet irradiation as necessary, (3
) There are a method of mixing Sb203 with a curable resin while stirring it with a mixer, and a method of curing it by heat treatment or ultraviolet irradiation if necessary.

In these methods, the mixing ratio of 5b203 and curable resin is 1 part of curable resin to 100 parts of 5b203.
~50 parts by weight is appropriate; if the curable resin is less than 1 part by weight, the effect of improving properties such as sulfur stain resistance will be insufficient, and if it exceeds 50 parts by weight, it will not meet the flame retardant standards for synthetic resins. As a result, the same amount or more of curable resin as 5b203 added to achieve this will be added, and depending on the type of synthetic resin, mechanical strength such as tensile strength and breaking strength may decrease, moldability An abnormality begins to appear in the appearance of the product. Moreover, it is also negative from the economic point of view.

5b20 coated with curable resin as described above
3 refers to a single coating whose core is a single crystal particle, a multinuclear coating where a plurality of single coatings are combined, and a coating whose core is a state in which a plurality of single crystal particles are aggregated, etc. It is a mixture of , and there are also particles consisting only of curable resin.

Such a mixture is classified based on particle size using a sieve or a classifier, and used depending on the purpose. The particle size obtained ranges from 0.5 microns to several hundred microns, and the degree of improvement in transparency is low when the particle size is 5 microns or less, and when the particle size is 150 microns (100 mesh) or more, the degree of improvement in transparency is low. In the range, good results are shown in terms of transparency and sulfur stain resistance, but in the addition ratio, the flame retardant effect decreases, which is not preferable. Good, well-balanced results were obtained in the particle size range of about 5 to 150 microns.

In addition to improving the flame retardancy of synthetic resins by adding 5b2o3 coated with the curable resin according to the present invention, it also improves the transparency of synthetic resins compared to conventionally used 5b203, e.g. , FI for polyester resin during mixing molding work under high temperature? t,
It also has the effect of suppressing the decline. This makes it possible to greatly contribute to expanding the application to industrial fields where 5b203 cannot be used due to the drawbacks of conventional 5b2o3 and reducing costs.

The present invention will be specifically explained below according to Examples and Reference Examples. The amount used is based on a highly respected standard.

Example: 5,014 parts of deionized water was weighed in a stainless steel container, and while stirring using a propeller stirrer, 60 parts of a water-soluble acrylic resin liquid (manufactured by Toagosei Kagaku Co., Ltd., 9-4020) and a water-soluble melamine resin liquid were added. (Sumitomo Chemical Co., Ltd. M-
30W) Add 26 parts of the mixture and stir thoroughly. Approximately 5
After standing for a minute to defoam, the average particle size is 0.5 while stirring.
Micron antimony trioxide (Nippon Seiko Co., Ltd. A)
5,000 parts of TOX-S) were gradually added to prepare a dispersion.

The composition of the Kono dispersion is 5b2o3/resin=100/1. This dispersion was dried with a spray dryer (experimental machine manufactured by Mitsubishi Kakoki Co., Ltd.) to obtain a white powder. The operating conditions of the spray dryer were as follows.

Spray nozzle diameter 2.01m Dispersion liquid supply rate 236 N/Hr Drive air pressure s, oKri/d 11 parts for hot air people 250-270'C.

Temperature for exhaust air: 120'C.

A coarse particle portion of the white powder dried in the drying tower was collected using a cyclone separator, and the remaining fine particle portion was collected using a bag filter.

When the white powder of the fine particles thus obtained was observed under an electron microscope, most of the particles were spherical, and the particle size was approximately 3 to 12 mm.
It was 0 micron. This white powder appears to be in the form of a core of 5b203 coated with thermosetting acrylic melamine resin or an aggregate thereof.

3 parts of this white powder and PVA (3 parts manufactured by Nippon Zeon Co., Ltd.)
03 EP) 100 parts, 50 parts of DOP, and 3 parts of organic tin stabilizer were mixed and heated to 150 to 1
After kneading at 55°C, 0.20 a for transparency test.
For the flammability test and the sulfidation resistance test, a sheet having a thickness of 3iJx was formed and used for each test. Transparency tests are conducted using a haze meter (Model H() M-2D, manufactured by Nuga Test Instruments Co., Ltd.), and sulfur resistance tests are conducted using a color difference meter (Suga Test Instruments Co., Ltd., model H() M-2D). Color difference value by ODE-OH-4P type (manufactured by Co., Ltd.),
The flammability test was evaluated based on the oxygen index using an oxygen index flammability tester (Model 0N-1 manufactured by Suga Test Instruments Co., Ltd.) based on JISK-7201.

Examples 2 to 5 The composition of the dispersion (sb2o3/resin) was changed by the method of example 1, that is, in example 2, 5b2o3/resin = 1
0012, Example 3 is 5b203/resin =, I00/3
The same test was conducted using 5b2o3/resin = 1.0015 in Example 4 and 5b2o3/resin = 100/10 in Example 5.

Comparative Example As a comparative example for Example 1, a test was conducted in the same manner as Example J using the antimony trioxide (ATOX-3) used in Example 1 as it was.

The test results of Examples 1 to 5 and Comparative Example 1 are shown in the following table.

Examples 6 to 7 Antimony trioxide (PATOx-O manufactured by Nippon Seiko Co., Ltd.) having a crystal grain size of 15 microns and having a purity different from the antimony trioxide used in the examples was used, and was obtained in the same manner as in Example 1. A similar test was conducted on In addition, in Example 6, %1. ) l) 2 (J3/resin = 100/3,
In Example 7, 5b2o3/resin = 100/5.

Example 8 300 g of the white powder obtained in Example 4 was spread on aluminum foil to a thickness of about 1 to 2 thick, and dried in a dryer to a thickness of 150 to 160 g.
After heat treatment at a temperature of 30 minutes, a test was conducted in the same manner as in Example 1.

As can be seen from the above test results, antimony trioxide coated with a thermosetting resin showed significantly superior results in terms of transparency and sulfidation resistance, compared to antimony trioxide that was not coated with a thermosetting resin.

Example 9 In Example 1, thermosetting water-soluble methylol polyvinyl urethane resin (Mitsui Toatsu Chemical Co., Ltd. P-3000) was used instead of acrylic and lumelamine resin, and 5b20
A white powder was obtained by a spray drying method using 3/resin as 100/3, and the same test as in Example 1 was conducted.

Example 10 In Example 1, a thermosetting water-soluble melamine resin (Nikaratsuku MW-40 manufactured by Sanwa Chemical Co., Ltd.) was used instead of the acrylic melamine resin, and 5b203/resin was
A white powder was obtained as 075 by a spray drying method, and the same test as in Example 1 was conducted in 1-j.

Example 11 In Example 1, a thermosetting water-soluble phenol resin (BRL-1202 manufactured by Showa Union Gosei Co., Ltd.) was used in place of the acrylic melamine resin, and the 5b203/resin ratio was set to 1.0015, and the resin was dried by a spray drying method. A test similar to Example 1 was conducted using a yellowish brown powder.

Example 12 In Example J, acrylic emulsion resin (Aron AP-JO4, East 111th Synthetic Chemical Industry Co., Ltd.) and thermosetting water-soluble melamine resin (Nikaratsuku M, manufactured by Sanwa Chemical Co., Ltd.) were used instead of the acrylic melamine resin. , W-40)
using a mixture of (melamine resin content 20%), 5b2
03/Resin 10015 was used to obtain a white powder by spray drying, and a test was conducted in the same manner as in Example 1.

Comparative Example 2 Antimony dioxide (ATOX-8) was mixed with alkoxylan (
A comparative test was carried out in the same manner as in Example 1 using a sample that had been surface-treated using Daihachi Kagaku Kogyo Co., Ltd.).

The test results of Example 9-1-2 and Comparative Example 2 are shown in the following table.

- As shown in the table, coatings made with alkoxylan-based treatment agents had no effect on improving transparency, and only a slight improvement was observed in sulfidation resistance, which was significantly greater than coatings made with thermosetting resins. A difference can be seen.

Example 13 Antimony trioxide (ATOx-8) 1 in a stainless steel container
000 parts, 71.5 parts of an organic solvent-based thermosetting melamine resin (Sumimar M-55 manufactured by Sumitomo Chemical Co., Ltd.) and an appropriate amount of ethyl cellosolve were mixed uniformly with a metal spatula to form a paste. . 5b203/resin was 10015, and the paste-like mixture of both was transferred to a vat made by Hou and placed in a dryer at 300°C.

The mixture was further heated at 150° C. for 60 minutes.

It was taken out of the dryer and allowed to cool, and after 24 hours it was ground in a grinder, and the white powder that passed through a 200 mesh sieve and the white powder with a mesh size of 200 to 150 mesh were collected and treated in the same manner as in Example 1. The test was conducted.

Examples 14 to 17 In Example 13, 5b203/resin was 100/]0
．． 300/20. 100/40.100150 and the powder passed through a 200 mesh sieve was tested in the same manner as in Example 1.

Comparative Example 3 In Example 13, an organic solvent-type thermoplastic acrylic resin liquid (manufactured by Takuya Gosei Kagaku Co., Ltd.) was used instead of the thermosetting resin, and the white powder passed through a 200 mesh sieve using 5b203/resin as 10015. The body was collected and tested in the same manner as in Example 1.

The test results of Examples 13 to 7 and Comparative Example 3 are shown in the following table.

Patent Applicant Hiki Seiko Co., Ltd. Representative Patent Attorney Kiyodo Kodo Kobe True Procedural Amendment (Method) October 1980 Japan Patent Office Commissioner Kazu Wakasugi Failure 1, Indication of Case 1988 Patent Application No. 115767 2, Title of the invention: Flame retardant composition 3, Relationship to the case of the person making the amendment Patent applicant address: 2 Shimomiyabi-cho, Shinjuku-ku, Tokyo (40) Akira Seto, Representative of Nippon Seiko Co., Ltd.

Claims (2)

[Claims] (1) Flame retardant composition in which antimony dioxide is coated with a curable resin (2) The flame retardant composition according to claim 1, which contains 1 to 50 parts by weight of a curable resin per 100 parts by weight of antimony trioxide.