JPH0493361A - Abrasion-resistant resin composition - Google Patents

Abstract

PURPOSE:To obtain the title compsn. which is suitably applied to the part which is subject to abrasion or damage by friction, impact, etc., in various equipment and thereby effectively improves the maintenability of the equipment by compounding a thermosetting resin, an abrasion-resistant material, a whisker, and a carbon fiber as essential components. CONSTITUTION:The title compsn. comprises 9-75wt.% thermosetting resin, 20-90wt.% abrasion-resistant material, 0.05-40wt.% whisker, and 0.05-25wt.% carbon fiber. As the whisker, at least one whisker selected from the group consisting of compds. shown by a general formula: A2O.nTiO2 (wherein A is an alkali metal; and n is 1, 2, 4, 6, or 8) is used. Examples of the abrasion- resistant material are an impact-resistant metal, a metal compd., a natural mineral, a ceramics, etc.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention is applied to parts of various equipment that are easily worn out or damaged by friction, impact, etc., to impart wear resistance and improve equipment maintainability. This invention relates to a resin composition that is effective for increasing wear resistance.

(Prior art) Conventionally, as a method of imparting wear resistance to the surface of a substrate that requires wear resistance, a rubber sheet containing metal particles, ceramic particles, ceramic tiles, etc. or attached to the surface is attached to the surface of the substrate. Methods such as pasting with an adhesive and methods in which a resin composition prepared by mixing various synthetic resins with an abrasion resistant material are applied to the surface of the substrate and then cured have been implemented. Particularly in the latter method, wear-resistant resin compositions consisting of thermosetting resins and wear-resistant materials have come to be used heavily.

(Problem to be solved by the invention) However, with the method of attaching a rubber sheet with a wear-resistant material inside or attached to the surface of the substrate, it is extremely difficult to use it on sharply bent surfaces, small diameter curved surfaces, and work inside pipes. and
Furthermore, if used for a long period of time even after installation, problems such as peeling of the wear-resistant material and peeling of the rubber sheet may occur.

Furthermore, uniformly kneading the wear-resistant material and the rubber with low fluidity takes time and effort, and there are also problems in terms of workability.

On the other hand, the abrasion-resistant resin composition made of a thermosetting resin and an abrasion-resistant material used to impart abrasion resistance is superior to other conventional methods in terms of ease of manufacture and application, and abrasion-resistant performance. Are better. However, the following problems remain.

In a wear-resistant resin composition composed of a thermosetting resin and an abrasion-resistant material, if the mixing ratio of the wear-resistant material is increased in order to improve the wear-resistant performance, the fluidity of the wear-resistant resin composition decreases, making it difficult to work during manufacturing and installation. This not only reduces the properties of the thermosetting resin and the wear-resistant material, but also weakens the bond between the thermosetting resin and the wear-resistant material, causing the wear-resistant material or the wear-resistant resin composition to peel off from the substrate after application. If the mixing ratio of the wear-resistant material is lowered, the workability will be improved or the wear-resistant performance will be lowered. In addition, even if workability is somewhat inferior, increasing the mixing ratio of wear-resistant materials may improve wear resistance to a certain extent, or may cause wear damage to the other object.
In some cases, this may not only reduce the quality of the object, but also cause equipment to become clogged or interfere with operation. Furthermore, it has poor heat resistance, which limits its use in many areas.

(Means for Solving the Problems) In order to solve the above-mentioned problems, the present invention provides a wear-resistant resin composition that includes a thermosetting resin, a wear-resistant material, whiskers, and carbon fibers as its compounding composition. This paper proposes a wear-resistant resin composition with characteristics.

The whisker has the general formula % (-A is an alkali metal, n is 1.2.4.6.8
) is at least one of the whiskers of the compound represented by . Whiskers are perfect crystals with almost no structural defects, and their mechanical strength is close to ideal, so they can be mixed into conventional wear-resistant resin compositions to increase wear resistance and heat resistance, as well as impart clear flow properties to the composition. . The compound alkali titanate represented by the above formula is a white needle-like crystal, and its whiskers are inorganic short fibers with a diameter of 0.2 to 0.5 μm and a length of 10 to 20 μm, and a large aspect ratio. The alkali metal represented by A in the formula includes sodium, potassium,
Examples of compounds include rubidium, titanic acid,
Examples include potassium, sodium, and rubidium of nititanic acid, tetratitanic acid, hexatitanic acid, and hetitanic acid. Among these compounds, sodium hexatitanate, potassium hexatitanate, and rubidium hexatitanate are the most promising in terms of the stability of compound whiskers, the manufacturing process of the wear-resistant resin composition, the implementation method, and the wear-resistant performance. Potassium titanate is most preferred. Moreover, hydrates of these compounds can also be applied.

Note that the whiskers are synthesized by various manufacturing methods, such as a firing method, a slow cooling firing method, a melting method, a melt method, a flux method, a hydrothermal method, etc., and the manufacturing method is not specified.

Examples of thermosetting resins used in the present invention include urethane resins, epoxy resins, unsaturated polyester resins, epoxy acrylate resins, furan resins, polyimide resins, silicone resins, etc., and are not particularly limited.
They can be used alone or in combination. Among these thermosetting resins, urethane resins or epoxy resins are preferred, and both corrugated and two-component types can be used.

Examples of the wear-resistant material used in the present invention include metals with excellent impact resistance, metal compounds, various natural ores, and various ceramics. Particularly preferred are ceramics represented by silicon carbide, boron carbide, molten alumina, alumina zirconia, etc., and granules obtained by crushing, sintering, or pulverizing these natural or artificial high-hardness compounds are particularly preferred. These wear-resistant materials may be used alone or in combination of two or more. The shape of the wear-resistant material is not particularly limited, such as spherical, polyhedral, cylindrical, prismatic, etc., and materials of different shapes and sizes may be used in combination.

The carbon fiber used in the present invention has high strength and is excellent in abrasion resistance, chemical resistance, heat resistance, etc. For example, polyacrylonitrile (hereinafter abbreviated as rPAN) is oxidized to form a blackened fiber and then infusible. There are pitch-based carbon fibers obtained by oxidizing and infusible PAN-based carbon fibers obtained by using the PAN-based carbon fibers as a raw material, but there are no particular limitations thereto.

Even if carbon fiber is blended into a conventional wear-resistant resin composition, no significant improvement in wear resistance is observed, but when used in combination with whiskers, the effect is significantly greater than when whiskers and carbon fibers are used alone. Significant improvements in abrasion resistance, heat resistance, and thermal shock resistance were observed.

In the wear-resistant resin composition of the present invention, preferred blending ratios of the thermosetting resin, wear-resistant material, whiskers, and carbon fibers are as described below.

Thermosetting resin 9 to 75 wt%, particularly preferably 15 to 6
5 wt%, wear-resistant material 20-90 wt%.

Particularly preferably 30 to 80 wt%1 whisker 0.
05-40 wt%, particularly preferably 0.5-20 wt%
, 0.05 to 25 wt% carbon fiber, particularly preferably 0.05 to 25 wt% carbon fiber.
It is 5 to 15 wt%.

If the blending amount of the thermosetting resin is less than 9 wt%, it will be difficult to mix other blended raw materials such as wear-resistant materials, whiskers, and carbon fibers, and these additives will be peeled off from the produced wear-resistant resin composition.
The fallout becomes severe. Moreover, when it exceeds 75 wt%, wear resistance decreases.

If the amount of the wear-resistant material is less than 20 wt %, the wear resistance will be poor, and the wear-resistant resin composition will likely peel off or chip off the substrate surface. If it exceeds 90 wt%, there will be no clear flowability (not only will it become difficult to manufacture and apply the wear-resistant resin composition, but also the wear resistance will decrease).

If the whisker content is less than 0.5 wt%, thermal shock abrasion resistance will be poor, and if it is less than 0.05 wt%, the ability to impart abrasion resistance and clear flow properties to the wear-resistant resin composition will not be recognized. Addition of 1wt% or more of whiskers made it possible to prevent abrasion damage to the opposing object, but 5wt% or more of whiskers
If it exceeds 40 wt %, the coating work tends to deteriorate, and if it exceeds 40 wt %, the abrasion resistance tends to decrease.

When the blending amount of carbon fiber is 0.05 wt% or more, wear resistance and heat resistance are improved, and when it exceeds 0.5 wt%, excellent thermal shock abrasion resistance is obtained. At 15 wt% or more, abrasion resistance and clear flow properties tend to decrease.

The essential active ingredients of the wear-resistant resin composition of the present invention are a thermosetting resin, a wear-resistant material, whiskers, and carbon fibers. Colloidal cica, organic bentonite, hydrogenated castor oil, finely divided calcium carbonate, vinyl chloride powder and known thixotropic agents, solvents, hardening accelerators, plasticizers, stabilizers, organic or inorganic fibers other than carbon fibers Additives such as fillers, colorants, antifoaming agents, flame retardants, electromagnetic wave sealants, antistatic agents, etc., such as aluminum powder, alumina powder, and silica powder, may be used as appropriate within the range that does not impair wear resistance. .

The wear-resistant resin composition of the present invention includes a thermosetting resin, a wear-resistant material,
It can be obtained by uniformly mixing whiskers and carbon fibers or the above-mentioned additives, or by applying a thermosetting resin to the surface of a substrate and scattering an abrasion resistant material, whiskers and carbon fibers on the surface.

In producing the wear-resistant resin composition of the present invention, before blending the wear-resistant material, whiskers, and carbon fibers into the thermosetting resin, a chemical surface treatment such as a silane coupling agent, a titanium coupling agent, a resin, a chemical solution, etc. The bonding between the thermosetting resin and the additive can be facilitated and strengthened by treatment or physical surface treatment such as plasma etching.

The substrate to which the abrasion resistant composition of the present invention is applied can be made of any material as long as abrasion resistance is required, and examples thereof include metal, wood, glass, concrete, and the like. When applying to porous materials such as wood or concrete, or surfaces with cracks, seal the damaged areas with putty, powder, resin, etc., and use blasting or oil-based cleaning as necessary. It is also effective to perform surface treatment such as wiping. Further, peeling of the wear-resistant layer can be prevented by removing rust from the surface of the substrate, treating it with phosphoric acid, and treating the surface with a coupling agent.

In addition, we remove rust from the surface of the substrate, treat it with phosphoric acid, treat the surface with a coupling agent, and if necessary, apply a primer to the surface of the substrate in advance to prevent the peeling of the wear-resistant layer and further ensure wear resistance. I can do it. The primer used is not particularly limited, and may be a known one-component or two-component primer, or one that has good adhesion to the substrate surface and good adhesion between the wear-resistant material and the wear-resistant resin composition. Those with excellent properties are preferable. Examples include two-component epoxy resin primer, wave-type moisture-curable urethane resin primer, modified silicone primer, and phenoxy resin primer. The amount of primer applied is
Although not particularly limited, it is usually 30 to 500 g/m2.

If necessary, a top coat may be applied on the surface of the wear-resistant layer formed on the substrate surface using the wear-resistant resin composition of the present invention. [It promotes wear performance.]

(Operation and Effect of the Invention) By using the abrasion-resistant resin composition of the present invention, it is possible to apply the abrasion-resistant resin composition to the inside of a pipe, which was almost impossible with the conventional method of attaching a rubber sheet containing an abrasion-resistant material to the substrate surface. We were able to solve problems such as peeling of wear materials and peeling of rubber sheets. In addition, by adding whiskers and carbon fibers, compared to conventional wear-resistant resin compositions consisting of thermosetting resin and wear-resistant material, not only the wear resistance, heat resistance, and thermal shock resistance are improved, but also the resistance to wear is improved. The abrasion resin composition is given clear flowability and spreadability, making preparation work and application work to the substrate surface extremely easy.

In addition, as wear resistance improves, wear and tear on the opposing object are almost eliminated, resulting in lower grain quality due to abrasion and damage during transportation of grain, silo storage, etc., and damage to equipment due to abrasion debris from metals and ores. This has resulted in significant improvements in problems such as operational obstruction due to clogging and shortened equipment life due to belt wear.

Furthermore, heat resistance and thermal shock resistance have been dramatically improved, making it possible to impart wear resistance to equipment used in high-temperature work fields.

Therefore, transport pipes for gases, liquids, solids, slurries, etc.
In particular, the inner surfaces of bends, the inner surfaces of slurry pump casings, the walls of cyclones, hoppers, shooters, etc., the working surfaces of pulley idlers, etc., the inner surfaces of silos, quay walls,
This will make it easier and more reliable to prevent wear on the splash zones of bridge piers, simplify maintenance of these equipment, and greatly contribute to this type of industry.

(Examples) Next, specific examples and comparative examples of the wear-resistant resin composition of the present invention will be described.

The abrasion resistance test method and thermal shock abrasion resistance test method conducted in the present examples and comparative examples are as follows.

[Abrasion resistance test]

Substrate with wear-resistant layer (A) 25°C1 (B) 130°C
'C and (C) 500 each in an atmosphere of 200℃
Immediately after holding the wear-resistant layer for 20 cycles, strongly contact the surface of the wear-resistant layer with a resinoid-type round whetstone (diameter 2゜5-5-1l125 with a grain size of No. 40) at a rotation speed of 120 Orpm for 3 seconds at 2-second intervals. The surface condition of the specimen and the surface condition of the resinoid type grindstone were observed.

[Thermal shock abrasion test]

(A> The test piece is heated from room temperature to SO'C over 1 hour and immediately immersed in cold water at 5°C. After carrying out 20 cycles of this thermal shock test, the above-mentioned abrasion test is carried out. conduct,
Observe the surface condition of the specimen and grindstone.

(B) In (A), the high temperature range is 180'c and the low temperature range is 2
The water was at 5°C.

(Example 1) 80 parts by weight of Sumiepoxy ELA-128 (part name manufactured by Sumitomo Chemical Co., Ltd., epoxy resin), Sumiepoxy ELA
20 parts by weight of -301 (part name, epoxy resin manufactured by Sumima Kagaku Kogyo Co., Ltd.), Sumicure P740 (produced by Sumima Kagaku Kogyo Co., Ltd.)
Co., Ltd. part name, hardening agent for polyamide-based epoxy resin) 4
After thoroughly mixing 1 part of 5-weight and 2 parts by weight of Sumicure D (part name, curing accelerator for epoxy resin, manufactured by Sumima Kagaku Kogyo Co., Ltd.) to obtain a thermosetting resin composition, immediately alumina zirconia crushed particles (average 430 parts by weight (particle size: 1.2 mm), 25 parts by weight of sodium tetratitanate whiskers, 6 parts by weight of carbon fibers and 23 parts by weight of calcium carbonate powder were added and thoroughly mixed to obtain a wear-resistant resin composition.

This wear-resistant resin composition was applied to a thickness of 5 ann on the surface of a 300 mm x 300 on x 3- steel plate that had been subjected to sandblasting and primer treatment in advance. The application work could be carried out smoothly using a flat trowel.

After curing at room temperature for one day, after-curing was performed in an oven at a temperature of 50°C for 5 hours to prepare a test piece having an abrasion-resistant layer.

The above-mentioned abrasion resistance test and thermal shock abrasion resistance test were conducted on the obtained test pieces, and the results are shown in Table 1.

(Example 2) A wear-resistant resin composition was produced using the same composition as in Example 1, except that potassium hexatitanate whiskers were used instead of sodium tetratitanate whiskers in Example 1, and the same treatment was performed. Test pieces were prepared in this manner and subjected to the abrasion resistance test and thermal shock abrasion resistance test described above, and the results are shown in Table 1.

(Example 3) 150 parts by weight of the same thermosetting epoxy resin composition as the thermosetting resin composition obtained in Example 1, 325 parts by weight of crushed alumina zirconia (average particle size 1.2 an), and 65 parts by weight of boron nitride were added. parts by weight, 7 parts by weight of potassium hexatitanate whiskers, 23 parts by weight of carbon fibers, 15 parts by weight of calcium carbonate, and 15 parts by weight of clay powder were added and thoroughly mixed to obtain a wear-resistant #greasy composition.

A test piece with a thickness of 5 m was prepared from this abrasion-resistant resin composition in the same manner as in Example 1, and the above-mentioned abrasion resistance test and thermal shock abrasion resistance test were conducted. The results are shown in Table 1.

In addition, the mixing operation and the coating operation of the composition during preparation of the wear-resistant resin composition were easy.

(Example 4) 100 parts by weight of Smear Tube MC;-IL (part name manufactured by Sansei Kako Co., Ltd., unsaturated polyester resin), 0.5 parts by weight of 8% cobalt octinate, and Sanhard SL (Sansei Kako Co., Ltd.) 25050 parts by weight of crushed alumina zirconia particles (average particle size 1.5 wm) 200 parts by weight of fused alumina ceramic sand (average particle size θ, 1 mm), 25 parts by weight of potassium hexatitanate whiskers and 25 parts by weight of carbon fibers were added and mixed uniformly to prepare a wear-resistant resin composition.

This abrasion-resistant resin composition was applied to the surface of a 300mm x 300mm x 3m steel plate that had been sandblasted and primed in advance to a thickness of 5mm, cured at room temperature for 1 day, and then placed in an oven at a temperature of 40°C for 5 hours. A specimen having a wear-resistant layer was prepared by curing.

The mixing operation during the preparation of the wear-resistant resin composition and the application operation of the composition were easy. The test piece was subjected to an abrasion resistance test and a thermal shock abrasion resistance test in the same manner as in Example 1, and the results are shown in Table 1.

(Example 5) Polyflex FL-37 (Daiichi Kogyo Seiyaku Co., Ltd. MI brand name, polyisocyanate compound, NGO content 6.5
%) 96 parts by weight and 1 part by weight of colloidal silica 4 parts by weight, 3.3゜dichloro-4,4-diaminodiphenylmethane 19.5 parts by weight, 18 parts by weight of dioctyl phthalate, and 8 parts by weight of clay powder. , colloidal silica 3
parts by weight, a composition containing 1.5 parts by weight of a silane coupling agent is used as a curing agent, and this main ingredient and curing agent are mixed at a mixing ratio of 2:1.
(weight ratio) to obtain a thermosetting resin composition, immediately after mixing 250 alumina zirconia crushed particles (average particle size 2 mm)
Parts by weight, 50 parts by weight of fused alumina ceramic sand, 12 parts by weight of potassium hexatitanate whiskers, 7 parts by weight of carbon fiber, 30 parts by weight of clay powder, and 1 part by weight of titanium coupling agent.
parts by weight were added and mixed well to obtain an anti-wear composition.

This abrasion-resistant resin composition was applied to a thickness of 5 m on the surface of a 300 m x 300 x 3 m steel plate that had been sandblasted and primed in advance, and cured at room temperature for 7 days to create a test piece with an abrasion resistant layer. .

The mixing operation during the preparation of the wear-resistant resin composition and the application operation of the composition were easy.

The test piece was subjected to an abrasion resistance test and a thermal shock abrasion resistance test in the same manner as in Example 1, and the results are shown in Table 1.

(Example 6) 8 parts by weight of potassium hexatitanate whiskers and 10 parts by weight of carbon fiber were added to 150 parts by weight of the same thermosetting resin composition as prepared in Example 5, and mixed well to obtain a thermosetting resin paste. Ta.

Pre-sandblasted and primed 300
A vinyl chloride frame plate with a height of 5mm is fixed around a steel plate measuring m x 300mm x 3mm, and a thermosetting resin paste is first applied to a thickness of about 1m, and then a wear-resistant material is filled on top of it, and the steel plate is The steel plate was left to shake for several minutes from the back side, and while the paste was still unhardened, the steel plate was turned over to remove the wear-resistant material that had not become densely hardened. After hardening to the touch, the paste was further applied on top of it, filled with wear-resistant material, shaken, and excess wear-resistant material removed.Finally, a thermosetting resin paste was top coated to form a layer of wear-resistant resin composition with a thickness of 5 m. Formed.

A specimen with a wear-resistant layer was prepared by curing and curing for 7 days.

The ratio of the total amount of thermosetting resin paste used to the total amount of wear-resistant material was 50.70 by weight.

The test pieces were subjected to an i11 abrasion test and a thermal shock abrasion test in the same manner as in Example 1, and the results are shown in Table 1.

(Example 7) A test piece similar to Example 6 was prepared by applying the same thermosetting resin composition and wear-resistant material as prepared in Example 3 according to the method of Example 6, and the wear-resistant Tests and thermal shock abrasion resistance tests were conducted, and the results are shown in Table 1.

However, the ratio of the total amount of thermosetting resin composition used to the total amount of wear-resistant material was 28:82 by weight.

(Comparative Example 1) A wear-resistant resin composition was prepared in exactly the same manner as in Example 2, except that potassium hexatitanate whiskers and carbon fibers were not used, and test pieces were prepared to test the wear resistance. Abrasion tests and thermal shock abrasion tests were conducted, and the results were presented in the first
Shown in the table. Application of the abrasion resistant resin composition during the preparation of the test piece required considerable force, making it difficult to handle with a trowel, and furthermore, it was difficult to smooth the surface.

(Comparative Example 2) A wear-resistant resin composition was prepared in exactly the same manner as in Example 2, except that titanium oxide powder was used instead of potassium hexatitanate whiskers and carbon fibers, and a test piece was prepared. The samples were prepared and subjected to an abrasion resistance test and a thermal shock abrasion resistance test, and the results are shown in Table 1. The wear-resistant resin composition was harder than that of Example 2 (and the application work was not easy).

(Comparative Example 3) A test piece was prepared in exactly the same manner as in Example 2 except that potassium hexatitanate whiskers were not used in Example 2, and a wear resistance test and a thermal shock abrasion test were conducted. are shown in Table 1. The wear-resistant resin composition was harder than that of Example 2, and the application work was not easy.

(Comparative Example 4) A test piece was prepared in exactly the same manner as in Example 2 except that carbon fiber was not used in Example 2, and a wear resistance test and a thermal shock abrasion test were conducted. Shown in the table. Preparation and application of the wear-resistant resin composition were easy as in Example 2.

In the table, abrasion resistance columns A, B, and C indicate the holding temperatures of the specimens at 25°C, 130″C, and 200°C.

Thermal shock and abrasion resistant manufacturing bath A is a cycle of 80°C and 5°C, and tank B is a cycle of 180°C and 25°C.

The symbols in the table are ◎; Almost no change O: Some wear With low wear △2: A lot of wear, and some peeling of the wear-resistant material is observed. shows.

From the results of Examples and Comparative Examples, the wear-resistant resin composition of the present invention has a resistance of +1! It can be seen that the preparation work of the composition and the work of applying the substrate/\\ are easier than the wear resin composition, and the wear resistance, heat resistance, and thermal shock abrasion resistance are superior.

(Note) All values are the average values of three repetitions.

Claims (1)

[Claims] 1. In the wear-resistant resin composition, the blending composition thereof is as follows:
A wear-resistant resin composition comprising a thermosetting resin, a wear-resistant material, whiskers, and carbon fibers. 2 The whisker has the general formula A_2O・nTiO_2 (in the general formula, A is an alkali metal, and n is 1, 2, 4, 6, 8
The wear-resistant resin composition according to claim 1, wherein the composition is at least one whisker of a compound represented by the following. 3. The composition of the wear-resistant resin composition is 9 to 75 wt% of thermosetting resin, 20 to 90 wt% of wear-resistant material, 0.05 to 40 wt% of whiskers, and 0.05 to 25 wt% of carbon fiber.
The wear-resistant resin composition according to claim 1.