JPS5947255A - Resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having improved resistance to heat and chemicals, strength, etc., consisting of a specified arom. polyester and an inorg. fiber. CONSTITUTION:99-50wt% arom. polyester having an intrinsic viscosity of 0.3- 3dl/g, composed of structural units of formula I and/or II (wherein X is a substituted or unsubstituted 1-10C bivalent hydrocarbon group, -O-, -S-, -SO2-, -CO-; R, R' are each a monovalent group selected from 1-20C alkyls, aralkyl, allyl, alkoxyl, aryloxyl, allylalkoxyl and their substd. groups, halogen and their mixture; p, q, p+q=1-8; m, n are each 0, 1 with the proviso that nnot equal to 0 when m=1; the molar ratio of formula I /(formulas I +II) being 1-0.01) obtd. by reacting an arom. dicarboxylic acid halide with a bisphenol, is mixed with 1-50wt% inorg. fiber having an average length of at least 0.1mm. and an average particle size of 1-50mu, such as potassium titanate fiber.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel resin composition comprising an aromatic polyester copolymer and an inorganic fiber.

Aromatic polyester copolymers containing terephthalic acid and isophthalic acid and bisphenols have been known for a long time. The first manufacturing method is the interfacial polymerization method, that is, the method of mixing aromatic dicarboxylic acid halide dissolved in an organic solvent that is incompatible with water and bisphenols dissolved in an alkaline aqueous solution (Japanese Patent Publication No. 4 O-
1959), the second 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. 37-5599), and the third is a method in which phenyl esters of aromatic dicarboxylic acids and bisphenols are reacted. A transesterification method in which esters are heated with
7, 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, films, and fibers, either alone or as a resin composition. It has a purpose.

Specifically, the present invention relates to a resin composition comprising an aromatic polyester and an inorganic fiber as shown below, and which has improved heat resistance, strength, chemical resistance, etc.

The aromatic polyester used in the present invention has the general formula (1
) and/or (II).

(In the formula,
A group selected from R, R'; a monovalent group selected from alkyl, allyl, aralkyl, alkoxyl, alkoxyl and allylalkoxyl groups having 1 to 20 carbon atoms and substituted products thereof, halogen and mixtures thereof, I); C11I
) + (1 = integer from 1 to 8, m, niQ or 1, where m = 1
When n ~ o1 and (I) and (1) nomo zy ratio is (1)
/(1) +(If) -t ~o, OL te exists.

Furthermore, by adding weight and weight, equation (1) is expressed by the following equation m.

(wherein, From the viewpoint of high heat resistance, (I) and (
In I), the acid components are terephthalic acid and Isophthalic acid
It is preferable that 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 (1) is essential for the polymer of the present invention, which has superior electrical properties as well as heat resistance, alkali resistance, and water resistance compared to commercially available aromatic polyesters. It is intended to give. The molar ratio in the polymer is (I) / (I) + (I) = 1 to 0
．． It is preferable to set it as 01, more preferably 0.99~
It is 0.15. Furthermore, it is more preferable that the structural units of (r) and (It) are randomly arranged in large numbers in the polymer, and 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 preferred structure of the bisphenol component is represented by the general formula and (V).

(X; R, ~R4; m, n are the same as above) Preferred specific examples of small groups include a, 1, 5. g-tetramethy)v C-dihydroxydiphenyl, 3.3', 5
゜Gutetraphenyl-4,4'-dihydroxydiphenyl, bis(3,5-dimethyl-4-hydroxyphenyl)methane, bis(3,5-diphenyl-4-hydroxyphenyl)methane, bis(3,5- dichloro-4-hydroxyphenyl/I/)methane, bis(3,5-dibromo-4-hydroxyphenyl)methane, 2,2-bis(
3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-diphenyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane , 2,2-bis(
3,5-dibromo-4-hydroxyphenyl)propane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)-cyclohexane, t,t-his(3,5-1
Phenyl-4-hydroxyphenyl)-cyclohexane, bis(3,5-dimethylzlz-4-hydroxyphenyl)sulfone, bis(3,5-diphenyl-4hydroxyphenyl)sulfone, bis(3,5-dimethyl-4 −
hydroxyphenyl)ether, bis(8,5-cymethy)I/-4-hydroxyphenyl)thioether, bis(3,5-dipheny)v-4-hydroxyphenyl)ketone, 2,2-bis(3,5- dimethyl-4-hydroxypheni)V)-hexafluoropropane, ■, 1-
bis(3,5-dimethy1v-4-hydroxyphenitv)
) -2,2,2-) dichloroethane and the like.

Preferred specific examples of (V) include 4,4-dihydroxydiphenyl, 4,4-dihydroxydiphenylmethane,
■, ■-bis(4-hydroxyphenyl)ethane, 2.
2-bis(4-hydroquinpheni)V) propane, 1
．． 1-bis(4-hydroxyphenyl)cyclohexane, 4.4-dihydroxydiphenyl ether, 4.4-
Examples include dihydroxydiphenylthioether, 4,4-dihydroxydiphenyl sulfone, and 4,7-dihydroxydiphenyl ken.

In the above example, in each of (G) and (V), 2
It is of course possible to use only two ingredients.

One example of a method for producing the aromatic polyester polymer using these compounds or derivatives thereof is to chloride terephthalic acid dichloride (partially converted into isophthalic acid dichloride). Dissolves in hydrogen halogenated hydrogen such as methylene. 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, a phase transfer catalyst is added and dissolved in either or both of the liquids in an amount of 10.0 mol % to the total amount of the liquid. 2'gf is then cooled to 0-10°C and reacted all at once or continuously under vigorous stirring. The polymerization reaction can be carried out at any temperature from 0 to 50°C, and a polymerization time of 1 to 5 hours is usually sufficient.

Examples of the above phase transfer catalysts include benzyl) IJ butylammonium chloride, trioctylmethylammonium chloride, N-laurylpyridinyl J chloride,
Salts such as tetrabutyl fluoronium bromide, triethyl occudecyl fluorophonium bromide, 18-
Examples include crown ethers such as crown-6, dibenzo-18-crown-6, dicyclohexyl-18-crown-6,18-diazacrown-6,1,10-dithia-18-crown-6, and cryptands. .

The aromatic polyester thus produced alone has a high heat distortion temperature and excellent mechanical properties. In order to expect better thermal and mechanical properties, it is generally known to form a composite material by adding a reinforcing material such as glass fiber. Regarding aromatic polyester, reinforcement with glass fiber (Japanese Patent Application Laid-Open No. 49-34945) has been disclosed. As a result of further intensive research into improvements using inorganic fibers, the present inventors found that the polymer of the present invention can be used as a reinforcing material in a wide range of ways, and has a high thermal deformation temperature, impact strength, tensile strength, flexural strength, and thermal expansion coefficient. It has been found that greater improvements in dimensional stability, chemical resistance, etc. can be achieved compared to commercially available aromatic polyesters.

Inorganic fibers that can be used in the present invention include glass fibers, mineral fibers, gypsum fibers, potassium titanate fibers, and carbon fibers. The amount of these fibers used is 1% to 99% to 50% by weight of aromatic polyester,
Heavy view% weight is small. As the glass fiber, any of the commonly used glass strands, rovings, milled fibers, glass cloth, glass mats, etc. can be used. The things that have been applied are light and heavy. As described in the examples, the aromatic borie ether polymer of the present invention was found to have higher thermal properties than the commercially available polymer of the formula below.

(However, iso/tele-1/1) Mineral fibers and gypsum fibers are relatively inexpensive and have a sufficient strength-improving effect, so they are economical and have great industrial value.

Molded products made from blends with potassium titanate fibers not only have a more improved surface appearance, but also further reduce the excellent low coefficient of thermal expansion of the aromatic polyester polymer of the present invention, improving the dimensional stability of the molded products. Let it be. Although carbon fiber is relatively expensive, it has been found to be effective not only in improving strength but also in suppressing the tendency for strength to decrease due to hot water immersion, which is generally a drawback of aromatic polyester.

In the second composition, the fiber length is on average Q,
1 mm or less, and those with an average diameter of 1 to 50 microns are used.

For example, the following method can be used to mix the aromatic polyester copolymer and inorganic fiber according to the present invention.

■ A method in which resin and chopped strands, cut fibers, or milled fibers are mixed in a predetermined ratio and then formed into pellets by extrusion molding.

■ After melt-coating or solution impregnating the roving with resin,
How to cut to desired length.

■ A method in which resin powder or sheets, chopped strands, and woven fabric are layered alternately and then compression molded.

■ A method in which rovings are lined up and impregnated with resin in an extruder and molded.

In particular, for woven fabrics, those mixed with aramid fibers can also be used.

Generally, from the viewpoint of extrusion or injection molding, a blend of inorganic fiber and a thermoplastic resin has lower moldability than a case where the blend is not blended. For this improvement, it is also possible to use other vinyl resins or uncured epoxy resins. Still, a small amount of anti-aging agent, antioxidant, etc. may be added in consideration of thermal deterioration, oxidation, etc. of the polymer.

The inorganic fiber-containing aromatic polyester thus produced can be used as an engineering resin due to its excellent thermal and mechanical properties.

Examples include bearings, gears, switch-related parts, rigid printed circuit boards, reflectors, heat-resistant fans, diaphragms, etc.

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

Example 1 Production of aromatic polyester copolymer Bisphenol A 223.7 g, 3.3', E), etetramethyl bisphenol F 125.6 g, balanodoxyphenol 7.0 Lj, sodium thiosulfate 2
．． 40q, 4N-NaOH 960ml and water 1660ml
1 was mixed in a nitrogen atmosphere and cooled to prepare an alkaline aqueous solution of bisphenol. On the other hand, terephthalic acid dichloride 304. ,! M was dissolved in 2500 ml of methylene chloride in a nitrogen atmosphere and cooled. The cooling temperature is 2° in both cases.
It is C. Meanwhile, 500 ml of water was added to the 81 separable flask.
m4', methylene chloride 500πt1 Benzyltributylammonium chloride 4.67 (J) as a catalyst was charged in a nitrogen atmosphere and cooled in the same way. While stirring vigorously, the above two liquids were each pumped for 816 seconds. After the addition was completed, 1.
After 5 hours, 8.4 g of benzoyl chloride dissolved in 100*f of methylene chloride was 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 5 times, pv
An equal amount of water containing Aaooppm was added. While dispersing the polymer solution in the pPVA aqueous solution by stirring vigorously, heat the Jaquera 1-, adjust the internal temperature to around the boiling point of methylene chloride, and from that state gradually distill off the methylene chloride over about 8 hours. did. After 8 hours, stirring and heating were stopped, and the polymer became granular and settled at the bottom of the separable flask. After filtration, the polymer was dried at 80°C to remove residual methylene chloride and water. The yield of polymer was 540 g (98%). The viscosity of the polymer was [η]-〇, 56 (32°C, in chloroform).

Example 2 The polymer produced in Example 1 and glass fibers (average diameter 9 μm, length average 3 mm) were thoroughly mixed so that the latter amounted to 30% by weight, and then extruded into chips at 300°C. Then,
The obtained pellet was molded at a temperature of 320°C and an injection pressure of 1470°C.
A test piece was prepared at kg/ctA and a mold temperature of 145°C. As a comparative example, commercially available aromatic polyester (U-100
A test piece was prepared in the same manner for a test piece (manufactured by Unitika Co., Ltd.). The results are shown in Table 1.

Table 1 The numerical value in O is the value when glass fiber is not blended.

Thus, it can be seen that the improvement effect on the Izot impact value and heat distortion temperature is greater than that of commercially available products.

Example 3 In the same manner as in Example 2, mineral fiber (
PMF, Ji, m, Walter Re5source
Table 2 shows the results using carbon fibers (manufactured by Trading Card Co., Ltd.) and carbon fibers (manufactured by Trading Card Co., Ltd.).

Table 2 Sample pieces using the carbon fibers in Table 2 were immersed in boiling water for two weeks, and changes in strength were compared. The results are shown in Table 3.

Table 3 Values within 0 are values before immersion in boiling water.

Example 4 Similar to Example 2, potassium titanate fibers were used instead of glass fibers. The coefficient of thermal expansion of the molded product is 2, Q
L 0-5Crn/cm low power).

Patent applicant Kanebuchi Chemical Industry Co., Ltd. Agent: Patent attorney Makoto Asano

Claims (1)

[Scope of Claims] (1) 99 to 50% by weight of an aromatic polyester having the following general formula (I) and/or (1) as a constituent; or an unsubstituted divalent hydrocarbon group, -O-, -S-; a group selected from -5O2- and -C○-, RlE;
Charcoal FJt l~20 alkyl, allyl, aralkyl,
a monovalent group selected from alkoxyl, alkoxyl and allyl alkoxyl groups and their substituted products, halogens and mixtures thereof, p, qiI)+(1=an integer of 1 to 8, m
, n, ;0 or 1, but when m=1, n\0, and (I)
The molar ratio of and (1) is (1)/ (1) + (1) -t
~0.01% by weight) of inorganic fibers. (2) The molar ratio of (I) and (II) is (1)/(
The aromatic polyester resin compound according to claim 1, wherein I) + (II) -0.99 to 0.15. (3) The aromatic polyester resin composition according to claim 1, wherein (1) is represented by the following general formula (2). (In the formula. 9. The aromatic polyester resin composition according to claim 1, which is No. 9. (5) The intrinsic viscosity of the polymer is 0.3 to 3. Odβ/g(3
2°C in chloroform), the aromatic polyester resin composition according to any one of claims 1 to 4. (6) The aromatic polyester resin composition according to claim 1, wherein the inorganic fiber is selected from glass fiber, mineral fiber, potassium titanate fiber, gypsum fiber, and carbon fiber.