JPS6043296B2 - Continuous manufacturing device for molded products using reactive resin and method for manufacturing polyurethane resin molded products using the device - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to the use of a reactive resin consisting of two or more components having a pot life (time from mixing to the start of gelation) of at least several seconds to 20 minutes after mixing, in foamed or non-foamed form. The present invention relates to a continuous manufacturing device for molded products that are used to continuously integrate molded products in the form of a film or a layer of appropriate thickness with other substrates, and a method for manufacturing molded products using the manufacturing device.

More specifically, the present invention relates to a continuous manufacturing apparatus and a manufacturing method particularly suitable for producing molded products having a wide product width, such as film-like products or layered molded products. Conventionally, reactive resins (hereinafter referred to as "reactive resins") have a pot life of several seconds to several tens of minutes after mixing.Reactive resins are all compounds that are composed of at least two or more components and that react and solidify with or without heating. This refers to resins such as polyurethane, polyester, epoxy, and acrylic.

Therefore, the reactive resin referred to in this item 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 coating equipment such as a doctor knife or reverse roll coater is used, or spraying equipment is used to avoid equipment that may cause gelation. are using.

The former uses a delayed catalyst and a large amount of solvent, as seen in dry urethane leather, to dilute the reactive mixture, reduce the reaction rate, evaporate the solvent by heating, and dry it at high temperature. How to react. Alternatively, a method of masking with a reactive group and removing the mask by heating is known. As mentioned above, when a delayed catalyst is used, productivity decreases and a product with good physical properties cannot be obtained. In addition, 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 spray with a traverse device must be reciprocated many times, which affects not only physical properties but also productivity. It is inevitable that there will be a decline in

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. 3096. The manufacturing apparatus and method disclosed in this publication are as follows. That is, raw materials consisting of multiple components are fed to a mixer, mixed in the mixer, and then the reactive mixture is advanced under pressure through an extrusion die along a plurality of paths having equal distances and equal flow resistance. , the individual streams are recombined into a single, laterally expanding stream that is extruded from the die exit in a time less than the gelation time. In this case, the residence time is made substantially equal in all sections, the branch passages are terminated in a series of triangular passages (fishtail die), and the bases of the triangular passages are aligned. , and must be interconnected with the triangular passageway adjacent to the die exit. However, it is practically impossible to create a structure in which the passage distance, residence time, flow resistance, etc. are kept equal.

This is because when multiple passages are branched within a die, the flow resistance is always slightly different, and a large amount of fluid flows toward the side with lower resistance, so the flow rate at the die exit is not equal, making it difficult to apply uniformly. becomes. 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 gelled product of the reactive resin is generated at the dead center in a short period of just a few minutes, and the gel is attached to the dead center. Thus,
Due to gelation in the branch channels, the balance of flow in each branch channel is disrupted, making it impossible to distribute the same amount of water, making it impossible to achieve the intended purpose. Furthermore, the gelled material flows out, adheres to the inside of the die and blocks it, or flows out into the product, resulting in a defective product. Generally, the discharge distribution of the fish tail type die used tends to have a large flow rate in the center, so in the case of a cluster die consisting of multiple dies, the thickness adjustment lip is adjusted in a complicated manner to It is necessary to change the outlet gap to achieve a uniform discharge amount.

However, such adjustment requires a lot of time, and it is difficult to make fine adjustments during the work, which poses problems in terms of production. 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 for a short time and preliminary work 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.

Based on this conclusion, the present inventors previously developed an extrusion die without branching paths, and by using this die, they completed an apparatus and method for manufacturing molded products advantageously continuously. . (Japanese Patent Application No. 51-699) This device includes pump means for metering and conveying each component necessary for manufacturing a molded article from a reactive resin, and stirring and mixing of the components metered and supplied from these pump means. Molding comprising a mixing means, a means for extruding the stirred and mixed reactive mixture, introducing it into a die, and causing it to flow out from the die outlet, and a means for continuously integrating the extruded mixture with the base material. In the device for manufacturing products, the extrusion die has one inlet,
The manifold of the die is a coat hanger type in which the opening angle is 120 degrees or more and less than 175 degrees, and the groove width and volume at both ends and the center of the manifold are larger than that at the inlet as it goes from the inlet to the end. is set equal to or less than. Some manufacturing equipment is suitable for producing products with a narrow width, but is not suitable for producing products with a large width.

The present inventors have developed a device that can operate more stably for long periods of time, even for products with a wide product width or thin product thickness, and a device that can be operated for a long time even when the inside of the die is maintained. As a result of intensive research into the development of a device that produces a good product without gelation, we developed a system that includes multiple pumps for metering and transporting each component of the reactive resin, and an independent means for stirring and mixing the components metered and supplied from these pumps. By providing two stirring mixers and flowing the stirred and mixed reactive mixture from the two stirring mixers into a coat hanger-shaped die through two separate die inlets, The present invention was completed based on the discovery that it is possible to further shorten the residence time.

That is, the present invention can prevent the reaction liquid from gelling and adhering to the wall of the die by shortening the residence time in the die as much as possible, and even if the die has the same width, the raw material inlet Compared to a single die, it can operate stably for a long time.

Also, in general, for wide products, the die is larger than for narrow products, so the residence time is correspondingly longer. Therefore, the gelation phenomenon gradually occurs, making it impossible to operate for a long time. Therefore, reducing the reactivity of the reactive resin causes problems in terms of product properties and productivity. By arranging two reactive resin stirring mixers and introducing the reactive resin into two die inlets as in the present invention, the purpose can be achieved without reducing the reactivity. In addition, the raw materials consisting of each component are supplied to one mixer, and after mixing in this mixer, the reactive mixture is divided under pressure into two passages equidistant and having equal flow resistance, and separated into separate passages. It is conceivable that the water may flow into two inlets, but in this method, a dead point will always occur at the curved part of the branch road, similar to the method described in Japanese Patent Publication No. 50-3096. Ru.

A gelled product of the reactive resin is generated at the dead center in a short period of several minutes, and the gel is attached to the dead center. This makes it impossible to operate stably for a long time, making it impossible to achieve the intended purpose. In addition, the gelled material may flow out, adhere to the inside of the die and block it, or flow into the product, resulting in a defective product. The first object of the present invention is to provide a new manufacturing apparatus and manufacturing method that can continuously manufacture a wide range of molded products using reactive resin without reducing reactivity. be.

A second object is to provide a novel continuous manufacturing apparatus and manufacturing method for reactive resin moldings that can be operated continuously for long periods of time by minimizing the adhesion of gelled substances in an extrusion die.

The third objective is to expand the reactive mixture after mixing in an extrusion die without branching the passage, and to use a die that has a single inner surface and is essentially a die rather than a die consisting of an assembly of small dies. It has a coat hanger shape in which the interior is not divided into two or more parts, and the residence time of the reactive mixture from the two separate inlets to the outlet at the exits at both ends of the die is approximately equal to 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 for reactive resin molded articles in which the residence time is shorter than the average residence time.

The fourth objective is to provide an apparatus and method for manufacturing molded products using reactive resins that can be manufactured stably over a long period of time even with large product widths, extremely thin product thicknesses, and low manufacturing speeds. is to provide.

A fifth object is to provide a novel continuous manufacturing apparatus and manufacturing method for molded products using a reactive resin that is improved so that linear stripes do not appear in the product.

A sixth object is to provide a novel manufacturing apparatus and method for manufacturing a molded product using a reactive resin, which can be applied to form a block foam as thick as 1 meter.

Still another object of the present invention is to provide an apparatus and method for continuously producing molded products that can be applied to products with excellent physical properties and a wide range of characteristics at low cost. Another object of the present invention is to provide an apparatus and method for continuously manufacturing molded products using a reactive resin, which does not change the thickness or physical properties of the product 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. One object of the present invention is to provide a novel continuous manufacturing apparatus and manufacturing method for a molded product that can ensure good cells when molding a foam. Next, the continuous manufacturing apparatus and manufacturing method for molded products according to the present invention will be specifically explained in comparison with conventional ones.

First, the apparatus described in Japanese Patent Publication No. 50-3096 will be explained with reference to FIGS. 1 and 2.

In this device, the reactive mixture flowing from the die inlet 1 is 30a, 30b, 30c, and 30d, respectively.
It flows into the fish tail inlet 31 of the small die, expands at the small fish tail die 32, and equalizes the flow at the base 33a of the fish tail die. The device also includes a release groove 34 after the fishtail die. As already pointed out, this device is designed to have equal distances and distances and equal flow resistance so that the same amount of reactive liquid mixture flows at all points from the inlet 1 to the inlet 31 of the fish tail die. In practice, this is difficult. This is because if the flow resistance differs even slightly in each branch path, a large amount of the mixture tends to flow in the direction where the flow resistance is resisted, and this is difficult to avoid in terms of manufacturing. In addition, dead points always occur at the branching points 35, 36, and 37, and a gelled product is generated within a short period of time. Due to this gelled material, the amount of inflow to each part at the inlet 31 of the small fishtail die after the branch passage becomes unbalanced over time, making long-term operation difficult. Further, at the junction point 33b of each fishtail die, a linear striped pattern is generated, and the gelled material is also caused to flow out to the center of the product. In other words, the present invention uses an extrusion die consisting of an assembly of small dies that has disadvantages due to division into a plurality of passages and a surface that is prone to gel formation when flowing the reactive mixture into the extrusion die. In order to eliminate the drawbacks arising from this, we began and completed the development of an extrusion die in which the reactive mixture flows through a single die inlet and the interior of the die is not substantially divided into two or more parts.

When applying these reactive mixtures to extrusion dies, there is a concern that gelled substances may adhere to the inside of the die, especially the sides and exit of the die, making it impossible to operate the device continuously. will occur. Regarding gel formation, assuming that a reactive mixture flows into a certain extrusion die and flows out from the outlet, whether or not it is easy to form a gel of the reactive mixture in 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 how many times the mixture replaces the inside of the die within the time period until the reactive mixture starts to react and the viscosity increases rapidly (rate-limiting). Expressed as a formula, f: How many times the reactive mixture replaces the inside of the tie within the time until the reaction becomes rate-determining, or the number of times the reaction is replaced.

a: Amount of reactive mixture flowing into the die (e/Mi
n).

b: Time from mixing the reactive mixture until the reaction becomes rate-limiting (Mln) The reaction rate-limiting time refers to the mixing conditions under which the reactive resin component is actually introduced into the die using the stirring mixer as a means of carrying out the present invention. The viscosity is measured using a viscometer immediately after stirring to reach the temperature of the die, and the time required for the viscosity to begin to increase is expressed in minutes.

In addition, especially for urethane foam, foaming starts from mixing.
These include foams formed by the reaction of isocyanate and water, and foams formed by the vaporization of low-boiling solvents due to the heat of reaction between isocyanate groups and active hydrogen. . After the reaction has progressed a considerable amount
For those that start foaming or those that start foaming by post-heating, the reaction rate-limiting time is determined by the increase in viscosity. c: The internal volume of the die (e), that is, from this formula, the larger the f value, the more times the liquid will be replaced, the more fresh the reactive mixed liquid will be, and the less gelled material will be generated inside the die. become.

As can be seen from this equation, either (1) the amount of reactive mixture flowing into the extrusion die is increased, or (2) the reactivity is decreased (
It is better to increase the rate-determining time) or (3) lower the die internal volume.

However, if the amount of the mixture in (1) is increased, the number of conveyor speeds for conveying the release paper etc. 100 m/min, and if the curing time is 4 minutes, the length of the belt conveyor alone in the production equipment would reach over 1000 n1, which would increase the cost of the equipment, which is a practical problem. Furthermore, if the reactivity in (2) is reduced, the physical properties of the product and the productivity will be reduced, and furthermore, the foam will not form normal cells, making it impossible to put it to practical use. In addition, although it is good to reduce the internal volume of the die in (3), if this reduces the flow uniformity and creates a dead center inside the die, the f value will apparently increase. real f
The value will decrease. That is, in the same die internal volume, it is preferable that the residence time of the liquid is equal at all points from the die inlet to the die outlet. That is, the present inventors previously proposed in Japanese Patent Application No. 51-69909 that it is possible to 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. Developed an extrusion die.

However, even in this extrusion die, if the product width is wide (1 m or more), the internal volume of the die increases and the above-mentioned f value decreases. Therefore, we developed a die whose f value does not decrease even when the product width becomes wider. In other words, if the internal shape of the die is appropriately selected by having two inlets,
It is now possible to easily manufacture a wide range of products without sacrificing the advantages of the 1-699 designation. i.e., without dividing the reactive mixture into a plurality of equidistant and equal flow resistance paths.
By selecting the shape of the die, it has become possible to change the cross-sectional area and flow velocity of each part within the die, thereby making it possible to equalize the residence time at each part of the outlet. Furthermore, this has been made possible by appropriately selecting the opening angle of the manifold expanding from separate die inlets, the shape of the groove, the volume of the groove, the relationship between the groove volume and the volume excluding the groove, the die gap, etc. Furthermore, by making the flow particularly large at the die end and increasing the outflow amount from the die end, it was possible to further reduce the gelling and formation at the end. The part with a large amount of outflow at the end is several centimeters to 1C! r
1, so no problem arises in terms of yield. In addition, in coat hanger dies, since the groove is provided partway from the die inlet to the end, it is easy for dirt to get stuck at the end, which can easily cause problems. Providing grooves that are shaped like this is effective in that respect as well. In the continuous manufacturing apparatus of the present invention, the extrusion die does not branch into an aggregate of small dies, and the interior of the die is not substantially divided into two or more parts, but instead forms a hanger. There is. This extrusion die is formed so that the opening angle of the manifold at the raw material inlet is from 120 degrees to 175 degrees (in Fig. 3, O indicates the above opening angle). It is configured such that the ratio of internal volume to groove volume is from 1:0.1 to 1:10.
Furthermore, the minimum gap of the above die excluding the manifold is 1
．． It is less than 5 mm. In addition, the groove width and volume at both ends of the manifold are continuously equal to or smaller than those at the inlet port toward the end of the manifold. Dl, D2, D3). The manufacturing method of the present invention will be explained using an example in which it is applied to polyurethane resin.The following conditions must be maintained in the coat hanger type extrusion die.

However, F, a, b, and c are the same as shown above.

In addition, if the gap between the dies is set to 1.5 mm or less,
The reaction rate-limiting time increases rapidly.

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 8. 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, suppressing the reaction. This is thought to be due to the fact that they have a tendency to Also, the opening angle of the manifold at the die inlet where the raw material is introduced and the groove depth,
The relationship is that as the opening of the manifold at the raw material die inlet becomes larger, it is necessary to increase the groove depth!
Ru.

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

In this case, since the weight of the product on the sides of the product increases, it is generally preferable that the groove depth is 1 mm or less. According to this invention, even without having a branch passage inside the die, the residence time of the raw material at the end of the die outlet (from the inlet to the outlet)
can be approximately equal to or less than the average residence time at the exit across the width of the die.

In particular, with the die of this invention, the internal volume can be significantly reduced compared to a body tail die or an assembly of small body tail dies, and furthermore, the internal volume can be significantly reduced compared to the die described in Japanese Patent Application No. 1983-699. This greatly reduces the residence time of the reactive mixture in the die. 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. 5 shows a coat hanger-shaped die having one inlet in the invention of Japanese Patent Application No. 1982-699, and FIG. 6 shows the flow characteristics of a mixture with respect to time in the coat hanger-shaped die according to the present invention. Give an example.

The lines in the figure indicate equal residence times from the inlet of the die. As is clear from this, in the coat hanger type die of the present invention, the residence time at the exit portion is approximately equal over the entire width.

In the die of the present invention, the end residence time is at most twice to one time or less than the average residence time. This is true even when producing thick layer urethane block foam.
This shows that the surface can be made flat. The raw material viscosity that can be applied in this invention may be one that is compatible with gear pumps, plunger pumps, etc.
0,000 centipoise or less, preferably 6,000 centipoise or less. 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. Next, the configuration of the apparatus and method of the present invention will be specifically explained with reference to FIGS. 7 and 9.

In the figure, numerals 10a and 10b are tanks for each reactive raw material component, and 11a, 11b, 11c and 11d are pumps for measuring and conveying. 12a and 12b are mixing chambers containing a stirrer for mixing and stirring, 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. be.

Each reactive component supplied from tanks 10a and 10b is
A fixed amount is metered by pumps 11a, 11b and 11c, 11d and sent to mixing chambers 12a, 12b.

The reactive liquid mixture mixed in the mixing chambers 12a, 12b is preferably sent to the die 13 by pressure pumps 28a, 28b, flows into a certain shape, is extruded, and is then guided by a backup roll 15. material 14
A mixture layer 16 is transferred on top and integrated with the substrate. In this case, a mixing chamber 12a for mixing and stirring
, 12b should be closer to the extrusion die, and preferably integrated. Further, depending on the formulation, a portion other than the stirring portion, that is, a mixing function may be included in the extrusion tie 13. 3 and 4 show a coat hanger-shaped die 13 according to the present invention, FIG. 3 is a partially cutaway front view, and FIG. 4 is a vertical sectional side view of AN (7) in FIG. , 1 is two separate inlets for the reactive mixture, 2 is a manifold, and 26 is a die front member, 2
7 is a die back member.

3 is a variable lip, and 4 is a fixed lip. 5a
5b is a lip fixing bolt, and 5b is a lip adjustment bolt.

A die gap 6 is formed by both the members 26, 27 and the lips 3, 4. Further, 7 is a jacket for controlling die temperature. Further, 8 is a plate for fixing the jacket, and 9 is an outlet of the die. In this practical example,
The magnitude of θ is 90 degrees or more and less than 180 degrees, and the width of the manifold is in the relationship D1≧D2, Dl≧D3, and the cross-sectional area of D1 is equal to or larger than the cross-sectional area of D3, which is the cross-sectional area of D2. . Note that by making the D1 width and D1 cross-sectional area larger than the D2 width and D2 cross-sectional area, as well as the D3 width and D3 cross-sectional area, the residence time can be made uniform. Die gap 6
is 1.5 mm or less, preferably 1 mm or less, and the ratio of the die internal volume excluding the manifold 2 to the manifold volume is preferably 1:0.1 to 1:10. After mixing in two independent mixing chambers, the reactive mixture flows in from two separate die inlets 1, enters the manifold 2, flows to both shoulders of the manifold, and also partially flows out into the die gap 6. , flows toward the die outlet 9.

The opening angle 0 of the manifold, the manifold widths Dl, D2, D3, and the cross-sectional area thereof can be appropriately determined within the above ranges so that the residence time at the die outlet 9 is approximately equal or short at both ends. The reactive mixture is discharged from the die outlet 9 before the rate of reaction of the reactive mixture becomes rate-determining (the time from when the reaction occurs to when the viscosity starts to increase) and is transferred onto a continuously running base material. FIG. 9 shows an example of the manufacturing process of the present invention.

Here, a reactive liquid mixture is discharged from the outlet 9 of an extrusion die 13 arranged substantially perpendicular to the direction of movement of the base material 14, and is applied onto the base material 14 supported by a backup roll 15. Form layer 16. Layer 16 is base material 1
4 is supported by a carrier roll 18, enters a cure open 19, is reacted and solidified, and is separated into a base material 14 and a product 25 by a peeling roll 20. The base material 14
and product 25 are wound up on base material winding roll 22 and product winding roll 24, respectively. Product 25 above
may be foam or non-foam, and
The base material 14 and the product 25 may be integrated.

Base materials used for integration include cloth, paper, metal film, plastic film, and endless belt. It is also possible to press and integrate another material onto the applied layer.

Further, 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. The reaction may be stopped by setting the pump supply amount of the catalyst, polyol, isocyanate, etc. in excess of the components to zero, and the inside of the die may be washed with the remaining components. Preferably, the device is then completely shut down. This is because in an extrusion die, a quick opening device is required because if the entire device is shut down at once, the reactive mixture remaining in the die will gel within the die. Also, even when cleaning by flowing pressurized air and solvent at the same time as the die center L
In some cases, only the end of the die can be cleaned, but the end of the die cannot be cleaned. Even in this extrusion die, it is preferable to clean the inside of the die with the remaining components after removing one or more of the necessary components, and then further 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 wash it rapidly. In addition, in the case of block foam, the foamed resin is generally discharged onto a release paper tilted by a conveyor belt using a traverse, but in this invention, the discharged liquid is Because of its uniformity, the angle of inclination of the conveyor can be sloped exclusively to the foaming curve of the foam, making it 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 this 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 this invention include an organic polyisocyanate, a catalyst, and if necessary, a polyol, a crosslinking agent, a cell stabilizer, a blowing agent, a filler, etc., and the polyol and isocyanate are reacted together in advance. The starting material may be one obtained by synthesizing a prepolymer having a terminal isocyanate group. More specifically, any organic polyisocyanate may be used, such as hexamethylene diisocyanate,
There are tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, 1,5 naphthalene diisocyanate, etc. As for the polyol, as mentioned above, you can use it freely, for example, polyether polyols, polyester polyols, and diene polyols are representative examples. polyethers with a molecular weight of 200 to 15,000 and having 2 to 8 hydroxyl groups in one molecule (
ethylene glycol, glycerin, pentaerythritol, hexanetriol, trimethylolpropane, sorbitol, sucrose, etc., polymerized with alkylene oxides such as ethylene oxide and propylene oxide), dibasic acids such as adipic acid, and ethylene glycol, etc. Polyesters with a molecular weight of 500 to 10,000 obtained by condensation with polyhydric alcohols and 1.2 bonds or 1.2 bonds with a molecular weight of 500 to 4,000.
There are diene polyols which mainly have 4 bonds, and the selection of their type and molecular weight is determined as appropriate depending on the intended polyurethane resin. For flexible polyurethane foam, molecular weight of 2-4 functionality is 400-6000.
polypropylene ether polyol with a molecular weight of 250 to 100 with 3 to 8 functionality in rigid polyurethane foam.
For urethane elastomers, it is common to select polypropylene ether polyol with a molecular weight of 0.0, polytetramethylene ether glycol with a molecular weight of 800 to 3000 for urethane leather, and polyester polyol with a molecular weight of 800 to 3000 for urethane leather. Agents include aromatic diamines such as methylenebisorthochloroaniline and 3,3'' dichlorobenzidine, and low molecular weight alcohols such as 1,4 butanediol.As blowing agents, water,
There are reactive types such as boric acid and non-reactive types such as monofluorotrichloromethane.Furthermore, the catalysts include conventionally known tertiary amine catalysts such as triethylenediamine, triethylamine, and N-methylmorpholine. and metal salt catalysts such as stannath octate and dibutyltin dilaurate, and these organic polyisocyanates, catalysts, polyols, crosslinking agents, blowing agents,
Cell stabilizers, fillers, and the like can be appropriately selected depending on the type of polyurethane product intended and other conditions. Examples are shown below.

Parts are parts by weight. Example 1 4 parts of water, 0.15 parts of triethylenediamine, 0.3 parts of N-methylmorpholine, and stannous octate to 1 (1) part of a polyol with a molecular weight of 3000, which is obtained by addition polymerizing propylene oxide to glycerin. 0.3 parts, silicone oil 1. CB1 tolylene diisocyanate (T-8
0.24/2.6 isomerization 80/20) At Hakube, the mixture was charged into two gear pump foaming machines and stirred and mixed.

In this case, the polyol component tank and isocyanate tank are heated with dry air for 30 minutes before starting the equipment.
．． A pressure of 0 kg/Ci was applied, and the tank pressure was set to 3.5 k9/CIL immediately before starting the foaming machine. The stirred and mixed liquid has an internal volume of 0.213e1, a die width of 1.8n1, and an inflow rate of 2 into a coat hanger die with lip adjustment at 2 inlets.
．． Injection was performed at 215e/Min.

The f value at this time is 3. The flow rate at the undyed outlet is 1.23rT1
/Min. The reactive mixture flowing out of the die is
When the coating was applied onto a release paper running at m/min with the die exit close to the surface and the coating layer was cured in the open at 120 degrees C for 4 minutes, a good thin foam sheet was obtained. Although it was operated continuously for several hours, there was no gelation and no problems occurred. Comparative Example 1 For comparison, each component was stirred and mixed according to the formulation of Example 1 using a foaming machine equipped with one mixer.

In this case, a pressure of 3.0 kg/d is applied to the polyol component tank and the isocyanate tank with dry air before the equipment is operated, and a pressure of 3.5 kg/d is applied immediately before the foaming machine is operated. The tank pressure was set to . The stirred and mixed liquid has an internal volume of 0.285', a die width of 1.8rr, and an inlet of 1.
Flow rate 2.2 to the coat hanger die with lip adjustment
Injection was performed at 15'/min.

At this time, the f value is 3.0, and the flow velocity at the die exit is 1.23r1
It was 1/Min. The reactive mixture flowing out of the die was coated onto a release paper running at 4 m/min close to the die outlet, and the coated layer was cured at 120 degrees C open for 4 minutes. After continuous operation for several hours, a small amount of gelled material adhered to the side of the die outlet. There were no problems at all in the center of the product. Compared to Example 1, the surface smoothness of the product was poor, and in particular, the product could not be of practical use after being operated for more than 1 hour. Example 2 A compound prepared by adding 2 moles of propylene oxide to 1 mole of aniline to 100 parts of a butadiene polyol (manufactured by Idemitsu Petrochemical Co., Ltd., trade name PolyBDR-45HT) (manufactured by Appsion Co., Ltd., trade name Isonol cm100) 21
．． 58 parts of tolylene diisocyanate (8024/2 screw ratio 80/20), 25.27 parts of dibutyltin dilaurate, and 0.3 parts of dibutyltin dilaurate were charged into a foaming machine equipped with two mixers, stirred, and discharged.

This reactivity. The mixed liquid was heated to an inner volume of 0.213e and a die width of 1.
It was injected into a coat hanger die with lip adjustment having two 8rT11 inlets at an inflow rate of 2.2151/Min. The f value at this time is 2. g. The flow rate at the die exit is 2.46TT1
/Min. The reactive mixture flowing out of the die outlet was applied onto a running aluminum film at 3n1/min. 1. After continuous operation for a long period of time, a very small amount of gelled material adhered to the side of the die exit, but there was no problem at all in the center of the product.

Comparative Example 2 For comparison, the formulation of Example 1 and 1.231)/M
The experiment was conducted using a lip-equipped fishtail die with a die width of 1 m and one inlet at the discharge rate of an in-foaming machine.

The internal volume of the fishtail die was 0.46'. Therefore, the flow velocity is 1.54 m/Min, . f = 0.75, and the discharge state was cloudy in the center, but a large amount was discharged, and the other side of the die was foamed and discharged slowly. After about 3 minutes, the side of the die turned into a gel, and the experiment was completed. I was unable to continue. Comparative Example 3 A reactive mixed liquid was injected into the same coat hanger die as in Example 2 at a discharge rate of 0.885 e/Min using the formulation of Example 2.

At that time, the f value was 1.1, and the flow velocity at the exit of the die was 0.984 m.
/Min. Up to 2 powders were discharged in almost good condition, but after that, the gelled material started to adhere to the outlet of the die, making it impossible to apply a uniform thickness over the entire width.

[Brief explanation of the drawing]

Figure 1 is a partially cutaway front view of a conventional continuous forming device;
FIG. 2 is a cross-sectional side view of the same, FIG. 3 is a partially cut-away front view of the die according to the present invention, FIG. 4 is a cross-sectional side view of the same, and FIG. FIG. 6 is a front view showing the flow elapsed time, FIG. 6 is a front view of the die according to the present invention, FIG. 7 is a schematic system diagram showing an embodiment of the present invention, and FIG. 8 is a diagram showing the reaction rate-limiting (cream time). A graph showing the relationship with the die gap, FIG. 9, is a process diagram of the present invention. 1... Inflow port, 2... Manifold,
3...Variable lip, 4...Fixed lip, 5a, 5b...Bolt, 6...Die gap, 7...Jacket, 8...Plate, 9...Exit of die, 10a, 10b...
...tank, 11a, 11b, 11c, 11d...
・Pump, 12a, 12b...Mixing chamber, 13...Extrusion die, 14...Base material, 15...Backup roll, 16...
・Mixture layer, 17...Base material unwinding roll, 18.
... Carrier roll, 19 ... Cure oven, 20 ... Peeling roll, 21 ...
- Drive roll, 22...Base material winding roll, 2
3...Nip roll, 24...Product winding roll, 25...Product, 27...Die back member, 26...Die front member, 28a, 2
8b...Pressure pump, 30a, 30b, 30c, 30d
...Branch, 31...Fishtail entrance,
32...Fish tail die, 33a...Base of the fish tail die, 33b...Joint point of the fish tail die, 34...Release groove, 35,3
6, 37... Branching point.

Claims (1)

[Scope of 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 supplied from these pump means, and this stirring and mixing. producing a molded article comprising means for introducing the extruded reactive mixture into a die using an extrusion or a pressure pump and causing it to flow out from the die outlet; and means for continuously integrating the extruded mixture with the substrate. In this apparatus, two stirring mixers are provided as the mixing means, and the outlet of each stirring mixer is separately connected to the two inlets of the die, and the die has an opening angle of its manifold of 120 degrees or more. It is a coat hanger-shaped die with an angle of less than 175 degrees, and the ratio of the internal volume of the die excluding the manifold to the volume of the manifold is set to 1:0.1 to 1:10, and the width and volume of the manifold are the same as those of the injection port. 1. An apparatus for continuously producing a molded product using a reactive resin, characterized in that the pressure is set to be equal to or lower than that of the injection port as it goes from the end to the end. 2 Claim 1 in which the minimum gap within the die excluding the manifold is 1.5 mm or less
An apparatus for continuously producing molded products using the reactive resin described in 1. 3. An apparatus for continuously producing a molded article using a reactive resin according to claim 1, wherein both ends of the manifold continuously pass through 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 When producing a molded article with polyurethane resin or foamed polyurethane resin, each necessary reactive component is measured and conveyed, and the metered components are stirred and mixed separately with two stirring mixers, and each reaction obtained is The mixture is introduced separately from the inlets into a coat hanger-shaped die having two inlets with a manifold opening angle of 120 degrees or more and less than 175 degrees, and the mixture is continuously integrated with the base material. At the same time, the amount of the reactive mixture introduced into the extrusion die (l/min) is a, the reaction rate-limiting time (min) after mixing the reaction mixture is b, the actual volume of the reactive mixture in the die (mixer (including the volume from the outlet to the die inlet) (
l) is c, and the number of times the reactive mixture replaces the inside of the die within the time period until the reaction occurs and the viscosity rapidly increases is f, and the value of f=(a×b)/c is f≧1. A method for producing a polyurethane resin molded article, characterized by satisfying .3. 6. The method for producing a polyurethane resin molded article 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.