JPS5819336A - High effeciency foamed body of thermotropic liquid crystal polymer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] The present invention provides a high-performance foam made of liquid crystal foam.
It is something to do. The foams of the invention exhibit excellent mechanical properties.

This type of lamp is very useful in applications where excellent mechanical properties such as a high strength/weight ratio are required.

High performance foam products, especially transportation vehicles, building materials,
**Si equipment and office equipment are often used. but%! Lightweight and high-performance products in the industry [What is most needed is transportation and storage. 41 and automobile 11*,
The main uses include structural elements and under K-nets. Building elements such as trunks, nets and doors require high mechanical properties. # Applications under the net require excellent solvent resistance and the ability to withstand high temperatures, along with poor mechanical properties such as tear strength, impact strength and initial elongation. It will drop significantly. As a result of its research, it has been published in the conventional Oike Plastics O application category S light.

Unfoamed OiI crystal 4 remer products manufactured by conventional methods such as extrusion or injection molding are
It is well known in the mining industry that it exhibits a very high anisotropy of 4% in physical properties in the transverse direction (TD) and in the transverse direction (TD). This is it, MD! ! Even if it is very suitable, the TDlI value is very low. moreover,
The core part of the crystals is essentially in an unoriented state 1, and when looking at section II, a very sharp epidermal layer - part II structure is observed.

It is also known that highly aromatic liquid crystalline remers have excellent high temperature stability and flame resistance as well as excellent solvent resistance, and that foams of liquid crystalline remers can also be produced (U.S. Pat. No. L77814 Z). O:3.804.805
: 3,859,251:3,890,256:4.2
38,600 and Published PCT Application No. WO791010
(See 3G).

Additionally, it is known to those skilled in the art that when a liquid crystal four-dama shaped article is heat treated, its melting point, molecular weight, and mechanical properties increase (see, e.g., U.S. Patent No. 13,975.4
87: 4,183,895 and 4.247,51
(see 4).

The present IjIK provides a foam that exhibits desirable mechanical properties with improved thermal, flammability and solvent stability. This foam has the following structure (however, at least a part of the hydrogen atoms bonded to the ring may be an alkyl having 1 to 4 carbon atoms,
About 10 moles of a repeating structural unit represented by H1 (which may be substituted with a substituent selected from the group consisting of 1 to 40 alkoxy groups, phenyl, substituted phenyl, and combinations thereof) - It is possible to form an anisotropic melting property by containing it in an amount of more than -. Completely aromatic rigid foam/j
Consisting of 7w-.

The kx of the present invention also has about 1 repeating unit containing a naphthalene structure.
A foam made of a completely aromatic hard foamed thermotropic liquid crystal 4 remer containing 0.07 Ru or more is heated by a heat section sufficient to raise the melting temperature of the remer by at least 10°C. % thermal, combustion and solvent stability, and exhibits lil' mechanical properties. - A method of manufacturing a foam is also provided.

The invention further provides about 1 repeating unit comprising a naphthalene structure.
It is present in an amount of 0 mole or more to raise the melting temperature of the polymer by at least about 1θ°C. I? It consists of a fully aromatic thermotropic liquid crystal 4-limer that has been previously heat treated at a time and temperature sufficient to . Foams are also provided that have excellent thermal, flammability and solvent stability and exhibit desirable mechanical properties.

Thermotropic liquid crystal F remers are I remers that are liquid crystalline (ie also anisotropic) in the melt phase. This kind of streamer has % liquid crystalline I1% liquid crystalline I and 1 anisotropic I
Various uses for Yr have been described from I1IK. To put it simply, this type of streamer! - It is considered to be a regular parallel array of butterfly molecular chains. Manufactured from monomers in which the molecules are arranged in this way, often in the form of liquid crystals or liquid monomers, usually with a plurality of chain extension bonds in either a coaxial or parallel relationship. be done.

Such polymers readily form liquid crystals (ie exhibit anisotropy) in the molten phase. Such properties can be confirmed by a conventional polarization test method using orthogonal polarizers. More specifically, the confirmation of the anisotropic melt phase I! teeth,
The 4rymer of the present invention is optically anisotropic, which can be carried out by observing a sample placed on an L-its hot stator under a nitrogen atmosphere at a magnification of 40 times using a Leitz polarizing microscope. That is, it transmits light when examined between orthogonal polarizers. If a sample is optically anisotropic, it will transmit polarized light even when it is at rest.

Thermotropic liquid crystal suitable for use in the present invention -9-
f- contains about 10 moles or more of repeating structural units containing a naphthalene moiety, such as %6-oxy-2-naphthoyl, 2°6-y oxynaphthalene, and 2,6-f/cal xynaphthalene, and is anisotropic. The fully aromatic I-resters and fully aromatic ester-amides used in the present invention are fully aromatic I-remers that are capable of forming a molten phase. 1 in the sense of adding at least one aromatic ring to the main chain
It is considered to be completely aromatic.

Examples of fully aromatic polyesters that can be used in the present invention and satisfy the above characteristics are disclosed in commonly assigned US Pat. No. 4,161.470:4,219,461 and 4.
, 256,624: and U.S. Patent Application No. 128.
759 (filing date March 10, 1980): 128.7
78 (March 1980): 169.014
(July 15, 1980) and 19°4,196
(October 6, 1980) K has been disclosed. Examples of fully aromatic esters (ester-amides) are disclosed in commonly assigned US patent application Ser. No. 214.557 (filed December 9, 1980). The fully aromatic esters disclosed therein and Isu (Ester-A2D) General #C are prepared at temperatures below about 400°C, preferably at about 350°C.
An anisotropic melt phase can be formed at very low temperatures.

The thermotropic liquid crystal f-remer of the present invention has at least one aromatic ring attached to the main chain of the %4-remer, and further includes another structural unit that allows the /9-mer to exhibit anisotropy in the melt phase. Examples of such units include units derived from aromatic 12-ols, aromatic amines, aromatic V-carboxylic acids, and aromatic hydroxy acids, as shown below. , but not limited to these).

The units can be present in various proportions. However, as mentioned above, the I remer contains as few as about 10 moles, preferably about 10 to 90 moles, and more preferably at least about 20 moles.

Fully aromatic compounds, including fully aromatic esters and esters, suitable for use in the present invention! - can be formed by a variety of ester-forming methods that can react two X-organic monomer compounds that have functional groups that form the required droplets by condensation.

For example, the functional group ir of these organic monomer compounds,
* k t > An acid group, a hydroxyl group, an ester group, an acyloxy group, an acid halide, an adenyl group, etc. may be used. In the above-mentioned organic compound lamp, it is possible to carry out the reaction without the presence of a heat exchange fluid, as compared to the melt acidolysis method. In this method, the monomers are heated together to form a molten solution of the reactants. As the reaction continues, the OI remer particles become cloudy in the liquid. Vacuum tubes may be applied to facilitate the removal of amphoteric substances (eg mineral water with vinegar) during the final stages of incubation.

U.S. Pat. No. 4,083,829 K, entitled "Melt Processable Thermotropic Fully Aromatic Polyesters," describes a slurry polymerization process that can also be employed to form the fully aromatic polyesters used in the present invention. . In this way, a solid product Ks is obtained in a cloudy state in the lamp heat exchange medium.

The melt acidolysis method described above and U.S. Pat. No. 4.083
. (ie, as a lower acyl ester). Preferably, the lower acyl group has a vertical prime number of about 2 to 4. Preferably, the acetate ester of such an organic monomer reactant is subjected to the reaction.

Sa acidolysis method or “U.S. Patent No. 4.0 & I, 8
Catalyst O which can be optionally used in any of the above slurry methods
Typical examples include dialkyltin oxide (e.g. dibutyltin oxide), V-aryltin oxide? ', mII
Gaseous forms such as antimony titanium oxide, alkoxytitanium silicates, titanium alkoxides, alkali and alkaline earth metals of carfonic acids (e.g., zinc acetate), Lewis II (e.g., BFs), hydrogen halodides (e.g., HCl) Examples include acid catalysts. The amount of catalyst used is generally a big deal! - based on the total amount of tnte about 0.001 to 1 fs% II
[#0.01 to 0.2 weight-.

Motoya Ij1#IC use (suitable fully aromatic/lj
Maha, tends to be virtually insoluble in common solvents;
Therefore, it is unsuitable for solution processing. However, as already mentioned, these remers can be readily processed by conventional 011 melt processing methods.

41K Preferred fully aromatic I remer Vi interfluoro
It is somewhat (eg, less than about 1 weight) soluble in phenol.

The fully aromatic/reesters suitable for use in the present invention generally have a weight average molecular weight of about 2,000 to 200,000.
, preferably about 10,000 to so,ooo.

Good IL for III# (is @20,000~25,000
It is.

On the other hand, suitable fully aromatic ester-amides generally have a molecular weight of about 5,000 to 50,000. Preferably F
i about 10,000 to 30,000, for example 15.00
0 to 17,000. Such molecular weight determinations can be made by standard 11J methods that do not involve solution formation of the polymer, as well as by delta-meation chromatography, such as by quantifying end groups by infrared spectroscopy on compression molded films. Can be implemented. It is also possible to make a pentafluorophenol solution and measure the molecular weight using light scattering.

The above fully aromatic esters and poly(esters)
Amide) Hamayu, Pentafluorophenol K at 60℃
O, 1 weight - When dissolved at a concentration of about 2
．． 0tu/f, 7t approximately 2.0-10.0al
The logarithmic viscosity C1,V,) of t is generally denoted.

4IK Preferred Fully Aromatic/17-mer U.S. Pat.
．． 161.470: 4,184,996 and also 2
56,624.

For the purposes of the present invention, the aromatic ring present in the main chain of the limmer component or at least a portion of the hydrogen atoms bonded to the aromatic ring may be substituted. , such substituents include alkyl groups having up to 4 carbon atoms, alkoxy groups having up to 4 carbon atoms, halodane, and other aromatic rings such as phenyl and substituted phenyl.

The foams of the present invention may be formed by any suitable conventional method such as extrusion, injection molding, etc. For example, a thermotropic fluid/remer pellet is mixed with a powdered blowing agent, and this mixture is extruded through a suitable orifice (e.g., a slit die) at a high temperature (e.g., the melting temperature of the remer). The foam tube can be formed by extrusion.

The foam decomposes at the extrusion temperature, creating a gas of nitrogen or carbon dioxide inside the extruded reamer melt, thereby forming a foam. Extruded foamed dF97-tube with forced air flow 1 as appropriate
Rapid cooling or cooling.

The extrusion device oms used is not particularly limited, and any OIf
You can use powerful equipment. Examples of suitable extrusion equipment, Joe
l Pradoa ed. “U.S. Plastic Engineering Togane Plastic Engineering Han F Tsuck” 4th edition, VanNostran
dRe1nhold Co, (1976),
156-203 pages.

liquid crystal? The temperature and pressure conditions under which the remer can be extruded are not limited to ti% in the method of the present invention (these conditions can be easily determined by cancer manufacturers). is about 250-350tC
)II! Within the range (/'Jmarf)jl temperature release RK, te)
o Temperature: approx. 100~5000psi, (7,0~35
01Q/ed).

The thermotropic liquid crystal polymers of the present invention generally have a temperature of about 0.1 to 0.75 f/j 011 degrees after foaming. Preferably, the density of such foamed reamer is about 0.
It is in the range of 3 to 0.75 f/j. In addition, the foamed thermoplastic liquid crystal I reamer of the present invention, the f
Depending on the reamer, it will be in the range of about 250-320°C.

By pressing the liquid crystal I and the liquid crystal I, a wide variety of structural articles can be formed. For example, a sheet can be formed by extrusion molding from the Shukusho I Remer T die. The "sheet" and line used here! ! Sheets, slabs, etc. in this technical field 4! It will be understood that this includes the various relatively thin, substantially #cxF-like structure panes that are sometimes referred to as "."

The liquid crystal I-remer can also be extruded from a suitable die to form a barrel or tube (eg, a delta tube).

The expanded liquid crystal polymers of the present invention can also be used to form molded structural articles, such as by screw set injection molding. Foaming agent and pelleted poly! The mixture with - is put into a squerier set injection type IiL type device O-hotsu/arm -. In this apparatus, the mixture is heated to a high temperature (beyond the melting temperature of the I9mer).

A suitable gold mK is injected, which is held at a temperature 6 degrees lower than the melting temperature of the polymer. The I-rimmer is then allowed to cool and released from the mold. The temperature and pressure conditions under which the liquid crystal 19 Y- can be formed are not specified, but can be determined by a person skilled in the art.

Preparation of the Foamed I Remer of the Invention Conventional high temperature blowing agents can be used. For example, suitable blowing agents include (but are not limited to) those commercially available under the following trade names: Expand@z S P↑(
5-7z = consists of lutoterazolka; sold at $t@pan
Ch@m1cal Co-), Fie@l THT(
Consisting of trihydrazine triazine
trialp Chemical), Celoge
n HT 550 (composed of hydrazone derivative; sold I
Jn1roy Todoroki ICh@m1cal) and Kem
tee 500 (Sold by gh@rwin-Wiilia
ms Chemical). A blowing agent like this is about 2
Decomposes at temperatures within the range 40-310°C.

Decomposition of blowing agents is temperature- and time-dependent.

It is important to match 1 degree of decomposition with 11 degrees of processing of bori i-. 4! - If the foaming agent decomposes before it is sufficiently melted, the cell structure will be poor.

1kll dissatisfied! There are jin and tun that give the appearance of men. The amount of blowing agent required generally ranges from about 0.1 to 100 ml by weight depending on the amount of gas produced by the blowing agent and the desired density reduction rate.
Become within. Preferably, the amount of blowing agent used is about 0.2 to 0.
．． It will be within the range of 5-weight.

In addition, if a suitable chemical blowing agent is selected, the foaming action can be controlled by controlling the temperature and/or the blowing pressure. Controlling the foaming action by temperature is more reliable than by pressure. Therefore, it is preferable to use a chemical agent.

It is also possible to form a foamed 4-eymer by blowing a suitable gas into the molten I-remer. However, it is extremely difficult to ensure a sufficient distribution tube for gas using such a method.

Foaming various fillers and reinforcements! - May be used to improve various properties of. For example, the foam can be reinforced using suitable reinforcing materials such as glass fibers. Such reinforcements generally have a weight of less than about 5 ts, preferably about 2 ts, based on the weight of the pond body.
Amounts of 0 to 50°C elevation may be used. In addition, IF4 departments,
*Positive fillers such as anti-oxidizing agents and nucleating agents may be added. General 1 to 4I of such fillers! The dose is about 0.2~
10 weight, good IL (within the range of about O,S to 2 weight).

The foams of the present invention exhibit excellent mechanical properties due to the orientation of the I-rimer molecules and the effects of heat treatment.

Specifically, this foam has a smaller directional anisotropy than an unfoamed reamer. Such foams with reduced directional anisotropy are self-reinforcing and have mechanical properties comparable to fiber-reinforced/V-mum materials. The orientation of the $17mer molecules around the bubble of the a-bubble is caused by the two-wheel extensional flow field of the expanding ZNfl during the foaming process. The rod-like portion of the liquid crystal f-remer can be easily oriented and oriented by the flow of such flow, and can be maintained in the biaxial orientation obtained.

As a result of this decrease in directional anisotropy, the vertical direction (MD
) The mechanical properties measured by K in the transverse direction (TD) (value per unit weight of the foam) are improved relative to the mechanical properties measured by K.

The 91OW pond body also exhibits high combustion and thermal stability and excellent ism and chemical resistance as a result of its ``button streamer'' properties. The polymer used in the foam of the present invention was 't, this!' The melting temperature 1 IC is high enough that the i-foam is more favorable than the hot zone IIK as described below (example, about 250'C or higher)! show. The foam of the present invention expands when heated to a sufficiently high temperature to enhance its flame resistance.

The mechanical properties of the foam produced according to the invention can be further improved by subjecting it to a forming IIK heat treatment. Netsubu l! #: The increase in the molecular weight of this liquid crystal 1ymer and the increase in its degree of agglomeration (and the simultaneous increase in the melting temperature of the 1ymer) improve the properties of the foam.

The heating of the foam m can be carried out in an inert atmosphere (eg nitrogen, carbon dioxide, argon, helium) or in a flowing oxygen-containing atmosphere (eg air). The use of a non-oxidizing atmosphere O is preferred to avoid possible thermal degradation. For example, the foam may be heated to a temperature approximately 10 to 30 DEG C. lower than the melting temperature of the liquid crystal remer (at this temperature, the temperature is up to 1 for the foam material). The heat treatment temperature is
Bori! -〇The melting temperature is preferably as high as possible within a range that does not exceed the melting temperature. As the melting temperature of the Kdle remer increases during heat treatment, it is preferable that the heat treatment temperature is gradually increased accordingly.

Heat treatment times generally range from a few minutes to several days (or more), such as from 0.5 to 200 hours or more. Preferably the hot section [1 is carried out for 1 to 48 hours, typically about 5 to 30 hours.

Generally, the heat treatment time varies depending on the heating temperature of 11K,
The higher the heat treatment temperature used, the shorter the treatment time. Therefore, the melting point is high? Since the remer can be applied to a tube with a higher heat treatment temperature without causing the remer to decompose, the heat treatment time can be shortened.

Heat section 11it, /! The melting temperature of J-mer is at least 10
Preferably, the reaction is carried out under conditions sufficient to raise the temperature by .degree. As a result of heat treatment, the melting temperature of the foamed liquid crystal glitter is approximately 2
It is preferable for 41 to increase the temperature by 0 to 50°C. The upper and outer range of the obtained melting temperature depends on the temperature at which the hot part NK is used, and the higher the heat treatment temperature, the larger the range of increase. In this regard, it is stated herein that the I-reamer is capable of exhibiting anisotropy in the molten phase below the temperature at which the I-reamer is said to exhibit such properties at temperatures below that temperature before its heat treatment. Please note that the meaning is

The molecular weight of iyw- and its melting point a increase when unfoamed liquid crystal I remer is heated, but? It has been found that pigeonholes in which the remer has been foamed prior to such heat treatment have a greater degree of melting and greater increase in molecular weight of the I remer.

Such an increase is evidenced by the higher melting temperature of 6 parts of the foam. The basic #C is composed of a skin layer and 6 parts, and the skin layer of the foam has a density that is higher than that of the wick of the foam.It is thin%/h! m (eg, several nm thick), the 6 parts occupy substantially the entire volume of the foam (excluding skin*t).

It is less dense than the epidermal layer. The skin layer is a result of the extrusion or injection molding process, such as the effects of foam-remer flow/mother turn and shear forces. I! The thickness of the skin layer is also related to the cooling rate and injection speed; the higher the cooling rate and the lower the injection molding speed, the thicker the skin layer will be formed.

Foamed liquid crystal I reamer of the present invention, higher local orientation
It is believed that the surrounding bubbles are busy, which promotes further polymerization reaction of the chain terminals.

Also, by-products of such reactions diffuse more easily through the foam and are removed.

Furthermore, this enhanced polymerization reaction leads to the formation of a foamed overlying mer that exhibits better balanced mechanical properties (i.e., the difference between longitudinal and transverse tensile strengths is reduced). In fact, the resulting foam has a relatively higher lateral strength.

The chemical resistance also increases with heat treatment, and the solubility in pentafluorophenol, which is one of the rare solvents that can dissolve thermotropic liquid crystal f-rimers, continues to decrease as the electrothermal treatment time increases, until the foamed material minimum(
It becomes impossible to dissolve even in an amount equivalent to 0.1 weight of rice cake.

Therefore, when we refer to dissolution of thermotropic liquid crystal limmer herein, we mean such dissolution prior to heat treatment of the foam.

The developed Wi4 will be further explained using the following examples.

However, the examples should be considered as illustrations of the present invention, and the present invention is not limited to these specific examples.

Example 1 40 moles of p-oxybenzoyl units and 6-oxy-2
- Consists of 60% naphthoyl units and has a logarithmic viscosity of 6
．． Ot) Nermotropic liquid crystal polymer pellets,
10 weight glass fibers and various amounts of powdered E
Mix with xpandex 5-FT blowing agent and at a temperature of 280°C! A test piece is formed by injection molding in a mold at 2t°C. Various specimens produced by this molding method are tested to determine their tensile, bending and impact properties. The tensile Wk characteristics are American standard test mA8TM D638
, bending properties are A8TM D79G, impact properties are FiAsT.
MD2561C therefore performs a constant. Samples 1-5
Samples 6 to 10 were formed using molds with different wear dimensions, which clearly accounts for the different density reduction rates obtained for these two samples. The test results are shown in Tables 1 and 1!2 below.

Table 1 1 None G foaming) 1.51 23.1 3.
21 1.492 0.2 1.18 18.
0 2.64 1.253 0.5 1.16 1
5-0 1.80 1.254 1.0 1.20
17.5 2.34 1.275 2.0 1.1
7 16.0 1.98 1.2511g2 Table 6 μ unreleased/II) 1.51 29.1
1.52 2.037 0.2 1.41 2
3.4 1.16 1.718 0.5 1.
37 23.2 1.19 1.269
1.0 1.37 22.1 1.1
9 1.081G 2.0 1.36
22.5 1.20 1.08 As shown by the results of Example 1, the foamed fully aromatic monotropic liquid crystal/rimer structure of the present invention has a significantly lower density. However, the tensile, tensile and impact properties of the structure made of this foamed I reamer are still sufficiently high to enable good results to be obtained using it.

Practical example 2 6-oxy-2-naphthoyl unit 25-t-lura and p-
A pellet of thermotropic liquid crystal I remer, consisting of 75 moles of oxybenzoyl units and having a logarithmic viscosity of 9.9, was powdered with 0.2% by weight of @mt@c 500 blowing agent and 1.0% by weight of Merck. (nucleating agent). This mixture is extruded at 307 DEG C. through a 10.15 mm x 1.65 mm sheet die and wound at 0.37 m/mm. Use a static mixer immediately before extruding the mixture from the die to ensure uniform mixing of blowing agent and melt.

Cut the test piece from the pressed and ejected foam sheet, and then pull it!
I properties are tested to ASTM D638, Type V [LL$] to measure both longitudinal (MD') and transverse (TD) directions. An unfoamed sheet of the same dimensions made from the same foamer and manufactured by the same method was also tested, and the results were as follows. ! Force t - constant. The average density of the foamed sheet is 0.77 f/W, while the average density of the unfoamed sheet is 1.4 f/Cr.

It is. 5 for each foamed and unfoamed sample.
The tensile properties of each test piece are added by S and the average value is determined to obtain the various values shown in Table 113 and Table 4 below.

Table 3 $14!1 5.00” 2.28 0.398 4.65
6.49 0.261L33b2.2B 0.743
8.68 6.49 0.487 (Note) a Uncorrected value of extruded product b Density 14 Value after correction to f/α (i.e., average density of unfoamed sample) Example 2 The mechanical property (per foam weight) K measured in the vertical direction (MD) is different from the lateral direction (
TD) has been demonstrated to exhibit relatively improved mechanical properties. For example, 1liI after density reduction correction
t- Looks like consistent foaming in the lateral direction? The tensile strength of the reamer is substantially comparable to the corresponding 11 [K] of the unfoamed sheet.
8.68 vs. to, so), while the initial modulus exceeds the corresponding plating of the unfoamed sheet (
0.487 vs. 0.420).

In addition, the amount by which the tensile properties (TD) decreases from the tensile properties (MD) (i.e., the difference in the IIIJ values between the two) is smaller for the foamed remer than for the corresponding tensile properties of the unfoamed remer. It has become. That is, as a result of foaming, the foam reamer's tensile properties are reduced, but in reality, as a result of foaming, the strength in the transverse direction (TD) is relatively higher than that in the longitudinal direction (MD). In fact, the tensile properties are much more multidimensional (i.e., exhibiting a more balanced anisotropy), so that this O-foamed 4-rimer can be used in applications where multidirectional tensile strength is desired.

Example 3 p-oxybenzoyl single fff60 mol% s 2 @
It consists of 20 moles of s-V oxynaphthoyl units and 20 moles of terephthaloyl units, and has a logarithmic viscosity of 5.41.
2)? -4) Robic liquid crystal lrimer pellets, 30
Several pieces of foamed and unfoamed sheet material were obtained by extrusion from a 4 inch (10ag) K11lion tube at 0°C. Foam sample production was performed using Fiel TIT powdered blowing agent (0.1% by weight) mixed with 0.1% by weight of mineral oil.
5% by weight) 1, and by gluing the pellet 1/Cf14 before extrusion. The density of the unfoamed sample is 1.4 f/(X) as the average value of five samples.The density of the foamed sample is reduced to 0.58 f/x, which is a density reduction rate of 59
Corresponds to %. The degree of difficulty in melting is 295°C for all samples.

A portion of the sample is heat treated at 280° C. for 24 hours and then at 310° C. for an additional 24 hours. According to this, the strict answer 11f is 34
Increases by 1'cK.

All samples were tested on Mu8TM D638, type vK therefore extrusion II (i.e. before heat treatment) and after hot section 11, and their tensile properties were determined vertically (MD) and transversely ('1'D).
) in both directions. This test result will be
It is shown in Table and Table 6.

Table 5 (Atsuji j! Button 1161! 7m 1g, 3 1.59 1.80
11.6 2.45 1.07 (Note) Samples 7a and 8a represent K-corrected samples 7 and 8 with a density of 1.4 f/ff: (ie, unfoamed sample 011 degrees).

As the results of Example 30 demonstrate, heat treatment of this thermotropic liquid crystal reamer foam yields clear advantages.

Specifically, the tensile strength, elongation, and initial modulus 2,2 of the foamed I remer all significantly increased as a result of heat treatment.

The results of Example 3 also show that the heat-treated foam of the present invention has mechanical properties (per weight of foam) K measured in the transverse direction (TD) K It also shows relatively high mechanical properties. For example, when looking at the value after density reduction is corrected, the tensile strength (TD) of the foamed I remer exceeds the tensile strength (TD) of the unfoamed I remer. More importantly, the unfoamed foamer shows only a slight increase in tensile strength (TD) upon heat treatment.

When foamed 19 Y- is heat treated, it shows a sharp increase in tensile strength (TD) of -65-. From these results, the heat-treated foamed 4-rimer can still provide desirable tensile properties in both the vertical and transverse directions;
It is very suitable for structural applications that require light weight.

Example 4 Thermotropic liquid of Example 3 + IIP9-r-tO,
Mix with 2 parts by weight of a blowing agent (Kemtee 500) and 1 part by weight of the inorganic filler wollastonite (nucleating agent). This mixture is screw-extruded through a sheet die to form both foamed and unfoamed sheet samples. The Shodosha fact of the foam sample is 0.61. Heat treat a portion of the sample tube at a temperature set to rise continuously. Specifically, the sample was dried at 130°C for 12 hours, and the temperature was raised to 260°C (over 4 hours), and then to 310°C over 20 hours. The melting behavior is determined by scanning differential calorimetry on the extrudates (before heat treatment) and on the heat treated products.

O melting peak before heat treatment is % of unfoamed sample and foamed sample.
Regarding the /-h deviation, both the IIIFJj layer and the 6th part are the 7th epidermal layer 330°C 328°C Core II 321U 327°C A significant advantage is shown by the data in Table WE7 in Example 4. Effect of heat treatment J! depends on molecular orientation, ie, the greater the orientation, the greater the effect. As shown in Table 7, the increase in melting temperature of 6 parts after hot section N by 11 degrees was greater for the foamed product than for the unfoamed product. This indicates that the orientation of the foam is quite uniform throughout the cross section Kb, and the degree of orientation is very high, very close to the degree of orientation of the unfoamed skin.

Unfoamed-+Jj-(DI!1ffijit!, qmz
The rise in the melting peak of the foamed skin layer is lower than that of the lee+ro skin layer, but the rise in the melting peak of the foamed skin layer is also lower because the volume of the skin layer is relatively smaller than the total volume of the foam. Since it only occupies a small portion, it is not a disadvantage.

Example 5 Thermotrubic liquid crystal I remer pellets containing 75 moles of p-oxybenzoyl units and 25 moles of 6-oxy-2-toyl units and a logarithmic viscosity of 9.9 were prepared.
4 inches (10aI) from 1111m to 93
--Extrusion to obtain both 1-foamed and unfoamed O sheet samples. The production of foamed samples was carried out using Celog as the blowing agent.
enHT 550 (0,1 weight S) and @mt
ee 500 (0, double [use 1.

If you mix this with the pellets from the IB building, it will work just fine.

All samples (foamed and unfoamed) exhibit a degree of melting of 30111:.

Both foamed and unfoamed samples are subjected to thermal J6 processing.

The treatment is warm! lj from 130℃ to 260℃
This is done by increasing the temperature to 310° C. for 11 hours. Foamed and unfoamed O for each sample! ! By keeping the melting temperature of the cortical layer and 6 parts constant, the results shown in Table 8 of the 9th order are obtained.

II8 Table 1 (unfoamed) 334℃ 332℃2 (unfoamed) 338℃ 334℃3 (foamed)'
342℃ 342℃4 (foaming) b34
Celogen HT at 1°C 338°C (la 0.1 wt-°)
560: Foam density = 0.52 f/cd b Kamtee with 0.2 weight mass 500: Foam density = 0.75 f/al As already pointed out in Example 4, the thermal processing of the foam sheet The melting temperature of 6 parts can be increased significantly over the melting temperature of 6 parts of the unfoamed sheet, indicating that the foamed polymer may be more amenable to heat treatment than the unfoamed I reamer.

More books! Although the principles, preferred embodiments, and practical application methods have been described, these are not intended to be limiting, and are merely
For illustrative purposes only, the present invention should not be construed as limited to the particular embodiments disclosed above. Modifications within the scope of the invention may be made by those skilled in the art.

Claims (1)

[Claims] The following repeating structural unit: (However, at least a portion of the hydrogen atoms present may optionally be an alkyl group with a base number of 1 to 4, or a carbon 1!
The alkoxy group of numbers 1 to 4, phenyl, substituted phenyl, and a substituent selected from the group consisting of zero or combinations of these (1) to #1O mole or more It consists of a completely aromatic rigid foam I remer that can form an anisotropic melt phase, and has excellent thermal stability, flame resistance and solvent resistance, and exhibits better mechanical properties such as 114 strength. Se←噌4y4-rimer foam. (2) The scissors fully aromatic I remer exhibits a logarithmic viscosity of at least 2.0 #/f when dissolved in pentafluorophenol at 60°C with a weight-tolerance of 0.1 The foam according to item 1. (3) A patent claim in which the fully aromatic/IJ mer exhibits a log viscosity of about 2.0-10.0 m/f when dissolved in 0.1 wt. The foam according to item 2. (Claim 1) The foam according to J#IC, wherein the 47# fully aromatic zymer is capable of forming an anisotropic melt phase at a temperature lower than about 400°C. The foam of claim 1, wherein the foam is present in an amount of at least about 20 moltiO. (6) The density of the wrinkled foam is approximately 0.1 to 1.0 t/-
The foam according to claim 1. ff)# The foam of claim 6, wherein the foam has a density of about 0.3 to 0.7 f/-. (8) The foam of claim S, wherein the wrinkled fully aromatic remer is selected from the group consisting of fully aromatic I-liesters and fully aromatic esters. (9) The foam according to claim 8, wherein the #/rimer is a fully aromatic ester. The fully aromatic ester is essentially the following repeating structural units (1) and (1): (However, at least some of the hydrogen atoms bonded to the ring F!, optionally an alkyl group having 1 to 4 carbon atoms, (optionally substituted with a substituent selected from carbon J11-40 alkoxy group, hexyl, phenyl, substituted 7-yl, and combinations thereof), and units! Claim 9 consisting of a melt-processable fully aromatic I-liester capable of forming an anisotropic melt phase, containing about 10 to 90 moles of the unit and about 10-10 moles of the unit
Foams as described in Section. αυ #I The standard It with about 65 to 85 moles of real ester
11. The foam according to claim 10, which comprises: 63#/reester contains about 15 to 35 mol-〇 units! The foam according to item 10. αJ The fully aromatic/lyester is essentially the following repeating structural unit 1; ■, square and V: square General formula -E-0-Ar-0- Dioxyaryl units represented by 0 (meaning a divalent group containing at least one aromatic ring), dioxyaryl units represented by 0 (meaning a divalent group containing at least one aromatic ring), At least a part of the hydrogen atoms present may optionally be an alkyl group having 1 to 4 carbon atoms,
~4 alkoxy groups, optionally substituted with a substituent selected from the group consisting of 10rn, phenyl, substituted phenyl and combinations thereof, and the basic I
About 20 le 40 or less. more than 5 moles g6 and less than about 30 moles, and more than 5 moles,
A melt processable fully aromatic compound capable of forming an anisotropic melt phase containing an amount of about 30 moles or less? A foam according to claim OfliWAme consisting of a polyester. Axis: Approximately 20 to 30 moles of the f-reester - 〇 Monodouji! , about 25 to 40 moles - 〇, unit! , about 15-25 mol 9IO
14. The foam according to claim 13, which contains carbon dioxide and about 15 to 25 moles of carbon dioxide. (c) The fully aromatic ester essentially consists of the following repeating structural units 1.1 and 1: 厘 general formula +0-mu r-0- (wherein Ar is 2 containing at least one aromatic ring) (meaning a valence group)
dioxyaryl unit, containing at least one aromatic ring 2
(meaning a valence group), (however, at least a part of the hydrogen atoms bonded to the ring may optionally be an alkyl group having 1 to 4 carbon atoms, a 1 to 4 carbon alkyl group,
~4 alkoxy groups, halodane, phenyl, substituted phenyl, and combinations thereof, optionally substituted with a dead substituent), and at the fist position It
- a melt-processable fully aromatic composition capable of forming an anisotropic melt phase containing about 5 to 45 moles of unit 1 and about 5 to 45 moles of unit layer. Claim 9 (Go foam) consisting of Group J9 esters.
16. The foam of claim 15, wherein the foam comprises about 10 to 40 moles of sO units, and about 15 to 25 moles of sO units. aTS skeleton fully aromatic I-reester is essentially the following repeating structural unit! and I: (However, in the above unit, at least a part of the hydrogen atoms bonded to the aromatic ring may be substituted. In that case, this arbitrary substituent line is an alkyl group having 1 to 4 carbon atoms, 1 to 4 carbon atoms, 4 alkoxy group, halogeno, phenyl,
Substituted phenyl and combinations thereof) and having about 10 to 90 molar units of unit I and about 1 to 90 molar units of it The foam according to item 9. 18. The foam of claim 17, wherein the special ester comprises a layer of about 50 to 80 molar units (2) and about 20 to 50 molar units. a9# The fully aromatic I-reester consists essentially of the following repeating structural units 1, 1.1 and N: may be selected from the group consisting of luci and combinations thereof: karana 9;
and about 5 to 70 moles of the unit Itt, about 5 to 70 moles of the unit Itt10 to 45 mole-1
10. The foam of claim 9 comprising a melt processable fully aromatic I-lyester capable of forming an anisotropic melt phase and containing W units in an amount of about 10 to 45 moles. Claim 19: ■ The #bori ester contains about 15 to 25 moles of units I, about 25 to 35 moles of units, about 20 to 30 units, and about 20 to 30 Wt. Note @0 foam. Qυ The I remer essentially consists of the following repeating structural units 1, 1
．． 1 and optionally W: ) means a divalent group containing a l1IO aromatic ring)
, Otori +Ymu r-Z+ (where Ar is at least ll
10 Divalent group containing an aromatic ring, Y is 0, NH or HNR
1Z means NH''t or NR, respectively, R means an alkyl group having 1 to 6 carbon atoms or an aryl group)
% W (-0-Ar'-0÷ (wherein, Ar' means a divalent group containing at least one aromatic ring), (however, at least -m of the IIIK-bonded hydrogen atoms is
Optionally, an alkyl group having a vertical prime number of 1 to 4, a carbon number of 1 to 4
(which may be polysubstituted with a substituent selected from the group consisting of an alkoxy group, arn, phenyl, substituted phenyl, and combinations thereof), and the unit
0 to 90 mol - 1 unit layer is about 5 to 457 ru, unit layer is about 5 to 45 mol 9! , and the unit (■) in a molar content of about 0 to 40 molar O. The foam according to claim 1, comprising an anisotropic melt-phase tube-formable fully aromatic foam (Ester-Ken P) containing units (2) in an amount of about 0 to 40 molar O. - Contains repeating units containing a naphthalene structure in an amount of about 10% or more, and O11! The melting temperature of the remer should be at least M1 at a low temperature.
Excellent thermal stability, flame resistance and solvent resistance, consisting of a fully aromatic rigid foamed I remer capable of forming an anisotropic melt phase, previously heat treated for a time sufficient to raise the temperature by 0°C; Thermotropic liquid crystal-rimer foam exhibiting desirable mechanical properties such as high strength. (to) The fully aromatic I remer is dissolved in pentafluorophenol at 60°C by 0.1 wt.
It claims a logarithmic viscosity of at least 2.0 #/f when dissolved at #1 degree! ! N. The foam according to item 22. Q4 The naphthalene-containing units of the fully aromatic/limer are selected from the group consisting of 6-oxy-2-naphthoyl units, 2°612 oxynaphthalene units, and 2.6-y calxinaphthalene units. Range 2nd
The foam according to item 2. @ Mukuro fully aromatic mercury is lower than about 400℃ before heat treatment IIt! Ki? Claims that can form an anisotropic melt phase when l1lf
The foam described in item zz. @ The fully aromatic/9-mer is essentially the following anti-II structural unit I, Alkyl group % leg prime number of 4 1
Substitution selected from the group consisting of ~40 alkoxy groups, ^ro'-r>, phenyl, t*phenyl, and combinations thereof! consisting of a melt-processable fully aromatic ester capable of forming an anisotropic melt phase, containing about 30 to 70 moles of the unit (GK) (optionally substituted) The foam according to claim 22. 27. The foam of claim 26, wherein the I-reester comprises about 40 to 60 moles of units I, and about 2 to 30 to 30 moles of units. (To) Wrinkled fully aromatic polymers have an essentially Argentine repeating structure in positions ■ and I: (However, at least a part of the hydrogen atoms bonded to the ring may optionally be JP. Carbon number 1 to 4 (optionally substituted with a substituent selected from the group consisting of an alkyl group having 1 to 4 vertical prime numbers, an alkoxy group having 1 to 4 vertical primes, a halodane, a) EL, a substituted 7 EL, and a combination thereof), and the unit
Claim 22 comprises a melt-processable fully aromatic ester capable of forming an anisotropic melt phase, containing from about 10 to 90 7 l*, 10 to 90 mol units of units. Memo @ 0 body. @ Claims r where the #bori ester contains about 65 to 85 moles - 1! ! i. The foam according to item 28. 1 according to claim 28, wherein the ester contains about 15 to 35 moles of I.
1 pond body. 0υ Fully aromatic 19-mer is essentially the following repeating structural unit 1.1 and rin: ■ General formula 10-m r-o+<where Arts is a divalent group containing at least 41 aromatic rings. A dioxyaryl unit represented by (meaning a divalent group containing at least one aromatic ring) a dioxyaryl unit represented by (meaning a divalent group containing at least one aromatic ring); moiety, optionally an alkyl group having 1 to 4 carbon atoms, 1 carbon number
~4 alkoxy groups, phenyl, substituted phenyl, and combinations thereof. About 5 to 45 moles of 1 unit I,
and containing monofEkl in an amount of about 5 to 45 mol-〇,
23. A foam according to claim 22, comprising a melt processable fully aromatic/lyester capable of forming an anisotropic melt phase. (To) Wrinkles? Approximately 20 to 80 moles of realester - 〇 units 1.
A foam disposed in claim 31 comprising a unit layer of about 10 to 40 molar units and a unit layer of about 10 to 40 molar units. @ Scissors Fully aromatic-limer essentially consists of the following structural units 1, 1. Dioxyaryl unit represented by the general formula ÷0-mr-0- (wherein Ar means a divalent group containing at least one aromatic ring), at least %1 containing 2 aromatic rings
(meaning individual groups) is a xaryl unit, (however, at least some of the hydrogen atoms bonded to the ring may optionally be an alkyl group having 1 to 4 carbon atoms, carbon a
x to 4 alkoxy groups, halodane, phenyl, substituted phenyl, and combinations thereof, consisting of %A) and containing about 20 to 40 moles of units qI1. , unit 1tlOsolq
More than IIt-, less than about SO+Le, unit layer t5 mol 96
more than about 30 moles or less, and the unit y is 5 moles St.
The foam according to claim 22, comprising a melt processable fully aromatic/9 ester capable of forming an anisotropic melt phase, containing O in an amount of more than about 30 moles or less. N 1m, 1! Claim I wherein the ester contains about 20 to 30 mol units, about 25 to 40 mol units, about 15 to 25 mol units, and about 15 to 25 mol units! The foam according to item 33. II A fully aromatic 4-rimer, essentially the following repeating structural units i, i, and optionally Iv: means a divalent group containing one aromatic ring), Y-Ar- Z÷ (in the formula,
Ar is a divalent group containing at least 1110 aromatic rings, Y is 0
, NH or N1%2 means NH or NR, respectively, R means an alkyl group having 1 to 6 carbon atoms or an aryl group), ■ +O-Mr'-0-) (Formula Ar' means a divalent group containing at least one aromatic 1111), (however, at least -mm of hydrogen atoms bonded to the ring, optionally an alkyl group having 1 to 4 carbon atoms, carbon [by a substituent selected from alkoxy groups of numbers 1 to 4, halogeno, phenyl, substituted phenyl, and combinations thereof]
(may be substituted) to 1, and the unit ■ is approximately 1
It is possible to form an anisotropic melt phase containing 0 to 90 moles of units, about 5 to 45 moles of units, about 0 to 40 moles of units, and about 0 to 40 moles of units. The foam according to claim 22, comprising a melt-processable fully aromatic poly(ester-amide). C31# foam? The melting temperature of the remer is approximately 20-50℃.
23. The foam of claim 22, which has been previously heat treated for a time and temperature sufficient to increase the temperature. A foam according to Range 1136. @ The foam according to claim 36, wherein the silver plating treatment time is about 0.5 to 200 hours. (to) The foam according to claim 38, wherein the silver plating treatment time is about 1 to 48 hours. - A patent claim in which the wrinkle heat treatment time is about 5 to 30 hours.
The foam according to item 39. -ρ W of the skeleton body! degree is approximately 0.1~0.75 t/-
The O battery as claimed in claim 22. - I as described in claim 22, wherein the silver plating treatment is carried out in a non-oxidizing atmosphere! O foam. Sir Patent Claim 01 in which the silver plating treatment is performed in a nitrogen atmosphere
11! 1. The foam according to item 42. - containing about 10 moles or more of repeating units containing naphthalene structures to form a fully aromatic rigid foam polymer capable of anisotropic melt phase tube formation, the foam being formed at a temperature below the melting temperature of the polymer. heat treatment for a time sufficient to raise the melting temperature of the polymer by at least 10°C. Excellent thermal stability, flame resistance, and solvent resistance, high strength, etc. A method for producing a thermotropic liquid crystal four-limer foam exhibiting poor mechanical properties. A patent claim that shows a logarithmic viscosity of at least 2.0a7t when dissolved in interfluorophenol at 60°C at 0.1wt-11f before being subjected to 1lt- of skeleton heat treatment. Scope O method described in item 44. - the fully aromatic zyY-O1m naphthalene-containing unit is 6
-oxy-2-naphthoyl units, 2,6-V oxynaphthalene units and 2,6-zocal is xinaphthalene units. 45. The method of claim 44, wherein the fully aromatic/limer is capable of forming an anisotropic molten phase at temperatures as low as about 400 DEG C. before being subjected to silver plating. - the fully aromatic I remer is essentially based on the following repeating structure 1. Alkyl 1, carbon number x
-4 alkoxy groups, halogens, phenyl, substituted phenyls, and combinations thereof), and the unit I in an amount of about 30 to 70 molar 111144. The method of claim 111144, comprising a melt-processable fully aromatic dF-reester capable of forming anisotropic melt interphases. n about 40 to 60 mol of the 4-lyester unit layer;
about 20 to 30 molar units of Units I and about 20 molar units. The t4# fully aromatic-rimer has essentially the following repeating structure I
# position l and square: (However, at least a part of the hydrogen atoms bonded to the ring may optionally be an alkyl group having 1 to 4 carbon atoms, a carbon number 1
~4 alkoxy groups (optionally substituted with a substituent selected from the group consisting of phenyl, substituted phenyl, and combinations thereof), and a nest position t
Claim 4 consisting of a melt processable fully aromatic/IJ ester capable of forming an anisotropic melt phase containing from about 10 to about 90 mole 1 single position in an amount of about 40 to 60 mole
The method described in Section 4. 6 phantom A unit of about 65 to 55 moles of the 4-lyester
- A method according to claim 50, comprising: (To) Unit 1 with about 1'5 to 35 moles of Mukuro f-rester
51. The method of claim 50, wherein the method is a tortoise comprising: - The fully aromatic group i- is essentially the following repeating structural units (1), (2) and the square: (2) General formula ÷0-mu r-0± (wherein, a divalent compound containing at least one aromatic ring at the Ar position) a dioxyaryl unit represented by 1k (both mean a divalent group containing one aromatic ring), a V car-xaryl unit represented by 1k (both mean a divalent group containing one aromatic ring), (optionally), alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, halogens, phenyl, substituted phenyls, and combinations thereof. and containing about 10 to 90 moles of unit I, about 5 to 45 moles of the unit layer, and about 5 to 45 moles of the unit layer,
45. The method of claim 44, comprising a melt processable fully aromatic I-liester capable of forming an anisotropic melt phase. (mouth) The I-lyester is about 20 to 80 moles or more! ,
54. The method of claim 53, comprising about l[theta] to 40 molar units and about l[theta] to 40 molar units. (To) The fully aromatic 4y-mer is essentially the following repeating structural unit! ，! , I and P/: 厘 Dioxyaryl unit represented by the general formula 0-Mr~0÷ (wherein MrF! means a divalent group containing at least one aromatic ring), 0 0 but not (also means a divalent group containing an aromatic ring) is a xaryl unit, (provided that at least -* of the hydrogen atoms bonded to the ring)
h, case p, alkyl group having 1 to 4 carbon atoms, carbon &1
~4 alkoxy groups, phenyl, substituted phenyl, and combinations thereof may be substituted with a substituent that has been retired from A), and the unit ■
about 20 to 40 moles, the unit layer is more than 7 moles and less than about 50 moles, the unit layer is more than 5 moles and less than about 30 moles, and the unit WtS moles is more than 30 moles - Claims consisting of a melt-processable fully aromatic ester capable of forming an anisotropic melt phase, containing in the following amounts:
11144. The method according to paragraph 11144. @1Ik11! 920 to 30 moles of lyester - 〇Dangayaxia, approx.! 5-40'! - Ru 〇 unit seal, about 15 to 25 moles - 〇 * ㎘ and about! 56. The method according to claim 55, which contains 5 to 25 moles of units of WYr. 6η The fully aromatic I remer essentially consists of the following repeating structural units I, I, III and in the case 9■: "means a divalent group containing one aromatic ring" +Y-Mr-Z ÷(
In the formula, mrtl is a 2 radical containing at least 1110 aromatic rings, YaO, ME or aNR, Z#-! NH't7' means NR1 and R means an alkyl group having 1 to 6 carbon atoms or an alkyl group), V ÷ 0-mubee〇+ (wherein, mubi is (means a divalent group containing at least one aromatic ring), (provided that at least some of the hydrogen atoms bonded to the ring are substituted with an alkyl group having 1 to 4 carbon atoms) (may be substituted), and the unit 1 is about 5 to 45 7 ru, the unit type is about 5 to 45 7 ru, and the unit layer is about 5 to 45%.
45. The method according to claim 44, comprising a melt-processable fully aromatic ester (ester-amide) capable of forming an anisotropic melt phase, containing an amount of units yt#o to 40 moles. @ Melting temperature FILt of scissor body f, I lima - about 20~
45. The method of claim 44, heat treating for a time and at a temperature sufficient to increase the temperature by 50<0>C. ■ The heat treatment temperature is approximately 10 to 3 liters lower than the melting temperature of I remer.
56. The O method according to claim 55, wherein the O1i degree is within the 0°C low-range. - The method of claim 1, wherein the heat treatment time is about 0.5 to 200 hours. 61. The method of claim 60, wherein the heat treatment time is about 1 to 48 hours. - Claim S, wherein the heat treatment time is about 5 to 30 hours.
O method described in paragraph 61. 45. The method of claim 44, wherein the foam has a density of about 0.1 to 0.75 F/-. (Incorporated) The method according to claim S, wherein the heat treatment is performed in a non-oxidizing atmosphere. I! 65. The method according to claim 64, wherein the 9# heat treatment is performed in a nitrogen atmosphere.