Polypropylene lining

FIELD OF THE INVENTION AND RELATED ART STATEMENT
The present invention relates to a heated/melted polypropylene lining, a lining powder, a polypropylene resin composition for lining and a method for preparing the polypropylene lining, which are applicable to metal (carbon steel) materials for use in an exhaust gas desulfurization device, a gas purification plant, a seawater-fresh water converter, a thermal power plant and the like.
Heretofore, as the polypropylene lining, there is known the so-called sheet lining in which the surface of a sheet or a pipe of the polypropylene is treated by corona discharge or with a mixed solution of concentrated sulfuric acid and chromic acid to impart adhesive properties to the surface, coated with an adhesive such as an epoxy resin, and then stuck on a material to be lined. However, the so-called heated/melted polypropylene lining has not been suggested at all in which a material to be lined is heated up to a temperature more than the melting point of the polypropylene, and the heated surface of the material is then sprinkled with a polypropylene powder to form a film thereon, as in the case of the lining of a polyethylene and a fluororesin. In addition, there has been neither marketed nor suggested a lining powder for heated/melted polypropylene lining in which a material to be lined is sprinkled with the powder, and this powder is then heated/melted.
Furthermore, there have not been suggested a polypropylene sheet lining in which a material to be lined is heated up to a temperature more than the melting point of a polypropylene, a sheet or a stick of the polypropylene having adhesive properties is then fused to the heated surface of the material to form a lining and to thereby secure the adhesion of the polypropylene sheet or stick to the metal.
In addition, another lining method has not been suggested at all in which a metal surface is sprinkled with a polypropylene powder, and the powder is then heated/melted, and then cooled/solidified.
The above-mentioned polypropylene lining, in which the surface of a sheet or a pipe is treated, coated with an adhesive, and then used for lining, has the following problems, and so it is scarcely applied on an industrial scale:
(1) Since the adhesive is used for the lining, a defect such as an adhesive failure tends to occur.
(2) The polypropylene sheet or pipe is pressed against a material to be lined by worker's hands or by the use of a suitable tool to achieve the adhesion, and therefore it is difficult to apply the polypropylene lining to a material having a complicate shape such as a bent portion of a pipe or a T-shaped pipe, or a material having a small diameter.
(3) When metal pipes are lined, polypropylene pipes which have been previously extruded by an extruder are used. Therefore, in a plant in which the metal pipes having various diameters are used, the polypropylene pipes which are fit for the diameters of these metal pipes are required. Thus, for the manufacture of these polypropylene pipes having the various diameters, many molds are necessary, which increases the cost of the polypropylene pipes.
In general, the polypropylene has been used for injection-molded articles, extruded articles, films and the like, but the commercially available polypropylene can adhere to the metal surface while it is in a heated/melted state, but it peels therefrom inconveniently when it is cooled/solidified. Therefore, as described above, one of the polypropylene lining techniques has been only put to practical use, and this practical polypropylene lining comprises treating the surface of the extruded sheet or pipe to modify the surface, i.e., to impart adhesive properties to the surface, and then lining a metal material with the sheet or the pipe by the use of an adhesive.
As described above, the commercially available polypropylene cannot be stuck on the metal material by a heating/melting method, because the solidification shrinkage ratio of the polypropylene is large; creep stress caused by the case where the solidification shrinkage remains for a long period of time even at a relatively low temperature (ordinary temperature) is much larger than when a polyethylene or a fluororesin is used; and there is the influence of an additive such as an aggregate which is added to the polypropylene in order to improve mold release properties in the step of the injection molding or the extrusion, but detail factors are indefinite.
OBJECT AND SUMMARY OF THE INVENTION
In view of the above-mentioned technical level, the present invention has been completed, and an object of the present invention is to provide a heated/melted polypropylene lining material and its lining powder which can maintain excellent chemical resistance, heat resistance and mechanical properties of the polypropylene and which has excellent adhesive properties.
Another object of the present invention is to provide a lining material and its lining powder for metals which can maintain excellent chemical resistance, heat resistance and mechanical properties of the polypropylene and which can inhibit the deterioration of the resin.
Still another object of the present invention is to provide a polypropylene resin composition for lining which can maintain excellent chemical resistance, heat resistance and mechanical properties of the polypropylene and which has excellent adhesive properties, and a method for preparing this composition.
A further object of the present invention is to provide a method for extremely simply lining a metal (carbon steel) with a polypropylene.
The present inventors have intensively conducted experiments and investigations with the intention of developing a heated/melted polypropylene lining technique using a powder which can be applied to metal materials or similar materials having intricate shapes as well as large and small diameters, and as a result, they have found that after a heating/melting step, the polypropylene, when used singly, peels at the time of cooling/solidification, but when the polypropylene is mixed with a maleic acid-modified polypropylene in a suitable ratio, the resin does not peel to obtain a good lining film having strong adhesive force.
That is, the inventions are directed to:
(1) a polypropylene lining characterized by comprising a heated/melted mixture of a maleic acid-modified polypropylene and a polypropylene in a weight ratio of the maleic acid-modified polypropylene/the polypropylene=10/1 to 1/10,
(2) a polypropylene lining powder characterized by comprising a mixture of a maleic acid-modified polypropylene powder having an average particle diameter of 500 .mu.m or less and a polypropylene powder in a weight ratio of the maleic acid-modified polypropylene powder/the polypropylene powder=10/1 to 1/10, and
(3) a polypropylene lining powder obtained by melting and kneading a mixture of a maleic acid-modified polypropylene and a polypropylene in a weight ratio of the maleic acid-modified polypropylene/the polypropylene=10/1 to 1/10, and then milling the mixture so that an average particle diameter may be 500 .mu.m or less.
A metal which is useful in applying the present inventions is usually carbon steel. Furthermore, the content of maleic acid in the maleic acid-modified polypropylene which can be used in the present invention is 0.05 wt% or more, preferably in the range of from 0.1 to 1.0 wt%.
In the present invention, a mixing ratio of the maleic acid-modified polypropylene to the polypropylene depends upon the kind and the grade of selected maleic acid-modified polypropylene and polypropylene. If the mixing ratio of the maleic acid-modified polypropylene is too high, chemical resistances such as acid resistance and alkali resistance deteriorate, and if it is too low, adhesive force declines and the lining tends to peel. Hence, the proper mixing ratio is in the range of from 10/1 to 1/10.
With regard to the particle diameter of the powder suitable for the heated/melted lining, if it is less than 500 .mu.m or less, a film having a uniform thickness can be obtained, but preferably, it is in the range of from 100 to 300 .mu.m. Even if the powder having an average particle diameter of more than 500 .mu.m is used, the lining film can be formed, but a long time is taken to melt the powder for the film formation, and the surface of the film becomes a rough state, which makes it impossible to form the lining film having a uniform thickness.
The lining material of the present invention is formed from the maleic acid-modified polypropylene and the polypropylene in a weight ratio of from 10/1 to 1/10. When the lining material is in a heated/melted state, both of these components are melted, and when the lining material is cooled/solidified, a carbonyl group contained in the maleic acid-modified polypropylene is strongly bonded to a metal, whereby the lining film having strong adhesive force can be obtained.
The heated/melted polypropylene lining material and the lining powder can be provided which can be applied to a high-temperature region to which a conventional polyethylene lining and rubber lining cannot be applied. In addition, this lining powder is excellent in chemical resistance and can also be applied to pipes having a complicate shape and different diameters.
Heretofore, in a device which is used in a high-temperature region and in severely corrosive circumstance to which the polyethylene lining and the rubber lining cannot be applied, a precious high-grade stainless steel or an expensive fluororesin-based lining material has been used. The polypropylene lining material and the lining powder of the present invention can be applied to such a device under the severe conditions, and the raw materials of the lining material and the powder are the fairly inexpensive maleic acid-modified polypropylene and polypropylene. Thus, the very inexpensive lining material and powder can be provided, and they have large values from industrial and economical viewpoints.
Furthermore, the present inventors have found that a good lining film which does not peel and which has strong adhesive force can be obtained by mixing a modified polypropylene and an ethylene propylene rubber with a polypropylene in a suitable ratio.
That is, the inventions are directed to:
(1) a polypropylene lining for a metal characterized by comprising a heated/melted mixture of 1 to 20 wt% of an ethylene propylene rubber and a mixture of a maleic acid-modified polypropylene and a polypropylene in a weight ratio of the maleic acid-modified polypropylene/the polypropylene=10/1 to 1/100,
(2) a polypropylene lining powder obtained by adding 1 to 20 wt% of an ethylene propylene rubber powder having an average particle diameter of 500 .mu.m or less to a mixture of a maleic acid-modified polypropylene powder having an average particle diameter of 500 .mu.m or less and a polypropylene powder in a weight ratio of the maleic acid-modified polypropylene powder/the polypropylene powder=10/1 to 1/100, and then mixing them, and
(3) a polypropylene lining powder obtained by adding 1 to 20 wt% of an ethylene propylene rubber to a mixture of a maleic acid-modified polypropylene and a polypropylene in a weight ratio of the maleic acid-modified polypropylene/the polypropylene=10/1 to 1/100, mixing them, melting and kneading the mixture, and then milling the same so that an average particle diameter may be 500 .mu.m or less.
A metal which is useful in applying the present inventions is usually carbon steel. Furthermore, the content of maleic acid in the maleic acid-modified polypropylene which can be used in the present invention is 0.01 wt% or more, preferably in the range of from 0.1 to 1.0 wt%.
The content of the propylene in the ethylene propylene rubber which can be used in the present invention is usually in the range of from 10 to 40 wt%. In the present invention, a mixing ratio of the maleic acid-modified polypropylene to the polypropylene depends upon the kind and the grade of selected maleic acid-modified polypropylene and homopolypropylene, but the proper mixing ratio is in the range of from 10/1 to 1/100. The higher the mixing ratio of the maleic acid-modified polypropylene is, the stronger the adhesive force of the lining to the metal is. A ratio of the ethylene propylene rubber which is mixed with the above-mentioned mixture depends upon the kind and the grade of selected ethylene propylene rubber, but the proper mixing ratio is in the range of from 1 to 20 wt%. If the mixing ratio of the ethylene propylene rubber is too high, the strength of the lining declines.
Moreover, if the particle diameter of the powder suitable for the heated/melted lining is 500 .mu.m or less, the film having a uniform thickness can be formed. Even if the powder having the average particle diameter more than 500 .mu.m is used, the lining film can be formed, but a long time is taken to melt the powder for the film formation, and the surface of the film becomes a rough state, which makes it impossible to form the lining film having the uniform thickness.
The lining material of the present invention can be formed from the substance in which 1 to 20 wt% by outer percentage of the ethylene propylene rubber is added to the mixture of the maleic acid-modified polypropylene and the polypropylene in a weight ratio of the maleic acid-modified polypropylene/the polypropylene=10/1 to 1/100. When the lining material is in a heated/melted state, both of the maleic acid-modified polypropylene and the polypropylene are melted, and when the lining material is cooled/solidified, a carbonyl group contained in the maleic acid-modified polypropylene is strongly bonded to a metal, whereby the lining film having strong adhesive force can be obtained.
On the other hand, when the lining material comprising the substance in which the ethylene propylene rubber is added to the mixture of the maleic acid-modified polypropylene and the polypropylene is in the heated and melted state, the maleic acid-modified polypropylene, the polypropylene and the ethylene propylene rubber are melted. The mixture of the maleic acid-modified polypropylene and the polypropylene (hereinafter referred to as "modified polypropylene" sometimes) is different from the ethylene propylene rubber in fluidity and solidification temperature, and therefore, when the lining material is cooled/solidified, the ethylene propylene rubber is solidified in a dispersed state in the modified polypropylene.
Since the creep stress of the ethylene propylene rubber is very small, the ethylene propylene rubber stretches at the time of solidification shrinkage and the stress is instantly relived to a level smaller than adhesive force. Hence, the lining which does not peel can be obtained.
In the lining powder for obtaining the lining of the present invention, the ethylene propylene rubber is added to the modified polypropylene, and therefore, owing to the stress relief function of the ethylene propylene rubber, the amount of the maleic acid-modified polypropylene can be reduced, as compared with a case where no ethylene propylene rubber is added.
The lining powder of the present invention can be melted and kneaded by the use of a melting kneader, and then milled so that an average particle diameter may be 500 .mu.m or less to obtain a fine lining powder having the further improved adhesive properties. The mixing state of the thus obtained fine lining powder is more uniform than the mixture of the modified polypropylene, the ethylene propylene rubber having the small particle diameter.
Furthermore, the present inventors have found that when an antioxidant is added to an adhesive polypropylene prepared by mixing a polypropylene with a modified polypropylene and an ethylene propylene rubber, a tough film having good surface properties can be obtained without impairing adhesive properties and without deteriorating the resins.
That is, the inventions are directed to:
(1) a polypropylene lining for a metal characterized by comprising the steps of adding 1 to 20 wt% of an ethylene propylene rubber to a mixture of a maleic acid-modified polypropylene and a polypropylene in a weight ratio of the maleic acid-modified polypropylene/the polypropylene=10/1 to 1/100, further adding 0.1 to 1.0 wt% of an antioxidant to the mixture, heating/melting the resulting powder, and then cooling/solidifying the same to form a lining layer,
(2) a polypropylene lining powder obtained by adding 1 to 20 wt% of an ethylene propylene rubber powder having an average particle diameter of 500 .mu.m or less to a mixture of a maleic acid-modified polypropylene powder having an average particle diameter of 500 .mu.m or less and a polypropylene powder having an average particle diameter of 500 .mu.m or less in a weight ratio of the maleic acid-modified polypropylene powder/the polypropylene powder=10/1 to 1/100, further adding 0.1 to 1.0 wt% of an antioxidant to the mixture, and then mixing them, and
(3) a polypropylene lining powder obtained by adding 1 to 20 wt% of an ethylene propylene rubber to a mixture of a maleic acid-modified polypropylene and a polypropylene in a weight ratio of the maleic acid-modified polypropylene/the polypropylene=10/1 to 1/100, further adding 0.1 to 1.0 wt% of an antioxidant to the mixture, melting and kneading the resulting mixture, and then milling the same so that an average particle diameter may be 500 .mu.m or less.
A metal which is useful in applying the present inventions is usually carbon steel.
The content of maleic acid in the maleic acid-modified polypropylene which can be used in the present invention is 0.01 wt% or more, preferably in the range of from 0.1 to 1.0 wt%.
The content of the propylene in the ethylene propylene rubber which can be used in the present invention is usually in the range of from 10 to 40 wt%. Moreover, in the present invention, the melt flow rate of the polypropylene is preferably between 0.1 and 40.
In the present invention, a mixing ratio of the maleic acid-modified polypropylene to the polypropylene depends upon the kind of selected maleic acid-modified polypropylene and polypropylene, but the proper mixing ratio is in the range of from 10/1 to 1/100. The higher the mixing ratio of the maleic acid-modified polypropylene is, the stronger the adhesive force of the lining to the metal is. A ratio of the ethylene propylene rubber which is mixed with the above-mentioned mixture depends upon the kind of selected ethylene propylene rubber, but the proper mixing ratio is in the range of from 1.0 to 20 wt%. If the mixing ratio of the ethylene propylene rubber is too high, the strength of the lining declines.
In the present invention, preferable examples of the antioxidant include high-molecular weight phenol-based antioxidants and phosphites (and phosphonites), and the amount of the antioxidant to be used depends upon the kind of antioxidant, but the proper amount is in the range of from 0.1 to 1.0 wt% by outer percentage based on the weight of the modified polypropylene.
A typical example of the antioxidant is a combination of a phosphorus-based working stabilizer such as tris(2,4-di-t-butylphenyl) phosphite and at least one selected from the group consisting of hindered phenol-based pentaerythrityltetrakis�3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate!, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene and tris-(3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate.
If the particle diameter of the powder is 500 .mu.m or less suitable for the heated/melted lining, a film having a uniform thickness can be obtained. Even if the powder having the particle diameter larger than this size is used, the lining film can be formed, but a long time is taken to melt the powder for the film formation, and the surface of the film becomes a rough state, which makes it impossible to form the lining film having the uniform thickness.
The lining material of the present invention can be formed by adding 1.0 to 20 wt% of the ethylene propylene rubber to the mixture of the maleic acid-modified polypropylene and the polypropylene in a weight ratio of the maleic acid-modified polypropylene/the polypropylene=10/1 to 1/100, and further adding the antioxidant to the mixture. When the lining material is in a heated/melted state, both of the maleic acid-modified polypropylene and the polypropylene are melted, and when the lining material is cooled/solidified, a carboxyl group contained in the maleic acid-modified polypropylene is strongly bonded to a metal, whereby the lining film having strong adhesive force can be obtained.
On the other hand, when the lining material is in a heated/melted state, the ethylene propylene rubber added to the mixture of the maleic acid-modified polypropylene and the polypropylene is melted in the polypropylene, and when the lining material is cooled/solidified, the ethylene propylene rubber is dispersed in the polypropylene and the modified polypropylene, because the maleic acid-modified polypropylene, the polypropylene and the ethylene propylene rubber are different from each other in fluidity and solidification temperature. Since the creep deformation stress of the ethylene propylene rubber is very small, the ethylene propylene rubber stretches at the time of solidification shrinkage and the stress is instantly relived to a level smaller than adhesive force. Hence, the lining which does not peel can be obtained.
In addition, the antioxidant has a function for inhibiting the main chain of the polypropylene from thermally decomposing, and therefore the employment of the antioxidant permits thermal deterioration in the heating/melting step to decrease. In the lining powder of the present invention the antioxidant is added to the mixture of the polypropylene, the modified polypropylene and the ethylene propylene rubber, so that the thermal deterioration can be inhibited in the heating/melting step and so a tough film can be formed.
The lining powder of the present invention can be melted and kneaded by the use of a melting kneader, and then milled so that an average particle diameter may be 500 .mu.m or less to obtain a fine lining powder having the further improved adhesive properties. The mixing state of the thus obtained fine lining powder is more uniform than the mixture of the modified polypropylene, the ethylene propylene rubber and the antioxidant having the small particle diameter.
Furthermore, the present inventors have intensively conducted experiments and investigations with the intention of developing a lining material which can be manufactured from a polypropylene sheet or a polypropylene stick having good adhesive properties, and as a result, they have found that when an antioxidant is added to an adhesive polypropylene prepared by mixing a polypropylene with a modified polypropylene and an ethylene propylene rubber, a tough film having good surface properties can be obtained without impairing adhesive properties and without deteriorating the resins.
That is, the inventions are directed to:
(1) a polypropylene lining sheet or stick comprising a resin composition obtained by adding 1 to 20 wt% of an ethylene propylene rubber to a mixture of a maleic acid-modified polypropylene and a polypropylene in a weight ratio of the maleic acid-modified polypropylene/the polypropylene=10/1 to 1/100, and further adding 0.1 to 1.0 wt% of an antioxidant to the mixture, and
(2) a polypropylene lining method characterized by comprising the step of thermally fusing a sheet or a stick of a polypropylene resin composition of the above-mentioned (1) to a member to be lined.
The content of maleic acid in the maleic acid-modified polypropylene which can be used in the present invention is 0.01 wt% or more, preferably in the range of from 0.1 to 1.0 wt%.
The content of the propylene in the ethylene propylene rubber which can be used in the present invention is usually in the range of from 10 to 40 wt%. Moreover, in the present invention, the melt flow rate of the polypropylene is preferably between 0.1 and 40.
The sheet of the polypropylene resin composition according to the present invention is linable on the surface of a metal irrespective of its thickness, and when the sheet is thermally fused on the metal, a film having good adhesive properties can be formed. Furthermore, the stick of the polypropylene resin composition according to the present invention is linable on the surface of a metal irrespective of its thickness, and when the stick is arranged in one direction and thermally fused on the metal, a film having good adhesive properties can be formed. Thus, the stick is applicable for the repair of the lining.
The sheet or the stick of the polypropylene resin composition of the present invention can be fused on the surface of a metal to obtain a lining film having good adhesive properties to the metal.
Furthermore, the inventions are directed to:
(1) a lining method of a polypropylene characterized by comprising the steps of sprinkling the surface of a metal with a maleic acid-modified polypropylene powder, heating/melting the powder, sprinkling the melted maleic acid-modified polypropylene powder layer with a polypropylene powder, heating/melting the powder, and then cooling/solidifying the same to form a lining layer of the polypropylene, and
(2) a lining method of a polypropylene characterized by comprising the steps of sprinkling the surface of a metal with a maleic acid-modified polypropylene powder, heating/melting the powder, cooling/solidifying the same, sprinkling the resulting maleic acid-modified polypropylene film layer with a polypropylene powder, heating/melting the powder, and then cooling the same to form a lining layer of the polypropylene.
The content of maleic acid in the maleic acid-modified polypropylene which can be used in the inventions in claims 12 and 13 is 0.05% or more, preferably in the range of from 0.1 to 1.0%.
The maleic acid-modified polypropylene has a carbonyl group, and if heated/melted and then cooled/solidified, the maleic acid-modified polypropylene can be bonded to a metal. Thus, the present invention intends that the maleic acid-modified polypropylene film layer is first formed on the surface of the metal, and the polypropylene film is then formed on the maleic acid-modified polypropylene film layer.
The maleic acid-modified polypropylene has compatibility with the polypropylene, and so they can be bonded to each other by the heating/melting. Thus, the polypropylene lining of the present invention having the polypropylene film on its outer periphery can be obtained.
The film layer of the maleic acid-modified polypropylene interposed between the metal surface and the polypropylene film layer is preferably as thin as possible in order to improve the heat resistance of the polypropylene film. However, the minimum thickness of the film layer of the maleic acid-modified polypropylene depends upon the particle diameter of the maleic acid-modified polypropylene powder to be used for the film formation, and so the practical thickness of the film layer is in the range of from 50 to 200 .mu.m.

BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a sectional view of a matrix lined with a polypropylene.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
A preferable embodiment of the inventions will be described.
The pellets of a maleic acid-modified polypropylene having a maleic acid modification ratio of from 0.01 to 1.0 wt% and the pellets of a polypropylene having a melt flow index of 1.0 were separately milled by means of a refrigeration mill using liquid nitrogen, and each powder was classified by sieves into portions having average particle diameters of 1,000 .mu.m, 500 .mu.m, 300 .mu.m and 100 .mu.m. Afterward, the maleic acid-modified polypropylene powder was mixed with the polypropylene powder in blend ratios in Table 1 to obtain lining powders.
Furthermore, the pellets of the above-mentioned maleic acid-modified polypropylene was mixed with the pellets of the above-mentioned polypropylene in blend ratios shown in Table 1, and each mixture was then kneaded by means of a melting kneader, milled by the refrigeration mill, and then classified by the sieves to obtain lining powders having average particle diameters of 1,000 .mu.m, 500 .mu.m, 300 .mu.m and 100 .mu.m.
Next, a 70-mm-long, 200-mm-wide, 5-mm-thick carbon steel plate was degreased, shot-blasted, heated on a heated plate so that its surface temperature might be 250.degree..+-.20.degree. C., sprinkled with the above-mentioned powder, and then heated/melted to obtain a lined steel plate having a film thickness of 1.5 mm. Afterward, the observation of the surface state of each lining, the measurement of adhesive force by a 90.degree. peel method in a wide of 10 mm, and a durability test for 6 months under conditions of 5% H.sub.2 SO.sub.4 and 100.degree. were carried out. The results are set forth in Table 1.
TABLE 1______________________________________ Maleic Acid Modification Ratio Weight Ratio of of Maleic Acid- Maleic Acid-Modified Kind of Modified Polypropylene PolypropyleneNo. Lining Powder (%) to Polypropylene______________________________________1 Mixed powder 0.01 10/12 " 0.05 1/13 " 0.5 1/54 " 1.0 1/105 " 0.5 20/16 " 0.5 1/207 " 0.5 1/58 " 0.5 1/59 " 0.5 1/5______________________________________ Average Particle Surface Diameter of State Adhesive Force Lining Powder after (kgf/ State afterNo. (.mu.m) Lining 10 mm width) Durability Test______________________________________ 1 500 Good 4 Color changed slightly 2 500 " 7 No problem 3 500 " 8 " 4 500 " 7 " 5 300 " 12 Color changed, fine cracks occurred 6 300 Peeled -- -- 7 300 Good 10 No problem 8 100 " 11 " 9 1000 Rough 6 "______________________________________ Maleic Acid Modification Ratio Weight Ratio of of Maleic Acid- Maleic Acid-Modified Kind of Modified Polypropylene PolypropyleneNo. Lining Powder (%) to Polypropylene______________________________________10 Melted & 0.01 10/1 kneaded11 Melted & 0.05 1/1 kneaded12 Melted & 0.5 1/5 kneaded13 Melted & 1.0 1/10 kneaded14 Melted & 0.5 20/1 kneaded15 Melted & 0.5 1/20 kneaded16 Melted & 0.5 1/5 kneaded17 Melted & 0.5 1/5 kneaded18 Melted & 0.5 1/5 kneaded______________________________________ Average Particle Surface Diameter of State Adhesive Force Lining Powder after (kgf/ State afterNo. (.mu.m) Lining 10 mm width) Durability Test______________________________________10 500 Good 5 Color changed slightly11 500 " 8 No problem12 500 " 10 "13 500 " 9 "14 300 " 12 Color changed, fine cracks occurred15 300 Peeled -- --16 300 Good 11 No problem17 100 " 12 "18 1000 Rough 7 "______________________________________
A preferable embodiment of the inventions will be described.
The pellets of a maleic acid-modified polypropylene having a maleic acid modification ratio of from 0.01 to 1.0 wt%, the pellets of a polypropylene having a melt flow index of 1.0 and the pellets of an ethylene propylene rubber having a polypropylene content of from 10 to 40% were separately milled by means of a refrigeration mill using liquid nitrogen, and each powder was classified by sieves into portions having average particle diameters of 1,000 .mu.m, 500 .mu.m and 100 .mu.m. Afterward, the resulting powders were mixed in blend ratios in Table 2 to obtain lining powders.
Furthermore, the pellets of the above-mentioned maleic acid-modified polypropylene, the above-mentioned polypropylene and the above-mentioned ethylene propylene rubber were mixed in blend ratios shown in Table 2, and each mixture was then kneaded by means of a melting kneader, milled by the refrigeration mill, and then classified by the sieves to obtain lining powders having average particle diameters of 1,000 .mu.m, 500 .mu.m and 100 .mu.m.
Next, a 70-mm-long, 200-mm-wide, 5-mm-thick carbon steel plate was degreased, shot-blasted, heated on a heated plate so that its surface temperature might be 250.degree..+-.20.degree. C., sprinkled with the above-mentioned powder, and then heated/melted to obtain a lined steel plate having a film thickness of 1.5 mm. Afterward, the observation of the surface state of each lining, the measurement of adhesive force by a 90.degree. peel method in a wide of 10 mm, and a durability test for 6 months under conditions of 5% H.sub.2 SO.sub.4 and 100.degree. were carried out. The results are set forth in Table 2.
TABLE 2______________________________________ Weight Ratio Maleic Acid Propylene of Maleic Modification Content in Acid-Modified Ratio of Maleic Ethylene Polypropylene/ Acid-modified Propylene Ethylene Kind of Polypropylene Rubber Propylene Rubber/No. Lining Powder (%) (%) Polypropylene______________________________________ 1 Mixed powder 0.01 25 1/0.4/1 2 " 0.05 25 1/0.4/1 3 " 0.10 25 1/0.4/1 4 " 0.50 25 1/0.4/1 5 " 1.00 25 1/0.4/1 6 " 0.50 10 1/0.4/1 7 " 0.50 40 1/0.4/1 8 " 0.50 25 1/0.2/1 9 " 0.50 25 1/0.025/110 " 0.50 25 10/1.2/111 " 0.50 25 5/0.7/112 " 0.50 25 1/0.21/1______________________________________ Average Particle Diameter of Lining Powder Surface State Adhesive Force State afterNo. (.mu.m) after Lining (kgf/10 mm .phi.) Durability Test______________________________________ 1 100 Good 4 No problem 2 100 " 11 " 3 100 " 13 " 4 100 " 14 " 5 100 " 16 " 6 100 " 12 " 7 100 " 11 " 8 100 " 12 " 9 100 " 14 "10 100 " 17 "11 100 " 15 "12 100 " 14 "______________________________________ Weight Ratio Maleic Acid Propylene of Maleic Modification Content in Acid-Modified Ratio of Maleic Ethylene Polypropylene/ Acid-modified Propylene Ethylene Kind of Polypropylene Rubber Propylene Rubber/No. Lining Powder (%) (%) Polypropylene______________________________________13 Mixed powder 0.50 25 1/1.2/1014 " 0.50 25 1/5.7/5015 " 0.50 25 1/12.2/10016 " 0.05 25 1/23.3/20017 " 0.50 25 1/1.2/1018 " 0.50 25 1/1.2/1019 Melted & 0.01 25 1/0.4/1 kneaded20 Melted & 0.05 25 1/0.4/1 kneaded21 Melted & 0.10 25 1/0.4/1 kneaded22 Melted & 0.50 25 1/0.4/1 kneaded23 Melted & 1.00 25 1/0.4/1 kneaded24 Melted & 0.50 10 1/0.4/1 kneaded______________________________________ Average Particle Diameter of Lining Powder Surface State Adhesive Force State afterNo. (.mu.m) after Lining (kgf/10 mm .phi.) Durability Test______________________________________13 100 Good 14 No problem14 100 " 13 "15 100 " 12 "16 100 Peeled -- --17 500 Good 14 No problem18 1000 Rough 11 "19 100 Good 6 "20 100 " 12 "21 100 " 15 "22 100 " 15 "23 100 " 18 "24 100 " 12 "______________________________________ Weight Ratio Maleic Acid Propylene of Maleic Modification Content in Acid-Modified Ratio of Maleic Ethylene Polypropylene/ Acid-modified Propylene Ethylene Kind of Polypropylene Rubber Propylene Rubber/No. Lining Powder (%) (%) Polypropylene______________________________________25 Melted & 0.50 40 1/0.4/1 kneaded26 Melted & 0.50 25 1/0.2/1 kneaded27 Melted & 0.50 25 1/0.025/1 kneaded28 Melted & 0.50 25 10/1.2/1 kneaded29 Melted & 0.50 25 5/0.7/1 kneaded30 Melted & 0.50 25 1/0.2/1 kneaded31 Melted & 0.50 25 1/1.2/10 kneaded32 Melted & 0.50 25 1/5.7/50 kneaded33 Melted & 0.50 25 1/12.2/100 kneaded34 Melted & 0.50 25 1/23.3/200 kneaded35 Melted & 0.50 25 1/1.2/10 kneaded36 Melted & 0.50 25 1/1.2/10 kneaded______________________________________ Average Particle Diameter of Lining Powder Surface State Adhesive Force State afterNo. (.mu.m) after Lining (kgf/10 mm .phi.) Durability Test______________________________________25 100 Good 12 No problem26 100 " 13 "27 100 " 15 "28 100 " 19 "29 100 " 17 "30 100 " 15 "31 100 " 15 "32 100 " 14 "33 100 " 12 "34 100 Peeled -- --35 500 Good 16 No problem36 1000 Rough 12 "______________________________________
A preferable embodiment of the inventions will be described.
The pellets of a maleic acid-modified polypropylene having a maleic acid modification ratio of from 0.01 to 1.0 wt%, the pellets of a polypropylene and the pellets of an ethylene propylene rubber having a polypropylene content of from 10 to 40% were separately milled by means of a refrigeration mill using liquid nitrogen, and each powder was classified by sieves into portions having average particle diameters of 1,000 .mu.m, 500 .mu.m and 100 .mu.m. Afterward, the resulting powders were mixed with a high-molecular weight phenol-based antioxidant and another antioxidant (IRGANOX B215, made by Ciba-Geigy) containing a phosphite (or a phosphonite) in blend ratios in Table 3 to obtain lining powders.
In this connection, the antioxidant (IRGANOX B215) used herein was a mixture of pentaerythrityltetrakis�3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate! and tris(2,4-di-t-butylphenyl) phosphite in a ratio of 1:2.
Furthermore, the above-mentioned maleic acid-modified polypropylene, the polypropylene, the ethylene propylene rubber and the antioxidant were mixed in blend ratios shown in Table 4, and each mixture was then kneaded by means of a melting kneader, milled by the refrigeration mill, and then classified by the sieves into portions having average particle diameters of 1,000 .mu.m, 500 .mu.m and 100 .mu.m to obtain lining powders.
Next, a 70-mm-long, 200-mm-wide, 5-mm-thick carbon steel plate was degreased, shot-blasted, heated on a heated plate so that its surface temperature might be 250.degree..+-.20.degree. C., sprinkled with the above-mentioned powder, and then melted to obtain a lined steel plate having a film thickness of 1.5 mm.
Afterward, the observation of the surface state of each lining, the measurement of adhesive force by a 90.degree. peel method in a wide of 10 mm, and a durability test for 6 months under conditions of 5% H.sub.2 SO.sub.4 and 100.degree. were carried out.
The results are set forth in Tables 3 and 4.
TABLE 3__________________________________________________________________________ Maleic Acid Modification Ratio of PP Content Weight Ratio Kind of Modified PP* in EPR** Melt Flow of ModifiedNo. Lining Powder (%) (%) Rate of PP PP/EPR/PP__________________________________________________________________________ 1 Mixed Powder -- 25 0.5 --/0.1/1.0 2 " 0.10 25 0.5 1.0/0.2/1.0 3 " 0.50 25 0.5 1.0/0.2/1.0 4 " 1.00 25 0.5 1.0/0.2/1.0 5 " 0.50 25 0.5 1.0/0.2/1.0 6 " 0.50 25 0.5 1.0/0.2/1.0 7 " 0.50 25 0.5 1.0/0.2/1.0 8 " 0.50 25 5.0 1.0/0.2/1.0 9 " 0.50 25 15.0 1.0/0.2/1.010 " 0.50 25 30.0 1.0/0.2/1.0__________________________________________________________________________ Amount of Antioxidant to Mixture Average of Modified Particle Diameter PP, EPR and PP of Lining Powder Surface State Adhesive Force State afterNo. (%) (.mu.m) after Lining (kgf/10 mm width) Durability Test__________________________________________________________________________ 1 0.25 100 Good Peeled -- 2 0.25 100 " 12 No problem 3 0.25 100 " 14 " 4 0.25 100 " 13 " 5 -- 100 Air bubbles 15 Air bubbles 6 0.50 100 Good 15 No problem 7 1.00 100 " 14 " 8 0.25 100 " 16 " 9 0.25 100 " 15 "10 0.25 100 Partial liquid 15 " suspension__________________________________________________________________________ Maleic Acid Modification Ratio of PP Content Weight Ratio Kind of Modified PP* in EPR** Melt Flow of ModifiedNo. Lining Powder (%) (%) Rate of PP PP/EPR/PP__________________________________________________________________________11 Mixed powder 0.50 10 5.0 1.0/0.2/1.012 " 0.50 40 5.0 1.0/0.2/1.013 " 0.50 25 5.0 5.0/0.6/1.014 " 0.50 25 5.0 10.0/1.1/1.015 " 0.50 25 5.0 1.0/2.6/25.016 " 0.50 25 5.0 1.0/10.1/100.017 " 0.50 25 5.0 1.0/0.4/1.018 " 0.50 -- 5.0 1.0/--/1.019 " 0.50 25 5.0 1.0/0.2/1.020 " 0.50 25 5.0 1.0/0.2/1.0__________________________________________________________________________ Amount of Antioxidant to Mixture Average of Modified Particle Diameter PP, EPR and PP of Lining Powder Surface State Adhesive Force State afterNo. (%) (.mu.m) after Lining (kgf/10 mm width) Durability Test__________________________________________________________________________11 0.25 100 Good 14 No problem12 0.25 100 " 16 "13 0.25 100 " 18 "14 0.25 100 " 17 "15 0.25 100 " 15 "16 0.25 100 " 14 "17 0.25 100 " 15 "18 0.25 100 " 2 Peeled19 0.25 500 " 14 No problem20 0.25 1000 Rough 15 Rough__________________________________________________________________________ Note *means a polypropylene, and **means an ethylene propylene rubber.
TABLE 4__________________________________________________________________________ Amount of Average Maleic Acid PP Antioxidant Particle Modification Content Melt Weight to Mixture of Diameter Surface Adhesive Ratio of in Flow Ratio of Modified PP, of Lining State Force State after Kind of Modified PP* EPR** Rate Modified EPR and PP Powder after (kgf/10 DurabilityNo. Lining Powder (%) (%) of PP PP/EPR/PP (%) (.mu.m) Lining width) Test__________________________________________________________________________21 Melted & kneaded -- 25 0.5 --/0.1/1.0 0.25 100 Good Peeled --22 " 0.10 25 0.5 1.0/0.2/1.0 0.25 100 " 14 No problem23 " 0.50 25 0.5 1.0/0.2/1.0 0.25 100 " 17 "24 " 1.00 25 0.5 1.0/0.2/1.0 0.25 100 " 16 "25 " 0.50 25 0.5 1.0/0.2/1.0 -- 100 Rough 16 "26 " 0.50 25 0.5 1.0/0.2/1.0 0.50 100 Good 17 "27 " 0.50 25 0.5 1.0/0.2/1.0 1.00 100 " 17 "28 " 0.50 25 5.0 1.0/0.2/1.0 0.25 100 " 18 "29 " 0.50 25 15.0 1.0/0.2/1.0 0.25 100 " 17 "30 " 0.50 25 30.0 1.0/0.2/1.0 0.25 100 Partial liquid 18 " suspension31 Melted & kneaded 0.50 10 5.0 1.0/0.2/1.0 0.25 100 Good 17 No problem32 " 0.50 40 5.0 1.0/0.2/1.0 0.25 100 " 18 "33 " 0.50 25 5.0 5.0/0.6/1.0 0.25 100 " 20 "34 " 0.50 25 5.0 10.0/1.1/1.0 0.25 100 " 18 "35 " 0.50 25 5.0 1.0/2.6/25.0 0.25 100 " 17 "36 " 0.50 25 5.0 1.0/10.1/100.0 0.25 100 " 17 "37 " 0.50 25 5.0 1.0/0.4/1.0 0.25 100 " 18 "38 " 0.50 -- 5.0 1.0/--/1.0 0.25 100 " 3 Peeled39 " 0.50 25 5.0 1.0/0.2/1.0 0.25 100 " 17 No problem40 " 0.50 25 5.0 1.0/0.2/1.0 0.25 100 " 17 "__________________________________________________________________________ Note: * means a polypropylene, and ** means an ethylene propylene rubber.
A preferable embodiment of the inventions will be described.
EXAMPLE 1
The pellets of a maleic acid-modified polypropylene having a maleic acid modification ratio of from 0.01 to 1.0 wt%, the pellets of a polypropylene, the pellets of an ethylene propylene rubber having a polypropylene content of from 10 to 40%, a high-molecular weight phenol-based antioxidant and another antioxidant (IRGANOX B215, made by Ciba-Geigy) containing a phosphite (or a phosphonite) were mixed with in blend ratios shown in Tables 5 and 6, and each mixture was then kneaded by means of a melting kneader, and then molded by the use of a sheet molding machine to obtain sheets having film thicknesses of 200 .mu.m, 500 .mu.m, 1,000 .mu.m and 2,000 .mu.m.
In this connection, the antioxidant (IRGANOX B215) used herein was a mixture of pentaerythrityltetrakis�3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate! and tris(2,4-di-t-butylphenyl) phosphite in a ratio of 1:2.
Next, a 70-mm-long, 200-mm-wide, 5-mm-thick carbon steel plate was decreased, shot-blasted, and then heated on a heated plate so that its surface temperature might be 250.degree..+-.20.degree. C., and the above-mentioned sheet was pressed against the heated steel plate to fuse it thereon, thereby obtaining the steel plate lined with the polypropylene sheet.
Afterward, the observation of the surface state of each sheet lining, the measurement of adhesive force by a 90.degree. peel method in a wide of 10 mm, and a durability test for 6 months under conditions of 5% H.sub.2 SO.sub.4 and 100.degree. were carried out.
The results are set forth in Table 5.
TABLE 5__________________________________________________________________________ Amount of Maleic Acid PP Antioxidant Thickness Modification Content Melt to Mixture of of Sheet Surface Adhesive Ratio of in Flow Modified Modified PP, of PP Resin State Force State after Modified PP* EPR** Rate PP/EPR/PP EPR and PP Composition of (kgf/10 mm DurabilityNo. (%) (%) of PP (weight ratio) (%) (.mu.m) Lining width) Test__________________________________________________________________________1 -- 25 0.5 --/0.1/1.0 0.25 500 Metal surface Peeled -- peeled2 0.10 25 0.5 1.0/0.2/1.0 0.25 500 Uniform and good 14 No problem3 0.50 25 0.5 1.0/0.2/1.0 0.25 500 " 12 "4 1.00 25 0.5 1.0/0.2/1.0 0.25 500 " 13 "5 0.50 25 0.5 1.0/0.2/1.0 -- 500 Air bubbles 13 Air bubbles6 0.50 25 0.5 1.0/0.2/1.0 0.50 500 Uniform and good 14 No problem7 0.50 25 0.5 1.0/0.2/1.0 1.00 500 " 14 "8 0.50 25 5.0 1.0/0.2/1.0 0.25 500 " 15 "9 0.50 25 15.0 1.0/0.2/1.0 0.25 500 " 16 "10 0.50 25 30.0 1.0/0.2/1.0 0.25 500 " 16 "11 0.50 10 5.0 1.0/0.2/1.0 0.25 500 Uniform and good 15 No problem12 0.50 40 5.0 1.0/0.2/1.0 0.25 500 " 15 "13 0.50 25 5.0 5.0/0.6/1.0 0.25 500 " 16 "14 0.50 25 5.0 10.0/1.1/1.0 0.25 500 " 16 "15 0.50 25 5.0 1.0/2.6/25.0 0.25 500 " 17 "16 0.50 25 5.0 1.0/10.1/100.0 0.25 500 " 14 "17 0.50 25 5.0 1.0/0.4/1.0 0.25 500 " 14 "18 0.50 -- 5.0 1.0/--/1.0 0.25 500 Partially peeled 2 Peeled19 0.50 25 5.0 1.0/0.2/1.0 0.25 200 Uniform and good 15 No problem20 0.50 25 5.0 1.0/0.2/1.0 0.25 1000 " 16 "21 0.50 25 5.0 1.0/0.2/1.0 0.25 2000 " 15 "__________________________________________________________________________ Note: * means a polypropylene, and ** means an ethylene propylene rubber.
EXAMPLE 2
The pellets of a maleic acid-modified polypropylene having a maleic acid modification ratio of from 0.01 to 1.0 wt%, the pellets of a polypropylene, the pellets of an ethylene propylene rubber having a polypropylene content of from 10 to 40%, a high-molecular weight phenol-based antioxidant and another antioxidant (IRGANOX B215) containing a phosphite (or a phosphonite) were mixed with in blend ratios shown in Table 6. Each mixture was then kneaded by means of a melting kneader, and then extruded through a cylinder head to obtain strands, and sticks were prepared from the strand.
Next, a 70-mm-long, 200-mm-wide, 5-mm-thick carbon steel plate was degreased, shot-blasted, and then heated on a heated plate so that its surface temperature might be 250.degree..+-.20.degree. C., and the above-mentioned stick was pressed against the heated steel plate to fuse it thereon, thereby obtaining the steel plate lined with the polypropylene.
Afterward, the observation of the surface state of each lining, the measurement of adhesive force by a 90.degree. peel method in a wide of 10 mm, and a durability test for 6 months under conditions of 5% H.sub.2 SO.sub.4 and 100.degree. were carried out.
The results are set forth in Table 6.
TABLE 6__________________________________________________________________________ Amount of Maleic Acid PP Antioxidant Size of Modification Content Melt to Mixture of Stick of Surface Adhesive Ratio of in Flow Modified Modified PP, PP Resin State Force State after Modified PP* EPR** Rate PP/EPR/PP EPR and PP Composition of (kgf/10 mm DurabilityNo. (%) (%) of PP (weight ratio) (%) (mm) Lining width) Test__________________________________________________________________________22 0.50 25 0.5 1.0/0.2/1.0 0.25 3 Good 15 No problem23 0.50 25 5.0 1.0/0.2/1.0 0.25 3 " 14 "24 0.50 25 15.0 1.0/0.2/1.0 0.25 3 " 16 "25 0.50 25 30.0 1.0/0.2/1.0 0.25 3 " 14 "__________________________________________________________________________ * means a polypropylene, and ** means an ethylene propylene rubber.
A preferable embodiment of the inventions will be described in reference to FIG. 1.
In FIG. 1, reference numeral 1 is a metal matrix (carbon steel) having a diameter of 120 mm and a thickness of 5 mm in which the surface of the metal matrix is cleaned by degreasing, washing and blasting, numeral 2 is a maleic acid-modified polypropylene film formed by heating/melting (250.degree..+-.20.degree. C.) a maleic acid-modified powder having a melt index of 10 and an average diameter of 100 .mu.m on the surface of the metal matrix 1. Numeral 3 is a polypropylene film formed by heating/melting (250.degree..+-.20.degree. C.) a polypropylene powder having a melt index of 5 and an average diameter of 100 .mu.m on the maleic acid-modified polypropylene film 2. The formation of the polypropylene film 3 can be carried out at a time when the previously formed maleic acid-modified polypropylene film 2 is still in a melted state or in a cooled/solidified state. In Table 7, there are shown the results of the adhesive force and the durability test (for 6 months under conditions of 5% sulfuric acid and 100.degree. C.) of the polypropylene lining materials which lining has been made by two methods of the present invention.
TABLE 7__________________________________________________________________________ Thickness of Thickness of Thickness of Thickness of Film of 0.05% Film of 0.5% Film of 1.0% Film of 0.01% Thickness Maleic Acid- Maleic Acid- Maleic Acid- Maleic Acid- of Poly- Modified Modified Modified Modified propylene Adhesive Force Polypropylene Polypropylene Polypropylene Polypropylene Film Surface State after Lining State afterNo. (.mu.m) (.mu.m) (.mu.m) (.mu.m) (.mu.m) after Lining (kgf/10 mm Durability__________________________________________________________________________ Test1 None None None None 2000 Peeled from -- -- metal surface2 None None None None 200 Peeled from -- -- metal surface3 200 None None None 1000 Uniform & good 7 No problem4 None 50 None None 2000 " 12 "5 None 200 None None 2000 " 11 "6 None 500 None None 2000 " 10 "7 None 1000 None None 1000 " 10 Wavy wrinkles occured slightly8 None 2000 None None 500 Wrinkles occured 10 Wavy wrinkles slightly on poly- occured slightly propylene film layer9 None None 200 None 1000 Uniform & good 12 No problem10 None None None 200 1000 " 2 Peeled__________________________________________________________________________

Number	Date	Country
5-8488	Jan 1993	JPX
5-111473	May 1993	JPX
5-141760	Jun 1993	JPX
5-279138	Nov 1993	JPX
5-279139	Nov 1993	JPX

Number	Name	Date
3932368	McConnell et al.	Jan 1976
4237037	Takahashi	Dec 1980
4455344	Matsuyama et al.	Jun 1984
4506056	Gaylord	Mar 1985
4606953	Suzuki et al.	Aug 1986
4675210	Clayton et al.	Jun 1987
4957968	Adur et al.	Sep 1990
5091260	Wong	Feb 1992
5185398	Kehr et al.	Feb 1993
5202192	Hope et al.	Apr 1993
5256226	Marzola et al.	Oct 1993

Number	Date	Country
0 360 646	Mar 1990	EPX
0 370 786	May 1990	EPX
62-273083A	Nov 1987	JPX
2 097 809	Nov 1982	GBX

	Number	Date
Parent	527092	Sep 1995
Parent	285998	Aug 1994
Parent	184290	Jan 1994

Polypropylene lining

Information

Patent Number

Date Filed

Date Issued

Inventors

Original Assignees

Examiners

Agents

CPC

US Classifications

Field of Search

US

International Classifications

Abstract

Description

Claims

Priority Claims (5)

Parent Case Info

US Referenced Citations (11)

Foreign Referenced Citations (4)

Non-Patent Literature Citations (1)

Divisions (3)