JP5257379B2 - Heat-resistant phenolic resin composition, heat-resistant pad using the same, and method for producing heat-resistant pad - Google Patents

Description

  The present invention relates to a heat-resistant phenol resin composition that can withstand contact with a metal product in a high-temperature state, a heat-resistant pad using the same, and a method for producing the heat-resistant pad.

  In the manufacturing process of steel products, various heat-resistant materials are used in factory lines that perform secondary processing and processing of steel wires and steel sheets. Steel wires and steel sheets after hot / cold rolling and annealing treatment are wound in a coil shape and handled, but they are used as a pedestal for the purpose of preventing wrinkles when transporting and holding steel coils in this high temperature state. Uses a heat-resistant contact member.

  In the low temperature process, PE / PP composite material or wood is used as the contact member. Since these have lower hardness than the steel coil to be contacted, they do not wrinkle the wire. However, PE / PP composite materials and wood cannot be used in high temperature processes because they do not have heat resistance. Therefore, it is considered to use a heat-resistant rubber material reinforced with carbon fiber for the table, but satisfactory results have not been obtained. Therefore, a metal member is mainly used as the contact member in such an application. However, it is unavoidable that the metal member and the hot steel coil are in contact with each other. Often, when high temperature steel coils are contacted for only a short time, wood may be used to prevent wrinkling at the expense of heat resistance and durability.

  In Patent Document 1, as a material having heat resistance and wear resistance of a cylindrical body support portion that supports a steel coil such as a winding coil after hot rolling, the material has heat resistance such as graphite, and more than a steel coil. It is disclosed that the use of a soft material prevents the steel coil from being marked with a support portion. However, the use of graphite generally increases the cost significantly.

  On the other hand, conventionally, a laminated molded article made of a high-strength fiber cloth and a phenol resin has been provided. Since the phenol resin is a thermosetting resin having relatively high heat resistance, it can be used in a high temperature environment. In Patent Document 2, a base material woven using a spun yarn obtained by blending glass fiber, aramid fiber and polynosic fiber is used as a base material, and this is impregnated with a thermosetting resin as a matrix such as a phenol resin. The resin impregnated sheet (prepreg) is laminated and heated and pressed to produce a resin laminate, and this resin laminate is used as a guide plate for a hot run table from a finish rolling mill to a winder in a continuous hot steel rolling mill. It is disclosed to use.

  However, although the resin laminated plate described in Patent Document 2 is a plate in contact with a high-temperature steel plate, it is not used for an application in which the steel plate is always in contact, but has heat resistance enough to withstand short-time contact. It ’s just that. That is, it cannot withstand the use in which a steel coil having a temperature of about 400 ° C. and several tons is placed and held for a long time.

Japanese Patent Laying-Open No. 2005-219076 JP 2005-296965 A

  In this way, when the steel coil is transported and stored in the hot / cold rolling process and the annealing process, wrinkles are generated in the coil by contacting the metal stand. In low-temperature processes, PE / PP composite materials and wood can be installed at the contact points. However, there is no material that can be safely used in the process at about 400 ° C, and it is not possible to take measures to protect steel coils. Is the current situation.

  Therefore, in view of the above-described situation, the present invention intends to solve the problem that the steel coil has heat resistance and strength capable of transporting and storing the steel coil in a contact state even at a process of about 400 ° C., and the cost is increased. It is in providing a heat resistant pad using the heat resistant phenol resin composition and a method for producing the heat resistant pad.

  In order to solve the above-mentioned problems, the present invention is characterized in that a heat-resistant substrate made of rock wool and polyparaphenylene benzobisoxazole (PBO) fibers is impregnated with a phenol resin, and is heat-pressed and cured. A phenol resin composition was constituted (claim 1).

  And as for the said heat-resistant base material, it is preferable that rock wool is 40-95 wt% and PBO fiber is 5-60 wt% (Claim 2).

  Further, the heat-resistant substrate is 50 to 80 wt% and the phenol resin is 20 to 50 wt% (Claim 3), more preferably the heat-resistant substrate is 70 to 75 wt% and the phenol resin is 25 to 30 wt% ( Claim 4).

  And, the present invention provides a heat-resistant pad comprising a heat-resistant layer made of the above-mentioned heat-resistant phenol resin composition and a base material made of a laminated molded product obtained by impregnating a glass fiber cloth with a phenol resin. (Claim 5).

  The present invention also includes a heat-resistant layer material obtained by impregnating a phenol resin with a heat-resistant substrate made of rock wool and polyparaphenylene benzobisoxazole (PBO) fibers, and a plurality of sheet materials obtained by impregnating a glass fiber cloth with a phenol resin. A method for producing a heat-resistant pad is provided, in which a heat-resistant pad is formed by laminating a laminated base material and pressurizing and heat-treating the heat-resistant layer on the surface of the base material. (Claim 6).

  Here, in the manufacturing method of a heat resistant pad, the characteristic technique employ | adopted regarding a heat resistant layer is the same as the above-mentioned heat resistant phenol resin composition.

  According to the heat-resistant phenol resin composition of the present invention and the heat-resistant pad using the same, it can withstand the contact temperature of a metal product at 400 ° C. and can prevent the surface of the metal product from being wrinkled. In addition, the heat-resistant pad of the present invention ensures basic mechanical strength and thickness by the base material, and has a high heat resistance in the heat-resistant layer, so it has an unprecedented superiority with both features at the same time. Heat resistant pad. This prevents the steel coil from being wrinkled by using the heat-resistant pad of the present invention as a contact member for the table when the steel coil is transported and stored in the hot / cold rolling process and annealing process. This eliminates the need for selecting a steel coil with a pinch as in the prior art, and can greatly improve work efficiency and yield.

  In addition, according to the heat-resistant pad manufacturing method, a heat-resistant layer material obtained by impregnating a phenol resin with a heat-resistant substrate made of rock wool and PBO fibers and a plurality of sheet materials obtained by impregnating a glass fiber cloth with a phenol resin are stacked. Laminated base materials are laminated, pressed and heated to form a heat-resistant pad with a heat-resistant layer integrated on the surface of the base material, so that the interface between the heat-resistant layer and the base material is continuously strong. Since they are integrated, they do not peel off from the interface even if they are subjected to a thermal history.

It is sectional drawing of the heat resistant pad which concerns on this invention. It is a perspective view which shows the layout of the high temperature thing contact test of a heat resistant pad. It is a graph which shows the contact jig after making the contact jig heated to 410 degreeC contact a heat resistant pad, A part temperature, and B part temperature. It is a graph which shows the change of the A section temperature after making the contact jig of different initial temperature contact a heat resistant pad. It is a perspective view which shows embodiment of the coil skid which attached the heat resistant pad of this invention to the contact part. It is the perspective view of the use condition which similarly mounted the steel wire rod coil on the coil skid. The use state which mounted the steel plate coil in the coil skid which attached the heat resistant pad of this invention to the contact part is shown, (a) is a front view, (b) is a perspective view.

  Next, an embodiment of the heat-resistant phenol resin composition of the present invention will be described in detail. The heat-resistant phenol resin composition of the present invention is characterized in that a heat-resistant base material composed of rock wool and polyparaphenylene benzobisoxazole (PBO) fibers is impregnated with a phenol resin and subjected to pressure thermosetting.

  The rock wool used in the present invention is Magaltima fiber (manufactured by Mag Co., Ltd.). Magaltima fiber is a short fiber produced by centrifuging natural ore at a high temperature and centrifuging. As for heat resistance (according to JIS R3450), the ignition loss rate of 800 ° C. × 30 minutes is 0.5%, and the melting temperature is 1000 ° C. The fiber diameter is 4-8 μm, the asbestos component is 0%, there is no carcinogenicity, and it conforms to the EU directive.

  The polyparaphenylene benzobisoxazole (PBO) fiber used in the present invention is Zylon (registered trademark of Toyobo Co., Ltd.). Zylon is a fiber obtained by crystal spinning a PBO fiber having a rigid and extremely linear molecular structure. Zylon is a fiber that has higher strength and higher elastic modulus than carbon fibers and has the highest heat resistance and flame retardancy among organic fibers, and has a decomposition temperature of 650 ° C.

  Specifically, the heat-resistant base material is produced in the range of 40 to 95 wt% of rock wool (Magnaltima fiber) and 5 to 60 wt% of PBO fiber (Zylon), and the proportion of PBO fiber is as small as possible. Set. Increasing the proportion of rock wool is naturally advantageous for heat resistance.

  The heat-resistant phenolic resin composition of the present invention is prepared by preparing a prepreg sheet obtained by impregnating and drying the phenolic resin on the heat-resistant base material and hot pressing it to obtain a heat-resistant material having a predetermined thickness. is there. Here, the heat resistant substrate is 50 to 80 wt%, the phenol resin is 20 to 50 wt%, and more preferably, the heat resistant substrate is 70 to 75 wt% and the phenol resin is 25 to 30 wt%.

  Specifically, a resole-type or novolac-type phenol resin is applied to a heat-resistant substrate. However, when the phenol resin is less than 20 wt%, a blur is generated, and the resin can be sufficiently impregnated at 25 wt% or more. On the other hand, if the phenol resin exceeds 50 wt%, the heat resistance deteriorates, which is not preferable. If it is 30 wt%, the effect is sufficient.

  The heat-resistant material made of the heat-resistant phenolic resin composition of the present invention thus produced has a feature that it has high heat resistance and little thermal deterioration, so that it is less worn.

Here, the heat-resistant material of the example is 25 to 30 wt% with respect to a heat-resistant base material made of a multi-woven cloth having a thickness of 14 mm and a basis weight of 8 kg / m ² with 80 wt% of Magmartima fiber and 20 wt% of PBO fiber. A prepreg obtained by uniformly applying a resol type phenolic resin, drying and removing the solvent was cut into an appropriate size and heated at a temperature of 180 ° C. for a predetermined time while applying a constant pressure of 5 MPa.

  Next, the manufacturing method of the heat-resistant pad 1 which laminated | stacked the heat-resistant layer 2 which consists of the heat-resistant phenol resin composition of this invention, and the base material 3 which consists of a laminated molding product which impregnated the glass fiber cloth with the phenol resin is demonstrated. To do. Increasing the thickness of the heat-resistant material made of the above-mentioned heat-resistant phenolic resin composition in order to give the mechanical strength enough to withstand even a few tons of steel coil placed is costly. Not right. Therefore, the heat-resistant pad 1 used in such an application has a two-layer structure of a heat-resistant layer 2 made of a heat-resistant phenol resin composition and a base material 3 made of a laminated molded product in which a glass fiber cloth is impregnated with a phenol resin, The heat resistant layer 2 ensures sufficient heat resistance, and the base material 3 secures a thickness sufficient to give mechanical strength.

First, mug Altima fiber 80 wt%, in the PBO fibers 20 wt%, thickness 14 mm, with respect to heat-resistant substrate made of a multi-woven cloth having a basis weight of 8 kg / m ^2, the 25～30Wt% of resole phenolic resin, coated Apply evenly using a roll. Then, it is put into an electric furnace and dried, and the solvent is removed to prepare a heat-resistant layer material (heat-resistant layer prepreg).

  On the other hand, a sheet-like prepreg (base material prepreg) prepared by impregnating glass fiber cloth 60 wt% with phenol resin 40 wt% and drying it is prepared.

  The heat-resistant layer prepreg and the base material prepreg are cut into a predetermined size, and the size and quantity are aligned. In this embodiment, one heat-resistant layer prepreg and 20 to 30 base material prepregs are used. Then, the heat-resistant layer prepreg is put into an electric furnace set at 100 ° C. immediately before molding to remove moisture absorption. Further, the base material prepreg is put into an electric furnace set at 100 ° C. to remove moisture absorbed and to perform a semi-curing treatment of the phenol resin.

  Then, one heat-resistant layer prepreg and 28 base material prepregs are stacked and integrally formed by hot pressing. The molding conditions are a molding pressure of 5 MPa and a molding temperature of 180 ° C. Thereafter, post cure is performed to complete the curing of the phenolic resin. The heat resistant pad 1 manufactured in this way is shown in FIG. In the heat resistant pad 1, the heat resistant layer 2 has a thickness of about 8 mm, and the base material 3 has a thickness of about 18 mm. The interface between the heat-resistant layer 2 and the base material 3 is continuous and completely integrated.

  In order to evaluate the thermal conductivity of the heat resistant pad 1 and the presence or absence of cracks, a high temperature contact test was conducted. The test arrangement is shown in FIG. The heat-resistant pad 1 of the present invention was cut out to 100 mm × 100 mm, and a contact jig 4 having a planar shape of SUS310S and 120 mm × 120 mm and having a weight of 5 kg was placed thereon after being heated to a predetermined temperature. A thermocouple is embedded in advance at the interface between the heat-resistant layer 2 and the base material 3, and a thermocouple is mounted on the back surface of the base material 3. ) And the temperature change of the back surface portion (B portion) of the base material 3 was measured.

  FIG. 3 shows the temperature change of the contact jig 4 and the temperature changes in the A part and the B part in a state where the contact jig 4 heated to 410 ° C. is placed on the heat resistant layer 2 of the heat resistant pad 1. The measurement result is shown. The temperature of part A indicates heat transfer from the heat-resistant layer 2 to the base material 3. The temperature of the contact jig 4 decreases with time due to heat radiation into the air and heat transfer to the heat resistant pad 1. And the temperature of A part rises after contact of the contact jig | tool 4, becomes the maximum after about 10 minutes, and falls gradually with the temperature fall of the contact jig | tool 4 after that. Despite the temperature of the contact jig 4 being 410 ° C., the temperature of the part A did not reach 300 ° C. at the maximum. Thereby, it can be seen that even the base material 3 which is inferior in heat resistance to the heat-resistant layer 2 can sufficiently withstand. In addition, the back surface temperature (temperature of the B part) of the base material 3 did not exceed 150 ° C. at the maximum. During the test, no material destruction, smoke generation, ignition, deformation, or crack of the heat resistant pad 1 occurred. Further, after the test, the outer surface and the inner surface of the heat-resistant layer 2 and the contact surface of the contact jig 4 were observed, but there was no problem at all. Incidentally, in the case of only the base material 3, cracks occurred due to the contact of the contact jig 4 at 410 ° C.

  FIG. 4 shows the temperature change of the interface portion (A part) between the heat-resistant layer 2 of the heat-resistant pad 1 and the base material 3 when the initial temperature of the contact jig 4 is 450 ° C., 400 ° C., 350 ° C. Show. Thereby, it turns out that the maximum value of the temperature of A part becomes about 100 degreeC lower than the initial temperature of the contact jig 4. FIG. At each initial temperature of the contact jig 4, the heat-resistant pad 1 after contact was observed. As a result, when contacted at 450 ° C., cracks occurred in the base material 3 and smoke was generated. Thereby, it is highly likely that delamination, base material strength deterioration, and smoke generation will occur in applications where contact is made at a temperature of 450 ° C. or higher. On the other hand, when it contacts at 400 degrees C or less, it turned out that a crack and smoke generation do not generate | occur | produce and the effect of the heat resistant pad 1 of this invention is acquired.

  Next, based on FIG.5 and FIG.6, embodiment of the coil skid 5 which attached the heat resistant pad 1 of this invention to the contact part is described easily. The coil skid 5 is installed in the coil cooling / conveying line after the annealing process, and the heat-resistant pad 1 is placed on the upper surface of the cradle 6 and the side surface of the support member 7 suspended from one end of the cradle 6. Attached. The table 6 includes two parallel support rails, and the upper surfaces of both heat-resistant pads 1 and 1 provided thereon are inclined so that stress applied to the circumferential surface of the steel coil is not concentrated. Yes. In other words, the heat-resistant pad 1 is attached so that the surface of the heat-resistant layer 2 faces the tangential direction with respect to the circumferential surface of the steel material coil. The stand 6 has a length of about 3 m, and the support member 7 has a height of about 150 cm.

  As shown in FIG. 6, a steel wire coil 8 having a diameter of 150 cm, an axial length of 70 cm, and a weight of 2 t is placed on a pedestal 6 as a steel coil, and held in a state where it is caught on a support member 7. did. Actually, six steel wire coils 8 having a temperature of about 400 ° C. were placed.

  As a result of an actual machine use test for 7 months, no flaws were found on the portion of the steel wire coil 8 that was in contact with the heat-resistant pad 1. Further, the heat-resistant pad 1 provided on the pedestal 6 has a curved surface due to end wear, but is kept in surface contact with the coil. The heat-resistant pad 1 provided on the support member 7 is kept in a surface contact state, and wear hardly progresses. Although abrasion powder (yarn) was generated from the heat-resistant pad 1, it did not adhere to the coil product and had no influence on the work site. Further, it was confirmed that there was no damage and deformation of the heat-resistant pad 1 and there was no problem in terms of strength. The heat-resistant pad 1 provided on the pedestal 6 was in a state where the heat-resistant layer 2 having a thickness of 8 mm before use remained 3 mm or more and could be used continuously. The required life of the coil skid 5 with respect to the heat-resistant pad 1 is from half a year to one year, and thus it has been found that the coil skid 5 can sufficiently withstand practical use.

  Table 1 shows a comparative test between Examples 1, 2, and 3 in which the thickness of the heat-resistant layer 2 is 2 mm, 4 mm, and 8 mm, Comparative Example 1 without the heat-resistant layer 2 and only the base material 3, and Comparative Example 2 in the case of a metal. The results are summarized.

  Examples 1 and 2 (2 mm and 4 mm specifications) are relatively easy to manufacture because of their small thickness. Although the heat-resistant layer provides an anti-rust effect, the wear margin is thin and the product life is short. In the 2 mm specification of Example 1, the heat insulation effect is small and the amount of heat transfer to the base material is large, so that cracks occur. In the 4 mm specification of Example 2, there is a possibility that cracks may occur depending on the resin application state (resole resin content) of the heat-resistant layer. On the other hand, in the 8 mm specification of Example 3, since the thickness is thick and the rigidity is strong, a normal impregnation machine for production cannot be used, resulting in poor production efficiency or high cost. Since the product life is long and the contact temperature of 400 ° C is low, the heat transfer to the base material can be suppressed by the heat insulation effect, and it can be kept below the heat resistance limit temperature of the base material. Can be prevented.

  Since the comparative example 1 consists only of a base material without a heat-resistant layer, it has no heat resistance and cracks are generated, so that it cannot be used at all. Comparative Example 2 is a metal contact member, but has no anti-mold effect as described in the conventional example.

  The heat-resistant pad 1 having a two-layer structure of the heat-resistant layer 2 and the base material 3 according to the present invention adjusts the thickness of the heat-resistant layer 2 according to required specifications. As a heat-resistant pad used when a steel coil is transported and stored in a hot / cold rolling process or an annealing process, the thickness of the heat-resistant layer is preferably set to at least 8 mm with a margin.

  FIG. 7 shows a usage example in which the steel plate coil 9 is placed on the coil skid 5 described above. Other examples of use of the heat-resistant pad include contact members such as a reversing device, C hook, and fork with respect to the steel coil.

1 heat-resistant pad,
2 heat-resistant layer,
3 Base material,
4 Contact jig,
5 Coil skid,
6 stand,
7 support members,
8 Steel wire coil,
9 Steel sheet coil.

Claims (9)

  A heat-resistant phenol resin composition, wherein a heat-resistant base material composed of rock wool and polyparaphenylene benzobisoxazole (PBO) fibers is impregnated with a phenol resin and subjected to pressure heat curing.   The heat-resistant phenol resin composition according to claim 1, wherein the heat-resistant base material is 40 to 95 wt% of rock wool and 5 to 60 wt% of PBO fibers.   The heat-resistant phenol resin composition according to claim 1 or 2, wherein the heat-resistant substrate is 50 to 80 wt% and the phenol resin is 20 to 50 wt%.   The heat-resistant phenol resin composition according to claim 3, wherein the heat-resistant substrate is 70 to 75 wt% and the phenol resin is 25 to 30 wt%.   A heat-resistant layer made of the heat-resistant phenol resin composition according to any one of claims 1 to 4 and a base material made of a laminated molded article in which a glass fiber cloth is impregnated with a phenol resin are laminated. Heat resistant pad.   A heat-resistant layer material made by impregnating a phenolic resin into a heat-resistant substrate made of rock wool and polyparaphenylenebenzobisoxazole (PBO) fibers, and a base material in which a plurality of sheet materials made by impregnating a glass fiber cloth with a phenolic resin are overlapped A method for producing a heat-resistant pad, comprising: laminating a material, pressurizing and heat-treating to form a heat-resistant pad having a heat-resistant layer integrated on a surface of a base material.   The method for producing a heat resistant pad according to claim 6, wherein the heat resistant substrate is 40 to 95 wt% of rock wool and 5 to 60 wt% of PBO fiber.   The method for producing a heat resistant pad according to claim 6 or 7, wherein the heat resistant substrate is 50 to 80 wt% and the phenol resin is 20 to 50 wt%. The method for producing a heat resistant pad according to claim 8, wherein the heat resistant substrate is 70 to 75 wt% and the phenol resin is 25 to 30 wt%.

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