JPS617356A - Resin composition - Google Patents

Abstract

PURPOSE:To provide a resin composition of high mechanical strength afforded with flame-retardancy, electrical conductivity and fire resistance, comprising synthetic resin, carbon black, inorganic fiber, flame-retardant, and at least two sorts of compounds selected from titanium dioxide, zirconium oxide and silicon dioxide. CONSTITUTION:The objective composition comprising (A) 20-70pts.wt., on a solid basis, of at least two sorts of compounds selected from (i) titanium compounds (titanium dioxide, titanic acid or titanium secondary sulfate), (ii) zirconiun compounds (zirconium oxide, zirconic acid, or zirconium sulfate), and (iii) silicon compounds (silicon dioxide or colloidal silicic acid anhydride), (B) 5- 20pts.wt. of carbon black (e.g. furnace black, channel black), (C) 10-50pts.wt. of inorganic fiber (e.g. E- or C-glass fiber or ceramic fiber, with a length <=30mm.) (D) 15-60pts.wt. of a thermoplastic or thermosetting resin liquid or solid at ordinary temperatures, and (E) 0-20pts.wt. of flame retardant, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a resin composition used as a raw material for various molded products in the field of industrial materials and building materials in the field of construction.

[Technical background of the invention and its problems]

Conventionally, flame retardant properties have been imparted using compositions containing various synthetic resins as main components, or flame retardant materials with good mechanical strength and heat-resistant alloys such as polyimide resins or fluorine resins have been used as main components. There are many compositions that have high heat resistance, and molded products made from these compositions include, for example, mechanical parts such as valves and gears in the industrial materials field, various electrical insulation parts, and in the architectural field. There are flame-retardant or heat-resistant paints, waterproof sealants, and various FRP building materials.

However, since synthetic resins form the main component or matrix of these industrial material parts and building materials, these resin compositions reflect the drawbacks of synthetic resins and do not have flame retardancy or heat resistance in terms of resistance to fire heat. At best, it does not provide fire resistance.

[Purpose of the invention]

In view of the above-mentioned problems, the present invention adds at least two types of inorganic materials such as titanium oxide, zirconium oxide, and silicon oxide, carbon black, and inorganic fiber to a synthetic resin, although there are slight differences in performance depending on the type of synthetic resin. It is used in various industrial materials fields to provide resin compositions with good mechanical strength, flame retardancy, conductivity, and fire resistance. By sex,
A resin composition useful for various molded products in the industrial materials field that require mechanical strength, conductivity, and fire resistance, or for building materials that require mechanical strength, ll1w properties, and fire resistance in the architectural field. This is what we are trying to provide.

[Summary of the invention]

In the present invention, at least two kinds of inorganic materials such as titanium oxide, zirconium oxide, and silicon oxide, carbon black and inorganic binding string are added and blended into a synthetic resin. In addition to the heat resistance, inorganic materials and one layer of carbon provide properties that can withstand fire heat, such as flame retardancy and fire resistance, and inorganic aN# provides mechanical strength, which requires continuous heat resistance and resistance to fire heat. The company has expanded its use to include mechanical parts such as special valves, and various parts in gas-fired drying ovens.

Furthermore, if the synthetic resin is made into a liquid resin or a rubber-like resin, it becomes possible to use it as a fire-resistant sealing shrine or backing shell.

[Structure of the invention]

The inorganic materials constituting the present invention, carbon black, inorganic Il miscellaneous materials, synthetic resins, and their blending amounts and blending methods will be described in detail.

■Inorganic materials Titanium oxide, zirconium oxide, and silicon oxide are inorganic materials that are produced by drying temperatures of 200 to 300°C during the manufacturing process or thermal decomposition of titanium compounds, zirconium compounds, and silicon compounds. included. In the case of titanium compounds, titanium oxide, titanic acid, titanium sulfate, titanium chloride, titanium■
Oxyacetylacetate, oxides such as titanium alkoxide, acids, inorganic salts, chlorides, organic titanium compounds, and zirconium compounds such as zirconium oxide, zirconic acid, zirconium sulfate, zirconyl nitrate, zirconyl acetate, and zirconyl oxychloride. , zirconyl oxysulfate 1, zirconyl ammonium carbonate, zirconyl chloride,
Zirconium oxides such as acetylacetonate and zirconium alkoxide, acids, inorganic salts, organic zirconium compounds, and silicon compounds such as silicon oxide, colloidal silicic anhydride, silicon tetrachloride, organic oxides such as monoammonium , acids, inorganic salts, chlorides, and organosilicon compounds.

In addition to the above, inorganic materials also have rice 1-down, etc.
Clay, mica, talc, glass powder, as needed.
Fire resistant There is no problem in adding or blending them as long as they do not impair the properties.

■Carbon black “Carbon black is a fine black powder that is usually produced by furnace black, acetylene black, and thermal black manufactured by the Seven-Head Ness method, channel black, disk black, and German naphthalene black manufactured by the impact method. It is possible to use commercially available products such as, and it is also possible to use a type in which carbon black, which is obtained by treating inorganic fibers with Kanibon in a high-temperature reducing atmosphere, is fixed and integrated on the surface of the inorganic fibers. can.

Examples of this type include carbon black-fixed potassium titanate fibers, and carbon fibers such as carbon fibers can also be used.

(2) Inorganic fibers As the inorganic fibers, glass fibers, ceramic fibers, rock wool fine fibers, and alkali titanate fibers can be used alone or in combination.

The glass fiber has a composition of 5i0255-65%, Aj
! zOa O~15%, Na200~15%, 8203
4-12%, Ba00-5%, Zn00-5%, Ca0
1-18%, Hg01-6%, 200-4%, Ti
Q2, trace components such as FeO 1% or less (all of the above are old %
) glass fibers of the so-called E or C glass composition can be used. Although the appropriate fiber length is not particularly limited, it is preferably 30 m or less.

Adjustment of the m set length can be carried out arbitrarily, for example, by changing the distance between the teeth of the roping cutter.

The ceramic fiber has a composition of 5iOz5-49%, A
j! 20394-50%, CaO, HgO, 32Q3,
Na2Q.

20, Ti0z, FeO, etc. are less than 1% (
In any of the above cases, a ceramic 11i resin consisting of 100% carbon fibers can be used, but as in the case of the glass fibers, it is preferable to use fibers with a length of 30 seconds or less, although this is not particularly limited.

Ceramic fibers that are suitable for this purpose may be commercially available ceramic fibers that have been cut and their length adjusted, or, for example, Zance Manville 111! J Temp Strumf Eye Bar Q etc. can be used.

The rock wool fine fiber has a composition of 5iOz35-50%, A
120310-15%, CaO20-40%, 8005
~25%, trace components such as TiOz, HnO, FeO, etc. are 1
% (all of the above are wt%), and the fiber length is 700 μm, which is not particularly warm but does not substantially contain non-fiber particles.
m or less can be used. If non-fiber particles are mixed into the rock wool fine 11I fibers or the fiber length is less than 700 μm, the smoothness and appearance of the molded product will be impaired, so the upper limit of the fiber length is preferably 700 μm or less. As a method for making these ceramic fibers and rock wool fine fibers to a desired fiber length, for example, when dry crushing with a pressure kneader, the degree of pressure is varied, or an aqueous dispersion in which inorganic fibers are dispersed in water. 1000~200 Orp when wet grinding liquid with super mixer
Any fiber length can be obtained by changing the high-speed stirring of m and the processing time.

Furthermore, when trying to remove non-mM particles, for example, a water flow rate of 150-200j! This can be carried out by means such as a wet cyclone that utilizes a centrifugal force of /min.

The alkali titanate fiber has a composition of general formula 820, n
Tioz (H stands for 1-iSNa, k, n is a positive real number of 8 or less) with a fiber diameter of 0.1 to 0.7 μm and a fiber length of around 10 μm. can be used.

It may be preferable to use the above-mentioned inorganic material 111111 which has been surface-treated with a silane coupling agent or the like from the viewpoint of dispersibility or mechanical strength. Silane coupling agents as such surface treatment agents include γ-aminopropyl 1-ethoxysilane, vinyl tris β-methoxyethoxysilane 1, γ-methacroxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltrimethoxysilane. Silane, etc. are effective and the treatment amount of the above coupling agent is 0.05-1.0% for Y4 fiber.
A sufficient effect can be obtained at approximately 0%.

■9 Synthetic resins As synthetic resins, thermoplastic and thermosetting resins that are liquid or solid at room temperature can be used as appropriate depending on the application, but common ones include polyethylene, polypropylene, polyvinyl chloride, Representatives include polymethyl methacrylate, borisdylene, 8BS resin As resin, polyisobutylene, polyvinyl acetate, polynylidene chloride, and SBR.
Various synthetic rubbers, engineering plastics such as polyethylene or polybutylene terephthalate, polycarbonate, aliphatic polyamides such as 6-nylon and 66-nylon, polymetaphenylene isophthalamide, aromatic polyamides, polyimides, polyether salts, etc. Thermosetting resins such as polyphenylene oxide, polyacetal, silicone resin, fluorocarbon resin, epoxy resin, melamine resin, polyurethane resin, diallyl phthalate resin, phenol resin, and unsaturated polyester resin are used.

■.Composition and blending method Regarding the blending ratio of each component mentioned above, from the viewpoint of fire resistance, moldability, and mechanical properties of the resin composition, the preferred ratio is titanium oxide + zirconium oxide + Silicon oxide 20-70 parts by weight, carbon black 5-20 parts by weight, inorganic miscellaneous 10-50 parts by weight, synthetic resin 15-6 parts by weight
The content ranges from 0 parts by weight to 0 to 20 parts by weight of the flame retardant + others. The resin composition having the above-mentioned preferable blending ratio can be used as a molding material such as pellets or liquid resin by a melt extrusion method or the like.
mpound) or BMC (Bulk Mold)
In addition, in the form of a putty-like amorphous compound formed by the cross-contact method, it is supplied to a processing manufacturer or a construction manufacturer, where it is manufactured into a final shape that suits the purpose of each of the various industrial and architectural fields. Generally, it is molded and used by extrusion molding, index molding, mold molding, etc., or by on-site construction.

(Effects of the Invention) According to the present invention, at least two kinds of inorganic materials such as titanium oxide, zirconium oxide, and silicon oxide, and carbon black and inorganic fibers are added and blended into a synthetic resin.
When IC encounters fire heat, in a humidity range of 200°C or higher and below the softening temperature of inorganic fibers, the thermal decomposition products of carbon black and resin, inorganic materials, and inorganic material III are fixed and fired, and then titanium oxide and oxidized Inorganic materials such as zirconium and oxidation) react with carbon from resin and carbon black to form carbides (these carbides have a high melting point) on the surface of the inorganic material, resulting in heat and fire resistance. For example, by using FRP building materials as a building material, or liquid resins or rubber-like resins as synthetic resins, paints, sealants, and backing agents that have fire resistance can be obtained. Further, as molded products, it can be used for mechanical parts such as special valves that require continuous heat resistance or resistance to fire heat, and parts in gas-fired drying ovens. Furthermore, since the blending of carbon black imparts electrical conductivity, it can be used, for example, in antistatic molded products in various fields.

[Embodiments of the invention]

The present invention will be described in detail.

Example 1 Component Amount (parts by weight) Zirconium oxide 15 Silicon dioxide thread 65 Carbon black 20 Glass chopped strand 40 Phenol resin 1
00 Methanol
60 Zinc Stearate 3
Among the above ingredients, firstly, except for the glass chopped strands and methanol, other raw materials (2 Ky in solid content)
was kneaded in a Laikai machine, methanol was added thereto, and then glass chopped strands were added. The resulting resin composition was spread finely in a dryer at 40°C, 4 hours, 6
It was dried at 0° C. ihr to evaporate methanol to obtain a non-sticky phenol resin composition.

The above phenol resin composition was put into a mold coated with a silicone male mold material of 20 cm x 20 c IR1 spacer 3 m, and the phenol resin composition was put into a mold with a pressure of 80 Kg101, a press temperature of 150°C, and a time of 30 minutes to form phenol. A prototype resin FRP board was manufactured. The physical properties of the obtained FRP board are as follows.

Oxygen index 65-67, specific gravity 2.120, thickness 2.9 #1
11, bending strength 581 K9/r, d, tensile strength 231
Ky/al.

Heat resistance (evaluated by tensile strength) Original (untreated) 231Ny/ai100℃
Heat treatment for 30 minutes 24: 1g/cd 150℃ 30 minutes heat treatment 240 to 9/cd 200℃ 30 minutes heat treatment
221 to 9/m 250℃ 30 minutes heat treatment 145/
(y/cd 300℃ 30 minutes heat treatment 149kg/c
d At around 200℃, the tensile strength slightly decreases, or after 3
It maintains 65% of its original strength up to 00°C, and has good heat resistance.

Heat-resistant acetylene I--Civana from phenol FRP board 1
I released the OCR and did a flame test.

The surface temperature at this time had reached 1030°C to 1060°C, but even after applying the burner for more than 10 minutes, the sample surface remained
It turned white and became slightly red due to the heat of the fire, but no penetration or deformation was observed, indicating that it had fire-resistant performance.

Example 2 Component Amount (parts by weight) Zirconium oxide 15 Silicon dioxide 30 Carbon black 10 Milled fiber 15 Potassium titanate tlAt4 5 Vinyl chloride resin 15 Plasticizer (DOP) ? Rosin 2 cheap
Fixing agent 1 Approximately 8 kg of the above blend was kneaded at a temperature of 130 to 140°C in a pressure kneader, then formed into a sheet with a thickness of 2 m using a calendar roll at 130 to 140°C, and further heat-treated at 150°C for 20 minutes. Then, we made a flexible vinyl chloride resin sheet. The physical properties of the obtained sheet are as follows.

Thickness 2. ．． 03m, specific gravity 2.013, oxygen index 72.
74, tensile strength tn, 3gy/aa, electrical resistance 7.3X
106Ω.

Heat resistance (evaluated by tensile strength) Original (untreated) 47.389/l: d10
Heat treatment at 0℃ for 30 minutes 47.9 to 9/r:d150℃
30 minute heat treatment 49.5 to 9/d 200℃ 30 minute heat treatment 53.1 to 9/Cd 250℃ 30 minute heat treatment 69.389/c #1 The strength increases slightly at 250℃, but this is due to the stretching effect during calendering. Something,
It does not mean that the strength has essentially increased. But 250
No deterioration in strength was observed up to ℃, and the heat resistance was also found to be good.

A test similar to that of Fire Resistance Example 1 was conducted;
Even after heating with a burner for 0 minutes, the resin melted and covered some parts, but there was no major deformation or penetration, indicating that it had fire resistance.

Example 3 Component Amount (parts by weight) Titanium oxide (rutile type) 2.0 Zirconium oxide 15 Silicon dioxide 1
5 Carbon black 10.0 Potassium titanate fiber @ 5.0 Rock wool fine fiber 5.0 Isobutylene resin 5.0 Butyl rubber solution 25.0 Aluminum hydroxide 16.95 Cobalt naphthenate 0.05 Stearin 9 1 .0 10 parts by weight of solvent naphtha (solvent) was added to 90 parts by weight of the above blend, and kneaded little by little in a small bench kneader to obtain a viscous putty-like resin composition.

This putty-like material was spread with a trowel on a glass plate for about 2am, and left for one day and night to obtain a flexible sheet. The 24 Hrs water absorption rate of this sheet was 0.2 wt%, showing no water absorption at all and good waterproof properties. In addition, for the joints of the hollow extruded cement board with a thickness of 50 m (joint 1J: 20 m),
A glass foil of 10009/'Id with a thickness of 10 m was used as a back-up material, and then sealed with the above putty-like material and air-dried for 3 days and nights to make a prototype waterproof joint. After natural curing (3 days), this cement board with joints (17F
There is a joint at 50 cps in the center of LX1m), J
When a 60-minute fire resistance test was conducted in accordance with I5A-1304, the temperature on the back side of the joint was 193°C, passing the 60-minute fire resistance grade, and it was found to have fire resistance.

Comparative Example Ingredients Amount (parts by weight) Glass chopped strand 40 Phenol resin
100 Zinc stearate Calcium 3 carbonate 100 Methanol
60 The above formulation was molded in the same manner as in Example 1, and phenolic resin FRP was molded.
I made a prototype board. The physical properties of the obtained FPR plate are as follows.

Oxidation index 64-66, specific gravity 2.119, thickness 2.9#1
1 Bending strength 567Ky/cd, tensile strength 227N9/c
i.

Heat resistance (evaluated by tensile strength) Original (untreated) 227 to 9/r: t110
Heat treatment at 0°C for 30 minutes 232 to 9/ci 150°C 30
minute heat treatment 22ONy/c11200℃30 minute heat treatment 203Kg/m250℃30 minute heat treatment 1
28Kg/cd 300℃ 30 minutes heat treatment 101Kg
/cd The strength deterioration increases from a temperature of around 200°C.

Fire resistance: 1 higher than Fnor FRP board using an acetylene torch burner
A flame test was conducted with a distance of 0c#I. The surface temperature at this time reached 1030℃~1060℃, and the sample
It penetrated within seconds, showed a distorted shape, and was found to have no fire resistance.

The above-mentioned Examples 1.2.3 and Comparative Examples show that the resin composition according to the present invention has good mechanical strength and external combustibility, and also has good conductivity and
The materials and test methods used in Examples 1.2.3 and Comparative Examples are as follows.

material Carbon black Furnace black manufactured by Asahi Carbon Co., Ltd.

ziconium oxide Zirconia powder manufactured by Shin Nippon Metal Chemical Co., Ltd.

1 mol of phenol, 1.5 mol of formalin, resol resin with caustic soda catalyst (111 degrees 80%, methanol solution).

silicon dioxide 200 mesh pass general commercial product.

zinc stearate Reagent-grade commercial product.

Glass chopped strand C86PE-221, 1/4 inch cut, manufactured by Nitto Boseki Co., Ltd.

PVC Kanebi M-1007° plasticizer manufactured by Kanebuchi Chemical Co., Ltd. DOP0 manufactured by Kyowa Hakko Co., Ltd. rosin Tylene 3902° stabilizer manufactured by Arakawa Chemical Co., Ltd. Ferro-based stabilizer manufactured by Nissan Fuichi Organic Chemical Co., Ltd.

potassium motanate fiber Moss manufactured by Otsuka Chemical Co., Ltd.

Milled fiber Glass milled fiber manufactured by Nittobo Co., Ltd. Butyl rubber solution Butyl rubber-065 manufactured by Exxon Chemical Co., Ltd. (50% cap 1° polyisobutylene Detrax 4T manufactured by Nippon Petrochemical Co., Ltd.).

stearic acid Reagent-grade commercial product.

Titanium oxide Rutile type S R-1° manufactured by Sakai Chemical Co., Ltd. Aluminum hydroxide manufactured by Showa Light Metal Co., Ltd. Heijirai 1-11-4M0 Cobalt naphthenate 6% concentration reagent-grade commercial product.

Rock wool microfiber Nittobo Co., Ltd. microfiber NI calcium carbonate 200 mesh pass general commercial product.

Measurement method based on oxygen index J 15K7201. Uses oxygen index combustion tester manufactured by Suga Test Instruments Co., Ltd.

Bending strength span 50M, width 20M crosshead speed 50#
Measured in /min. Measuring equipment: Tensilon manufactured by Toyo Ballwin.

A dumbbell-shaped test piece with a tensile strength of 13 InM in the center and 20 # in both ends and a length of 155 M, using Denjiron manufactured by Toyo Ballwin Co., Ltd., was provided at a crosshead speed of 50 mm for 1 minute.

Electrical resistance based on JISC6481. VMG-100 manufactured by Ando Electric Co., Ltd.
use.

Claims (1)

[Claims] (1) A resin composition characterized by adding and blending at least two kinds of inorganic materials such as titanium oxide, zirconium oxide, and silicon oxide, carbon black and inorganic fibers to a synthetic resin.