EP0318608A1 - Method and apparatus for the moulding of articles in polyurethane - Google Patents
Method and apparatus for the moulding of articles in polyurethaneInfo
- Publication number
- EP0318608A1 EP0318608A1 EP87117805.9A EP87117805A EP0318608A1 EP 0318608 A1 EP0318608 A1 EP 0318608A1 EP 87117805 A EP87117805 A EP 87117805A EP 0318608 A1 EP0318608 A1 EP 0318608A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- mould
- polyurethane
- time
- cavity
- polyurethane material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 156
- 239000004814 polyurethane Substances 0.000 title claims abstract description 156
- 238000000465 moulding Methods 0.000 title claims description 11
- 239000000463 material Substances 0.000 claims abstract description 105
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 239000007787 solid Substances 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims description 33
- 238000007906 compression Methods 0.000 claims description 31
- 238000006116 polymerization reaction Methods 0.000 claims description 21
- 239000006071 cream Substances 0.000 claims description 15
- 230000015572 biosynthetic process Effects 0.000 claims description 13
- 238000005755 formation reaction Methods 0.000 claims description 12
- 230000000875 corresponding Effects 0.000 claims description 3
- 230000002093 peripheral Effects 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 230000000149 penetrating Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 238000009472 formulation Methods 0.000 description 5
- 230000033458 reproduction Effects 0.000 description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N [N-]=C=O Chemical compound [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000005266 casting Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000011344 liquid material Substances 0.000 description 2
- 210000003027 Ear, Inner Anatomy 0.000 description 1
- 210000003128 Head Anatomy 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- -1 for example Chemical compound 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000000379 polymerizing Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
Definitions
- the present invention refers to a method and an apparatus for moulding articles in polyurethane material, as well as the articles obtained by the claimed moulding method.
- the invention further concerns a die mould construction or apparatus for the production of articles in polyurethane material according to the method referred to above, in particular for the production of shoe soles and portions thereof, articles for car industry and the like, as well as technical articles.
- a prescribed amount of liquid material consisting of a mixture of at least a polyole and an isocyanate with reactans, is charged by casting, pouring or by injection into the cavity of a mould.
- the mould must be in closed condition when the material is fed into the cavity by injection methods, or the same mould is open during charging with casting or pouring methods and than the mould must be immediately closed after the charging of the liquid polyurethane, to avoid overflow from the open mould.
- the mould remains closed untill the polymerization process is sufficiently advanced to open the mould for demoulding the shaped article.
- the liquid material will tend to foam or to partially expand into a closed space; it is therefore necessary to provide means for venting the air or gases from the mould, particularly the air which has been trapped within the polyurethane material and the internal walls of the mould, in order to prevent the formation of air bubbles or air cavities on the outer surface of the moulded article.
- the venting of air or gases which tends to adher to inner surface of the mould, is critical. To such end vents holes or small air exit channels are usually provided in suitable positions of the mould cavity.
- an object of this invention is to provide a moulding method for manufacturing articles of polyurethane material by which it is possible to eliminate or substantially reduce defects caused by air-bubbles on the outer surface of moulded articles.
- a further object of the invention is to provide moulded articles in polyurethane material, having an higher finishing degree of the outer surfaces.
- a further object of this invention is to provide a method for manufacturing articles moulded in compact anhydrous, or semi-compact polyurethane containing low percentages of water in their formulation, by using moulds having an extremely simple construction through which the air-bubble problem can be obviated and which allows to apply high pressures without producing excessive overflows to maintain at the minimum the wasted material.
- a method for moulding articles in polyurethane material having surfaces free from air bubbles or air cavities in which a liquid polyurethane material is fed into the cavity of a mould, characterized by the steps of: allowing said liquid polyurethane to start an initial phase of the polymerization process in which the polyurethane state changes into an intermediate polymeric or semi-solid condition between said liquid and solid states, maintaining the polyurethane in an unrestained an flowing condition; applying a pressure to the polyurethane at a time during said intermediate polymeric condition urging and compacting the same polyurethane towards the cavity of the mould; and maintaining the pressure on the polyurethane for at least part of the remaining time portion of the polymerization process.
- intermediate polymeric condition or semi-solid state means a condition of the polyurethane during the polymerizing process, which is successive to the liquid state at which the polyurethane material has been fed into the mould, and comprised within a time interval during which the passage of the polyurethane material from liquid to solid state takes place when the polyurethane material has not yet fully hardened or polymerized and remains in a state capable of subjecting to plastic deformations.
- the exact instant for applying the pressure to material in the mould may varies according to the formulation and characteristics of the polyurethane or according to other specific requirements of the moulded article; therefore on the ground of the general principles of this invention according to which the compression phase of polyurethane takes place into the mould during the polymerization process when the polyurethane material has begun but has not yet completed its transition from liquid to solid state, in practice the starting moment for applying pressure can be exactly determined by specific trials.
- the value of the pressure or compression applied to the polyurethane material will vary according to specific working conditions or characteristics of the material, from the shape and dimensions of the cavity in the mould or the moulded articles.
- the compression or the pressure exerted on the polyurethane material in the mould must be greater than the specific reaction exerted by semi-solid polyurethane to be compressed and compacted into the mould, and must be maintained for a period of time sufficient to allow compacted the polyurethane to assume a stable and definitive solid state.
- the pressure which must be applied to the polyurethane material may vary from few kg/sq.cm, for example from two kg/sq.ca up to and beyond one hundred kg/sq.cm.
- a particular aspect of this invention in so far as it relates to compact, anhydrous polyurethane materials is that the starting of compression is best chosen immediately after the material begins to gel (gel time) and before the moment at which a filament is formed (filament time).
- the starting of compression takes place after cream has begun to form (cream time), preferably after the beginning of the expansion phase and before the moment of filament formation (filament time).
- the moment for starting the compression phase of polyurethane material within the mould may be chosen between 10% and 70% of the time interval comprised between the gel time and the filament time, for compact anhydrous polyurethane materials, and likewise between the cream time and the filament time for semi-compact polyurethane materials containing a percentage of water.
- polyurethane Under certain conditions or in order to produce specific articles it is preferable to cause the polyurethane to flow during compression and to work with excess quantities of polyurethane material, also called “extra-charge", which may vary from 5% to 40% of the weight of the moulded article, further providing the mould with a compression chamber in which the cavity of the mould opens.
- Figures 1 to 4 show an open mould for the production of shoe soles in polyurethane material, obtained by pouring into the cavity of the mould a liquid polyurethane mixture produced in a suitable mixing head 9, from metered quantities of a polyole and an isocyanate for compact polyurethane.
- the mould 10 consists of a lower mould section 11 and an upper mould section or lid 12 to close the lower section 11.
- the lower section 11 of the mould comprises a shaped cavity 13 which reproduces the shape of the article to be produced, while the upper section or mould lid 12 presents a downwardly protruding male or plug member 14, capable of penetrating into the cavity 13 of the lower section of the mould.
- the plug member 14 may consist of a single piece or may by fixed in an interchangeable way to the closing lid 12 directly, or, as in figures 1 and 2, through an intermediate ram or piston member 15 which adapts into a compression chamber or cavity 16 at the lower mould section provided over and around the mould cavity 13 such as to constitute a widening extension of mould cavity capable of being totally or partially filled by an extra-charge of the polyurethane mixture.
- the lower section 11 of the mould may be fixed in an usual way to a support member or located on a turning table together with a respective lid or upper mould section 12, for example hinged at 18 to the turning table structure.
- Closing means 19 are provided for closing the lid 12 and locking the same against the lower part of the mould 11 said closing means being of any type, whether mechanical, hydraulic or pneumatic or their combination.
- Reference C in figure 1 indicates a settable time control device operatively connected to actuating means 19 to close the mould or to apply a pressure for compacting the semi-solid polyurethane material after a pre-fixed time delay from the feeding of the polyurethane into the mould.
- the polyurethane mixture provided by a mixing device 9 in liquid form is firstly poured or fed in the prescribed quantity into the mould cavity 13, with the mould in the open condition of figure 1; than the polyurethane mixture is let to change his physical state in an unrestrained condition to assume an intermediate polymeric or semi-solid state in which the polyurethane material may flow and may be compacted to assume and maintain the shape of the mould cavity.
- the mould When the polyurethane has reached the required semi-solid condition, well before the filament time, the mould is closed, and a pressure is applied to the material in the cavity 13 of the mould and in the compression chamber 16 by ram member 15, causing the same polyurethane to flow inside the mould cavity and to be compacted against the shaped surface of the mould cavity, thus removing or preventing the formations of air-bubbles or air cavities on the outer surface of the moulded article.
- the pressure on the polyurethane material is maintained for a length of time necessary the polyurethane to polymerize and to harden, than the moulded article may by demoulded.
- the intermediate ram member 15 of the upper lid 12 carries out a double function acting as both a compressing member for the polyurethane mixture in the mould cavity, and as a sealing member along the opposite, nearby edges of both sections 11 and 12 of the mould.
- the smaller length and width dimensions of the ram member 15 with respect to the lid 12 also define peripheral steps 20 and 21, respectively 22 and 23 on the opposite edges of both sections of the mould which, when the mould is closed, create a labyrinth seal to allow a strong pressure to be applied on the polyurethane mixture. It is nevertheless clear that both the mould and the sealing system can be differently obtained and changed from the above embodiment.
- Figure 4 of the attached drawings shows an enlarged view of the lower mould section 11 and of the polyurethane mixture 24, while figure 7 shows the bottom face of a moulded sole 30.
- the bottom 25 of the cavity 13 of the mould in figure 4 include cavities or grooves 26 which determine protrusions 29 at the bottom surface of the sole facing the ground. Small air-bubbles 27 may be trapped in these cavities or grooves 26 of the bottom surface of the mould cavity during the feeding of liquid polyurethane mixture which, due to the strong surface tension of the polyurethane which prevent the liquid to penetrate and fill said grooves.
- air-bubbles 27 remain trapped between the surface 25 of the bottom of the mould cavity and the polyurethane material 24, causing the formation of imperfections or corresponding air-cavities 28 on the surface of the moulded article 30.
- the moment at which the compression of the polyurethane material in the mould should occur, the period for which the required pressure should be applied and the value of the pressure may vary from material to material and may also depend on the shape and dimensions of the articles to be moulded.
- compression parameters In order to obtain good results, such compression parameters must be determined through preliminary trials, however it must occur within a time interval in the polymerization process of the polyurethane, which follows the end of the pouring or feeding step of the polyurethane into the mould cavity and which precedes the instant in which the filament forms, normally referred to as "filament time". It is in this time interval, specifically after the gelification phase or the formation of cream, in which one must act by compressing the polyurethane material into the mould in order to obtain the desired results. Better results may be obtain causing the polyurethane material to flow into the mould cavity during the closure of the mould as well as during the initial steps of the compression.
- the polyurethane material may be of a compact or anhydrous type, or alternatively of semi-compact type containing a certain quantity of water through the base formulation or through atmospheric humidity.
- the polyurethane material is obtained from a polyole for compact polyurethane, of polyether or polyester base, and from an isocyanate such as, for example, a phenyl-methane - 4, 4′ - deisocyanate prepolymer (MDI) which are mixed in the necessary quantities in order to obtain a required liquid mixture of polyurethane.
- MDI phenyl-methane - 4, 4′ - deisocyanate prepolymer
- the graph in figure 5 shows the characteristic periods of a compact anhydrous polyurethane, expressed in seconds.
- T0 represents the starting point for pouring or feeding the polyurethane mixture into the mould
- T1 represents the end of pouring or feeding phase.
- the time interval T1-T0 will vary from case to case and in general will depend on the quantity of the mixture to be fed into the mould 10 and on the delivery of the mixing apparatus.
- the polyurethane material case referred to the first characteristic time interval of the polymerization process is the period necessary for gelification, commonly called "gel time", indicated by T2 which represents the starting moment of the gelification phase of the polyurethane mixture.
- filament time The time necessary for filament formation, commonly called “filament time” starts at T2, and is defined by moment T3 in the diagram of figure 5 and, as known, the time before T3 constitutes an intermediary critical phase in the polymerization or hardening process of the polyurethane material. Further characteristic time intervals of this process are the so-called “tack-free time” indicated by T4, and the “pinch time” shown by T5, after which the moulded article can be removed from the mould.
- the starting point TX for applying the pressure or the compacting compression of the polyurethane material in the mould cavity may vary, depending on specific parameters relating to the type of polyurethane, as well as the characteristics of the article to be produced, in general terms it can be stated that the moment for closing of the mould in figure 1, being the starting moment for the compression of the polyurethane material, will occur between 10% and 70% of the time interval T2-T3 which runs from "gel time” T2 and "filament time" T3.
- the graph in figure 6, as in figure 5, indicates the characteristic moments in the polymerization process for a semi-compact polyurethane material which has absorbed or contains a percentage of water.
- times T0, T1, T3, T4, and T5 have the same meaning as the corresponding times indicated in figure 5; since the presence of water in the polyurethane composition brings about the formation of a cream, and given such cream to grow, or to expand by increasing its volume, the previously referred to time T2 has been substituted by time T6 being the instant cream begins to form, commonly called “cream time”, to which time T7 must be added immediately thereafter, called “expansion time”, from which the expansion phase of the mixture occurs in the mould; the expansion terminates at time T8 following time T5 referred above after which the moulded article may be removed from the mould.
- the time TX for exerting a pressure, or a compacting compression on the polyurethane material in the mould follows the time T1 at the end of the pouring or feeding step of the mixture into the mould, and preferably falls between the "cream time” T6 and the "filament time” T3, or, more precisely, after the expansion time T7 of the polyurethane material.
- the starting point TX for the compression of the polyurethane material or for the closing of the mould in an open mould pouring system will depend on the polyurethane material and on the characteristics of the article to be moulded. Such moment TX shall tend to occur, as a general guide, during a period again within 10% and 70% of the time interval running from the "cream time" T6 to the "filament time” T3.
- the amount of pressure to apply to the material in the mould as well as the manner of applying such pressure may be important.
- pressures exceeding 2kg / sq. cm In practice it is worthwhile to operate under much higher pressures, in the order of a few tens of kg sq. cm., and in certain cases even in the order of a few hundred kg /sq. cm. or beyond, according to the requirements of the article to be moulded.
- the same pressure or the same compressing action on the polyurethane material in the conditions specified above may take place in a single phase, gradually increasing the pressure, or in several successive steps, acting contemporaneously with increasing pressure levels applied to the entire free surface of the material in the mould or beginning from one or more distinct points and then extending the pressure to the entire free surface of the material within the mould cavity in such a way as to produce a partial flow of the material from the cavity inside the mould, already in polymerization stage, causing in this way a plastic flow within the entire mass of material which assists in adhering to the deepest and smallest cavities of the mould, eliminating any air bubbles to be trapped and preventing the formation of air bubbles on the surface of the moulded article.
- FIG. 1 and 2 illustrate by way of example the starting of the polymerization process and the change of state occurring between the initial liquid state of the mixture and the semi-solid state when, the material swells slightly.
- the polyurethane material in the mould is in an evolving polymeric state and is capable of being subjected to non-elastic or plastic deformations, maintaining a shape which ensures the perfect adhesion to the mould impression or design of the surface of the internal cavity of the mould.
- the invention further concerns a particular apparatus and mould structure conceived for manufacturing shoe soles of polyurethane material though not limited to these, in which the mould has been provided with e compression chamber and in which a plug member of the mould is supported by the lid through an intermediate ram portion having a ram action which applies final pressure to the material in the mould and to a greater surfaces area than that of the article to mould, thus allowing strong pressure to be applied and a better seal to be performed during the compression phase.
Abstract
A method for manufacturing moulded articles in
polyurethane; according to the invention, a
liquid polyurethane (24) is fed into the cavity
(13) of a moulded(10) and maintained in an
unrestrained condition to assume a flowing
polymeric condition intermediate between liquid
and solid states; a pressure is applayed to the
polyurethane material (24) at said polymeric
condition urging the polyurethane (24) against
the mould cavity (12) and removing air-bubbles
(27).
Description
The present invention refers to a method and an
apparatus for moulding articles in polyurethane
material, as well as the articles obtained by
the claimed moulding method. The invention
further concerns a die mould construction or
apparatus for the production of articles in
polyurethane material according to the method
referred to above, in particular for the
production of shoe soles and portions thereof,
articles for car industry and the like, as well
as technical articles.
According to Prior Art method of manufacturing
polyurethane articles, particularly polyurethane
shoe soles or portions thereof in compact and
semy-compact polyurethane, a prescribed amount
of liquid material consisting of a mixture of at
least a polyole and an isocyanate with reactans,
is charged by casting, pouring or by injection
into the cavity of a mould. The mould must be in
closed condition when the material is fed into
the cavity by injection methods, or the same
mould is open during charging with casting or
pouring methods and than the mould must be
immediately closed after the charging of the
liquid polyurethane, to avoid overflow from the
open mould. The mould remains closed untill the
polymerization process is sufficiently advanced
to open the mould for demoulding the shaped
article.
In the Prior Art methods for manufacturing
polyurethane articles the liquid material will
tend to foam or to partially expand into a
closed space; it is therefore necessary to
provide means for venting the air or gases
from the mould, particularly the air which has
been trapped within the polyurethane material
and the internal walls of the mould, in order to
prevent the formation of air bubbles or air
cavities on the outer surface of the moulded
article. The venting of air or gases which
tends to adher to inner surface of the mould, is
critical. To such end vents holes or small air
exit channels are usually provided in suitable
positions of the mould cavity. However in the
Prior Art production of polyurethane articles
having protrusions or particularly complex
markings and designs, for example in moulding of
the ground-most surfaces of shoe soles, or
whenever the articles require an extremely high
quality or finishing of the outer surface, the
presence of air bubbles or air cavities of even
of small dimensions, can not be prevented.
The above problem is prevalently due to the
fact that the internal pressure developed by
gases which causes the expansion or the foaming
of the polyurethane material against the
internal surfaces of the mould, is rather low
and little to more than one kg/sq.cm.; therefore
no possibility exist to increase said pressure
and to influence positively it from outside in
order to obtain more precise markings or designs
reproduction on the moulded article. In any
event, in the Prior Art method of manufacturing
polyurethane articles the pressure cannot be
increased to any significant extent.
Furthermore to apply a pressure to a liquid
polyurethane mixture into a closed cavity of a
mould in order to achieve higher compression
inevitably requires particularly complex
construction of the moulds to prevent the
overflowing of the mixture and in practice does
not adequately solve the problem of eliminating
air bubbles because the bubbles trapped between
the internal walls of the mould and the mixture
are merely compressed by the polyurethane
against the inside walls of the mould.
From tests and experiments it has been now
devised that the problem can be positively
solved by applying a pressure for compacting the
polyurethane mixture in the mould when the same
mixture is in a particular condition during the
polymerization process, in which the
polyurethane material is capable of assuming and
maintaining the shape of the internal
impressions or design of the cavity of the
mould.
Therefore an object of this invention is to
provide a moulding method for manufacturing
articles of polyurethane material by which it is
possible to eliminate or substantially reduce
defects caused by air-bubbles on the outer
surface of moulded articles.
A further object of the invention is to provide
moulded articles in polyurethane material,
having an higher finishing degree of the outer
surfaces.
A further object of this invention is to provide
a method for manufacturing articles moulded in
compact anhydrous, or semi-compact polyurethane
containing low percentages of water in their
formulation, by using moulds having an extremely
simple construction through which the air-bubble
problem can be obviated and which allows to
apply high pressures without producing excessive
overflows to maintain at the minimum the wasted
material.
According to the invention, a method for
moulding articles in polyurethane material
having surfaces free from air bubbles or air
cavities has been provided in which a liquid
polyurethane material is fed into the cavity of
a mould, characterized by the steps of: allowing
said liquid polyurethane to start an initial
phase of the polymerization process in which the
polyurethane state changes into an
intermediate polymeric or semi-solid condition
between said liquid and solid states,
maintaining the polyurethane in an unrestained
an flowing condition; applying a pressure to the
polyurethane at a time during said intermediate
polymeric condition urging and compacting the
same polyurethane towards the cavity of the
mould; and maintaining the pressure on the
polyurethane for at least part of the remaining
time portion of the polymerization process.
For the purpose of present invention,
"intermediate polymeric condition or semi-solid
state" means a condition of the polyurethane
during the polymerizing process, which is
successive to the liquid state at which the
polyurethane material has been fed into the
mould, and comprised within a time interval
during which the passage of the polyurethane
material from liquid to solid state takes place
when the polyurethane material has not yet fully
hardened or polymerized and remains in a state
capable of subjecting to plastic deformations.
The exact instant for applying the pressure to
material in the mould may varies according to
the formulation and characteristics of the
polyurethane or according to other specific
requirements of the moulded article; therefore
on the ground of the general principles of this
invention according to which the compression
phase of polyurethane takes place into the mould
during the polymerization process when the
polyurethane material has begun but has not yet
completed its transition from liquid to solid
state, in practice the starting moment for
applying pressure can be exactly determined by
specific trials.
The value of the pressure or compression applied
to the polyurethane material will vary according
to specific working conditions or
characteristics of the material, from the shape
and dimensions of the cavity in the mould or the
moulded articles. In general term the
compression or the pressure exerted on the
polyurethane material in the mould must be
greater than the specific reaction exerted by
semi-solid polyurethane to be compressed and
compacted into the mould, and must be maintained
for a period of time sufficient to allow
compacted the polyurethane to assume a stable
and definitive solid state. In any event, the
pressure which must be applied to the
polyurethane material may vary from few
kg/sq.cm, for example from two kg/sq.ca up to
and beyond one hundred kg/sq.cm.
A particular aspect of this invention in so far
as it relates to compact, anhydrous polyurethane
materials is that the starting of compression is
best chosen immediately after the material
begins to gel (gel time) and before the moment
at which a filament is formed (filament time).
In the case of semi-compact polyurethane
materials containing a certain percentage of
water, the starting of compression takes place
after cream has begun to form (cream time),
preferably after the beginning of the expansion
phase and before the moment of filament
formation (filament time). In general terms, the
moment for starting the compression phase of
polyurethane material within the mould may be
chosen between 10% and 70% of the time interval
comprised between the gel time and the filament
time, for compact anhydrous polyurethane
materials, and likewise between the cream time
and the filament time for semi-compact
polyurethane materials containing a percentage
of water.
Under certain conditions or in order to produce
specific articles it is preferable to cause the
polyurethane to flow during compression and to
work with excess quantities of polyurethane
material, also called "extra-charge", which may
vary from 5% to 40% of the weight of the moulded
article, further providing the mould with a
compression chamber in which the cavity of the
mould opens.
The method and apparatus according to this
invention will be further illustrated here below
with reference to the manufacturing of shoe
soles, it being understood, nevertheless, that
the invention may be applied for manufacturing
articles requiring a perfect and faithful
reproduction of the design of the shaping cavity
of a mould. In the drawings:
Figures 1 to 4 show an open mould for the
production of shoe soles in polyurethane
material, obtained by pouring into the cavity of
the mould a liquid polyurethane mixture produced
in a suitable mixing head 9, from metered
quantities of a polyole and an isocyanate for
compact polyurethane. In the illustrated
example, the mould 10 consists of a lower mould
section 11 and an upper mould section or lid 12
to close the lower section 11. The lower section
11 of the mould comprises a shaped cavity 13
which reproduces the shape of the article to be
produced, while the upper section or mould lid
12 presents a downwardly protruding male or plug
member 14, capable of penetrating into the
cavity 13 of the lower section of the mould. The
plug member 14 may consist of a single piece or
may by fixed in an interchangeable way to the
closing lid 12 directly, or, as in figures 1 and
2, through an intermediate ram or piston member
15 which adapts into a compression chamber or
cavity 16 at the lower mould section provided
over and around the mould cavity 13 such as to
constitute a widening extension of mould cavity
capable of being totally or partially filled by
an extra-charge of the polyurethane mixture. The
lower section 11 of the mould may be fixed in an
usual way to a support member or located on a
turning table together with a respective lid or
upper mould section 12, for example hinged at 18
to the turning table structure. Closing means 19
are provided for closing the lid 12 and locking
the same against the lower part of the mould 11
said closing means being of any type, whether
mechanical, hydraulic or pneumatic or their
combination. Reference C in figure 1 indicates a
settable time control device operatively
connected to actuating means 19 to close the
mould or to apply a pressure for compacting the
semi-solid polyurethane material after a
pre-fixed time delay from the feeding of the
polyurethane into the mould.
The working of the apparatus is now described:
the polyurethane mixture provided by a mixing
device 9 in liquid form is firstly poured or fed
in the prescribed quantity into the mould cavity
13, with the mould in the open condition of
figure 1; than the polyurethane mixture is let
to change his physical state in an unrestrained
condition to assume an intermediate polymeric or
semi-solid state in which the polyurethane
material may flow and may be compacted to assume
and maintain the shape of the mould cavity. When
the polyurethane has reached the required
semi-solid condition, well before the filament
time, the mould is closed, and a pressure is
applied to the material in the cavity 13 of the
mould and in the compression chamber 16 by ram
member 15, causing the same polyurethane to flow
inside the mould cavity and to be compacted
against the shaped surface of the mould cavity,
thus removing or preventing the formations of
air-bubbles or air cavities on the outer
surface of the moulded article. The pressure on
the polyurethane material is maintained for a
length of time necessary the polyurethane to
polymerize and to harden, than the moulded
article may by demoulded.
The use of an appropriate pressure for flowing
and compacting the polyurethane into the mould,
applied at a appropriate time as referred above,
in which the pressure value will depend from
properties and formulation of polyurethane
materials, as well as the flowing of the same
material at the above mentioned physical
conditions inside the mould, prevent the
formulation of air bubbles and air cavities on
the outher surface of the moulded article, and a
better reproduction of the design; furthermore,
applying a pressure on the polyurethane material
as referred above, will improve the properties
of moulded articles, such as the wear stand
allowing to produce articles, in particular shoe
soles or portion thereof, of reduced weight.
In the shown example, the intermediate ram
member 15 of the upper lid 12 carries out a
double function acting as both a compressing
member for the polyurethane mixture in the mould
cavity, and as a sealing member along the
opposite, nearby edges of both sections 11 and
12 of the mould. The smaller length and width
dimensions of the ram member 15 with respect to
the lid 12 also define peripheral steps 20 and
21, respectively 22 and 23 on the opposite edges
of both sections of the mould which, when the
mould is closed, create a labyrinth seal to
allow a strong pressure to be applied on the
polyurethane mixture. It is nevertheless clear
that both the mould and the sealing system can
be differently obtained and changed from the
above embodiment. In the present case for the
manufacturing of shoe soles, the use of a mould
in which the polyurethane mixture is poured in
an open mould has been shown, however the
invention is also applicable to injection
moulding systems providing the mould with ram
members and actuating means suitable for
applying a pressure on the polyurethane mixture
24, as described above.
Figure 4 of the attached drawings shows an
enlarged view of the lower mould section 11 and
of the polyurethane mixture 24, while figure 7
shows the bottom face of a moulded sole 30. The
bottom 25 of the cavity 13 of the mould in
figure 4 include cavities or grooves 26 which
determine protrusions 29 at the bottom surface
of the sole facing the ground. Small air-bubbles
27 may be trapped in these cavities or grooves
26 of the bottom surface of the mould cavity
during the feeding of liquid polyurethane
mixture which, due to the strong surface tension
of the polyurethane which prevent the liquid to
penetrate and fill said grooves. Therefore
unless said air-bubbles are removed before the
polymerization and hardening of the
polyurethane, air-bubbles 27 remain trapped
between the surface 25 of the bottom of the
mould cavity and the polyurethane material 24,
causing the formation of imperfections or
corresponding air-cavities 28 on the surface of
the moulded article 30.
As a result of trials and experiments undertaken
with compact or semi-compact polyurethane
materials, it has been discovered that the cause
of the above negative phenomena is due to an
insufficiency of pressure usually created by the
expansion process of the polyurethane material
in a closed mould and by the fact that the full
pressure mainly acts when the critical points of
the polymerization process has already occurred.
In the polymerization and hardening process of
the polyurethane material, a short period of
time exists in which the mass of material
changes from liquid to solid state. This change
from liquid to solid state occurs through
modification of the molecular structures of the
polyurethane material, allowing its assume a
semi-solid state as previously referred to.
According to the invention it has thus been
discovered that by applying a pressure or a
compression for compacting the polyurethane
material after the feeding into the mould has
been stopped, with a delay which can be
determinated in advance within a specific time
interval during the polymerization process when
the material has reached the referred to
semi-solid condition and is still in a flowable
state, it is possible to positively influence
the moulded articles, preventing the formation
of surface air- cavities and thereby obtaining a
perfect reproduction of the design of the mould
cavity.
The moment at which the compression of the
polyurethane material in the mould should occur,
the period for which the required pressure
should be applied and the value of the pressure
may vary from material to material and may also
depend on the shape and dimensions of the
articles to be moulded. In order to obtain good
results, such compression parameters must be
determined through preliminary trials, however
it must occur within a time interval in the
polymerization process of the polyurethane,
which follows the end of the pouring or feeding
step of the polyurethane into the mould cavity
and which precedes the instant in which the
filament forms, normally referred to as
"filament time". It is in this time interval,
specifically after the gelification phase or the
formation of cream, in which one must act by
compressing the polyurethane material into the
mould in order to obtain the desired results.
Better results may be obtain causing the
polyurethane material to flow into the mould
cavity during the closure of the mould as well
as during the initial steps of the compression.
The above is explained in greater detail with
reference to the graph of figures 5 and 6. As
described above, the polyurethane material may
be of a compact or anhydrous type, or
alternatively of semi-compact type containing a
certain quantity of water through the base
formulation or through atmospheric humidity.
Generally the polyurethane material is obtained
from a polyole for compact polyurethane, of
polyether or polyester base, and from an
isocyanate such as, for example, a
phenyl-methane - 4, 4′ - deisocyanate prepolymer
(MDI) which are mixed in the necessary
quantities in order to obtain a required liquid
mixture of polyurethane.
In detail, the graph in figure 5 shows the
characteristic periods of a compact anhydrous
polyurethane, expressed in seconds. T0
represents the starting point for pouring or
feeding the polyurethane mixture into the mould,
while T1 represents the end of pouring or
feeding phase. The time interval T1-T0 will vary
from case to case and in general will depend on
the quantity of the mixture to be fed into the mould
10 and on the delivery of the mixing apparatus.
In the polyurethane material case referred to
the first characteristic time interval of the
polymerization process is the period necessary
for gelification, commonly called "gel time",
indicated by T2 which represents the starting
moment of the gelification phase of the
polyurethane mixture. The time necessary for
filament formation, commonly called "filament
time" starts at T2, and is defined by moment T3
in the diagram of figure 5 and, as known, the
time before T3 constitutes an intermediary
critical phase in the polymerization or
hardening process of the polyurethane material.
Further characteristic time intervals of this
process are the so-called "tack-free time"
indicated by T4, and the "pinch time" shown by
T5, after which the moulded article can be
removed from the mould.
According to this invention, and in the case of
an anhydrous polyurethane material, it has been
found worthwhile to apply the pressure to the
material, for example through the same ram
action exercised by the closure of the lid 12 in
figure 1, or in other suitable way, at the
moment TX following the time T1 at the
completion the feeding of the mixture into the
mould, preferably between time T2 or
gelification time and time T3 or filament time.
Since the starting point TX for applying the
pressure or the compacting compression of the
polyurethane material in the mould cavity may
vary, depending on specific parameters relating
to the type of polyurethane, as well as the
characteristics of the article to be produced,
in general terms it can be stated that the
moment for closing of the mould in figure 1,
being the starting moment for the compression of
the polyurethane material, will occur between
10% and 70% of the time interval T2-T3 which
runs from "gel time" T2 and "filament time" T3.
The graph in figure 6, as in figure 5, indicates
the characteristic moments in the polymerization
process for a semi-compact polyurethane material
which has absorbed or contains a percentage of
water.
In the example of figure 6, times T0, T1, T3,
T4, and T5 have the same meaning as the
corresponding times indicated in figure 5; since
the presence of water in the polyurethane
composition brings about the formation of a
cream, and given such cream to grow, or to
expand by increasing its volume, the previously
referred to time T2 has been substituted by time
T6 being the instant cream begins to form,
commonly called "cream time", to which time T7
must be added immediately thereafter, called
"expansion time", from which the expansion phase
of the mixture occurs in the mould; the
expansion terminates at time T8 following time
T5 referred above after which the moulded
article may be removed from the mould.
In figure 6 as well, the time TX for exerting a
pressure, or a compacting compression on the
polyurethane material in the mould follows the
time T1 at the end of the pouring or feeding
step of the mixture into the mould, and
preferably falls between the "cream time" T6 and
the "filament time" T3, or, more precisely,
after the expansion time T7 of the polyurethane
material. As in the prior case, the starting
point TX for the compression of the polyurethane
material or for the closing of the mould in an
open mould pouring system, will depend on the
polyurethane material and on the characteristics
of the article to be moulded. Such moment TX
shall tend to occur, as a general guide, during
a period again within 10% and 70% of the time
interval running from the "cream time" T6 to the
"filament time" T3.
Trials have been carried out in different
working conditions for both types of material
using materials of the Italian firm Routinol,
sold commercially under the trade mark "Routinol
SP/A 65-90" and "Routinol SP/C 65-00B"
respectively. Moulds for manufacturing
shoe-soles having fine markings on the bottom
were used. In both cases optimal results that is
optimal reproductions of the impression or
design of the moulds, free from air bubbles,
were obtained closing the moulds or, more
precisely, starting the compression of the
polyurethane material, after approximately 15% ÷
25 seconds from the time T1, keeping the mould
closed for approximately 80 ÷ 130 seconds with
an approximately 25 ÷ 35 kg / sq. cm. pressure
value. In such conditions an extra-charges has
been provided, being an excess weight of
approximately 20 ÷ 25% of polyurethane material
fed into the mould, even if in general terms it
is possible to operate with extra-charges or
excess weights greater or less, the limits being
between 5% and 40% in weight with respect to the
moulded article.
Depending on the desired aims as a function of
the article to be moulded, the amount of
pressure to apply to the material in the mould
as well as the manner of applying such pressure
may be important. In general term it is
necessary to operate under pressures greater
than that which would be generated spontaneously
in a closed mould merely through self-expansion
of the mixture to compact the polyurethane
material, for example under pressures exceeding
2kg / sq. cm. In practice it is worthwhile to
operate under much higher pressures, in the
order of a few tens of kg sq. cm., and in
certain cases even in the order of a few hundred
kg /sq. cm. or beyond, according to the
requirements of the article to be moulded. The
same pressure or the same compressing action on
the polyurethane material in the conditions
specified above may take place in a single
phase, gradually increasing the pressure, or in
several successive steps, acting
contemporaneously with increasing pressure
levels applied to the entire free surface of the
material in the mould or beginning from one or
more distinct points and then extending the
pressure to the entire free surface of the
material within the mould cavity in such a way
as to produce a partial flow of the material
from the cavity inside the mould, already in
polymerization stage, causing in this way a
plastic flow within the entire mass of material
which assists in adhering to the deepest and
smallest cavities of the mould, eliminating any
air bubbles to be trapped and preventing the
formation of air bubbles on the surface of the
moulded article. The dotted lines in figures 1
and 2 illustrate by way of example the starting
of the polymerization process and the change of
state occurring between the initial liquid state
of the mixture and the semi-solid state when,
the material swells slightly. In this phase of
the polymerization process the polyurethane
material in the mould is in an evolving
polymeric state and is capable of being
subjected to non-elastic or plastic
deformations, maintaining a shape which ensures
the perfect adhesion to the mould impression or
design of the surface of the internal cavity of
the mould. It is stressed, nevertheless, that the
above description and illustrations through the
attached drawings are purely intended as example
of this invention, which in substance consists
of the application of pressure and the
compressing of polyurethane material in the
mould during its transitional phase between
liquid and solid states, maintaining such
compression at least until such time as the
polymerization process has yet to go beyond a
critical phase although not yet definitively
ended.
As referred to, the invention further concerns a
particular apparatus and mould structure
conceived for manufacturing shoe soles of
polyurethane material though not limited to
these, in which the mould has been provided with
e compression chamber and in which a plug member
of the mould is supported by the lid through an
intermediate ram portion having a ram action
which applies final pressure to the material in
the mould and to a greater surfaces area than
that of the article to mould, thus allowing
strong pressure to be applied and a better seal
to be performed during the compression phase.
Claims (18)
1. Method for moulding articles in
polyurethane material in which a liquid
polyurethane (24) is fed into the cavity (13) of
a mould (10) letting the same polyurethane (24)
to polymerize to a solid state and to assume the
shape of the cavity (13) of the mould (10)
characterized by the steps of: allowing said
liquid polyurethane (24) to start an initial
phase (11-13) of the polymerization process in
which the state of the polyurethane (24) changes
into an intermediate polymeric condition between
said liquid and solid states; maintaining the
polyurethane (24) in an unrestrained and flowing
condition; applying a pressure to compact the
polyurethane (24) at a time (TX) during said
intermediate polymeric condition urging the same
polyurethane towards the cavity (13) of the
mould (10); and maintaining the pressure on the
polyurethane for at least part of the remaining
time portion of the polymerization process.
2. Method according to claim 1,
particularly for compact anhydrous polyurethane
materials, in which, after the feeding of the
polyurethane material into the mould, the
polymerization process comprises a gel time (T2)
from which the gelification of the polyurethane
begins as well as a filament time (T3) in which
the formation of a filament may take place
characterized by compressing the polyurethane
material (24) in the mould (10) starting from a
time (TX) between the gel-time (T2) and the
filament time (T3).
3. Method according to claim 2,
characterized by the fact that the time (TX) for
starting the compression of the polyurethane
material (24) occurs within the 10% and 70% of
the time interval between the gel-time (T2) and
the filament time (T3).
4. Method according to claim 1, in
particular for semi-compact polyurethane
materials in which, after the time (T1) at which
the feeding of the polyurethane (24) into the
mould (10) is stopped, the polymerization
process comprises a cream time (T6) from which
the formation of a cream begins, as well as a
filament time (T3) in which the formation of a
filament of polyurethane may take place
characterized by compressing the polyurethane
material (24) in the mould (10) from a time (TX)
between the cream time (T6) and the filament
time (T3).
5. Method according to claim 4 in which,
from an intermediate expansion time (T7) during
the formation of the cream the polyurethane
material is subjected to an expansion of volume,
characterized by compressing the polyurethane
(24) in the mould (10) from a time (TX)
following said expansion time (T7).
6. Method according to claim 4,
characterized by the fact that the time (TX) at
which the pressure is applied to the
polyurethane material (24) in the mould (10)
occurs within 10% and 70% of the time interval
between the cream time (T6) and the filament
time (T3).
7. Method according to claim 1,
characterized by compressing the polyurethane
material by continuously increasing the pressure
during a single compression phase.
8. Method according to claim 1, and one
or more of claims 2 to 8, characterized by
applying the pressure to the polyurethane
material (24) in the mould (10) acting
contemporaneously on the whole surface area of
the material (24) in the mould cavity (13).
9. Method according to claim 1, and one
or more of claims 2 to 8, characterized by
applying the pressure to the polyurethane
material (24) in the mould starting from at
least one intermediate point on the upper
surface area of the material (24) in the mould
cavity (13), causing a flow of polyurethane
within said mould cavity (13).
10. Method according to claim 1,
characterized by compressing the polyurethane
material (24) in the mould (10) at pressure
value greater than 2 kg / sq. cm.
11. Method according to claim 1,
characterized by compressing the polyurethane
material (24) in the mould (10) at pressure
value greater than 10 kg / sq. cm.
12. Method according to claim 1,
characterized by compressing the polyurethane
material (24) in the mould (10) at a pressure value
greater than 100 kg / sq. cm.
13. Method according to any one of
preceding claims from 1 to 14, characterized by
feeding an extra-charge of polyurethane material
(24) into the mould cavity (13) with respect to
the weight of the moulded article.
14. Method according to claim 13,
characterized by the fact that the extra-charge
of the polyurethane material is between 5% and
40% of the weight of the moulded article.
15. Method according to claim 1,
particularly for moulding a shoe sole or portion
thereof in polyurethane materials, free from air
bubbles, in a mould comprising a lower mould
section (11) having a shaped cavity (13) having
a bottom surface defining the design of the
lower portion of the sole and an upper mould
section (12) having a plug member (14) which
penetrates the shaped cavity (13) of the lower
mould section (11), characterized by providing
said lower section (11) with a compression
chamber (16) in which said shaped cavity (13) of
the lower mould section (11) opens, feeding said
mould cavity (13) and compression chamber (16)
with an polyurethane material (24) until said
mould cavity (13) and at least a portion of said
compression chamber (16) are filled with liquid
polyurethane; allowing said polyurethane to
change from liquid state into said intermediate
polymeric condition; closing the mould to
penetrate said plug member (14) in the
polyurethane within said compression chamber
(16) and said mould cavity (13) causing a flow
of the polyurethane material between opposite
sealing surface of said upper and lower mould
sections (11,12) and applying a pressure on the
polyurethane material (24) within said
compression chamber (16) and said mould cavity
(13).
16. Apparatus for moulding articles in
polyurethane material, according to the method
of preceding claims, said apparatus comprising
first and second mould sections (11,12) defining
a mould cavity (13) for the article to be
moulded; actuating means (19) for opening and
closing said mould sections (11,12) and means
(9) for feeding a polyurethane mixture into said
mould cavity (13), characterized in that said
upper mould section includes ram means for
compressing the polyurethane material into the
mould cavity, and settable time control means
operatively connected to said actuating means
(19).
17. Apparatus according to claim 16 for
moulding polyurethane articles particularly but
not exclusively for moulding shoe soles, in
which the mould comprises a lower mould section
(11) defining a shaped cavity (13) for the
article to be moulded, and an upper mould
section (12) having a plug member (14)
penetrating into said cavity (13) of the lower
mould section (11), characterized in that said
lower mould section (11) further includes an
enlarged cavity (16) defining a compression
chamber for receiving an extra charge of
polyurethane material said enlarged cavity (16)
opening into and being positioned above said
mould cavity (13), and in that said plug member
(14) is attached to the upper moulded section
(12) by intermediate ram section (15).
18. Apparatus according to claim 17,
characterized in that the peripheral edges
(22,23) of the enlarged cavity (16) of the lower
mould section (11) and corresponding peripheral
edges (20,21) of said upper mould section (11)
an said intermediate ram section (15) comprise
matching stepped surfaces means around said
enlarged cavity (16).
Publications (1)
Publication Number | Publication Date |
---|---|
EP0318608A1 true EP0318608A1 (en) | 1989-06-07 |
Family
ID=
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