CN112920578A - Composite material and preparation method thereof - Google Patents

Composite material and preparation method thereof Download PDF

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Publication number
CN112920578A
CN112920578A CN202110148436.5A CN202110148436A CN112920578A CN 112920578 A CN112920578 A CN 112920578A CN 202110148436 A CN202110148436 A CN 202110148436A CN 112920578 A CN112920578 A CN 112920578A
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liquid crystal
polyimide
composite material
compatibilizer
crystal polymer
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CN112920578B (en
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陈志钊
徐俊
鲁纬
马文珍
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Guangdong Huazhixin Electronic Technology Co ltd
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Guangdong Huazhixin Electronic Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Abstract

The composite material and the preparation method thereof are composed of the following raw materials in parts by weight: (1)40-90 wt% of liquid crystal polymer; (2)9-60 wt% of polyimide; (3)0.5-5 wt% of a compatibilizer; the preparation method comprises the following steps: (a) and (4) preprocessing; (b) mixing; (c) mixing and extruding; according to the composite material, the polyimide and the compatibilizer react with the liquid crystal polymer to obtain the copolymer, so that the time for the chain segment of the copolymer to enter the hole on the metal surface is increased, the crystallization speed is delayed, the perfect combination of the composite material and the metal surface of an electrical element is ensured, the good air tightness is ensured, the air leakage condition is avoided, the liquid crystal polymer and the polyimide are connected and polymerized through the compatibilizer, and the heat resistance and the waterproof performance of the liquid crystal polymer and the polyimide are kept.

Description

Composite material and preparation method thereof
[ technical field ] A method for producing a semiconductor device
The invention relates to the field of liquid crystal polyester and polyimide composite materials, in particular to a composite material and a preparation method thereof.
[ background of the invention ]
Air cavity packages are widely used and are a chip packaging system consisting of a heat sink base, a lead frame and a cover. After the chip and wire are bonded to the base, the cover is covered over to provide environmental and mechanical protection for the chip and wire bond without contacting any of these components. Historically, ceramics or metals have been used for the base and cover, and thermoplastics generally do not have sufficient moisture barrier properties to achieve hermeticity.
Recently, a new thermoplastic named Liquid Crystal Polymer (LCP) has been introduced, which has excellent moisture resistance. The main reason for driving this alternative over the past few years is that the use of molded LCP's is much cheaper than ceramic or metal sealed packages.
Sealing electrical ports in LCP packages has long been a technical challenge. Although molded LCP has excellent moisture resistance, the gaps between the LCP and leads are prone to air leakage, mainly due to poor adhesion between the LCP and the metal. LCP is chemically inert, which is desirable in many applications, but it prevents good adhesion to other materials. Attempts have been made to injection mold LCP on metal pins, such as lead frames comprising a pair of spaced parallel bus bars with intermediate components connected by leads much like the rungs of a ladder. The LCP forming operation of RJR Polymer uses proprietary methods to seal the lead frame, however, it involves placing a small amount of epoxy on the frame during the molding process. A strong metal to LCP bond is formed. With increasing time and temperature, the epoxy becomes a pathway for moisture ingress.
Another common method for improving the air tightness between plastic and metal parts is to roughen the metal surface and then perform injection molding, so that the plastic enters the pores formed by roughening the metal surface, and the concave-convex metal surface and the plastic are combined in a staggered and interlocked manner, thereby improving the air tightness. For example, patent CN101743111 relates to a method for performing fine roughening treatment on the surface of a steel material, and then injecting resin to form interlocking bonding by the resin penetrating into the rough positions, thereby greatly improving the bonding force between the resin and the metal, but the method has a limited range of applicable resins and is only applicable to two resin types, namely polyphenylene sulfide resin and butylene terephthalate resin. This method presents great difficulties when applied to LCP's because LCP's have a fast crystallization rate and crystallize during injection without penetrating into the pores of the roughened surface of the metal, and tight bonding is not achieved.
[ summary of the invention ]
The invention aims to solve the problems, provides a composite material and a preparation method thereof, and solves the problems that the existing composite material has insufficient bonding strength with the metal surface, too high crystallization speed and cannot enter the metal surface micro-pores, and the production period is long.
In order to achieve the purpose, the invention adopts the following technical scheme:
the composite material comprises the following raw materials in parts by weight:
(1)40-90 wt% of liquid crystal polymer;
(2)9-60 wt% of polyimide;
(3)0.5-5 wt% of a compatibilizer;
the polyimide has the following structure:
Figure BDA0002931609250000031
wherein n is1And n2Are all numbers greater than zero, Ar1Is a structural unit of an aromatic tetracarboxylic dianhydride derivative, Ar2Is a structural unit of an aromatic diamine derivative, and R is an aliphatic structural unit;
the compatibilizer is an aliphatic diamine compound, and the chemical general formula of the compatibilizer is X- (NH)2)2Wherein X is a long-chain alkyl group with multiple carbon atoms, and the number of carbon atoms is 4-12.
Preferably, the polyimide is prepared by carrying out imidization reaction on tetracarboxylic dianhydride and organic diamine in a polar solvent, and then carrying out precipitation, washing and drying.
Preferably, the weight part ratio of the tetracarboxylic dianhydride to the organic diamine is 1: 0.95.
Preferably, the liquid crystal polymer is a liquid crystal polyester exhibiting liquid crystallinity in a molten state, and is preferably a liquid crystal polyester obtained by using an aromatic compound as a monomer raw material.
Preferably, the liquid crystal polyester is prepared by using an acidolysis reaction of hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid.
Preferably, the end group of the liquid crystal polyester is carboxyl, and the liquid crystal polyester reacts with the compatibilizer through the carboxyl.
Preferably, n in the polyimide2And n1+n2The quantity ratio of (A) is in the range of 0.3-0.7.
A method of making a composite material comprising the steps of:
(d) and (3) pretreatment: respectively putting the liquid crystal polymer and the polyimide into a cyclone crusher to be crushed into powder;
(e) and mixing: putting the powdery liquid crystal polymer, the polyimide and the compatibilizer into a mixer, and fully mixing for 20-30 min;
(f) and mixing and extruding: and adding the mixture into a screw extruder for melting and mixing to obtain a mixed melt, and extruding and granulating the mixed melt to obtain the composite material.
Preferably, in the step (a), the particle size of the liquid crystal polymer and the polyimide powder is 1 to 50 μm.
The contribution of the invention lies in: according to the composite material, the polyimide and the compatibilizer react with the liquid crystal polymer to obtain the copolymer, so that the time for the chain segment of the copolymer to enter the hole in the metal surface before crystallization is increased, namely the crystallization speed is delayed, the perfect combination of the composite material and the metal surface of an electrical appliance element is ensured, the good air tightness is ensured, the air leakage is avoided, the liquid crystal polymer and the polyimide are connected and polymerized through the compatibilizer, and the heat resistance and the waterproof performance of the liquid crystal polymer and the polyimide are preserved.
[ description of the drawings ]
FIG. 1 is a schematic diagram of a manufacturing scheme of the present invention;
[ detailed description ] embodiments
The following examples are further illustrative and supplementary to the present invention and do not limit the present invention in any way.
The composite material comprises the following raw materials in parts by weight:
(1)40-90 wt% of liquid crystal polymer;
(2)9-60 wt% of polyimide;
(3)0.5-5 wt% of a compatibilizer;
the polyimide has the following structure:
Figure BDA0002931609250000051
wherein n is1And n2Are all numbers greater than zero, Ar1Is a structural unit of an aromatic tetracarboxylic dianhydride derivative, Ar2Is a structural unit of an aromatic diamine derivative, and R is an aliphatic structural unit;
the compatibilizer is an aliphatic diamine compound, and the chemical general formula of the compatibilizer is X- (NH)2)2Wherein X is a long-chain alkyl group with multiple carbon atoms, and the number of carbon atoms is 4-12.
A composite material, mainly composed of liquid crystal polymer, polyimide and compatibilizer, wherein the weight component of the liquid crystal polymer is 40-90 wt%, the weight component of the polyimide is 9-60 wt%, the weight component of the compatibilizer is 0.5-5 wt%, the three are mainly liquid crystal polymers, the liquid crystal polymer is a novel thermoplastic plastic, can be represented by LCP, the liquid crystal polymer has good moisture-proof function, and is often made into a packaging body of an electrical appliance element, but because the combination degree of the liquid crystal polymer and the electrical appliance element is not enough (the liquid crystal polymer has fast crystallization speed, the liquid crystal polymer is crystallized when not deeply entering into pores on the roughened surface of the metal of the electrical appliance element in the injection molding process, the air leakage condition is easy to occur, namely, the air tightness is not good, so the polyimide and the diamine compatibilizer are mixed with the liquid crystal polymer, the diamine substance can be simultaneously combined with the anhydride end group in the polyimide and the end group (the end group is carboxyl) in the liquid crystal polymer, so that a copolymer is formed, and the crystallization speed of the copolymer of the polyimide and the liquid crystal polymer is reduced because the polyimide contains the aliphatic monomer chain segment (namely R), so that the copolymer starts to crystallize after penetrating into the pores on the roughened surface of the metal in the subsequent injection molding process of the material and an electronic element, thereby achieving the tight combination effect and enhancing the air tightness.
The compatibilizer is used for connecting the liquid crystal polymer and the polyimide, and both of the compatibilizer and the liquid crystal polymer can react with a group of the compatibilizer, so that a copolymer is formed, the crystallization speed of the copolymer formed by the compatibilizer, the liquid crystal polymer and the polyimide is reduced, the composite material can be perfectly combined with the metal surface in the injection molding process, and the good air tightness is ensured. Specifically, the compatibilizer is an aliphatic diamine compound, and the chemical general formula of the compatibilizer is X- (NH)2)2The X is a multi-carbon long-chain alkyl group, the number of carbon atoms is 4-12, the compatibilizer is an aliphatic diamine compound, on one hand, two amino groups of the aliphatic diamine compound can be respectively combined with carboxyl groups of the liquid crystal polymer and anhydride groups in the polyimide, so that the subsequently prepared material has excellent heat resistance and barrier property of the polyimide and the liquid crystal polymer, on the other hand, the addition of the compatibilizer further slows down the crystallization speed of the copolymer, and as the compatibilizer also contains an aliphatic chain segment structure, the crystallization speed of the copolymer can be delayed, the composite material can be further ensured to be perfectly combined with electrical equipment elements, and the condition of air leakage cannot occur.
The preferable carbon chain length of the compatibilizer is 4-12 carbon atoms, the carbon chain length is too short, the effect of slowing down the crystallization speed of the copolymer and the metal surface of the electrical element is not obvious, and the carbon chain length is too long, so that the heat resistance of the copolymer is reduced, and the heat resistance of the composite material is deteriorated.
According to the composite material, the polyimide and the compatibilizer react with the liquid crystal polymer to obtain the copolymer, so that the time for the chain segment of the copolymer to enter the hole on the metal surface is increased, the crystallization speed is delayed, the perfect combination of the composite material and the metal surface of an electrical element is ensured, the good air tightness is ensured, the air leakage condition is avoided, the liquid crystal polymer and the polyimide are connected and polymerized through the compatibilizer, and the heat resistance and the waterproof performance of the liquid crystal polymer and the polyimide are kept.
In a further description, the polyimide is prepared by carrying out imidization reaction on tetracarboxylic dianhydride and organic diamine in a polar solvent, and then carrying out precipitation, washing and drying.
In further detail, the weight part ratio of the tetracarboxylic dianhydride to the organic diamine is 1: 0.95.
The polyimide is prepared by carrying out imidization reaction on tetracarboxylic dianhydride and organic diamine in a polar solvent, and then carrying out precipitation, washing and drying, wherein the ratio of the weight parts of the tetracarboxylic dianhydride to the weight parts of the organic diamine is 1:0.95, further, because the number of the anhydride end groups in the polyimide is ensured to be enough to react with the compatibilizer, the reaction effect of the compatibilizer is enhanced, the proportion of the tetracarboxylic dianhydride is increased, and the polyimide is ensured to be mainly prepared from the anhydride end groups.
Further, the liquid crystal polymer is a liquid crystal polyester exhibiting liquid crystallinity in a molten state, and is preferably a liquid crystal polyester obtained by using an aromatic compound as a monomer raw material.
In a further aspect, the liquid crystalline polyester is prepared by acid hydrolysis of hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid.
The liquid crystal polymer shows liquid crystallinity in a molten state, can better react with a compatibilizer and polyimide, is preferably liquid crystal polyester prepared by using an aromatic compound as a monomer raw material, has better barrier property and heat resistance, and is suitable for being used as a packaging body of an electrical appliance element.
In a further aspect, the end group of the liquid crystal polyester is a carboxyl group, and the liquid crystal polyester reacts with the compatibilizer through the carboxyl group.
The end group of the liquid crystal polyester is carboxyl, the carboxyl can be generated by the hydroxybenzoic acid and the 6-hydroxyl-2-naphthoic acid in the acidolysis reaction, and the carboxyl can react with the amino of the compatibilizer, so that the compatibilizer plays a role in enhancing the compatibility of the liquid crystal polyester and the polyimide.
To explain further, n in the polyimide2And n1+n2The weight ratio of (A) is in the range of 0.3-0.7.
In polyimide n2Contains aliphatic structural units and can effectively reduce the crystallization rate, wherein n2The weight component of (A) accounts for 0.3-0.7 of the total weight component of the polyimide, if the proportion of the two components is too small, the crystallization speed can not be well delayed, and if the proportion is too large, the heat resistance of the polymer is poor, and the heat resistance of the composite material is influenced.
A method of making a composite material comprising the steps of:
(a) and (3) pretreatment: respectively putting the liquid crystal polymer and the polyimide into a cyclone crusher to be crushed into powder;
(b) and mixing: putting the powdery liquid crystal polymer, the polyimide and the compatibilizer into a mixer, and fully mixing for 20-30 min;
(c) and mixing and extruding: and adding the mixture into a screw extruder for melting and mixing to obtain a mixed melt, and extruding and granulating the mixed melt to obtain the composite material.
The pretreatment is to break the polyimide and the liquid crystal polymer into powder, so that the polyimide and the liquid crystal polymer can be fully contacted and mixed, and the subsequent mixing with a compatibilizer is facilitated.
The compatibilizer is mixed with the powder of the polyimide and the liquid crystal polymer and stirred in a mixer for 20-30min to ensure that the compatibilizer is filled between the polyimide and the liquid crystal polymer, so that the compatibilizer can be directly subjected to melt reaction with the polyimide and the liquid crystal polymer in a subsequent process.
And the mixing extrusion is to melt the mixture within 280-315 ℃ to form a copolymer, extrude and granulate the mixed melt, and cool the mixed melt to obtain the composite material.
More specifically, in the step (a), the particle size of the liquid crystal polymer and the polyimide powder is 1 to 50 μm.
The particle size of the powder of the liquid crystal polymer and the powder of the polyimide is 1-50 mu m, the finer the particle size of the powder of the liquid crystal polymer and the powder of the polyimide, the more uniform the mixing of the liquid crystal polymer and the compatibilizer, the better the subsequent smelting effect and the higher the smelting speed.
The invention is further illustrated by the following examples.
The composite materials and the preparation methods thereof in examples 1 to 6 each include the following steps,
(a) and (3) pretreatment: respectively putting the liquid crystal polymer and the polyimide into a cyclone crusher to be crushed into powder;
(b) and mixing: putting the powdery liquid crystal polymer, the polyimide and the compatibilizer into a mixer, and fully mixing for 20-30 min;
(c) and mixing and extruding: and adding the mixture into a screw extruder for melting and mixing to obtain a mixed melt, and extruding and granulating the mixed melt to obtain the composite material.
In the step (a), the particle size of the powder of the liquid crystal polymer and the polyimide is 1-50 μm.
In the step (c), the working temperature of the screw extruder is as follows: first zone 280 ° ± 5 °, second zone 290 ° ± 5 °, third zone 295 ° ± 5 °, fourth zone 300 ° ± 5 °, fifth zone 305 ° ± 5 °, sixth zone 310 ° ± 5 °, seventh zone 315 ° ± 5 °, eighth zone 310 ° ± 5 °.
Examples 2 to 5 in order to change the weight components of the liquid crystal polymer, polyimide and compatibilizer, the resulting composite was injection-molded with the metal surface of the treated electric device, and the resulting product was subjected to a gas tightness test. Examples 1 and 6 are tests conducted without the conventional compatibilizer, but the procedure is identical to examples 2-5 except that the compatibilizer is not added.
The airtightness test is realized by adopting 1014A test condition A4 in a GJB548A-96 method, specifically, a composite material is made into an unsealed shell, the shell is sealed at a vacuum joint, an inner cavity of the shell is vacuumized to be less than 0.01kpa, then an air bag or a spray gun is used for enabling the outside of the shell to receive the action of helium with the pressure of 236kpa, if the shell leaks, the external helium enters the vacuum joint through a gap, and the helium amount is detected by a detection instrument.
The results are shown in the following table.
Figure BDA0002931609250000091
Figure BDA0002931609250000101
From the above table, the helium permeability of the products made of the composite materials obtained in examples 1 to 6 was 2 x 10-12-2.3*10-5Pa·m3Between/s, where the helium flux of example 3 is minimal, only 2 x 10-12Pa·m3And/s, which shows that the air tightness is the best, examples 2 and 4 also have better air tightness, and example 1 and example 6 are both products added with a small amount of the compatibilizer, the air tightness of the composite material is far worse than that of examples 2-5, and the compatibilizer can remarkably improve the air tightness of the composite material within a certain range.
Examples 7-12 all used the procedure and parameters of example 3 except that the particle sizes of the liquid crystal polymer and polyimide powders were changed, and the test results are shown in the following table.
Figure BDA0002931609250000102
From the above table, the helium fluxes 1.1 x 10 of examples 7-12 can be obtained-12-3.9*10-8Pa·m3In the above table, as the particle size of the liquid crystal polymer and polyimide powder particles is smaller, the airtightness of the resulting product is better.
Examples 13-21 all used the procedure and parameters of example 3, except that the number of carbon atoms in the compatibilizer was changed, and the results are shown in the following table.
Carbon chain length n Value taking Heat resistance temperature (. degree. C.)
Example 13 4 102
Example 14 5 106
Example 15 6 108
Example 16 7 111
Example 17 8 120
Example 18 9 124
Example 19 10 120
Example 20 11 115
Example 21 12 110
From the above table, the heat resistance temperature of the composite materials obtained in examples 12-21 is between 102-124 ℃ and the heat resistance temperature of the composite materials is gradually increased when the carbon atom of the compatibilizer is between 4-9, which means that the heat resistance of the composite materials is increased with the increase of the carbon atom, but when the carbon atom is between 10-12, the heat resistance of the composite materials begins to decrease, mainly because the chain breaking recombination reaction of the compatibilizer easily occurs at high temperature due to the continuous growth of the carbon chain, and the compound with smaller carbon chain is formed, thus the heat resistance of the composite materials is decreased.
Examples a-e all use the procedure and parameters of example 3, except that n in the polyimide was changed2And n1+n2The results are shown in the following table.
Species of n2And n1+n2Ratio of Helium gas flux (Pa · m)3/s)
Example a 0.3 2.71*10-12
Example b 0.4 1.55*10-12
Example c 0.5 1.21*10-12
Example d 0.6 1.17*10-12
Example e 0.7 1.09*10-12
From the above table, it can be seen that examples a-e all have better air tightness, wherein the best air tightness of example e is 1.09 x 10-12Pa·m3S, n in examples a to e2And n1+n2The ratio is between 0.3 and 0.7, with n2And n1+n2The increase in the ratio, the better the gas tightness of the corresponding example, indicates that n2The larger the specific gravity of (a), the better the airtightness of the resulting composite material.
Although the present invention has been described with reference to the above embodiments, the scope of the present invention is not limited thereto, and modifications, substitutions and the like of the above members are intended to fall within the scope of the claims of the present invention without departing from the spirit of the present invention.

Claims (9)

1. The composite material is characterized by comprising the following raw materials in parts by weight:
(1)40-90 wt% of liquid crystal polymer;
(2)9-60 wt% of polyimide;
(3)0.5-5 wt% of a compatibilizer;
the polyimide has the following structure:
Figure FDA0002931609240000011
wherein n is1And n2Are all numbers greater than zero, Ar1Is a structural unit of an aromatic tetracarboxylic dianhydride derivative, Ar2Is a structural unit of an aromatic diamine derivative, and R is an aliphatic structural unit;
the compatibilizer is an aliphatic diamine compound, and the chemical general formula of the compatibilizer is X- (NH)2)2Wherein X is a long-chain alkyl group with multiple carbon atoms, and the number of carbon atoms is 4-12.
2. A composite material according to claim 1, wherein: the polyimide is prepared by carrying out imidization reaction on tetracid dianhydride and organic diamine in a polar solvent, and then carrying out precipitation, washing and drying.
3. A composite material according to claim 1, wherein: the weight part ratio of the tetracarboxylic dianhydride to the organic diamine is 1: 0.95.
4. A composite material according to claim 1, wherein: the liquid crystal polymer is a liquid crystal polyester exhibiting liquid crystallinity in a molten state, and is preferably a liquid crystal polyester obtained by using an aromatic compound as a monomer raw material.
5. A composite material according to claim 4, wherein: the liquid crystal polyester is prepared by the acidolysis reaction of hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid.
6. A composite material according to claim 4, wherein: the end group of the liquid crystal polyester is carboxyl, and the liquid crystal polyester reacts with the compatibilizer through the carboxyl.
7. A composite material according to claim 1, wherein: n in the polyimide2And n1+n2The weight ratio of (A) is in the range of 0.3-0.7.
8. A preparation method of a composite material is characterized by comprising the following steps:
(a) and (3) pretreatment: respectively putting the liquid crystal polymer and the polyimide into a cyclone crusher to be crushed into powder;
(b) and mixing: putting the powdery liquid crystal polymer, the polyimide and the compatibilizer into a mixer, and fully mixing for 20-30 min;
(c) and mixing and extruding: and adding the mixture into a screw extruder for melting and mixing to obtain a mixed melt, and extruding and granulating the mixed melt to obtain the composite material.
9. The method of claim 8, wherein the step of forming a composite material comprises: in the step (a), the particle size of the powder of the liquid crystal polymer and the polyimide is 1-50 μm.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5821319A (en) * 1995-04-13 1998-10-13 Mitsui Chemicals, Inc. Liquid crystal polyamide-imide copolymer
JP2001131411A (en) * 1999-11-08 2001-05-15 Teijin Ltd Resin composition, molded product and electronic part for surface mounting using these
US20020060309A1 (en) * 2000-09-01 2002-05-23 Jester Randy Douglas Blends of stretchable liquid crystal polymers with thermoplastics
US20030181626A1 (en) * 2002-03-19 2003-09-25 Lindway Martin John Preparation of polyimide polymers
JP2004256572A (en) * 2003-02-24 2004-09-16 Teijin Ltd Resin composition and its production method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5821319A (en) * 1995-04-13 1998-10-13 Mitsui Chemicals, Inc. Liquid crystal polyamide-imide copolymer
JP2001131411A (en) * 1999-11-08 2001-05-15 Teijin Ltd Resin composition, molded product and electronic part for surface mounting using these
US20020060309A1 (en) * 2000-09-01 2002-05-23 Jester Randy Douglas Blends of stretchable liquid crystal polymers with thermoplastics
US20030181626A1 (en) * 2002-03-19 2003-09-25 Lindway Martin John Preparation of polyimide polymers
JP2004256572A (en) * 2003-02-24 2004-09-16 Teijin Ltd Resin composition and its production method

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