JP2813802B2 - Wear resistant resin composition - Google Patents

Description

The present invention relates to a wear-resistant resin composition. More specifically, the present invention relates to an abrasion-resistant resin composition which is applied to the surface of a substrate of equipment or equipment which is liable to be worn or damaged by impact, friction, etc., and is effective for abrasion resistance maintenance.

(2) Prior Art Conventionally, as a method of imparting abrasion resistance to the surface of a substrate that requires abrasion resistance, a rubber sheet containing metal particles, ceramic particles, ceramic tiles, or the like is adhered to or adhered to the surface of the substrate. A method of attaching with an adhesive, a method of applying a resin composition obtained by mixing a wear-resistant material to various synthetic resins on the surface of a substrate, and curing the same have been carried out. In particular, in the latter method, a wear-resistant resin composition comprising a thermosetting resin and a wear-resistant material has come to be used heavily.

(3) Problems to be Solved by the Invention The above-mentioned wear-resistant resin composition comprising a thermosetting resin and a wear-resistant material used for imparting wear resistance is easy to manufacture and implement, and has a different wear resistance performance than conventional ones. It is superior to the above method.

The present inventor studied the method of imparting wear resistance using this kind of wear-resistant resin composition, and when trying to improve the wear resistance of the base material by increasing the mixing amount of the wear-resistant material, the fluidity of the composition was reduced. As a result, the workability is reduced, the bonding strength between the resin and the wear-resistant material is poor, and the wear-resistant material and the composition itself after the application are peeled off. When the mixing amount is small, the wear-resistant performance is naturally not exhibited. Although the workability is somewhat inferior, when the mixing amount is appropriate, the wear resistance performance is surprisingly exhibited, but on the other hand, it causes wear damage to the mating object, and in some cases, not only the quality of the mating object but also the It has been found that it leads to clogging and hindrance to driving.

The inventor of the present invention has investigated the surroundings of such circumstances in detail and has conducted intensive studies to solve the drawbacks of the conventional wear-resistant resin composition comprising a thermosetting resin and a wear-resistant material.

That is, an object of the present invention is to provide a wear-resistant resin composition capable of imparting improved wear resistance to a substrate and a method for imparting wear resistance using the same. It is still another object of the present invention to provide a wear-resistant resin composition which has better workability in mixing and preparing and applying the composition than conventional compositions of this kind, and which does not cause abrasion damage to a mating object.

(4) Means for Solving the Problems The present invention is a wear-resistant resin composition comprising a thermosetting resin, a wear-resistant material, and a whisker of a compound represented by the following formula.

A ₂ O · nTiO ₂ (where A represents an alkali metal, and n represents an integer of 1, 2, 4, 6, or 8.) The thermosetting resin used in the present invention is not particularly limited. For example, a urethane resin , Epoxy resin, unsaturated polyester resin, epoxy acrylate resin, furan resin,
Examples include a polyimide resin and a silicon resin. Among them, urethane resins are preferable, and as the urethane resin, both one-pack type and two-pack type are excellent. These thermosetting resins can be mixed and used as long as they have no adverse effect.

Examples of the wear-resistant material used in the present invention include impact-resistant metal compounds, various natural ores, and various ceramics. Especially silicon carbide, boron carbide, silicon nitride,
Ceramics represented by boron nitride, dissolved alumina, alumina zirconia, and the like are preferred, and granules obtained by crushing or sintering or crushing these natural or artificial high-hardness compounds are preferably used. Can be. Several of these wear resistant materials may be used in combination.

The shape of the wear-resistant material is not particularly limited, such as a sphere, a polyhedron, a cylinder, and a prism, and different shapes and sizes can be used in combination.

The compound represented by the following formula A ₂ O · nTiO ₂ (where A represents an alkali metal and n represents an integer of 1, 2, 4, 6, or 8) used in the present invention is a white needle-like alkali. Crystals, whose whiskers are about 0.2-0.5μ in diameter
It is an inorganic short fiber having a large aspect ratio and a length of about 10 to 20 μm (according to microscopy). In the formula, the alkali metal of A includes potassium, sodium, rubidium, and the like. Specific examples of the compound include titanic acid, dititanic acid, tetratitanic acid, hexatitanic acid, potassium, sodium and octitatinate. Although rubidium is mentioned, preferred compounds are sodium hexatitanate, potassium hexatitanate and rubidium hexatitanate. Among them, potassium hexatitanate is most preferred in view of the stability of the compound whisker, the production and execution of the wear-resistant resin composition, the effect on the performance, the effect, and the like.

Hydrates of these compounds can also be used.

The whisker of the compound of the formula can be prepared in various ways, for example by calcination,
It is synthesized by a slow cooling firing method, a melting method, a melt method, a flux method, a hydrothermal method or the like, and the production method is not particularly selected.

The preferred proportions of the thermosetting resin, the wear-resistant material and the alkali titanate whisker used in the present invention are 9-30% by weight of the thermosetting resin, 50-90% by weight of the wear-resistant material, and 0.5-20% by weight of the alkali titanate whisker. It is.

When the use amount of the thermosetting resin is 9% by weight or less, it is difficult to mix the wear-resistant material and the alkali titanate whisker, and the exfoliation and drop-off of these additives from the resulting composition becomes severe. 30
If the content is more than 10% by weight, abrasion resistance becomes poor.

If the use amount of the wear-resistant material is less than 50% by weight, the wear resistance is poor. If the use amount is more than 90% by weight, the work of mixing and applying the composition becomes difficult, and the cured composition is liable to peel off or drop off, resulting in poor wear resistance. Deteriorate. 0.5 to 20 alkali titanate whiskers
By using the amount by weight, the composition has a slipperiness and the mixing and coating operations are facilitated, and the cured composition has improved resistance to thermal shock.

Conventionally, in a composition not using alkali titanate whiskers, when the wear-resistant material is used in an amount of 70% by weight or more, the hardness rapidly increases, the sliding property is lost, and adjustment work and application work are difficult. It is possible to use more than 90% by weight. 0.5% by weight of alkali titanate whisker
In the following, the ability to impart a glide property to the resin composition is not recognized, and the resistance to thermal shock is poor. The addition of 1% by weight or more makes it possible to prevent wear damage of the mating object, but if it exceeds 20% by weight, the abrasion resistance tends to decrease.

The essential effective components of the wear-resistant resin composition used in the present invention are thermosetting resin, wear-resistant material and alkali titanate whisker, and if necessary, colloidal silica, organic bentonite, hydrogenated castor oil, fine-grained charcoal Well-known thixotropic agents such as cal, PVC powder, solvents, curing accelerators, plasticizers, stabilizers or silane coupling agents, surface treatment agents such as titanium coupling agents, organic or inorganic fibrous substances, alumina powder, silica Additives such as powders and the like, coloring dye pigments, defoamers, flame retardants, electromagnetic wave sealants, antistatic agents and the like can be appropriately used as long as the properties of the wear-resistant resin composition are satisfied.

The abrasion-resistant resin composition of the present invention is obtained by uniformly mixing a thermosetting resin, an abrasion-resistant material and an alkali titanate whisker or the above-mentioned additive, or applying a thermosetting resin to the surface of a substrate, and then abrading the surface. It can be obtained by spraying wear materials and alkali titanate whiskers.

In producing the wear-resistant resin composition of the present invention, before adding the wear-resistant material and the alkali titanate whisker to the thermosetting resin, the surface is previously treated with a silane coupling agent, a titanium coupling agent or a resin, a chemical solution, or the like. Treatment, physical surface treatment such as plasma etching, rusting of the substrate surface, phosphoric acid treatment, treatment with silane coupling agent, titanium coupling agent, etc. are also effective treatments. is there.

Further, it is preferable to apply a primer on the surface of the substrate in advance, if necessary, to achieve the object of the present invention. The primer used is not particularly limited, and may be any of known one-pack or two-pack primers, but preferably has good adhesion to the substrate surface, and has an interlayer between the abrasion-resistant material and the abrasion-resistant resin composition. Those having excellent adhesion are preferred. For example, a two-pack type epoxy resin-based primer, a one-pack type moisture-curable urethane resin-based primer, a modified silicon-based primer, a phenoxy resin-based primer and the like can be mentioned. The coating amount of these primers is not particularly limited, but is usually about 30 to 500 g / m ² .

If necessary, a top coat may be further applied on the surface of the wear-resistant layer formed on the surface of the substrate by the wear-resistant resin composition of the present invention, which promotes the effects of the present invention.

The substrate to which the abrasion-resistant resin composition of the present invention is applied is not limited to selecting the material if abrasion resistance is required,
For example, metal, wood, glass, concrete and the like can be mentioned. In the practice of the present invention, porous materials such as wood and concrete, cracked surfaces and cracked surfaces are sealed with putty, tono powder, resin, etc., and blasted as necessary. It is also effective to apply a surface treatment such as wiping of an oily component or a primer.

(5) Action and Effect of the Present Invention The wear-resistant resin composition of the present invention, which contains alkali titanate whiskers, has the same proportion of the wear-resistant material as the conventional wear-resistant resin composition. Also, the composition was rich in gliding properties and spreadability, making the preparation of the composition and the application of the substrate surface extremely easy, and the abrasion resistance was improved.

Further, the wear resistance of the mating object can be reduced or eliminated at the same time as the wear resistance is improved. As a result, the quality of grain has been reduced due to abrasion damage during transport of grain and silo storage work, etc., the operation has been hindered due to clogging of equipment due to wear debris of metals and ores, and the life has been shortened due to belt abrasion. It was started.

Furthermore, the resistance to thermal shock has been dramatically improved, and wear resistance can be imparted to equipment and facilities in the field of high-temperature work.

Although the reason for the development of such a novel effect of the present invention is not clear, it is considered that the novel effect is due to a complex action caused by a special crystal structure of alkali titanate whiskers.

By providing the wear-resistant resin composition of the present invention, transport pipes for gases, liquids, solids, slurries, etc., in particular, inner surfaces of bends, inner surfaces of casings of slurry pumps, walls of cyclones, hoppers, shooters, pulleys, idlers, etc. ,
The fact that the abrasion of the silo surface, the quay, and the splash zone of the pier, etc. has been easily and reliably prevented has a great significance in contributing to the seed industry and society.

Hereinafter, the abrasion-resistant resin composition of the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

Example 1 Sumiepoxy ELA-128 (Sumitomo Chemical Co., Ltd. product name,
80 parts by weight of epoxy resin, 20 parts by weight of Sumiepoxy ELA-301 (product name of Sumitomo Chemical Co., Ltd., epoxy resin), 45 parts by weight of Sumicure P740 (product name of Sumitomo Chemical Co., Ltd., curing agent for polyamide epoxy resin) And 2 parts by weight of Sumicure D (product name of Sumitomo Chemical Co., Ltd., curing accelerator for epoxy resin) are mixed well to obtain a thermosetting resin composition, and immediately thereafter, crushed alumina zirconia (average diameter 1.2 m)
m) 400 parts by weight, 80 parts by weight of sodium tetratitanate whisker and 23 parts by weight of calcium carbonate powder were added and mixed well to obtain a wear-resistant resin composition.

This abrasion-resistant resin composition was previously applied to the surface of a 300 mm x 300 mm x 3 mm steel plate which had been sandblasted and primed.
It was applied to a thickness of mm. The coating operation could be performed smoothly with a flat iron. 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 a wear-resistant layer.

An abrasion resistance test and a thermal shock abrasion resistance test were performed on the obtained test pieces in the following manner, and the results are shown in Table 1.

[Abrasion resistance test] The cycle of contacting the surface of the abrasion resistant layer with a resinoid type round whetstone with a grain size of 40 (205 mm in diameter, 25 mm in width) at a rotation speed of 1200 rpm for 2 seconds every 3 seconds for 20 cycles was performed. Observe the surface condition of the specimen and the surface condition of the resinoid whetstone.

[Thermal Abrasion Resistance Test] The test piece is heated from room temperature to 80 ° C. over 1 hour and immediately immersed in cold water at 5 ° C. After 20 cycles of this thermal shock test, the above-described wear test is performed, and the surface condition of the test piece and the grindstone is observed.

Example 2 A wear-resistant resin composition was prepared in the same manner as in Example 1 except that potassium hexatitanate whiskers were used instead of sodium tetratitanate whiskers. A test piece was prepared in this manner, and a wear resistance test and a thermal shock wear resistance test were performed. 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, 345 parts by weight of alumina zirconia granules (average diameter 1.2 mm), 5 parts by weight of potassium hexatitanate whisker, 18 parts by weight of calcium carbide powder were added and mixed well to obtain a wear-resistant resin composition.

A test piece having a thickness of 4 mm was prepared in the same manner as in Example 1 and subjected to an abrasion resistance test and a thermal shock abrasion resistance test. The results are shown in Table 1.

The mixing operation and the application operation of the abrasion-resistant resin composition were easy.

Example 4 100 parts by weight of Sumiup MG-1L (product name of Sanken Kako Co., Ltd., unsaturated polyester resin), 8% cobalt octenoate
0.5 parts by weight and Sunhard SL (Sanken Kako Co., Ltd. product name,
Immediately after mixing 1.5 parts by weight of peroxide), 200 parts by weight of alumina zirconia granules (average 1.5 mm), 200 parts by weight of fused alumina ceramic sand (average diameter 0.1 mm) and 100 parts by weight of potassium hexatitanate whisker were added. The resin composition was uniformly mixed to prepare a wear-resistant resin composition.

This abrasion-resistant resin composition was previously applied to a surface of a 300 mm × 300 mm × 3 mm steel plate which had been sandblasted and primed to a thickness of 4 mm, cured at room temperature for one day, and after-cured in an oven at a temperature of 40 ° C. for 5 hours. A test piece having a wear-resistant layer was prepared.

The mixing operation at the time of preparing the wear-resistant resin composition and the application work 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.
The results are shown in Table 1.

Example 5 Polyflex FL-37 (product name of Daiichi Kogyo Seiyaku Co., Ltd.
Polyisocyanate compound, NCO content 6.5%) A composition consisting of 96 parts by weight of colloidal silica and 4 parts by weight of colloidal silica as a main ingredient, 19.5 parts by weight of 3,3'-dichloro-4,4'-diaminodiphenylmethane, 18 parts by weight of dioctyl phthalate Parts, 4 parts by weight of Asbestos, 7 parts by weight of colloidal silica, and 1.5 parts by weight of a silane coupling agent are used as a curing agent, and the main agent and the curing agent are mixed at a mixing ratio of 2: 1 (weight ratio) and heated. After obtaining the curable resin composition, 50 parts by weight of alumina zirconia granules (average diameter 2 mm), 15 parts by weight of fused alumina ceramic sand, 16 parts by weight of potassium hexatitanate whisker and 30 parts by weight with respect to 30 parts by weight of the composition 1 part by weight of a coupling agent was added and mixed well to obtain a wear-resistant resin composition.

The abrasion-resistant resin composition was applied to a surface of a 300 mm × 300 mm × 3 mm steel plate previously subjected to sandblasting and primer treatment to a thickness of 4 mm and cured at room temperature for 7 days to prepare a test piece having a wear-resistant layer. .

The mixing operation at the time of preparing the wear-resistant resin composition and the application work of the composition were easy.

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

Example 6 To 150 parts by weight of the same thermosetting resin composition as prepared in Example 5, 80 parts by weight of potassium hexatitanate whiskers were added and mixed well to obtain a thermosetting resin paste.

300mm pre-sandblasted and primed
A 4 mm high PVC frame plate is fixed around a 300 mm × 3 mm steel plate, and a thermosetting resin paste is first applied to it to a thickness of about 1 mm, and abrasion resistant material is filled on top of it, and the back of the steel plate After a few minutes, the steel plate was turned over while the paste was uncured to remove the abrasion-resistant material that was not densely fixed. Further, a paste was applied thereon, and the abrasion resistant material was filled, shaken, left over, and the surplus abrasion resistant material was repeatedly removed. Finally, the paste was top-coated to form a 4 mm thick abrasion resistant resin composition layer. After curing for 7 days, a test piece having a wear-resistant layer was prepared.

Ratio of the total amount of the thermosetting resin paste used to the total amount of wear-resistant material (a mixture of 50 parts by weight of alumina zirconia granules (average diameter 1.2 mm), 15 parts by weight of fused alumina ceramic sand and 1 part by weight of titanium coupling agent) Is 50: 7 by weight
It was 0. The test pieces were subjected to the abrasion resistance test and the thermal shock abrasion resistance test in the same manner as in Example 1, and the results are shown in Table 1.

Example 7 Same thermosetting resin composition and abrasion resistant material as prepared in Example 5 (50 parts by weight of granulated alumina zirconia (average 1.2 mm), 15 parts by weight of fused alumina ceramic sand, 16 parts by weight of potassium hexatitanate whisker) And a mixture of 1 part by weight of a titanium coupling agent) were applied according to the method of Example 6 to prepare a test piece similar to that of Example 6, and subjected to a wear resistance test and a thermal shock wear resistance test. The results are shown in Table 1.

However, the ratio of the total amount of the used thermosetting resin composition to the total amount of the wear-resistant material was 30:80 by weight.

Comparative Example 1 A wear-resistant resin composition was prepared in exactly the same manner as in Example 5 except that potassium hexatitanate whiskers were not used, and a test piece was prepared. A thermal shock abrasion test was performed, and the results are shown in Table 1. The application of the abrasion-resistant resin composition at the time of preparation of the test piece required considerable force, and it was difficult to smooth the surface even though the ironing was difficult.

Comparative Example 2 A wear-resistant resin composition was prepared in exactly the same manner as in Example 5 except that titanium oxide powder was used instead of the potassium hexatitanate whisker, and a test piece was prepared. An abrasion resistance test and a thermal shock abrasion resistance test were performed, and the results are shown in Table 1. The wear-resistant resin composition is harder than that of Example 5,
The application operation was not easy.

Comparative Example 3 A test piece was prepared in exactly the same manner as in Example 5 except that carbon fibers (average fiber diameter 13 μm, average fiber length 130 μm) were used instead of the potassium hexatitanate whisker in Example 5, An abrasion test and a thermal shock abrasion test were performed and the results are shown in Table 1. The abrasion resistant resin composition was harder than that of Example 5,
The application operation was not easy.

In the table, A in the column of wear resistance and thermal shock wear resistance indicates a test piece, and B indicates a grindstone.

 ◎ The mark is almost unchanged.

 ○ mark has some wear.

 △ mark shows abrasion.

 The X mark shows a lot of wear, and peeling of the friction material is recognized.

From the results of Examples and Comparative Examples, the wear-resistant resin composition of the present invention is easier to prepare the composition and apply to the substrate than the conventional wear-resistant resin composition. It can be seen that the abrasion resistance is excellent and the mating object is not abraded and damaged.

Claims (1)

(57) [Claims] 1. A thermosetting resin of 9 to 30% by weight, a wear-resistant material of 50 to
A wear-resistant resin composition comprising 90% by weight and 0.5 to 20% by weight of a whisker of an alkali titanate compound represented by the following formula: A ₂ O · nTiO ₂ (where A is an alkali metal, and n represents an integer of 1, 2, 4, 6, 8)