JPS58180526A - Aromatic polyester and film or sheet made of same - Google Patents

Abstract

PURPOSE:To provide an arom. polyester copolymer having excellent moisture resistance, consisting of specified units. CONSTITUTION:An arom. polyester copolymer consists of a unit of formula I [wherein X is a 1-10C bivalent (substd.) hydrocarbon group, -O-, -S-, -SO2-, -CO-; R, R' are each a 1-20C alkyl, aryl, aralkyl, alkoxyl, aryloxyl, arylalkoxyl, halogen; p+q=1-8; m, n are each 0, 1 with the proviso that nnot equal to 0 when m=1] and a unit of formula II in a molar ratio of I /( I +II) of 1-0.01. A sheet made of the above copolymer has excellent moisture resistance and is suitable for use as a printed board.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel aromatic polyester copolymer with excellent moisture resistance.

Aromatic polyester copolymers containing terephthalic acid and isophthalic acid and bisphenols have been known for a long time. The first method for producing it is an interfacial polymerization method, that is, a method in which aromatic dicarboxylic acid halide dissolved in an organic solvent that is incompatible with water and bisphenols dissolved in an alkaline aqueous solution are mixed (Japanese Patent Publication No. 4 O-
1959), the second method is a solution polymerization method, that is, a method in which aromatic dicarboxylic acid halides and bisphenols are reacted together in an organic solvent (Japanese Patent Publication No. 67-5599). Transesterification method for adding bisphenols (Special Publication No. 58-15247)
, Special Publication No. 43-28119) are known. The aromatic polyester polymer thus obtained has excellent properties in terms of heat resistance, mechanical properties, and electrical properties, and can be used in a wide range of applications such as molded products and film fibers, either alone or as a resin composition. It has a purpose.

More specifically, the present invention relates to the aromatic polyester shown below. It consists of ingredients.

O.

0 0 (wherein, Xi is a substituted or unsubstituted divalent hydrocarbon group having 1 to 1 o carbon atoms, -0-t -s , Box= and -C
A group selected from O-, R', R'i a monovalent group selected from alkyl, allyl, aralkyl, alkoxyl, allyloxyl and hyalylalkoxyl groups having 1 to 20 carbon atoms, substituents thereof, halogen, and mixtures thereof. group, p, Q
i p+q an integer from -1 to 8, m, n; Q or 1; however, when m=1, n\0, and the molar ratio of (I) to the surface is (■)/(I) 10■-1 to 0. 01) More preferably, formula (■) is not represented by the following formula (III).

(In the formula, X, m, n; same as above, R1'-"R
41kJJ & represents a monovalent group selected from 1 to 4 alkyl groups, alkoxyl groups, soenyl groups, and halogen atoms) In particular, from the viewpoint of higher heat resistance, (■) Role ■
, the acid components are terephthalic acid and iodine.
The benzene nucleus of the terephthalic acid and isophthalic acid components may have a substituent such as an alkyl group or an alkoxyl group.

The component (I) is essential for the polymer of the present invention, which has superior electrical properties as well as superior properties in terms of heat resistance, alkali resistance, and water resistance compared to commercially available aromatic and polyesters. It is something that is given. The molar ratio in the polymer is preferably (■)/(I)+(Company) 21-001, more preferably 099-015. Furthermore, it is more preferable that the structural units of (I) and Tsukuda are not randomly arranged in the polymer, but are arranged regularly, such as alternately or in blocks.

The polymer of the present invention can be produced by the various methods described above.

As acid component it is preferred to use derivatives of terephthalic acid and/or isophthalic acid.

The structure of the preferred bisphenol component is represented by the general formulas (■) and (■).
It is expressed as

Preferred specific examples of R2R4 IO+x40H(V) (X; R+ to R4; m and n are the same as above) are shown in 3.3. '5.5'-tetramethyl-4,4'-dihydroxydiphenyl, 3゜ro, '5.5'-tetraphenyl-4,4'-dihydroxydiphenyl, bis(3,5-dimethyl-4-hydroxy phenyl)methane, bis(3,5-diphenyl-
4-hydroxyphenyl)methane, his(3,5-cyclo-4-hydroxyphenyl)methane, bis(3,5
-dibromo-4-hydroquinophenyl)methane, 2.2
-bis(3,5-dimethyl-4-hydroxyphenyl)
Propane, 2,2-bis(3,5-diphenyl-4-hydroxyphenyl)furopane, 2,2-his(s,5-
cyclo-4-hydroxyphenyl)propane, 2.2
-bis(3,5-dibromo-4-hydroxyphenyl)
Propane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)-cyclohexane, 1,1-bis(6
, 5-diphenyl-4-hydroxyphenyl)-cyclohexane, his(3,5-dimethyl-4-hydroxyphenyl)sulfone, bis(3,5-diphenyl-4-hydroxyphenyl)sulfone, bis(3,5-dimethyl) -4-hydroxyphenyl)ether, bis(3,5-
dimethyl-4-hydroxyphenyl)thioether, bis(3,5-diphenyl-4-hydroxyphenyl)ketone, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)-hexafluoropropane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl) -
Examples include 2,2,2-trichloroethane.

Preferred specific examples of (2) include 4.4'-dihydroxydiphenyl, 4.4'-dihydroxydiphenylmethane,
1,1-bis(4-hydroxyphenyl)ethane, 2.
2'-his(4-hydroxyphenyl)propane, 1.
1-bis(4-hydroxyphenyl)cyclohexane,
4.4'-dihydroxydiphenyl ether, 4.4'
Examples include -dihydroxydiphenylthioether, 4,4'-dihydroxydiphenylthioether, 4,4'-dihydroxydiphenylketone, and the like.

In the above example, it is of course possible to have two or more liquids in each of (goods) and (2).

To illustrate one method for producing the aromatic polyester polymer using these compounds or derivatives thereof, terephthalic acid dichloride (or a product partially replaced with isophthalic acid dichloride) is mixed with methylene chloride, etc. Soluble in halogenated hydrocarbons. On the other hand, an amount substantially equimolar to the total acid halide of the above bisphenol mixture is dissolved in an aqueous solution of caustic soda or potassium. Depending on the desired polymer molecular weight, a small amount of a molecular weight regulator such as monophenol, monothiophenol, or acid halides, a reducing agent, etc. is added to either of the two liquids. Furthermore, 01 to 100 mol % of a phase transfer catalyst based on the total amount of the catalyst is added and dissolved in either or both of the solutions. then 2
The liquid is cooled to 0-10°C and reacted all at once or continuously under vigorous stirring. Such a polymerization reaction is o
Polymerization can be carried out at temperatures ranging from 1.5 to 50.degree. C., and a polymerization time of 1 to 5 hours is usually sufficient.

Examples of the above phase transfer catalysts include salts such as benzyltributylammonium chloride, trioctylmethylammonium chloride, N-laurylpyridinium chloride, tetrabutylphosphonium gromide, triethyloctadecylphosphonium bromide, and 18-crown-6 , dibenzo-18-crown-6, dicyclohexyl-18-crown-6,18-:/azacrown-
Examples include crown ethers such as 6,1,1o-dithia-18-crown-6 and cryptands.

If the molecular weight of the aromatic polyester polymer thus produced is too low, the mechanical strength of the molded product will be low and it will be impractical. Moreover, if it is too high, the molding method will be severely restricted and it will be difficult to obtain a good molded product. The preferred molecular weight is its intrinsic viscosity (for example, 32°C in chloroform or a phenol-tetrachloroethane mixture (1:1 weight ratio)).
is 0.1 to 5. D cllj/l, preferably 0
3 to 5.0 dl/f.

The film or sheet made of the aromatic polyester polymer according to the present invention can be produced by a commonly known method. Examples include a casting method from an organic solvent solution and a melt extrusion method. The melt extrusion method can be carried out at any temperature above the melting point, but 200 to 400'C is usually used.

At this time, it is also preferable to add a small amount of a stabilizer to prevent decomposition and deterioration.

It is also preferable to impart better properties such as mechanical strength by further adding a stretching step. It has been found that the film or sheet of the present invention thus produced has unprecedented electrical properties.

Currently, several heat-resistant films or sheets are known that are used primarily for electrical applications. For example, polyethylene terephthalate. This is relatively inexpensive and has good mechanical and electrical properties, but its long-term use temperature is 120°C, which is poor in heat resistance compared to other products. On the other hand, polyimide-based, polyamide-imide-based, and polyoxadiazole-based materials are known, but although they have excellent thermal properties, they are very expensive and have poor long-term properties in a humid atmosphere, especially electrical properties. The problem is that the decline is large. Although polysulfone- and polyethersulfone-based materials are less expensive than the above-mentioned polyimide-based materials, their electrical properties are still significantly degraded under humid conditions. The same applies to commercially available aromatic polyesters. Films and sheets made of aromatic polyester copolymers according to the present invention can overcome these problems and can be provided at relatively low cost and with excellent properties. That is, high volume resistivity (>1
Furthermore, as shown in the examples below, it has excellent properties such that its physical properties hardly deteriorate even under humid conditions. It also has excellent dielectric constant and dielectric loss tangent. Of course, it is also excellent in mechanical strength such as tensile strength.

The films and sheets of the present invention are produced using the aromatic polyester of the present invention alone, but may be blended with other types of polymers, or may be made with heat stabilizers or oxidation An inhibitor, ultraviolet absorber, etc. may be used in combination.

Furthermore, it can also be made into a laminate with other films or sheet materials.

Due to such excellent properties, the film or sheet according to the present invention can be used in a wide range of applications, especially as an electrical insulating material. For example, flexible printed circuit boards, rigid printed circuit boards, 21-inch sensor films, etc.

The present invention will be explained below using specific examples, but the present invention is not limited only to these examples.

Example 1 Production of aromatic polyester copolymer 223.7 g of bisphenol A, 3.5 g. '5.5'
- Tethodimethylbisphenol F125.6g% Paramethoxyphenol 7, Of, Sodium Thiosulfate 240
g, 4N NaOH960m+1? and water 1660
Mt was mixed in a 11□ atmosphere and cooled to prepare an alkaline aqueous solution of bisphenol. On the other hand, 5,045 g of terephthalic acid cyclolide ' was dissolved in 2,500 liters of methylene chloride in an N2 atmosphere and cooled. The cooling temperature was 2'c in all cases. Meanwhile, in an 81 separable flask, 50 owl of water, 500 art of methylene chloride, and 467 ml of benzyltributylammonium chloride as a catalyst were added.
f was placed in an N2 atmosphere and cooled in the same manner. While stirring this vigorously, add 816 ml of each of the above two liquids.
Addition was made continuously by pump over a period of seconds. 8.4 g of benzoyl chloride 15 hours after completion of addition.
was dissolved in 100 g of methylene chloride and added.

After 20 minutes, stirring was stopped, and the methylene chloride solution containing the polymer and the aqueous solution containing common salt and sodium hydroxide were separated after about 10 minutes. After decanting the aqueous layer, the same amount of water was added and neutralized with a small amount of hydrochloric acid while stirring. After decanting again, water was added to wash and desalt. After repeating this operation five times, the same amount of water containing 300 ppm of PVA was added. By stirring vigorously, the jacket was heated while the polymer solution was dispersed in the PVA aqueous solution, the internal temperature was adjusted to around the boiling point of methylene chloride, and from this state methylene chloride was gradually distilled off over about 8 hours. After 8 hours, stirring and heating were stopped, and the polymer became granular and precipitated at the bottom of the separable flask. After the v5 filtration, the polymer was dried at 80° C. to remove residual methylene chloride and moisture. What is the yield of polymer? J40f (98%)
Met. The viscosity of the polymer was [η)=0.56 (52 in chloroform).

Example 2 Preparation of aromatic polyester copolymer sheet A sheet was prepared from the granular polymer prepared in Example 1 in the following manner. Heating roll (B 245℃, F225"C
) After kneading the polymer, heat press (290℃,
Preheat for 10 minutes, air bleed twice, pressure 100kQ/C41
After 0 minutes), a cooling press was applied for 10 minutes to obtain a light brown transparent sheet about 1.5 m thick.

Table 1 shows the physical properties of this sheet. When compared with the physical properties of a commercially available sheet (U-100, Biapheno-V A-terephthalic acid/isophthalic acid copolymer, manufactured by Unitika Hayashi) prepared in the same manner, the strength at break and Vicat softening point of the present invention were compared. You can see that the seat is excellent.

Table 1 Next, Table 2 shows the measurement results of the electrical properties of the sheet of the present invention.

Table 2 Thus, it can be seen that the sheet of the present invention has an excellent property in that the volume resistivity hardly changes even if it is kept in a humid atmosphere for a long period of time.

Patent applicant Kanebuchi Chemical Industry Co., Ltd. Representative Patent Attorney Makoto Asano

Claims (1)

[Scope of Claims] (1) A nine-aromatic polyester k having excellent moisture resistance and containing the following general formula (I) and/or (2) as a constituent component. In formula C, xI is a substituted or unsubstituted divalent selective hydrogen group having a prime number of 1 to 10, -o +, -8+, -80- and -
A group selected from 00-, R, R' l having 1 to 20 carbon atoms
0a JL/1 ali lI/, 1 arukoki V for Ara
A monovalent group selected from L, F&R and 79 CyashikokiVA/ groups and their substituents, halogens, and mixtures thereof, ν, qIp+ (1 = integer from 1 to B, m,
nI O or 1, but when m = 1, n\0, and σ)
The molar ratio of and ■ is (I) / (1) + (company) = 1 to 0.
01) (2) The molar ratio of (I) and beating is (■)
/(I)+([D=0.99-015, the aromatic polyester according to claim 1. (3> Claim 1, where (I) is expressed in terms of a general formula) aromatic polyester. (wherein, X, m, n; same as above, R1-R4;
The aromatic polyester according to claim 1, which is a monovalent group selected from an alkyl group, an alkoxyl group, a phenyl group, and a halogen atom having 1 to 4 carbon atoms. (5) The intrinsic viscosity of the polymer is 06 to 3.0 dl/f
(32°C, in chloroform) The aromatic polyester according to any one of claims 1 to 4. (6) A film or sheet with excellent moisture resistance made of an aromatic polyester containing the following general formula (I) and/or (2) as a constituent component. 0 0 0 (xi Re "': P* qi m* ni is the same as above, and the moa L/ratio of (I) and blood is (I)/(1
)+aD-1 to L1.01) (7) The film or sheet according to claim 6, wherein the film or sheet is for a printed wiring board.