Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From phenol – phenol ether – or inorganic phenolate
Reexamination Certificate
2002-09-05
2004-12-07
Hightower, P. Hampton (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From phenol, phenol ether, or inorganic phenolate
C528S171000, C528S172000, C528S173000, C528S176000, C528S272000, C528S274000, C528S289000, C528S322000, C528S350000, C528S352000, C528S353000, C528S183000, C528S185000, C528S189000, C528S193000
Reexamination Certificate
active
06828408
ABSTRACT:
CROSS-REFERENCE TO RELATED PATENT APPLICATIONS
Japan Priority Application 2001-273196, filed Sep. 10, 2001 including the specification, drawings, claims and abstract, is incorporated herein by reference in its entirety.
FIELD OF THE INVENTION
The present invention relates to an aromatic polyimide ester and a method for producing thereof.
BACKGROUND OF THE INVENTION
In recent years, various engineering plastics are being developed, and especially; a thermotropic liquid crystalline polymer showing an optical anisotropy in molten state, and excellent mechanical property by having a mesogenic structure with highly oriented shows excellent moldability.
The liquid crystalline polymer is oriented by injection molding, and therefore, a coefficient of linear expansion in machine direction (MD) is very small, but a coefficient of linear expansion in a direction transverse to flow direction (TD) shows an approximately as large as coefficient of linear expansion of thermoplastic resins. Accordingly a dimensional stability in transverse direction was not necessarily satisfactory.
On the other hand, as resins having a small coefficient of linear expansion, polyimide resins were known, but it has a water absorbing property.
As such resins that have feature of both a liquid crystalline polymer and polyimide resin, polyimide ester resins having imide bond and ester bond in a polymer molecule are known (Japanese Patent Publication No. 8-16155 B, Japanese Patent Publication No. 8-19236 B, and Japanese Patent Publication No. 8-19237 B). Although polyimide ester resins have excellent property of having a small coefficient of linear expansion and small water absorbing property; they have poor heat resistance, and therefore they tend to decompose by heat when melting process was carried out.
SUMMARY OF THE INVENTION
An object of the present invention is to provide an aromatic polyimide ester having a small coefficient of linear expansion and small water absorbing property, and moreover excellent heat resistance.
The present inventors found that a polyimide ester in which a repeating unit of a formula (IV) is ester-bonded in addition to repeating units of following formulas (I), (II), and (III), has a small expansion coefficient and small water absorbing property; and moreover excellent heat resistance, and thus the present invention was completed.
Namely, the present invention provides an aromatic polyimide ester comprising:
a repeating unit represented by a following formula (I),
a repeating unit represented by a following formula (II),
(n represents 0 or 1)
a repeating unit represented by a following formula (III),
and a repeating unit represented by a following formula (IV)
(in the formulas, -A- represents —O— or CO—, and is located in para-position or in meta position to an imide group, and X represents direct coupling, —O—, or —SO
2
—.),
and all of the said repeating units mutually bonded with each other through ester-bonds.
Reference designator n in the formula (II) represents 0 or 1. A preferable repeating unit represented by the formula (II) is as follows;
An aromatic polyimide ester of the present invention may include either of the units among them, and may include both of them by arbitrary ratios, and in view of a heat-resistance of resulted aromatic polymide, preferably may include only
wherein n in the formula (II) is 1.
A prefereable repeating unit represented by the formula (III) is following unit;
An aromatic polyimide ester of the present invention may include either units among them, and also may include both of them by arbitrary ratios.
Preferable repeating units represented by the formula (Iv) are the following repeating units wherein -A- is —CO—;
More repeating units represented by the formula IV) are the following units, wherein -A- is —O-preferable repeating units represented by the formula (IV) are the following repeating units, when -A- is —CO—.
In addition, an aromatic polyimide ester of the present invention may include one of any kind among them, and it may include two or more kinds of them by arbitrary ratios.
In view of heat resistance and availability, following units are preferable.
A mole ratio of repeating units in an aromatic polyimide ester of the present invention is preferably (I)/((II)+(III)+(IV)) is 30/70 to 90/10, more preferably 40/60 to 80/20, and still more preferably 50/50 to 70/30. And it is preferable that (IV)/((I)+(II)+(III)) is 0.9/99.9 to 30/70, more preferably 0.5/99.5 to 20/80, and still more preferably 1/99 to 10/90.
When the mole ratio of the repeating unit is out of the above-mentioned range, heat resistance of aromatic polyimide may be deteriorated.
An aromatic polyimide ester of the present invention may be produced by the following methods. An aromatic polyimide ester of the present invention may be produced, for example, by reacting a compound represented by a following formula (I′),
(Y
1
represents a hydrogen atom or R
1
CO)— (R
1
represents a hydrocarbon group with carbon numbers of 1 to 4), Z
1
represents a hydrogen atom or a hydrocarbon group with carbon numbers of 1 to 4)
a compound represented by a following formula (II′),
(n represents 0 or 1, Y
2
represents a hydrogen atom or R
2
CO(where R
2
represents a hydrocarbon group with a carbon number of 1 to 4), Y
3
represents a hydrogen atom or R
3
CO— (where R
3
represents a hydrocarbon group with carbon numbers of 1 to 4))
a compound represented by a following formula (III′),
(Z
2
and Z
3
represent independently a hydrogen atom or a hydrocarbon group with carbon numbers of 1 to 4 respectively, and Z
3
-O— CO-group is located in para-position or in meta position to Z
2
—O—CO-group) and a compound represented by a following formula (IV′-1, (IV′-2), or
(Y
4
represents a hydrogen atom or R
4
CO— (where R
4
represents a hydrocarbon group with carbon numbers of 1 to 4), Y
5
represents a hydrogen atom or R
5
CO— (where R
5
represents a hydrocarbon group with carbon numbers of 1 to 4), and Y
4
-A-group is located in para-position or in meta position to Y
5
-A-group.)
In a mole ratio of each compounds, (I′)/[(II′)+(III′)+{one of (IV′-1), (IV′-2) or (IV′-3)}] is preferably 30/70 to 90/10, more preferably 40/60 to 80/20, and still more preferably 50/50 to 70/30. And it is referable that {one of (IV′-1), (IV′-2) or (IV′3)}/((I′)+((II′)+(III′) is preferably 0.1/99.9 to 30/70, more preferably 0.5/99.5 to 20/80, and still more preferably 1/99 to 10/90.
In the above-mentioned formulas (I′), (II′), (III′), (IV′-1), (IV′-2), and (IV′-3), Y
1
represents a hydrogen atom or R
1
CO—, Y
2
a hydrogen atom or R
2
CO—, Y
4
a hydrogen atom or R
3
CO—, Y
4
a hydrogen atom or R
3
CO—, and Y
5
a hydrogen atom or R
4
CO—, respectively.
Here, R
1
, R
2
, R
3
, R
4
, and R
5
represent a hydrocarbon group with carbon numbers of 1 to 4, respectively. These hydrocarbon groups involve methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl, tert-butyl, etc. for example, and methyl group is preferable.
In addition, all of R
1
, R
2
, R
3
, R
4
, and R
5
may be the same, some of them may be the same and others may be different, or all of them may be mutually different from others.
Z
1
, Z
2
, Z
3
, Z
4
, and Z
5
represent a hydrogen atom or a hydrocarbon group with carbon numbers of 1 to 4, respectively. As the hydrocarbon group, the same as the above-mentioned groups may be mentioned. As Z
1
, Z
2
, Z
3
, Z
4
, and Z
5
, a hydrogen atom is preferable. In addition, all of Z
1
, Z
2
, Z
3
, Z
4
, and Z
5
may be the same, some of them may be the same and others may be different, or all of them may be mutually different from others.
As compound represented by the formula (I′), 4-acyloxy benzoic acid obtained by acylating 4-hydroxy benzoic acid using R
1
COOH(R
1
represents the same group as the above-mentioned groups) or derivative thereof, 4-hydro
Hirakawa Manabu
Okamoto Satoshi
Hampton Hightower P.
Sumitomo Chemical Company Limited
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