JPS6043295B2 - Continuous manufacturing device for molded products using reactive resin and method for manufacturing molded products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for producing foamed or non-foamed reactive resins consisting of at least two or more components having a pot life (time from mixing to the start of gelation) of at least several seconds to two powders after mixing. The present invention relates to a continuous production device for molded products used for continuous integration with other substrates in the form of films or layers of appropriate thickness, and a method for producing molded products using the continuous production device.

Conventionally, reactive resins have a pot life of several seconds to several tens of minutes after mixing.
Refers to all resins that consist of more than one type of component and solidify by reacting with heating or heating, such as polyurethane,
Resins such as polyester, epoxy, and acrylic.

Therefore, the reactive resin mentioned above includes both reactive thermoplastic resins and thermosetting resins. ) has been desired to be stably and continuously molded, but this generally involves difficult problems. The biggest reason for this is that when mixing reactive ingredients to manufacture a product in the desired shape, gelled products from the reaction adhere to some or all of the manufacturing equipment, making production unsustainable over a long period of time. It's for a reason. For this reason, in conventional continuous production equipment, the reaction rate of the reactive resin is slowed down and, for example, coating equipment such as a doctor knife or reverse roll coater is used, or spraying is performed while avoiding equipment that may cause gelation. using the device.

The former uses a delayed catalyst and a large amount of solvent, as seen in soft urethane leather, and is a reactive mixture. There are known methods such as diluting the substance, slowing down the reaction rate, evaporating the solvent to dryness by heating, and reacting at high temperature, or masking reactive groups in advance and removing the mask by heating. It is being When using a retarded catalyst as described above, raw! Productivity decreases and products with good physical properties cannot be obtained. Furthermore, in the method of reducing reactivity by using a large amount of solvent, the cost increases due to the use of the solvent, and the solvent evaporates due to heating, causing environmental pollution.
In addition, the latter requires multiple coats on the same coated surface in order to achieve a uniform product thickness, and the sprayer with a traverse device must be reciprocated many times, which affects not only physical properties but also productivity. A decline is inevitable. Therefore, in order to manufacture products with excellent physical properties and high productivity, it is necessary to rapidly gel the components of the reactive resin after mixing them. Applicable molding equipment is required.

One attempt to solve this kind of problem was
This is proposed in Publication No. 096. Tokuko Showa 50-3096
The device disclosed in the publication will be explained with reference to FIGS. 1 and 2. In this device, the reactive mixtures flowing in from the die inlet 1 are 2a, 2b, 2c and 2, respectively.
d, flows into the fish tail inlet 3 of the small die, expands at the small fish tail die 4, and equalizes the flow 7 at the base 5a of the fish tail die.
The device is also provided with a release groove 6 after the fishtail die. As will be described later, in this device, it is necessary to provide equal distance and equal flow resistance so that the reactive mixed liquid flows in the same amount at all points from the inlet 1 to the inlet 3 of the fish tail die. , which is difficult in practice.
This is because if the flow resistance differs even slightly in each branch path, a large amount of the mixture tends to flow toward the side with lower flow resistance, and this is difficult to avoid in terms of manufacturing.
In addition, dead points always occur at the branching points 7, 8, and 9, and a gelled product is generated within a short time. Due to this gelled material, the inflow amount of each part at the inlet 3 of the small fishtail die after the branch passage becomes unbalanced over time, making long-term operation difficult. In addition, a linear striped pattern is generated at the joint point 5b of each fishtail die, and the gelled material is also caused to flow out to the center of the product. In other words, raw materials consisting of multiple components. , and after mixing in the mixer, the reactive mixture is advanced under pressure through an extrusion tie along a plurality of paths having equal distances and equal flow resistance, each flow being They are recombined into a single, laterally expanding stream that is extruded from the die exit within a time shorter than the gelation time.

In this case, the residence times are substantially equal in all sections, the branch passages are terminated in a series of triangular passages (fistail die), the bases of the triangular passages are aligned, and It must be interconnected with the triangular passageway adjacent to the die outlet. However, it is practically impossible to create a structure that maintains equal passage distance, residence time, flow resistance, etc.

This is because when the passage is branched into multiple parts within the die, it is necessary to
Since the flow resistances are slightly different and a large amount of fluid flows toward the side with lower resistance, the amount of fluid flowing out from the die outlet is not uniform, making it difficult to apply uniformly. Furthermore, when a passage is branched into multiple parts, some of the branched passages have curved parts, and as a result,
Dead points will always occur during distribution. Then, a gel or compound of the reactive resin is generated at the dead point in a short period of just a few minutes, and the gel is attached to the dead point. As a result, gelation in the branch channels disrupts the flow balance in each branch channel, making it impossible to distribute the same amount of water, making it impossible to achieve the intended purpose. Furthermore, the gelled product may flow out, adhere to the dyna, block it, or flow into the product, resulting in a defective product. Furthermore, if a plurality of channels are branched, a linear striped pattern or the like will always be generated in the product from the confluence point. If the reactive resin is particularly foam-based, the reactive mixture in an anti-foamed state flows out from each confluence point of the branching path, and the product thickness in that area becomes thinner (due to expansion after exiting the die). ), it is not possible to obtain a good product due to poor physical properties. Generally, the discharge distribution of the fish tail type die used tends to have a large flow rate in the center, so in the form of a cluster die consisting of a plurality of dies,
It is necessary to make complicated adjustments to the thickness adjustment lip.

However, such adjustment requires a lot of time, and it is difficult to make fine adjustments during the work, resulting in problems with productivity. As described above, when this apparatus is used, even if a product that is good enough for practical use is obtained, production must be interrupted after a short period of time and cleaning operations must be performed frequently.

Also, assuming that manufacturing operations will be frequently interrupted,
Equipment must be constructed that takes into account the frequent opening of the die. In particular, the device disclosed in the above-mentioned publication has a structure in which a plurality of branch passages end in a series of triangular passages (fish tail die), so that the above-mentioned problem becomes even more serious.

Thus, after analyzing the above-mentioned problems, it was concluded that the path should not be branched when the reactive mixture flows into the extrusion die, and that having a branch path is fatal to this type of device. reached.

The present inventors have previously discussed the drawbacks of dividing a reactive mixture into multiple passages when it flows into an extrusion die, and the extrusion method that consists of an assembly of small dies with a side surface in the center that is prone to gel formation. In order to eliminate the drawbacks caused by the use of a die, we began and completed the development of an extrusion die in which a reactive mixture flows through the die inlet and the interior of the die is not substantially divided into two or more parts (Japanese Patent Application No. 1983- 699 issue).

That is, the continuous manufacturing apparatus includes a pump means for metering and conveying each component necessary for manufacturing a molded article with a reactive resin, a mixing means for stirring and mixing the components metered and conveyed from these pump means, and a mixing means for stirring and mixing the components metered and conveyed from these pump means. In an apparatus for manufacturing a molded article, the apparatus includes an outflow means for introducing the extruded reactive mixture into an extrusion die and causing it to flow out from the die outlet, and a means for integrating the extruded reactive mixture with a base material. The die is a coat hanger-shaped die with a manifold opening angle of 120 degrees or more and less than 175 degrees, and the groove width and volume at both ends of the manifold become equal to or smaller than that at the center toward the ends. This is a continuous manufacturing device for molded products using a set of reactive resins. Although the continuous production apparatus solved the problems of the conventional apparatus, it was found that there were problems in adjusting the reactive resin mixture flowing out from the die outlet and in stable operation.

l The present invention has been improved to solve this problem by interposing a pressure pump between the mixer and the die. If this pressure pump does not exist, the following problems will occur.

7(1) The reactive resin mixture stirred and mixed by the stirring mixer is spread into a flat plate in a narrow gap in the die, and a pressure loss occurs when it flows out from the die outlet.

The degree of this pressure loss varies depending on the viscosity of the raw material used, the amount of the mixture introduced into the die, changes in the shape of the die (particularly the thickness of the void in the die, etc.), and the like. (b) Since various raw materials can be used as reactive resin raw materials, these raw materials have a wide viscosity range, and in addition, various fillers can be used to obtain the physical properties required for the product. may be kneaded, which increases the viscosity.

The pressure loss increases due to such changes in the viscosity of the raw material. (b) The gap at the die exit is adjusted each time depending on the thickness of the product to be manufactured, or a change in the gap at the die exit, which is formed by a thin gap, causes a large change in pressure loss.

Further, since the internal volume of the die is made as small as possible under the conditions of residence time and uniform discharge amount at the discharge port, the pressure loss at the die becomes relatively large.

(c) Changes in the amount of reactive resin mixture introduced into the die also affect pressure loss.

(2) These pressure losses are transmitted from the die inlet to the pump through which each raw material component is metered and conveyed through the stirring mixer.

Pumps that meter and convey raw material components are required to stably meter and convey a set amount.

The desired physical properties can be obtained by changing the mixing ratio of each component of the reactive resin, catalyst, etc. Also, the reaction rate changes, so the reaction rate-limiting time changes, and if it is too early, the extrusion die Inconveniences such as gelation may occur. It is usually desirable to control the error in the mixing ratio of each component to within 3% at most, preferably within 1%. However,
When the change in pressure loss caused by the above (1) is added to the pump, it becomes difficult to adjust it, and accordingly, it becomes difficult to obtain a good product. The following methods can be considered as general methods to deal with such problems.

A: For the metering transfer pump, use a pump with high precision and pressure resistance that causes almost no fluctuation in the discharge amount due to pressure load.

B: Install a pressure regulating valve between the metering transfer pump and the mixer, and before connecting the die, tighten the valve and apply the same load as the pressure increased by connecting the die to the mixer inlet. It is confirmed in advance that a predetermined amount is being discharged, and when the die is connected (4), the pressure adjustment valve is opened and the discharge pressure is adjusted to be the same as that at the time of calibration, thereby obtaining a predetermined discharge amount.

C: Install a flow meter to directly measure the flow rate of each component,
The flow rate fluctuations that occur when connecting the die are read using a flow meter, and
Adjust the capacity of the metering pump to match the specified flow rate.

However, such common countermeasures have various drawbacks.

For countermeasure A, select a metering transfer pump that matches the properties of the raw material fluid to be used, and that is appropriate for each component consisting of two or more over the required discharge flow rate range. Must.

In this way, the selected pump performance is guaranteed only within a limited range, and changes in the raw material composition can significantly change conditions such as the viscosity of the raw fluid and the presence or absence of fillers. cannot adequately respond to changes. Therefore, in such cases, the pump must be selectively replaced each time. However, such highly accurate pumps are expensive, and using such pumps for each component and for each condition would result in very expensive equipment. In method B, the degree of increase in pressure loss due to die connection must be predicted in advance under each condition.

Then, before connecting the die, the valve provided for adjustment is throttled so that the pressure corresponds to the expected increase in pressure, and the discharge amount is measured. When the die is connected, the valve is opened and the discharge amount is measured. You must make sure that the pressure is the same as the expected pressure. However, it is difficult to accurately predict the increase in pressure that occurs when the die is connected, and in order to accurately match the pressure caused by the die connection and the pressure at the time of measuring the pump discharge amount, it is necessary to It requires repeated adjustments as described above. Furthermore, since this adjustment operation must be performed for each raw material component,
It takes a very long time. Further, while the reactive mixture is being supplied to the extrusion molding die, each component must be discharged in a predetermined amount and all components must be monitored to ensure that the set mixing ratio is maintained. In method C,
Applicable to various raw material component fluids used, and
It is necessary to select a flow meter that meets the applicable conditions such as temperature and pressure.

There are various types of flowmeters, but the flowmeters (orifice type, capacity type, rotation type, area type, purge type, etc.) that are usually available at relatively low prices have a limited range of applicability. There is.

(viscosity, presence/absence of fillers, pressure, etc.) Also, depending on the type of flowmeter used, problems such as high pressure loss may occur, so it is important to The precision required for a given mixing ratio. I can't get the degree. Electromagnetic flowmeters and flowmeters that utilize the Doppler effect can be used over a relatively wide range, but because they require high-performance electronic amplifiers, these meters cannot be used for each component separately. If installed, it would be a very expensive device.

The present inventors have solved the above-mentioned problems by installing a pump that pumps the reactive resin mixture between the mixer that mixes each component and the extrusion die so as to compensate for the pressure loss due to the flow inside the die. It has been found that this problem can be solved easily and economically by adjusting the capacity of the pressure pump so that the pressure in the mixer section is always constant.

In this way, we have discovered that each of the problems that arise when molding reactive resin using an extrusion die can be solved by the corresponding means and the configuration of the equipment as described above, and we have developed this book. Completed the invention.

The first object of the present invention is to
An object of the present invention is to provide a new apparatus and manufacturing method for continuously manufacturing molded products using a reactive resin. A second object of the present invention is to provide a new continuous manufacturing apparatus and manufacturing method for reactive resin moldings that can be operated continuously for a long time by minimizing the adhesion of gelled substances in an extrusion die. There is something to do.

The third object of the present invention is to provide a coat hanger type that does not require a branching passage when spreading the reactive mixture after mixing with an extrusion die, has a single inner surface, and is not a die and is made of a concentrated body of small dies. is a reactive resin molded product in which the residence time from the inlet to the outlet of the reactive mixture at the exits at both ends of the die is approximately equal to or smaller than the average residence time at the die exit. An object of the present invention is to provide a novel continuous manufacturing apparatus and manufacturing method.

A fourth object of the present invention is to provide an apparatus and a manufacturing method that can stably manufacture products even with extremely thick products and low manufacturing speeds. The fifth object of the present invention is to
It is an object of the present invention to provide a new manufacturing apparatus and method for reactive resin molded articles that are improved so that linear striped patterns do not occur in the product. A sixth object of the present invention is to provide an inexpensive manufacturing device and manufacturing method that can use a wide range of raw materials with various properties, can adequately handle various conditions, and further improves operability. is to provide. A seventh object of the present invention is to provide a novel manufacturing apparatus and method for manufacturing reactive resin molded products that are improved so that gelled products of the resin do not flow out into the center of the product.

An eighth object of the present invention is to provide a novel apparatus and method for producing reactive resin moldings that can be applied to molding thick block forms up to 1 meter in thickness. Another object of the present invention is to provide an apparatus and a method for continuously producing reactive resin molded products that do not change the product thickness or physical properties even after long-term operation.

Another object of the present invention is to provide an apparatus and method for continuously producing molded products, whether foamed or non-foamed. When molding the foam,
One object of the present invention is to provide a novel continuous manufacturing apparatus and manufacturing method for molded products that can ensure good cells. Next, a die used in the continuous production apparatus for molded products according to the present invention will be explained.

When the reactive mixture flows into the extrusion die, there are disadvantages of dividing it into multiple passages and the use of an extrusion die consisting of an assembly of small dies with an internal die surface that is prone to gel formation. In order to eliminate this drawback, this extrusion die allows the reactive mixture to flow through the die inlet and does not substantially divide the inside of the die into two or more parts.

When applying these reactive mixtures to extrusion dies, there is a concern that gelation may adhere to the interior of the die, especially the sides and exit of the die, making it impossible to operate the device continuously. arise. Regarding gel formation, assuming that a reactive mixture flows into a certain extrusion die and flows out from the outlet, the ease with which a gel of the reactive mixture is formed within that die depends mainly on the shape of the die. Due to the flow characteristics of the reactive mixture, the flow rate, viscosity, inflow rate of the mixture and the reactivity of the reactive mixture.

The volume, flow rate, and reactivity of the extrusion die can also be expressed separately as follows. In other words, it can be said that the number of times the mixture replaces the inside of the die within the time period until the reactive mixture starts a reaction (rate-limiting). Expressed in the formula, f: How many times the reactive mixture replaces the inside of the die within the time period until the reaction becomes rate-determining, the number of times of replacement a: Amount of the reactive mixture flowing into and supplied to the die ('/Mln) b: The time from mixing of the reactive mixture until the reaction becomes rate-limiting (Mln) The reaction rate-limiting time is the reaction rate-limiting time when the reactive resin component of the means for carrying out the present invention is actually introduced into the die under mixing conditions and at the temperature of the die, and immediately after stirring. The viscosity is measured using a viscometer, and the time taken for the viscosity to begin to rise from the initial viscosity is expressed in minutes.

In particular, in the case of urethane foams, it refers to the time from mixing to the start of foaming, which includes the foam due to the reaction of isocyanate and water and the reaction heat of the isocyanate groups with active hydrogen, which causes the low-boiling point solvent to evaporate. There are some that vaporize to form foam. In addition, for those that start foaming after the reaction has proceeded to a considerable extent, or those that start foaming by post-heating, the reaction rate-limiting time is defined as a 30% increase in viscosity. c:
Internal volume of the void from the mixer outlet to the die outlet (including the actual volume within the void from the mixer to the die inlet)
(e) That is, from this equation, as the f value is increased, the number of times the liquid is replaced increases, the freshness of the mixed liquid flowing in the gap increases, and gelled substances are not generated in the die. As can be seen from this equation, either (1) the amount of the reactive mixture flowing into the extrusion die is increased, (2) the reactivity is decreased (lengthening the rate determining time), or (3) the reactive mixture is increased.
It is better to reduce the volume of the flowing void. However, if the amount of mixture (1) is increased, thin products (for example, 1
In order to manufacture a product with a product weight of 50y/300y/Rrl (this sheet or foam sheet), it is necessary to set the conveyor speed for conveying the attached release paper etc. to several hundred m/min, and the curing time is 4. The length of the belt conveyor alone in the production equipment is over 1000n1, which increases the cost of the equipment and poses a practical problem. Furthermore, if the reactivity in (2) is lowered, the physical properties of the product and the productivity will be lowered, and furthermore, the foam will not be able to form normal cells and cannot be put to practical use. Although it is good to reduce the internal volume of the void in (3), if the internal volume of the extrusion die is made smaller than necessary, the flow uniformity will decrease and a dead center will be created inside the die. The f-value will apparently increase, but the actual f-value will decrease. That is, in the same die internal volume, it is preferable that the residence time of the liquid be the same at all points from the die inlet to the die outlet. That is, the present inventors have developed an extrusion die that can make the residence time as equal as possible at all points from the inlet to the outlet of the die, and at the same time reduce the internal volume of the die. That is, we have completed a die, manufacturing apparatus, and manufacturing method that can be stably and continuously used even when a small amount of reactive mixture flows into the die. By selecting the shape of the die, the cross-sectional area and flow velocity at each section within the die can be varied, without dividing the reactive mixture into multiple equidistant and equal flow resistance passages, thereby reducing the residence time at each section at the outlet. We have found that it is possible to make them equal to a. That is, it has been found that this can be achieved by appropriately selecting the opening angle of the manifold, the shape and volume of the manifold, the relationship between the volume of the manifold and the volume excluding the manifold, the tie gap, etc. Furthermore, it has been found that by particularly increasing the flow at the die end and increasing the outflow amount from the die end, gelation at the end can be further reduced. What is the number of parts with a large amount of outflow at the ends? ~1c! R.L.
There is no problem in terms of yield. In addition, in coat hanger-shaped dies, there is a groove halfway from the die inlet to the end, so it is easy for dirt to get stuck at the end.
This tends to cause problems, so providing a groove that penetrates the end to the die exit is effective in that respect as well. In addition, in a fishtail die, when the die width is doubled, the die internal volume is four times as large, and when the die width is tripled, the die internal volume becomes nine times as large.

In other words, when the die width increases by n times, the internal volume increases by N2 times. Therefore, when the die width, that is, the product width increases by 3 times, the inflow amount of the die reactive mixture increases by 3 times, but the die internal volume increases by 9 times. As a result, the f value eventually decreases. For this reason, safety rapidly decreases as the size increases, so it cannot be used in production. In the continuous manufacturing apparatus of the present invention, the extrusion die is not an assembly of branched small dies, and the inside of the die is not substantially divided into two or more parts, but is shaped like a coat hanger.

This extrusion die is formed so that the opening angle of the manifold at the raw material inlet is from 120 degrees to less than 175 degrees (in FIG. 9, θ indicates the opening angle.
The ratio of the die internal volume excluding the groove inside the die and the groove volume is 1:
It is configured to have a ratio of 0.1 to 1:10. moreover,
The minimum gap of the die excluding the manifold is 2.0 mm or less, preferably 1.5 mm or less. In addition, the groove width and volume at both ends of the manifold are continuously equal to or smaller than those at the center toward the ends. refers to ) Also, two coat hanger-shaped dies can be arranged in parallel to provide two injection ports. To further explain the method of the present invention, particularly in an example in which it is applied to polyurethane resin, the following conditions must be maintained in a coat hanger type extrusion die.

However, a: the amount of reactive mixture flowing into the extrusion die (
e/Min) b: Reaction rate-limiting time after mixing of the reactive mixture (Mln) c: Substantive volume within the die (e) (including the substantive volume within the gap from the mixer to the die inlet) Note that the gap between the die 1.
When the diameter is less than 5 mm, the reaction rate-limiting time becomes rapidly longer.

This was determined experimentally. When the curable resin enters the range below the above-mentioned gap, the reaction rate-determining time of the reaction liquid suddenly becomes longer. For example, when manufacturing a urethane foam sheet made of polyol, polyisocyanate, appropriate catalyst, cell stabilizer, water, etc., the relationship between the reaction rate-limiting time (cream time) after mixing and the die gap is as follows:
It will look like Figure 3. The reason for this is not clear, but it is likely that in this type of polymerization reaction, the reaction is further accelerated by the heat storage effect of the self-reaction heat from the first reaction. Most of it is absorbed by the die wall surface, which tends to suppress the reaction. Furthermore, regarding the relationship between the opening angle of the manifold at the die inlet for introducing the raw material and the groove depth, it is recognized that the groove depth needs to be increased as the opening of the manifold at the die inlet for the raw material becomes larger.

Furthermore, by continuously penetrating both ends of the manifold to the die outlet, gelation at the sides is prevented and continuous operation for a longer period of time is possible.

In this case, since the weight of the product on the side portions of the product increases, it is generally preferable that the groove depth is 1 mm or less. According to the invention, the residence time of the feedstock at the exit end of the die (from inlet to exit) can be approximately equal to or less than the average residence time at the exit over the width of the die.

In particular, in the die of the present invention, the internal volume can be significantly reduced compared to a body tail die or an assembly of small body tail dies, so that the residence time of the reactive mixture in the die can be significantly reduced. be shortened. Note that coating the inside of the die with fluorine-based resin (Teflon resin) or silicone resin can prevent the adhesion of reactive resin. FIG. 4 shows an example of the flow characteristics of a mixture over time in a coat hanger type die according to the present invention.

In order to compare this with the case of a conventional fishtail die, the same flow characteristics in this conventional die are shown in FIG. Note that the numbers shown in the figure indicate the number of seconds (residence time) from the inlet to the line in the figure.
As is clear from this, in the coated hanger type die of the present invention, the residence time at the outlet portion is
Almost equal.

In this fishtail die, the side residence time is generally 4 to 8 times the average residence time. In the die of the present invention, it is up to 2 times to 1 times or less. this is,
This shows that even when manufacturing a 7-layer urethane block foam, the surface can be made flat. Figure 6 shows polyisocyanate, polyol catalyst, water,
Conditions for successful use of extrusion dies in Urethane 9 foam with silicone surfactants are shown.

In addition to the f-value, the flow velocity inside the die is a problem because even if the f-value is satisfied, the liquid flow velocity between the inner surface of the die and the liquid contact area is close to zero, so it is difficult for fresh reactive mixed liquid to pass through the inner surface of the die. This is because there seems to be a minimum speed required for washing. The raw material viscosity that can be applied in the present invention may be any viscosity as long as it is compatible with gear pumps, plunger pumps, etc.
000 centipoise or less, preferably 6000 centipoise or less.

Furthermore, when the product is urethane foam, it is necessary to dissolve in advance an inert gas that can serve as bubble nuclei during foaming in the reaction components conveyed from the pump. If this condition is not met, as the pressure inside the die increases,
This results in a foam with a considerably large cell structure, making it difficult to put it to practical use. A foam that maintains a cell count of about 28 cavities/d under normal pressure will have a pressure in the die of 3 if the above conditions are not met.
k9/d, it decreases to about 4!1141/d, but when air is dissolved, it recovers to about 25 fences/d. Furthermore, in order to form fine cells, it is preferable to incorporate fine inorganic or organic powder into the urethane foam raw material as a gas adsorbent. That is, to give a concrete example, after stirring and mixing fine powder with a reactive component, an inert gas is dissolved under pressure. Although it depends on the type of powder, it is generally possible to adsorb the same volume to 5 times the volume of gas relative to the true volume of the powder used.

The amount of air dissolved in the urethane raw material is generally about 10 cc at 20°C and 11 atmospheres per 100 y of the raw material, which is extremely large even from this point of view. Suitable types of powder include, for example, silicon oxide, calcium carbonate, zeolite, carbon black, bulb, and starch. Urethane foams include flexible urethane foams, rigid urethane foams, semi-rigid urethane foams, and other elastomer sponges, and the present invention can be applied to any of them.

Located between the mixer used in the present invention and the die. A pressure pump for pumping mixed liquids is used to increase pressure due to changes in viscosity due to changes in raw material components, pressure changes due to changes in die gap settings, pressure changes due to changes in the amount of mixture supplied to the die, etc. The metering pumps for each raw material component must be operated in such a way that changes in the flow rate do not have such an effect, so the pressure in the mixer section must be adjusted to maintain a constant value at all times. Ru.

The value of this constant pressure varies depending on the performance of the pump, the pressure of the raw material tank, the properties of the resin to be molded, etc., and cannot be absolutely defined, but it is preferably 0.2 to 0 when using a pump for sails. It is desirable that it be in the range of .5 kg/d. This is because pumps normally used for metered conveyance have relatively stable performance within this range of pressure rise. In pressure fluctuations within this range, it is possible to maintain the variation range of the discharge flow rate approximately within the required range with respect to the calibration value of the discharge flow rate without any load due to the die connection of each component. For this reason, once it is confirmed for each pump that the variation in discharge flow rate in response to pressure fluctuations within this range is within the required variation range, it is no longer necessary to correct the discharge flow rate from then on. Because they don't. Ma・ta, about 0.2k
The presence of a pressure of 9/Clt or more is a preferable value to ensure the suction capacity of the pump used for pressure feeding to the die. Of course, if the pump used for pressure pumping is of high performance, the pressure value can be set to 0k9/Clt (gauge pressure) or negative. It cannot be used normally because it narrows the performance range of the pump.As mentioned above, the pressure in the mixer section is preferably in the range of 0.2 to 0.5 kg/Crft; It is possible to increase the discharge pressure range up to the maximum discharge pressure range of the pump with the lowest discharge pressure performance among the metering conveyance pumps.

For this purpose, a pressure regulating valve for adjusting and measuring the discharge pressure of each metering pump is required before the inlet of each component to the mixer. The set pressure is applied to the metering conveyance pump for each component, so when measuring the discharge amount, this set pressure is added to the pressure required to convey the specified amount of each component raw material to the mixer section. The pressure regulating valve is tightened so that each component has a predetermined flow rate, and when the pressure pump and die are connected, this valve is used for all operations. This operation is similar to the countermeasure for the problem mentioned earlier, that is, the countermeasure against the increase in pressure loss caused by the flow of the mixture in the die in the absence of a pressure pump, but, The big difference between this case and the corresponding method "B" is that the pressure increase can be set from the beginning, and its value can be adjusted by a pressure pump installed between the mixer and the die. Since a constant value can be maintained, there is no need for repeated calibration adjustment operations as seen in Countermeasure ゜゜B'2.This method allows the discharge pressure of the pump used for pressure feeding to be This means that the pump can be increased without damaging the main body, etc.For this reason, even in pumps used for pressure pumping, high precision pumps are not necessarily required, and from among a wide range of types, It is possible to select any pump.As mentioned above, a pressure pump is provided between the mixer and the die, and the reactive mixture is introduced into the extrusion die through this pump to obtain a molded product. , the pressure in the mixer section needs to be kept constant;
This is carried out by adjusting the capacity of the pressure pump so that the pressure between the pressure pumps becomes a preset constant pressure.

This can be done by the operator adjusting the pressure pump while checking the readings on the pressure gauge installed between the mixer section and the pressure pump, but it is also possible to The pumping capacity may be automatically or mechanically transmitted to the motor that drives the pressure pump to automatically adjust the pumping capacity.
As for the pressure gauge used here, pressure gauges such as the Bourdon tube type, which are measured by directly introducing liquid into the gauge, are not suitable; they are measured through a diaphragm, and reactive mixtures are It is preferable to use a pressure type that does not penetrate.

Examples of such methods include gauge-type devices with strain gauges attached to a diaphragm, devices that use piezoelectric elements, and devices that are measured using the pressure of gas or fluid sealed through a diaphragm. You can use Ru. Since the pump used in this manner generates heat as it operates, it is desirable that the temperature of the pump be controlled by a cold water shade supplied to a jacket or the like surrounding the pump. because,
The temperature of the reactive resin affects its reaction rate, and for a given reaction. This is because a deviation from the response rate-determining time may occur. In the extrusion die of the present invention, since the amount of gelled substances adhering to the extrusion die is small, there is no need to frequently open and clean the die.

Conventionally, when manufacturing operations are stopped, such as at the end of production, it is common practice to stop multiple pumps that supply the mixer at the same time and wash them with solvent and pressurized air. It is preferable to interrupt the reaction by setting the pump supply amount of at least one component, such as the catalyst, polyol, or isocyanate, to zero, and completely wash the interior of the die with the remaining component. Preferably, the device is then completely shut down. This is because in an extrusion die, if all the equipment is stopped at once, the reactive mixture remaining in the die will gel within the die, so a rapid opening device is required. or,
Even when cleaning by flowing pressurized air and solvent at the same time as the stop, there are cases where only the center of the tie can be cleaned and the edges of the die cannot be cleaned. Even in the extrusion die of this development, the remaining components are removed after removing one or more of the necessary components. After cleaning the inside of the die with the above components, it is even better to clean it with pressurized air, a solvent, or both.However, since the gelation reaction does not proceed in the die after stopping, it is not necessarily necessary to clean quickly.Also, in general, In the case of block foam, the foamed resin is discharged onto a release paper tilted by a conveyor belt using a traverse, but in this invention, the discharged liquid is said to have a uniform discharge amount. For the reason, the inclination angle of the conveyor is
It is possible to take a slope that exclusively matches the foaming curve of the foam, and it is possible to obtain a product with a nearly flat surface.

Applications of this invention include foam and non-foam backings,
Adhesive tape material, carpet backing, gasket,
Widely applied to leather, insulation materials, interior materials, etc.

Also included within the scope of this invention are laminating apparatus and methods. The resin applied to the present invention may be any reactive resin that has fluidity at room temperature or in a heated state, and is particularly suitable for foamed and non-foamed urethane resins.

The polyurethane resin raw materials used in the present invention include an organic polyisocyanate, a catalyst, and, if necessary, a polyol, a crosslinking agent, a cell stabilizer, a blowing agent, a filler, etc. ,
The starting material may be one synthesized from a prepolymer having terminal isocyanate groups. More specifically, examples of the organic polyisocyanate include hexamethylene diisocyanate, tolylene diisocyanate,
Diphenylmethane diisocyanate, xylene diisocyanate, 1,5 naphthalene diisocyanate, etc. Typical polyols include polyether polyols, polyester polyols, and diene polyols, with 2 to 8 hydroxyl groups in one molecule. polyethers with a molecular weight of 200 to 15,000 (ethylene glycol, glycerin, pentaerythritol, hexanetriol, trimethylolpropane, sorbitol, sucrose, etc., polymerized with alkylene oxides such as ethylene oxide and propylene oxide), adipic acid, etc. Polyesters with a molecular weight of 500 to 10,000 obtained by condensation of the dibasic acids of 2 and the above polyhydric alcohols such as ethylene glycol, and 1.2 bonds or 1.2 bonds with a molecular weight of 500 to 4,000. There are diene polyols mainly composed of polyurethane, and the selection of these types and molecular weights is determined appropriately depending on the target polyurethane resin.For flexible polyurethane foams, di- to tetrafunctional polyols with a molecular weight of 400 to 6,000 are used. Polypropylene ether polyol is used for rigid polyurethane foam, polypropylene ether polyol with a molecular weight of 250 to 1000 is used for rigid polyurethane foam, polytetramethylene ether glycol is used for urethane elastomer, and polytetramethylene ether glycol is used for urethane leather with a molecular weight of 800 to 3000. Generally, a polyester polyol having a molecular weight of 800 to 3,000 is selected, and as a crosslinking agent, aromatic diamines such as methylenebisorthochloroaniline and 3,3'' dichlorobenzine, and low molecular weight alcohols such as 1,4 butanediol are used. As blowing agents, there are reactive types such as water and boric acid, and non-reactive types such as monofluorotrichloromethane.Furthermore, as catalysts, conventionally known triethylenediamine, triethylamine, N- There are tertiary amine catalysts such as methylmorpholine and metal salt catalysts such as stannath octate and dibutyltin dilaurate, and these organic polyisocyanates, catalysts, polyols, crosslinking agents, blowing agents, cell stabilizers, and fillers. These can be selected as appropriate depending on the type of polyurethane product and other conditions.
The configuration of the manufacturing apparatus and manufacturing method of the present invention will be specifically explained with reference to FIG.

In the figure, 10a and 10b are tanks for each reactive raw material component, and 11a and 11b are pumps for measuring and conveying. 12 is a mixer incorporating an agitator for mixing and stirring, and 11p is a pressure pump.

13 is an extrusion die, 14 is a base material, 15 is a backup roll for supporting the base material, and 16 is a reactive mixture layer integrated with the base material.

Each reactive component supplied from tanks 10a and 10b is metered in a fixed amount by pumps 11a and 11b, and then transferred to mixer 1.
Sent to 2.

The reactive liquid mixture mixed in the mixer 12 is sent to the extrusion die 13 via the pressure pump 11p, flows into a certain shape, is extruded, and is placed on the base material 14 guided by the backup roll 15. The mixture layer 16 is then transferred to the base material and becomes a mixture layer 16 that is integrated with the base material. In this case, the closer the mixer 12 for mixing and stirring and the pressure pump 11p are to the extrusion die 13, the better, and if possible, it is desirable that they be integrated.

Further, depending on the formulation, a portion other than the stirring portion, that is, a mixing function and a pumping function may be included in the extrusion die 13. 8 to 10 show a coat hanger-shaped die 13 according to the present invention, FIG. 8 is a partially cutaway perspective view, FIG. 9 is a partially cutaway front view, and FIG.
The figure is a longitudinal side view of A, A'' in FIG.

Further, 20 is a die back member, and 21 is a die front member. 22 is a fixed lip, and 23 is a variable lip.
24a is a push bolt for lip adjustment, and 24b is a pull bolt for lip adjustment.

Both members 20, 21 and lips 22, 23
A die gap 25 is formed by this. Also, 26
27 is a release groove, and 27 is a die temperature control jacket.
Further, 28 is a plate for fixing the jacket, 29 is an inlet for a temperature regulating liquid, and 30 is an outlet of the die. In this implementation, the magnitude of θ is 120 degrees and less than 175 degrees, the width of the manifold is in the relationship D1≧D2, and the cross-sectional area of D1 is D
Equal to or greater than the cross-sectional area of 2. Note that by making the D1 width and D1 cross-sectional area larger than the D2 width and D2 cross-sectional area, the residence time can be made uniform. The die gap 25 is 1.5 mm or less, preferably 1 mm or less, and the ratio of the die internal volume to the manifold volume excluding the manifolds 19 and 26 is 1:0.1 to 1:1.
It is 0. The reactive mixture after mixing flows into the die inlet 17, enters the first manifold 19, flows to both shoulders thereof, and also partially flows out into the die gap 25,
It flows towards the die outlet 30.

The opening angle θ of the manifold, the manifold widths Dl and D2, and the cross-sectional area thereof can be appropriately determined within the above ranges so that the residence time at the die outlet 30 is approximately equal or both shoulders are short. The reactive mixture is discharged from the die outlet 30 before the rate-limiting reaction (the time from when the reaction occurs until the viscosity starts to increase) and is transferred onto a continuously running substrate. FIG. 11 shows an example of the manufacturing process of the present invention.

Here, a reactive mixture is discharged from the outlet, 31, of the extrusion die 13, which is arranged approximately perpendicular to the direction of movement of the substrate 14, and is applied onto the substrate 14, which is supported by a backup roll 15, to form a layer. form 16. The layer 16 is supported together with the substrate 14 on a carrier roll 33, enters a cure oven 34, is reacted and cured, and is transferred to a peeling roll 35.
At , the base material 14 and the product 40 are wound onto a base material winding roll 37 and a product winding roll 39, respectively.
The product 40 may be a foamed product or a non-foamed product, or the base material 14 and the product 40 may be integrated.

Base materials used for integration include cloth, paper, metal film, plastic film, and endless belt. Example 1A: B: Aniline to 95.3 parts of a mixture of 90.3 parts of butadiene polyol (manufactured by Idemitsu Petrochemical Co., Ltd., trade name PolyBDR45llT) and 5 parts of carbon black (manufactured by Mitsubishi Kasei Corporation/#30) 21.58 parts of a compound obtained by adding 2 moles of propylene oxide to 1 mole (product name: Isonol C-100, manufactured by Updillon Co., Ltd.), C: Tolylene diisocyanate (T-80 (manufactured by Nippon Polyurethane Co., Ltd.) 2,4/2,6 isomerism 25.27 parts of D: dibutyltin laurate, diluted with 9.7 parts of butadiene polyol, were metered and transported using a gear pump to maintain the above ratios. The mixture was stirred and mixed using a rotary mixer, connected to a gear pump for pressure feeding, and connected to force feed the mixed reactive resin to an extrusion die.

The discharge amount of each component was A: 953y at the time of calibration.
/Min,. B: 215.8y/Min. ．． C:252
．． 7y/Min,. D: 100y/min, and the total discharge amount was 1521.5g/min. A small pressure sensor of the diaphragm piezoelectric element type is inserted in front of the suction port of the pressure pump, and this signal is transmitted to the control device of the DC motor that drives the pressure pump, and the pressure at the pressure detector is The pressure pump was set to be driven so that the pressure was 0.2k9/d.

In addition, the pressure pump is equipped with a jacket that circulates temperature-controlled water to prevent the temperature from rising over time due to pump operation. I handled it so that it wouldn't happen. The width of the extrusion die is 0.8n1, and the internal volume of the die including the pump is 0.18.
' is a coat hanger die with an f value of approximately 3. The flow rate at the outlet of the transfer die was approximately 1.5 rn/min.

In addition, the physical properties of the obtained product were good, and when the flow rate from the die outlet was determined from the sheet, the total flow rate was 14 tons/min. The difference was 29.5 f/Min.

Comparative Example 1 A reactive mixed solution was fed under pressure to a 0.8n1 width fishtail die under the same formulation and conditions as in Example 1, except that the coat hanger die for comparison was changed to a fishtail die.

The internal volume of this die is 0.43e, the calculated f value is about 0.85, and the flow rate at the die exit is about 1.5n1/Ml.
It was n. Approximately 3 minutes after operation, a considerable amount of gelled material adhered to the side of the die exit, and the operation could not be continued. Comparative Example 2 The same conditions as in Example 1 were carried out except that the pressure pump was removed.

The calculated f value was approximately 5. When the machine was operated continuously for one hour, no gelled material was observed to adhere to the die outlet. When the flow rate from the die was determined from the sheet, it was 1385 q/Min. The physical properties of this product almost had the desired physical properties. The operation to correct the pressure loss in the die was troublesome and required constant attention from the operator, and in the case of long-term operation, some product unevenness occurred, which required a long time to inspect. Comparative Example 3 Using the same formulation as in Example 1, the total discharge amount of the reactive mixed liquid was set to 500 y/min using the same device.

The f value at this time was 1.18, and the flow velocity at the die exit was:
It was 0.49rr1/Min. At the beginning of operation, the discharge condition of the reactive mixture from the die outlet was good, and the discharge was almost uniform in the width direction of the die, but after the second powder, gelled substances started to adhere to both ends of the die, and the reaction mixture was discharged at both ends. The discharge amount decreased and the product did not have a uniform thickness, making it impossible to continue operation.

Example 2 A: 1 (4) parts of polyol G-400 (manufactured by Asahi Denka Co., Ltd.),
DAFCO 331. as a catalyst. ■ (manufactured by Sankyo Air Products Co., Ltd.) 1.5 parts, Polycat 8 (manufactured by Sanabbot Co., Ltd.) 1 part
．． 5 parts, foam stabilizer L-5350 (manufactured by Nippon Unicar Co., Ltd.) 1.
5 parts of water, 0.5 parts of water, milled fiber glass MF-B (manufactured by Asahi Glass Co., Ltd.) as a filler, and 12 parts of calcium carbonate 60 mesh (manufactured by Shiraishi Calcium Industries Co., Ltd.), B:
Isocyanate MOi-CR (manufactured by Mitsui Nisso Urethane Co., Ltd.)
116 parts of A and B are metered and conveyed using a mono-type pump and a gear pump to maintain the respective proportions, stirred and mixed with a rotary mixer, and connected to a mono-type pump for pressure feeding, and the mixed reactive resin is was coupled so as to be forced into an extrusion die.

The discharge amount of each component is A: 1000y/MinlB:
752y/Min, total discharge amount is 1752g
/Min.

A pressure detection mechanism similar to that in Example 1 was provided at the suction port of the pressure pump to control and drive the pressure pump. The extrusion die has a width of 1m and a die internal volume of 0.292f including the pump.
The coat hanger die had an f value of about 3 and a flow velocity at the die outlet of about 1.7 m/min.

The reactive mixed liquid discharged from the die outlet is directly below 1.2
It was uniformly coated on a vapor traveling at a speed of n1/Min, and then foamed to obtain a foamed polyurethane board with a thickness of 1-. Moreover, the physical properties of the obtained product were good.
Comparative Example 4 Using the same urethane resin as in Example 2, a reactive liquid mixture was directly introduced from a rotary mixer into the same die inlet as in Example 2 without using a pressure pump.

The internal volume of the die at this time is 0.142e, and the f value is:
It was about 6.2. When discharging to the mixer starts stirring,
The pump pressures for metering and conveying each of the A and B components increased significantly, and the pressure of the B component in particular showed large pulsations.

The obtained product had variations in hardness in the longitudinal direction during manufacture and did not exhibit good physical properties.

[Brief explanation of the drawing]

Fig. 1 is a vertical side view of a conventional continuous molding device, Fig. 2 is a partially cutaway front view of the same, Fig. 3 is a graph showing the relationship between reaction rate limiting and die gap, and Fig. 4 is FIG. 5 is a front view showing the flow elapsed time of the reactive mixture in the die according to the present invention, FIG. 5 is a front view showing the flow elapsed time in the case of the conventional example, and FIG.
7 is a schematic system diagram showing an embodiment of the present invention. FIG. 8 is a partially cutaway perspective view of a die according to the present invention. 9 is a front view of the same, FIG. 10 is a longitudinal sectional side view of the same, and FIG. 11 is a diagram of one process of the present invention. 10a, 10b: Tank, 11a, 11b: Pump, 1
1p: pressure pump, 12: mixer, 13: extrusion die,
14: Base material, 15: Backup roll, 16: Mixture layer, 17: Inlet, 18: Flare part, 19: Manifold, 20: Die back member, 21: Die front member, 22
: Fixed lip, 23: Variable lip, 24a, 24b: Bolt, 25: Die gap, 26: Release groove, 27: Jacket, 28: Plate, 29: Inlet, 30, 31: Die outlet, 32: Base material Unwinding roll, 33: Carrier roll, 34: Cure oven, 35: Peeling roll, 36
: Drive roll, 37: Base material winding roll, 38: Nippro roll, 39: Product winding roll, 40: Product.

Claims (1)

[Claims] 1. A pump means for metering and conveying each component necessary for manufacturing a molded article with a reactive resin, a mixing means for stirring and mixing the components metered and conveyed from these pump means, In an apparatus for manufacturing a molded article, the apparatus includes means for introducing a reactive mixture into an extrusion die, an outflow means for causing the reactive mixture to flow out from the die outlet, and a means for integrating the extruded mixture with a base material. The extrusion die has a manifold with an opening angle of 120 degrees or more.
It is a coat hanger-shaped die with an angle of less than 75 degrees, and the ratio of the internal volume of the die excluding the manifold to the manifold volume is set to 1:0.1 to 1:10, and the groove width at both ends of the manifold and 1. An apparatus for continuously producing a molded article using a reactive resin, wherein the volume is set to be equal to or smaller than that of the center toward the ends. 2. An apparatus for continuously producing molded products using a reactive resin according to claim 1, wherein the minimum gap within the die, excluding the manifold, is 1.5 mm or less. 3. An apparatus for continuously producing a molded product using a reactive resin according to claim 1, wherein both ends of the manifold continuously penetrate within the die to the die outlet. 4. An apparatus for continuously manufacturing a molded article using a reactive resin according to claim 1, wherein the inside of the die is coated with a fluororesin or a silicone resin. 5. Measure and convey each component necessary for manufacturing a molded article with a reactive resin, stir and mix the metered components, and force-feed the obtained reactive mixture to an extrusion die using a pressure pump,
The pumped mixture is transferred to the manifold at an opening angle of 120°.
In a method for producing a molded article in which the mixture is introduced into a coat hanger-shaped die having an injection port at a temperature of at least 175 degrees and is integrated with a base material, a urethane resin or a urethane foam resin is used as the reactive resin, The amount of reactive mixture (l/min) introduced into the extrusion die is a,
Reaction rate-limiting time (min) after mixing of reactive mixture
b, the real volume (l) of the reactive mixture in the die is c, (
c is the actual volume in the gap from the mixer to the die inlet (
When f is the number of times the reactive mixture replaces the inside of the die within the time until the reaction becomes rate-determining (including 1), f = (a
×b)/c, and satisfy f≧1.3, and set the maximum flow velocity in the die excluding the manifold to 0.8
A method for continuously producing a molded article using a reactive resin, characterized in that the rate is set at m/min or more. 6. A method for continuously producing a molded article using a reactive resin according to claim 5, wherein inorganic or organic fine powder is incorporated as a gas adsorbent in the urethane foam raw material of the reactive resin.