JP2002506109A - Multi-component miscible blends of nylon with improved properties - Google Patents

Abstract

(57) Abstract: A method for forming a very homogeneous melt blended mixture of a semicrystalline nylon homopolymer and a semicrystalline nylon copolymer. The blends have a single significant melting temperature rather than maintaining the melting point of the individual nylon components. In one embodiment, the blend has a greater difference between its melting temperature and its crystallization temperature than each of the semi-crystalline nylon homopolymer component and the semi-crystalline nylon copolymer component. In another embodiment, the blend has a melting temperature approximately equivalent to its semi-crystalline nylon homopolymer component.

Description

Description: FIELD OF THE INVENTION [0001] The present invention relates to nylon blends or, more particularly, to semi-crystalline nylon.
Extremely uniform melt blend mixing of homopolymer and semicrystalline nylon copolymer
A method for forming an object. The blends are very uniform,
Rather than maintaining the melting point of each nylon component, it has an essentially single melting point
. In one embodiment, the blend has a temperature between its melting temperature and its crystallization temperature.
Each of a semicrystalline nylon homopolymer component and a semicrystalline nylon copolymer component
With a greater difference. In another embodiment, the blend comprises a semi-crystalline
It has a melting temperature approximately equivalent to that of the Ron homopolymer component. [0002] The preparation of blends of nylon homopolymers and nylon copolymers involves
It is known in the art. However, nylon 6 (N6) and nylon 6
Polyamides such as 6 (N66), due to their relatively high crystallization rates,
Melt extrusion exhibits sufficient crystallinity and, instead, their stretching process (orient
ation process). Therefore, reducing the crystallization rate of nylons such as N6 and N66 has always been of interest. N under commercial processing conditions
6 and N66 melt blends, as indicated by their unique melting points,
Resulting in a heterogeneous product with separate phases of Reduce the crystallization rate of nylon
The most common approach for using random copolymers is to use
It is to use. N6, nylon 66, nylon 11, nylon 12, nylon
Copolyamide with other polyamides such as Ron 6T, nylon 46, etc.
There is a great deal of literature on the preparation of limers. Classified as random copolymer
Such copolymers have low low molecular weight related to both of the two homopolymers.
Melting temperature (T _m ) And large undercooling (ie, the difference between the melting and crystallization temperatures, ΔT = T _m -T _cc (° C.)). A large ΔT, which is a reflection of the slow crystallization rate, results in low crystallinity in the copolymer, which
Thus, properties such as ease of stretching (orientability) are improved. For example, YP
See Khanna, Polym. Eng. And Sci., 30 (4), 1615, 1990. The blend
, A certain proportion of semi-crystalline random core containing the same nylon as the homopolymer
Improved when formed from semi-crystalline nylon homopolymer with polymer
To form a homogeneous super-miscible blend with different properties
, Was discovered unexpectedly. [0003] US Pat. No. 5,206,309 states that N66 can be 0.1 to 99.9%.
Teaches heat stable films based on melt blends of N66 and N6 / N66
You. This patent requires that the present invention achieve a homogeneous miscible phase.
Ratio random copolymers are not described. US Patent 5,053,259
No. 5,344,679 are amorphous nylon, T _m > 145 ° C. and optionally a blend of 10-30% by weight of a polyamide homopolymer.
Teaching. U.S. Pat. No. 4,877,684 discloses nylon 6 and N6 / N66.
Claims a film based on a mixture of EP Patent No. 408,390 describes:
Any polyamide, along with amorphous polyamide or copolyamide, any
It discloses the use of copolyamides or mixtures of polyamides. Japanese Patent No. 1
No. 15,4752 is an aliphatic polyamide and partially aromatic with EVOH.
A film based on a mixture of amorphous polyamides is disclosed. AU Patent No. 88
No. 25700 is, for example, an aliphatic poly of nylon 6 or N6 / N66 copolymer.
Amides and amorphous polyamides are disclosed. All of these are likewise the invention
Of Nylon in Constant Ratio for Forming Homogeneous Miscible Phase Compositions
No copolymer is taught. U.S. Patent Nos. 4,647,483 and 4,665
No. 135, and No. 4,683,170, the total blend is 2.5-10%.
N6 / N66 or N6 / N rich in N6 to contain N66 or N12
9 shows a blend of N6 with 12 copolymers. The present invention
Because N66 can be incorporated without adverse effects on homogeneity, these patents
More effective than render. SUMMARY OF THE INVENTION A semi-crystalline nylon homopolymer and the same semi-crystalline nylon as the homopolymer
A homogeneous blend with a semi-crystalline copolymer containing
Melting point, large difference between its melting temperature and its crystallization temperature, and its semi-crystalline nylon
Providing blends with improved properties of the same melting temperature as homopolymers
Would be desirable. SUMMARY OF THE INVENTION The present invention provides a method for producing uniformly mixed semi-crystalline nylon.
And (a) an amount of about 30% to about 99%, based on the weight of the mixed nylon composition.
Of the solid particles of the semi-crystalline nylon homopolymer A and the weight of the mixed nylon composition
From about 1% to about 70%, based on the amount, of at least one different
Forming a mixture with a random semi-crystalline copolymer with nylon B
The amount of nylon A in the copolymer ranges from about 70% to about 70% based on the weight of the copolymer.
And the amount of nylon B in the copolymer is based on the weight of the copolymer.
Melt blending at least at the melting point of the nylon homopolymer A, from about 5% to about 30%.
And producing a uniformly mixed semi-crystalline nylon comprising:
The nylon composition has a single significant melting point and each nylon homopolymer A and nylon
Melting point and its melting point more than a copolymer of Ron A and at least one different nylon B
The difference between the crystallization temperatures is greater. [0006] The present invention also provides a method of making a homogeneously mixed semi-crystalline nylon composition.
Wherein the method comprises: (a) an amount of about 30% to about 99%, based on the weight of the mixed nylon composition.
Of the solid particles of the semi-crystalline nylon homopolymer A and the weight of the mixed nylon composition
From about 1% to about 70%, based on the amount, of at least one different
Forming a mixture with a random semi-crystalline copolymer with nylon B
The amount of nylon A in the copolymer ranges from about 5% to about 9% based on the weight of the copolymer.
5%, and the amount of nylon B in the copolymer is based on the weight of the copolymer.
Melt mixing at least at the melting point of the nylon homopolymer A by about 5% to about 95%.
And producing a uniformly mixed semi-crystalline nylon comprising:
The nylon composition has a single significant melting point approximately equal to the melting point of nylon homopolymer A.
It is a nylon composition having dots. [0007] The composition may further comprise a non-crystalline, amorphous nylon component.
No. These compositions are made by casting or blowing the nylon composition.
It is also useful in film production and in uniaxial or biaxial stretching. According to the present invention, one-component, homogeneous materials are determined by differential scanning calorimetry (DSC).
In a method that is measured to be present, even if a small amount of nylon component is mixed in most components
Good (eg, N66 in N6 or N6 in N66). The product of the present invention
, In a particular chemical composition (two T _m Only one melting point T _m Have
It differs from conventional mixing in that it has a reduced crystallization potential. Of the present invention
The product also has a higher T for a particular chemical composition of nylon. _m It is different from the conventional random copolymer from the viewpoint of reduced crystallization possibility. In addition,
According to Ming, non-homogeneity in both crystalline and amorphous phases is
Therefore, without measurement, N66, N12 and amorphous nylon
Several polyamides can also be incorporated into N6. Conventionally, miscibility in mixtures
Means one homogeneous amorphous phase, but the crystalline phase always has its unique T _m Shows the phase of In contrast, the present invention provides a multi-component miscible mixture having only one amorphous phase and only one crystalline phase as measured by DSC. [0009] BEST MODE FOR CARRYING OUT THE INVENTION In practicing the present invention, the composition comprises a semi-crystalline homopolymer of nylon A,
A semi-crystalline nylon which is a copolymer of nylon A and at least one different nylon
It is prepared by melt mixing with ILON B. The composition comprises a non-crystalline, amorphous,
Nylon copolymer C is also optionally included. The resulting composition has a single significant
It is determined to have a melting point. For the purposes of the present invention, only a single significant point
Having a second melting point is less than 35% of the main melting peak, as observed
, More preferably less than 20% of the main melting peak, most preferably the main melting peak.
Means less than 10% of the peak. Observe the intensity of this second melting peak.
For example, it is determined by a known DSC method. This method can be used for 25 hours under vacuum for several hours.
Analyzing the film to be tested after drying at 45 ° C. Primary and secondary DSC
The peak intensity is determined by the heat of fusion integrated over the melting range of the individual peaks.
Is determined. Preferably, the composition has only one melting point and no other melting point.
Absent. [0010] In one embodiment, the nylon component, when mixed in a first proportion, has a
The composition comprises more than each of the nylon homopolymer A and its copolymer,
There is a greater difference between the melting temperature and its crystallization temperature. In another example,
When the nylon components are mixed in a second proportion, the nylon composition is
It has a melting temperature approximately equal to the melting temperature of homopolymer A. In the context of the present invention
The melting temperature approximately equal to the melting temperature of nylon homopolymer A is
It means within about ± 5 ° C. of the melting temperature of the polymer A. First component of the composition of the present invention
Is a semi-crystalline nylon A, which can consist of a semi-crystalline polyamide homopolymer.
Is a homopolymer. Used in the present invention as a semi-crystalline homopolymer of nylon A
Suitable polyamides include aliphatic polyamides or aliphatic / aromatic polyamides
. As used herein, "aliphatic polyamide" refers to at least two aliphatic carbon atoms.
Thus, the repeating car as an integral part of the polymer chains separated from each other
A polyamide characterized by the presence of a bonamide group. These polyamides
Illustrative of the formula is the following general formula: Or a combination thereof (wherein R and R ¹ Are the same or different and are alkylene groups of at least 2 carbon atoms, preferably having about 2 to 12 carbon atoms.
It is a kylene group. ) Having a repeating monomer unit represented by
. As used herein, "aliphatic / aromatic polyamide"
It is characterized by the presence of repeating carbon amide groups as an integral part.
Here, the carbonyl moiety is an aliphatic moiety having at least two carbon atoms.
Thus, the nitrogen groups are separated by an aromatic moiety. Its aliphatic / good
Illustrative of aromatic polyamides are the following formulas: [Where R ^Two And R ^Three Is an alkyl having at least two carbon atoms
A len group, preferably an alkylene group having 2 to about 12 carbon atoms, or an aryl
Len, preferably substituted or unsubstituted phenylene, alkylene phenylene or dia
Alkylene phenylene, wherein the aliphatic moiety has 1 to 7 carbon atoms
, The permissible substituents are alkyl, alkoxy or halo, provided that R ^Two Is arylene and R ^Three Is alkylene, and R ^Two Is alkylene, and R ^Three Is arylene or dialkylenephenylene. )] Is a polyamide having a repeating unit. [0015] Examples of suitable aliphatic polyamides are formed by the reaction of a diamine and a diacid.
Polyamide homopolymers such as poly (hexamethylene adipamide)
Ron 6,6), poly (hexamethylene sebacamide) (nylon 6,10), poly
(Hexamethylenepimelamide) (nylon 7,7), poly (octamethylene
Lamid) (nylon 8,8), poly (hexamethyleneazeramid) (nylon 6
, 9), poly (nonamethyleneazeramid) (nylon 9, 9), poly (decamethi)
Lenazeramide) (nylon 10, 9). Useful aliphatic polyamide
Physically, they are formed by the polymerization of amino acids and their derivatives, such as lactams.
It is what is done. Useful polyamides are poly (4-aminobutyric acid) (nylon 4)
, Poly (6-aminohexanoic acid) (as nylon 6, poly (caprolactam)
Poly (7-aminoheptanoic acid) (nylon 7), poly (8-amino
Nooctanoic acid) (nylon 8), poly (9-aminononanoic acid) (nylon 9),
Poly (10-aminodecanoic acid) (nylon 10), poly (11-aminoundeca)
Acid) (nylon 11), poly (12-aminododecanoic acid) (nylon 12),
And nylon 46, nylon 66 and nylon 69. Mixtures of two or more aliphatic polyamides can also be used. Polyamides suitable for use in semi-crystalline nylon A are poly (caprolactam) and poly (hexamethylene amine).
Dipamide), and poly (caprolactam) is most preferred. In the practice of the present invention
The aliphatic polyamides used can be obtained from commercial sources or
It can also be manufactured by the manufacturing technology described above. For example, poly (caprolactam)
AlliedSignal, Morristown, NJ
Inc., under the registered trademark CAPRON. Examples of aliphatic / aromatic polyamides are
Poly (hexamethylene isophthalamide), poly (2,2,2-trimethylhexa)
Methylene terephthalamide), poly (m-xylene adipamide) (MXD6), poly (
p-xylene adipamide), poly (hexamethylene terephthalamide), poly (dodecamethylene terephthalamide) and the like. Two or more aliphatic / aromatic polyamides
Can also be used. The most preferred aliphatic / aromatic polyamide is poly (m-xy
Lenadipamide). Aliphatic / aromatic polyamides are manufactured by known manufacturing techniques.
It can be manufactured or obtained from commercial sources. The second component of the composition of the present invention is a semi-crystalline nylon, which is a nylon
A plus at least one other nylon B copolymer. Nylon A Plus The above semi-crystalline nylon, which is a copolymer of at least one other nylon B, can be formed by copolymerizing two different monomers as described for Nylon A. Copolymers formed from repeating units of the above aliphatic polyamide
Can be used for the production of polyamides. It is an explanation and not a limitation.
The amide is a caprolactam / hexamethylene adipamide copolymer (nylon 6,
6/6), hexamenthylene adipamide / caprolactam copolymer (nylon 6
, 6/6), trimethylene adipamide / hexamethylene azelaamide copolymer
(Nylon trimethyl 6,2 / 6,2), hexamethylene adipamide / hexame
Tyleneazeamide / caprolactam copolymer (nylon 6/6, 6/9, 6
). The number average molecular weight of nylon A and nylon A / nylon B copolymer is very wide
May be changed. These are enough to form a free standing film
High enough, but low enough to melt process the mixture. Such number
Average molecular weights are well known to those skilled in the art of film formation and are based on the formic acid viscosity (FAV) method (ASTMD-789).
Is usually at least about 5,000. In this method, 2
A solution of 11 g of aliphatic polyamide in 100 ml of 90% formic acid at 5 ° C. is used. Book
In a preferred embodiment of the invention, nylon A and nylon A / nylon B copolymer
Has a number average molecular weight of about 5,000 to about 100,000, preferably about 10,000.
00 to about 60,000, more preferably from about 20,000 to about 40,000.
0. Nylon compositions may also be non-crystalline, non-crystallizable (non-crys
tallizable), and may include amorphous nylon component C. amorphous
Nylons are well known to those skilled in the art and are commercially available. Amorphous Niro
The compound typically comprises at least one diamine and at least two different dibasic acids.
Is produced by reacting This product has no critical melting point and cannot be crystallized.
It is nylon. Amorphous nylon is Grivory 21 (from EMS, Switzerland)
And Zytel amorphous nylon (from DuPont). In a first aspect of the present invention, a composition as follows: having a single melting point.
And the difference between the melting point and the crystallization temperature of the composition is
Melting points and crystals of copolymers of nylon A and at least one different nylon B
A composition larger than the difference from the formation temperature can be produced. Achieve this result
The amount of nylon homopolymer A depends on the weight of the blended nylon composition.
From about 30% to about 99%, preferably from about 35% to about 85%, based on
And more preferably about 4% by weight of the blended nylon composition.
0% to about 60%. In this embodiment, a copolymer of nylon A and nylon B
Amount of about 1% to about 70% based on the weight of the blended nylon composition.
Range, preferably from about 15% to about 65%, more preferably the blend
About 40% to about 60%, based on the weight of the resulting nylon composition. In this first embodiment, the amount of nylon A in the copolymer depends on the weight of the copolymer.
Ranges from about 70% to about 95%, preferably by weight of the copolymer.
From about 70% to 90%, more preferably based on the weight of the copolymer.
The standard is about 70% to about 85%. The amount of nylon B in the copolymer is
In the range of about 5% to about 30%, preferably about 10% to
About 30%, more preferably from about 15% to about 15%, based on the weight of the copolymer.
30%. In the first embodiment of the present invention, when amorphous nylon is contained,
Rufus nylon is the weight of the blended nylon composition in the total composition.
About 1% to about 30%, preferably about 2% to about 25%, more preferably
It is present from about 5% to about 20%. In the second aspect of the present invention, the nylon composition also has a single melting point. Melting point
Is approximately equal to the melting point of nylon homopolymer A. To achieve this result,
The amount of ILON homopolymer A is based on the weight of the blended nylon composition.
Range from about 30% to about 99%, preferably from about 35% to about 85%, and
Preferably from about 40% to about 60% by weight of the blended nylon composition.
%. The amount of the copolymer of Nylon A and Nylon B is
In the range of about 1% to about 70%, preferably about 65% by weight of the composition.
% To about 15%, and more preferably based on the weight of the blended nylon composition.
The standard is about 60% to about 40%. In this second embodiment, the amount of Nylon A in the copolymer depends on the weight of the copolymer.
In the range of about 5% to about 95%, preferably about 10% to about 90%, by weight.
And more preferably from about 15% to about 85% by weight of the copolymer.
is there. The amount of copolymer B in the copolymer is about 9 based on the weight of the copolymer.
5% to about 5%, preferably about 90% to about 10%, more preferably
Or about 85% to about 15% based on the weight of the copolymer. When amorphous nylon is included in the second aspect of the present invention, the amorphous nylon
From about 1% to about 30% by weight of the blended nylon composition in the overall composition
Preferably about 2% to about 25%, based on the weight of the blended nylon composition,
More preferably, it is present in an amount from about 5% to about 20%. [0025] Optionally, the blend may contain additives commonly used in nylon compositions.
Can be. Examples of such additives are pigments, dyes, slip agents, fillers, nucleating agents
, Plasticizers, lubricants, reinforcing agents, anti-adhesives, oxidation stabilizers, oxidation inhibitors, heat stabilizers and
UV stabilizer. Preferably, they are about 10% based on the weight of the composition.
% Or less. The composition is obtained by dry blending solid particles or pellets of each nylon component,
The mixture is melted at a temperature of at least the melting point of the nylon A homopolymer.
Can be formed. Typical melting temperatures range from about 175 ° C to
About 260 ° C., preferably about 215 ° C. to about 225 ° C., more preferably about 220 ° C.
C. to about 223.degree. C. (for nylon 6). Blending in a suitable container
For example, it can be performed by an extruder, a roll mixer or the like. Blendin
The grinding is for the time necessary to obtain a substantially homogeneous blend. This is for those skilled in the art
Therefore, it can be easily determined. If necessary, cool the composition and
Cut into pellets or film for further processing, optionally by one skilled in the art.
The film can be uniaxially or biaxially stretched by a known means. The film of the present invention can be prepared by a conventional method (extrusion method) useful for producing a film.
). Typically, a melt flow of polyamide
Is fed through an extrusion die onto a casting roll, or the polyamide is
It can be introduced into blown film equipment. Optionally, the film
Drawing from film forming equipment, also referred to in the art as "longitudinal"
In the direction that corresponds to the direction of movement of the film to be moved, or “crossing” in the art.
Direction, also perpendicular to the longitudinal direction, uniaxially, or transverse to the longitudinal direction
The film can be biaxially stretched in both directions. The film of the present invention
Has sufficient dimensional stability, either longitudinally or transversely or in both directions
Crab at least 1.5 times, preferably more than 3 times, more preferably more than 3 times
It can be stretched many to about ten times. Typically for the use of the present invention,
The oriented film formed from the bright composition preferably has a draw ratio
About 1.5: 1 to about 6: 1, preferably at a draw ratio of about 3: 1 to about 4: 1.
It is. As used herein, the term "stretch ratio" refers to an increase in the dimension in the stretching direction.
You. Thus, a film having a draw ratio of 2: 1 has its length doubled during the drawing process.
Become. Generally, the film is stretched by passing through a series of preheating and heating rolls.
Is done. The heated film is better than the film entering the upstream nip roll.
It moves through a pair of nip rolls downstream at a high speed. This change in speed is
Compensated by stretching of the film. The film structure preferably has a thickness of between about 0.3 mil (7.6 μm) and about 5.0 mm.
(127.0 μm), preferably about 0.5 mil (12.7 μm) to about 1.5 mm
(37.5 μm). Flexible easily
Thickness that provides a transparent film is preferred, but meets specific needs and
It is understood that other film thicknesses that fall within the scope of the present invention can also be manufactured.
It should be. The composition produced according to the invention is a very homogeneous film
Is formed. The following non-limiting examples are provided to illustrate the invention. EXAMPLES The starting polymer used was gas chromatography (GC) using standard procedures.
Was analyzed by The accuracy of these measurements is ± 2%. The films were analyzed by differential scanning calorimetry (DSC) using a Seiko RDC-220 thermal analyzer equipped with an automatic system. Approximately 7.5 (± 0.5) mg of film sample is crimped into an aluminum pan and heated at 10 ° C / min at room temperature.
To about 280 ° C., and hold there for crystalline memory
memory) was erased. Subsequently, the sample was cooled from 280 ° C. to room temperature at a cooling rate of 10 ° C. and reheated at the same rate. A nylon 66 homopolymer
For film compositions, the upper DSC temperature was changed to about 300 ° C. Reported in Examples
T _m Are those obtained in the initial heating cycle, i.e.
Corresponding to the cast of "as received films." Super cooling (super-coo
ling) the reheating cycle T _m And T _cc Is reported as the difference between That is, it corresponds to the heating history loaded prior to the cooling cycle. T _cc The cooling curve is 1
Crystallizability of a particular sample during a 0 ° C / min cooling cycle
Which is integrated to calculate the heat of crystallization (DH _f , J / g). Nylon 6 rich
DH of 100% crystalline nylon 6 _f = 230 J / g, 10 ° C / min
Change in crystallinity during the cooling cycle scan (CI _DSC ,%) Was calculated. DH for nylon 66-rich samples _f = 188 J / g was used. Temperature and DH _f Calibration was assured by a two-point calibration using indium and tin metal standards. Commercially available grades of nylon used in this study, along with their usual compositions, are listed below.
Place: Nylon 6 [8207, AlliedSignal], Nylon 6 (95) / Nylon 66 (5) [AlliedSignal], Nylon 6 (85) / Nylon 66 (15) [AlliedSignal], Nylon 6 (80) / Nylon 66 ( 20) [AlliedSignal], nylon 6 (70) / ny
Ron 66 (30) [AlliedSignal], Nylon 6 (21) / Nylon 66 (79) [Monsant
o], nylon 66 [Zytel 101L, DuPont], nylon 6 (83) / nylon 12 (17) [Ube], and amorphous nylon [Zytel 330, DuPont]. [0031] Example 1 (comparison) Modification of Nylon 6 by Blending Nylon 66 Homopolymer In this example, a physical blend of nylon homopolymer, Nylon 6 and Nylon 66, in various proportions is prepared. Nylon 6 and nylon 6
The 6 dried pellets were physically mixed at the weight percentages shown in Table 1. This composition
The material is dried at 82 ° C for about 18 hours and has three heating zones (232 ° C, 257 ° C and 260 ° C)
Single screw extruder (Killion singl) equipped with two adapters (260 ° C)
Extruded with an e screw extruder (D = 1.5 in; L / D = 24/1). Melting temperature
Was measured as 267 ° C. After passing through an extrusion film die maintained at 260 ° C,
The output was applied on a roll maintained at 82 ° C. and then on a chill roll maintained at 43 ° C.
The overall thickness of the resulting film was about 2 mil. Film using nylon 66
For the composition, the extrusion temperature was increased by about 30 ° C. [Table 1] The melting pattern of each film is plotted in FIG. These data indicate that a physical mixture of two nylon homopolymers has two different melting points
2 shows that a composition is obtained. The control polymer has only one melting point. In addition, for such physical mixtures of homopolymers, the amount of supercooled DT is reduced.
Therefore, the crystal acceleration increases. Figure 1 shows that N6 (T _m , 222 ° C), N66 (T _m , 262
C) and DSC thermograms of their melt blended films. Two T _m By
As shown, these blends are non-homogeneous in the crystalline phase.
nous) and immiscible. Example
1 is a reduction in supercooling of nylon 6 by melt blending with nylon 66 homopolymer.
It shows a small, that is, an increase in crystal acceleration. Therefore, for the purpose of reducing the crystal acceleration of nylon 6, the nylon 66 homopolymer is blended by the usual process technology.
To do is not the intended procedure. [0034] Example 2 (comparison) Modification of Nylon 6 with Nylon 66 by Copolymerization Copolymerization Using commercially available random copolymer of Nylon 6 / Nylon 66 in the ratio shown in Table 2.
Otherwise, the operation of Example 1 is repeated. These are the monomers from nylon 6
Produced by copolymerizing raw material and monomer starting material of nylon 66
. To reduce the rate of crystallization of nylon 6 (ie, greater undercooling, DT
) Are well known (if not known, the only practical means) are nylon 66, nylon
Random copolymerization with other polyamides such as Ron 12, nylon 46, nylon 69
Is to make a body. [Table 2] The temperature data is plotted in FIG. 2, where these copolymers have a single melting temperature
But its melting temperature decreases as the amount of diluent nylon component increases
It is shown that. This is because N6 increases in N66-rich copolymers.
And when N66 is increased in the N6-rich copolymer. Homo
Such copolymers characterized by a reduced Tm compared to the Tm of the polymer
The coalescence is produced by a polycondensation reaction of the starting comonomer mixture. For example,
Ron 6 / Nylon 66 (50/50) copolymer is a 50:50 ratio of caprola.
Octam (ie monomer for nylon 6) and hexamethylenediamine
By the polymerization reaction of adipic acid (ie the monomer for nylon 66)
Be manufactured. This example demonstrates that such measures enhance supercooling.
To For example, the DT for nylon 6 is 38.4 ° C. (± 0.4).
, Which is then increased to 46.6 ° C (± 0.3) by the addition of 25% nylon 66 component.
First increase. Similarly, the DT for nylon 66 is 30.8 ° C. (± 0.3
) Which is brought to 39.8 ° C. (± 0.5) by the addition of 21% nylon 6.
To increase. Such copolymers have lower crystallization rates (i.e.,
Due to their larger DT), their rapid cooling rate is higher than their homopolymer counterparts during melt processing.
It exhibits a very low crystallinity. Therefore, such copolymers can be used in orientation / stretching applications.
Is a better material for [0037] Example 3 Nylon 6 / nylon 66 (84/16)
Modification of Iron 6 Homopolymer A composition comprising a commercially available nylon 6 homopolymer and a commercially available random N6 / N66 copolymer (8
6/14), except that it is a physical mixture with 6/14). table
3 gives the proportion of each polymer component, as well as the proportion of N66 in the overall composition
. [Table 3] * Possible phase separation ** Two Tm indicate phase separation The data plotted in FIG. 3 show that samples 2, 3 and 4 according to the invention
It has a melting temperature. Sample 4 probably has a second melting temperature.
However, if it is present, it is not noticeable. Low homopolymer content
Thus, Samples 5 and 6, which are outside the scope of the present invention, have a dual melting point. Trial from Figure 3
The data for Nylon 6 content of ingredients 2, 3 and 4 are similar to those from FIGS. 1 and 2.
Compared to the ILON 6 composition, the composition of the present invention has a single melting point that is not reduced.
Is shown. Example 3 and FIG. 3 show that N6 (84) / N66 up to 50%.
(14) The copolymer is melt-mixed into nylon 6 while maintaining a single Tm.
This suggests a completely homogeneous blend. The amount of copolymer is about
Above 65%, the composition tends to be heterogeneous. The maximum DT at 47 ° C is
Observed for the blend system according to the invention, which is one of the two blend components
Is much larger than that of
In case of synergistic interaction with N6 (84) / N66 (14) copolymer (Example 3
) Should be noted. Compared to a conventional random copolymer with the same N6: N66 ratio
The superiority of all these miscible blends is related to higher Tm and higher DT.
4 and 5; the physical blend of N6 and N66 is non-homogeneous.
And inferior for the smaller DT (FIG. 1 and Example 1). [0040] Example 4 Nylon 6 / Nylon 66 (75/25) random copolymer
Modification of Iron 6 homopolymer The melting point of a conventional nylon 6 / nylon 66 copolymer is compared with the formulation of the present invention.
You. [Table 4] * Two Tm, showing phase separation This example and FIG. 6 show that while maintaining a single Tm showing a completely homogeneous formulation,
Up to 50% nylon 6 (75) / nylon 66 (25) copolymer
6 shows that it can be melt-blended with homopolymer. About 50-80% copolymer
If so, the composition tends to be non-homogeneous. The maximum DT of this compounding system is
Note that it is 52 ° C., much higher than our components. I mean
, Nylon 6 homopolymer and nylon 6 (75) / nylon 66 (25) copoly
Synergy between the mers (Example 4). Conventional Niro with such miscibility
The superiority over the nylon 6 / nylon 66 equal random copolymer is the high Tm and
Shown in Figures 4-5 for the large DT, the physical properties of nylon 6 / nylon 66
The targeted formulation, like the small DT, is also inferior in terms of inhomogeneity (FIG. 1 and
Example 1). [0043] Example 5 Nylon 6 / nylon 66 (21/79)
Modification of Iron 6 Homopolymer This example demonstrates the use of nylon 6 (21) / nylon 66 (79) copolymer
Shows that blending with Ron 6 has no advantage in increasing DT.
are doing. As shown in FIG. 7, nylon 66 homopolymer is converted to nylon 6 (84
) / Nylon 66 (16) copolymer can be similarly modified by melt blending.
Can be. For example, 75% nylon 66 homopolymer and 25% nylon 6 (8
4) / Nylon 66 (16) copolymer is blended with nylon 66 homopolymer.
The same melting pattern as that of-can be obtained. Such miscibility containing 21% nylon 6
The formulation has a Tm of 47 ° C. higher than a conventional random copolymer containing 21% nylon 6.
(FIGS. 4 and 7) 79% nylon 66 which can be expected to have two Tm
And 21% nylon 6 (FIG. 1). As for undercooling
, N66-rich copolymer, ie, N6 (21) / N66 (79)
Compared to the Iron 6 (84) / Nylon 66 (16) copolymer, the DT of N66
Increase more effectively (FIG. 5). [Table 5] * Suggests somewhat broader melt transition, slight phase separation. Example 6 Nylon / Nylon 12 (83/17)
Modification of ILON 6 homopolymer. This example demonstrates that the invention is not limited to N6 and N66 systems only.
I do. For example, a random copolymer of N6 homopolymer and N6 (83) / N12 (17)
N12 can be incorporated into N6 by melt blending the polymer.
You. The resulting formulation is quite homogeneous, with one T _m Characterized only by. [Table 6] [0048] Example 7 A nylon 6 composition having reduced crystallinity. This example shows that by blending 17% amorphous nylon in N6,
Undercooling increases from 38.4 ° C. (± 0.4) to 43.8 ° C. (± 1.2)
(I.e., the crystallization rate is reduced), and the developable crystallinity is 28.8% (
± 0.5) to 23.2% (± 0.8). However,
By substituting a portion of the amorphous nylon with N66 according to
6-enriched N6 / N66 random copolymers (eg N6 (84) / N66 (
By blending 16)), these effects are further increased (Example 7).
. Note that the entire composition is still homogeneous, a single, and miscible phase
Should. Example 7 also uses a random copolymer N6 / N12.
This indicates that N66 can be replaced with N12. [Table 7] [0050] Example 8 A nylon 6 composition having reduced crystallinity. This example shows that the amount of amorphous nylon is kept the same and the N6 homopolymer
By substituting a portion of the N with the N6 (84) / N66 (16) copolymer.
Cold increase from 43.8 ° C (± 1.2) to 48.3 ° C (± 0.5);
And developable crystallinity from 23.2% (± 0.8) to 17.8% (± 0.5%).
). For example, film 2 and film 3 in Example 8
See the contrast of Other points when comparing Film 2 with Films 4-7
When the composition is similar to the above, the amount of amorphous nylon can be reduced from 17% to 5%.
And at the same time, developable crystallinity decreases and supercooling increases
It is shown to be. [Table 8] Examples 7 and 8 incorporate a multi-component polyamide in a single homogeneous and miscible phase.
The high degree of freedom of the present invention with respect to incorporation
Demonstrates improvements in properties such as speed and low viable crystallinity
And From these data, it can be seen that the composition of the present invention for homogeneous nylon compounding is
With a remarkable melting point, low crystallization rate, and low crystallinity of developability
You can see that there is. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph of the melting pattern of a melt-blended nylon film. FIG. 2 Melting pattern of nylon 6 / nylon 66 random copolymer film
Graph. FIG. 3 Nylon 6 homopolymer and nylon 6 / nylon 66 (84/16)
Graph of melting patterns of nylon films based on mixtures with random copolymers
. FIG. 4 is a graph of melting point and 66% nylon in nylon 6 film. FIG. 5 is a graph of supercooling and 66% nylon in nylon 6 film. FIG. 6: Nylon 6 homopolymer and nylon 6 / nylon 66 (75/25)
Graph of melting patterns of nylon films based on mixtures with random copolymers
. FIG. 7 is a graph of a melting pattern of a nylon film.

[Procedure amendment]

[Submission date] October 26, 2000 (2000.10.26)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

16. A nylon film formed by the method of claim 11.

[Procedure amendment]

[Submission date] March 23, 2001 (2001.3.23)

[Procedure amendment 1]

[Document name to be amended] Drawing

[Correction target item name] All figures

[Correction method] Change

[Correction contents]

FIG.

FIG. 2

FIG. 3

FIG. 4

FIG. 5

FIG. 6

FIG. 7

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 77:00 C08L 77:00 (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, G B, GE, GH, GM, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK , MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, UZ, VN, YU, ZW (72) Inventor Day, Eric Dee, United States 07974, New Jersey, Commonwealth Avenue, New Providence 188 F-term (reference) 4F071 AA54 AA55 AA84 AA87 AA89 AF11 BB02 BB07 BB08 BB13 BC01 BC04 4F210 AA29 AA29E AG01 QC01 QC QG01 QG18 4J002 CL003 CL01W CL03W CL05X

Claims (30)

[Claims] 1. A method of making a uniformly compounded semi-crystalline nylon composition, comprising: (a) semi-crystalline in an amount of about 30% to about 99% based on the weight of the compounded nylon composition. A mixture of solid particles of nylon homopolymer A; and a random semi-crystalline copolymer A of nylon with at least one different nylon B in an amount of about 1% to about 70% based on the weight of said compounded nylon composition. And the amount of nylon A in the copolymer is about 7% based on the weight of the copolymer.
0% to about 95% and the amount of nylon B in the copolymer is in the range of about 5% to about 30% based on the weight of the copolymer; and (b) Melt blending at least the melting point temperature of the nylon homopolymer A, wherein the nylon composition has only a significant single melting temperature and the nylon with the nylon homopolymer A and at least one different nylon B A process which has a greater difference between its melting temperature and its crystallization temperature than each of the copolymers A. 2. Nylon A and Nylon B are nylon 4, nylon 6, respectively.
The method of claim 1, wherein the method is selected from the group consisting of: nylon 9, nylon 11, nylon 12, nylon 46, nylon 66, and nylon 69. 3. The method of claim 1, wherein the nylon A is nylon 6, and the nylon copolymer A with at least one different nylon B is a copolymer of nylon 6 and nylon 66. 4. The method according to claim 1, wherein the amount of Nylon A in said mixture is in the range of about 35% to about 85% based on the weight of said compounded nylon composition,
2. The method of claim 1, wherein the amount of nylon copolymer A with is in the range of about 15% to about 65% based on the weight of the compounded nylon composition. 5. The nylon B in said mixture wherein the amount of nylon A in said mixture is in the range of about 40% to about 60% based on the weight of said compounded nylon composition.
2. The method of claim 1, wherein the amount of nylon copolymer A with is in the range of about 40% to about 60% based on the weight of the compounded nylon composition. 6. The nylon B in said copolymer wherein the amount of nylon A in said copolymer is in the range of about 70% to about 90% based on the weight of said copolymer.
2. The method of claim 1, wherein the amount of is in the range of about 10% to about 30% based on the weight of the copolymer. 7. The nylon B in said copolymer, wherein the amount of nylon A in said copolymer is in the range of about 70% to about 85% based on the weight of said copolymer.
2. The method of claim 1, wherein the amount of is in the range of about 15% to about 30% based on the weight of the copolymer. 8. The method of claim 1, wherein said mixture further comprises at least one amorphous nylon C that is a reaction product of at least one diamine with two or more diacids. . 9. The method of claim 8, wherein the amount of Nylon C in the mixture is in a range from about 1% to about 30% based on the weight of the compounded nylon composition. 10. The method of claim 8, wherein the amount of nylon C in the mixture is in a range from about 2% to about 25% based on the weight of the compounded nylon composition. 11. The method of claim 8, wherein the amount of Nylon C in the mixture is in a range from about 5% to about 20% based on the weight of the compounded nylon composition. 12. A nylon composition formed by the method of claim 1. 13. A nylon composition formed by the method of claim 8. 14. Cast or blow molded the nylon composition of claim 1,
And a film produced by appropriately uniaxially or biaxially stretching. 15. Casting or blow molding the nylon composition of claim 8,
And a film produced by appropriately uniaxially or biaxially stretching. 16. A method of making a uniformly compounded semi-crystalline nylon composition, comprising: (a) semi-crystalline in an amount of about 30% to about 99% based on the weight of the compounded nylon composition. A mixture of solid particles of nylon homopolymer A; and a random semi-crystalline copolymer A of nylon with at least one different nylon B in an amount of about 1% to about 70% based on the weight of said compounded nylon composition. And the amount of nylon A in the copolymer is about 5 based on the weight of the copolymer.
0% to about 95%, and the amount of nylon B in the copolymer ranges from about 95% to about 5% based on the weight of the copolymer; and Melt blending at a temperature around the melting point of polymer A, wherein the nylon composition has only a single effective melting temperature that is approximately equal to the melting temperature of nylon homopolymer A. 17. The method of claim 16, wherein each of nylon A and nylon B is selected from the group consisting of nylon 4, nylon 6, nylon 9, nylon 11, nylon 12, nylon 46, nylon 66, and nylon 69. . 18. The method of claim 16, wherein the nylon A is nylon 6, and the nylon copolymer A with at least one different nylon B is a copolymer of nylon 6 and nylon 66. 19. The amount of nylon A in the mixture ranges from about 35% to about 85%, based on the weight of the compounded nylon composition, and the amount of nylon copolymer A with nylon B is: About 65% by weight of the compounded nylon composition
17. The method of claim 16, wherein said range is about 15%. 20. The amount of nylon A in the mixture ranges from about 40% to about 60% based on the weight of the compounded nylon composition, and the amount of nylon copolymer A with nylon B is: About 60% by weight of the compounded nylon composition
17. The method of claim 16, wherein said range is about 40%. 21. The amount of nylon A in the copolymer is in the range of about 10% to about 90% based on the weight of the copolymer, and the amount of nylon B in the copolymer is less than the weight of the copolymer. 17. The method of claim 16, wherein the amount is in a range of about 90% to about 10% based on the weight of the composition. 22. The amount of nylon A in the copolymer is in the range of about 15% to about 85% based on the weight of the copolymer, and the amount of nylon B in the copolymer is less than the weight of the copolymer. 17. The method of claim 16, wherein the amount is in the range of about 85% to about 15% based on the weight. 23. The mixture further comprising two or more diacids.
At least one amorphous nylon C which is at least one reaction product with
17. The method of claim 16, comprising: 24. The method of claim 23, wherein the amount of Nylon C in said mixture is in the range of about 1% to about 30% based on the weight of said compounded nylon composition. 25. The method of claim 23, wherein the amount of Nylon C in said mixture is in the range of about 2% to about 25% based on the weight of said compounded nylon composition. 26. The method of claim 23, wherein the amount of Nylon C in the mixture is in a range from about 5% to about 20% based on the weight of the compounded nylon composition. 27. A nylon composition formed by the method of claim 16. 28. A nylon composition formed by the method of claim 23. 29. A film produced by casting and optionally uniaxially or biaxially stretching the nylon composition of claim 16. 30. A film produced by casting and optionally uniaxially or biaxially stretching the nylon composition of claim 23.