JPS5933355A - Resin composition - Google Patents

Abstract

PURPOSE:To provide a resin compsn. having improved moldability and dry heat enduracne, by bleeding a phosphite compd., an aliph. amide compd. and an epoxy compd. with an arom. polyester. CONSTITUTION:0.01-10pts.wt. phosphite compd. such as triethyl phosphite, 0.01- 20pts.wt. aliph. amide compd. such as stearamide and 0.01-10pts.wt. epoxy compd. such as phenyl glycidyl ether are blended with 100pts.wt. arom. polyester composed of structural units of formulas I and II [wherein X is a 1-10C bivalent hydrocarbon group, -0-, -S-, -SO2-, -CO-; R, R<1> are each a 1-20C alkyl, allyl, alkoxy, halogen, etc.; p+q=1-8; m, n are are each 0, 1 with the proviso that nnot equal to 0 when m=1; k, l are each 0, 1 with the proviso that lnot equal to 0 when k=1] in a molar ratio of I /( I +II) of 1-0.01.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resin composition comprising an aromatic polyester polymer, a heptatoosphite compound, an aliphatic amide compound, and an epoxy compound. Specifically, an aromatic polyester polymer or copolymer having the following general formulas I and (2) as constituent components (where x is a substituted or unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms, - 0-, -8-, -8o2- and -CO-
Divalent groups selected from 几, 几′; monovalent groups selected from alkyl, allyl, aralkyl, alkoxyl, alkoxyl and allyl alkoxyl groups having 1 to 20 carbon atoms and derivatives thereof, halogen atoms and mixtures thereof; , p
, q; I) - tq = integer from 1 to 8, m, n; Q or 1, however, when m = 1, n to 01, l; 0XJj: 1
However, when = t, the molar ratio of 1+ and (II) in the polymer is (I)/(1) -1-(ff) =
1-o, ot) 7 A resin composition containing an osphite compound, an aliphatic amide compound, and an epoxy compound, which has improved coloration and moldability during molding, and also has improved dry heat durability. .

Aromatic polyester polymers have been known for a long time. The first manufacturing method is an interfacial polymerization method, that is, a method in which aromatic dicarboxylic acid sybaride dissolved in an organic solvent that is not compatible with water and bisphenols dissolved in an alkaline aqueous solution are mixed (Japanese Patent Publication No. 40-1959). The second method is a solution polymerization method, that is, a method in which aromatic dicarboxylic acids and bisphenols are reacted together in an organic solvent (
The third method is a transesterification method in which aromatic dicarboxylic acid nophenyl ester and bisphenols are heated (Japanese Patent Publication No. 38-15247; Japanese Patent Publication No. 43-1989).
Several methods are known, such as the method using a phase transfer catalyst (28119) or a method using a phase transfer catalyst.

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 bodies, films, and fibers, either alone or as a resin composition. It has a purpose.

The polymers used in the present invention can be produced by a variety of methods. However, this polymer has poor moldability from the viewpoint of extrusion or injection molding, and requires high plasticizing temperature and injection pressure.

Furthermore, coloring during molding cannot be ignored. Furthermore, aromatic polyester compounds generally lack resistance to hydrolysis. When exposed to high temperature for a long time, main chain scission occurs and molecular debris becomes low.

For example, in the case of a molded product, this leads to low physical properties such as low strength I-, and therefore improvement thereof has been desired.

Several methods have been proposed to improve the dry heat durability of aromatic polyester polymers. For example, the use of organic phosphine (Japanese Unexamined Patent Publication No. 51-11 2042),
Organic carboxylic acid metal salts/epoxy compounds/phosphorus compounds (
JP-A-53-96054), epoxy/phosphorus compound (JP-A-53-104654), and treatment with a reducing agent (JP-A-51-30895). However, in each example, the specific disclosed example is that the aromatic polyester polymer is composed of terephthalic acid/isophthalic acid-bisphenol A, and the aromatic polyester polymer used in the present invention is particularly as follows: In the formula (V) described above, the effect was not sufficient.

As a result of intensive research to overcome these drawbacks, the present inventors found that moldability and dry heat durability can be significantly improved by using a phosphite compound, an aliphatic amide compound, and an epoxy compound in combination, and the present invention is presented. reached.

The aromatic polyester polymer used in the present invention has the above-mentioned (1) and (Ill) as constituent components, but preferably the molar ratio in the polymer is (1)/fl) 10 (II)
= 0.99 to 0.01. From the point of view of high heat resistance, the bisphenol residue in the formula (A is tl and tl) is expressed by hf ) no molar ratio Ka@)/(
III) VD-1 to 0.9 is preferred.

Preferably, the formula +1) is represented by the following formula (V).

(X, m, n; same as above, 几1 to 几4; carbon number 1
-4 alkyl groups and alkoxyl groups, phenyl groups, and monovalent groups selected from . Some of these aromatic nuclei may have substituents such as alkyl groups and alkoxyl groups.

The bisphenol component is represented by the following general formulas ◇'I) and (ff) and derivative residues thereof.

(Same as above for X, R, l~几4 + m+ n, and + IJ) (Vm) formula (DJL example shown, 3.3', 5.5'
-ytramethyl-4L4'-dihydroxydiphenyl,
3゜3',5.5'-tetraphenyl-4,4'-dihydroxydiphenyl, bis(3,5-dimethyl-4-hydroxyphenyl)methane, bis(3,5-diphenyl-4-hydroxyphenyl)methane , bis(3,5-dichloro-4-hydroquinphenyl)methane, bis(3,
5-dibromo-4-hydroxyphenyl)methane, 2.
2-bis(3,5-dimethino-4-hydroxyphenyl) furonokun, 2,2-bis(3,5-diphenyl-
4-hydroxyphenyl)propane, 2,2-bis(3
, 5-dichloro-4-hydroxyphenyl)furopane,
2,2-bis(3,5-dibromo-4-hydroxyphenyl)furopane, 1,1-bis(3,5-dimethyl-4
-hydroxyphenyl)-cyclohexane, 1,1-bis(3,5-diphenyl-4-hydroxyphenyl)-
Cyclohexane, bis(3,5-dimethyl-4-hydroxyphenyl)sulfone, bis(3,5-diphenyl-hydroxyphenyl)sulfone, bis(3,5-dimethyl-4-hydroxyphenyl)ether, bis(3
,5-cymethyJl/-4-hy)"roxyphenyl)thioether, bis(3,5-diphenyl-4-hydroxyphenyl)ketone, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)- Examples include hexafluoropropane, t,i-bis(3,5-dimethyl-4-hydroxyphenyl)-2,2,2-t!Jchloroethane, and the like.

Furthermore, the other bisphenol component (I
Specific examples of formula X) include 4,4'-dihydroxydiphenyl, 4,4'-dihydroquine diphenylmethane, 1
．． 1-bis(4-hydroxyphenyl)ethane, 2.2
-bis(4-hydroxyphenyl)propane, 1.1-
Bis(4-hydroxyphenyl)cyclohexane, 4.
Examples include 4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylthioether, 4,4'-dihydroquine diphenyl sulfone, 4,4'-dihydroxydiphenyl ketone, hydroquinone, resorcinol, and the like.

In the aromatic polyester polymer having such a structure, the component represented by the formula (V) imparts superior properties in terms of water resistance and alkali resistance compared to conventional commercially available products. However, although it has excellent heat resistance, it lacks extrusion or injection moldability due to the low flow during molding, and it also causes discoloration of the molded product, so improvements have been desired.

The phosphite compound used in the present invention is represented by the general formula (W) or (■) of F. The amount used is 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, per 100 parts by weight of the polymer.

(1,50 yen-P (vl) (in the formula, 几5
; 1 selected from alkyl, cycloalkyl, allyl, allylalkyl, and alkylaryl groups having 1 to 30 carbon atoms;
valence group) (In the formula, 几6.几7; hydrogen atom, alkyl, cycloalkyl, allyl, allylalkyl, alkylaryl group,
A monovalent group selected from polyhydric phenol residues or polyhydric alcohol residues) Specific examples of formula (■) include triethyl phosphite, tributyl phosphite, tridecyl phosphite, and triisodecyl phosphite. , tris (tridecyl phosphite), phenyldidecyl phosphite, phenyl cy(tridecyl) phosphite, diphenyl octyl phosphite, diphenyl decyl phosphite, diphenyl tridecyl phosphite,
Examples include tris(nonylphenyl)phosphite, 9(dinonylphenyl)-nonylphenylphosphite, tris(di-butylphenyl)phosphite, and the like. Furthermore, compounds represented by formula F are also compounds that can be used in the present invention.

(1(,8; C12-C15 alkyl group) 113L
IJIJ Specific examples of compounds represented by the general formula (Moe) include F
Examples include those shown below.

The aliphatic amide compound used in the present invention has 8 to 8 carbon atoms.
60 mono- or bis-aliphatic amides. The amount used is resin 100. 001~ for i setting part
The amount is 20 parts by weight, preferably 0.05 to 10 parts by weight. If it is less than this, the effect will be small, and if it is too much, other excellent properties such as heat resistance will be significantly lowered. Specific examples include stearic acid amide, palmitic acid amide, oleic acid amide, and lyrinic acid amide.

Examples include erucic acid amide, methylene bis stearyl amide, and ethylene bis stearyl amide.

By adding these phosphite compounds and bisamide compounds to the resin, moldability and coloration during molding can be sufficiently improved. However, the dry heat durability was insufficient.

As the epoxy compound used in the present invention, any organic compound having an epoxy group can be used, but monovalent or polyvalent glycidyl derivatives or oxirane derivatives are preferable. The amount used is 0.01 to 100M parts of resin.
The amount is 10 parts by weight, preferably 0.1 to 3 M parts.

Here, the oxirane derivative refers to a compound having an epoxy group that is not of chrycidyl type.

Specific examples of glycidyl derivatives include phenyl glycidyl ether, 2-phenyl-phenyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, butyl glycidyl ether, N
- Monoglycidyl compounds such as glycidyl phthalimide, glycidyl benzoate, glycidyl oleate, bisphenol A diglycidyl ether, 3.3', 5.5'-
Tetramethylbisphenol F tuclicidyl ether.

3,3',5,5'-tetramethylbisphenol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, polyalkylene glycol diglycidyl ether, cyclohexanediol diclycidyl ether, cyclohexane dimetatool diglycidyl ether, diglycidyl phthalic acid Diglycidyl compounds such as ester, diglycidyl isophthalate, diglycidyl salicylate, 4-glycidyloxybenzoic acid-cricidyl ester, hexahydrophthalic acid dicrycidyl ester.

Diglycerin triglycidyl ether, 1. l.

3-tris(p-glycidylox7)phenylprohaf, N, Nyri'J cydylaminophenyl grindyl ether, N, N, N', N'-tetraglycidyl diaminobenzene, N, N, N', N'-tetraglycidyldiaminodiphenylmethane, N, N, N'.

N'J tetraglycidyl hexamethylene diamine.

/ Examples include polyglycidyl compounds such as polyglycidyl gallic acid and polyglycidyl tannate.

/ Oxirane derivatives include styrene oxide, 9
, ], ]0-Epoxyalkyl stearate '9
．． Allyl 10-epoxystearate, 9.10-epoxystearic acid, epoxidized tall oil fatty e-2-ethylhexyl, 2-ethylhexyl epoxyhexahydrophthalate, 9゜10-epoxycalcium stearate, 2,3-epoxy - Monooxirane derivatives such as calcium 2-ethylhexoinate, epoxidized soyura, epoxidized flax, epoxidized castor oil, epoxidized zaflower, epoxidized linseed oil fatty acid butyl ester, 3.4-evoxine chlorohexane Methanol-9,10-epoxy stearate, 3.4-
Epoxin chlorhexane methanol-9,10-12,
Examples include polyoxirane derivatives such as 13-jepoxystearate and epoxidized polybutadiene.

Other compounds include bisphenol A-epichlorohydrin epoxy resin, novolac type epoxy resin,
Epoxy resins such as poly(hydroxystyrene)cricidyl ether can also be used.

By using the above-mentioned phosphorus compound, amide compound, and epoxy compound in combination, sufficient coloration prevention effect, fluidity effect, and dry heat durability during molding can be obtained.

Various methods can be used to incorporate these compounds into the aromatic polyester polymer. For example, the polymer granules or powder may be mixed with a V-type blender, Henschel mixer, super mixer, kneader, etc., or the polymer may be dissolved in an organic solvent and sprayed onto the polymer granules or powder. . Generally, when producing aromatic polyesters by interfacial polycondensation, the polymer is obtained as a solution of an organic solvent, so it is convenient to add it to the reaction system or to the solution after post-treatment such as neutralization and washing with water. .

In order to further improve heat resistance, weather resistance, oxidation resistance, etc., a small amount of antioxidant, anti-aging agent, and light stabilizer may be added to the aromatic polyester polymer composition of the present invention. If it is desired to impart flame retardancy, various conventionally known flame retardants can be added. Further, it can be reinforced by adding inorganic fibers such as glass fibers and metal whiskers, carbon fibers, organic fibers, and the like.

It goes without saying that coloring can be done by adding dyes, pigments, etc., and it is also possible to use inorganic fillers.

The aromatic polyester composition of the present invention thus produced can be used in a wide range of applications as molded bodies and Filno sheets for mechanical parts, electrical parts, etc. by various molding methods.

Hereinafter, the present invention will be explained by examples, but it is not limited only by these examples.

Example 1 Production of aromatic polyester Bisphenol A 228.7g, 3, 3', 5.5
'-f Tramethylbisphenol F125.6g, paramethoxyphenol 7.0g, sodium thiosulfate 24
960 ml of 09.4N-NaOH and 1660 ml of water were mixed in a 31 flask in an N2 atmosphere and cooled to 2°C to prepare an alkaline aqueous solution of bisphenol. on the other hand,
In another 31 flasks 304. terephthalic acid chloride.
5 g was added to 2500 ml of methylene chloride in an N2 atmosphere for 1.5 g. Dissolved and cooled to 2°C.

81 500ml of water in a separable flask! , 500 rnl of methylene chloride, and 4.67 g of benzyltributylammonium chloride as a catalyst were placed in a N2 atmosphere and cooled in the same manner. While vigorously stirring the mixture, the above two liquids were each added continuously using a pump for 800 seconds. 1.5 hours after the end of the addition, 8.4 I of benzoyl chloride was added to the system dissolved in 100 ml of methylene chloride.

After 20 minutes, stirring was stopped, and after about 10 minutes, the mixture was separated into a methylene chloride solution containing the polymer and an aqueous solution containing common salt and sodium hydroxide. After decanting the aqueous layer, water from the same layer was added and neutralized with a small amount of hydrochloric acid while stirring. After decanting the aqueous layer again, water was added to wash and desalt. This operation was repeated 5 times. After that, polyvinyl alcohol 300 I
) I) Added the same amount of water containing m. The jacket was heated while the two liquids were strongly stirred, the internal temperature was adjusted to around the boiling point of methylene chloride, and from this state, methylene chloride was gradually poured over a period of about 8 hours. Thereafter, stirring and heating were stopped, and the polymer became granular and precipitated at the bottom of the flask. After filtration, the polymer was dried at 80° C. to remove residual methylene chloride and water.

The weight of the polymer was 540 g (yield: 98 g). The intrinsic viscosity of the polymer was 0.56 delg (in chloroform at 32°C).

Example 2 The phosphite, aliphatic amide, and epoxy compound shown in Table I were blended into the polymer prepared in Example 1.

For Slow 4 and 5.6, the color of the strands coming out of the flow measuring device is light yellow and transparent, and it is a polymer! The color tone was superior to that formulated by J1 Germany.

Moreover, as can be seen from the examples of N[15 and No. 6, the addition of the epoxy compound is effective in improving the flow value and improves the moldability.

Table 1 Flow of aromatic polyester resin *High formula) l:
I-320°C,] 001 (g/cm"Pl: Tridecyl phosphite B1: Erucic acid amide (Diaamide L-200 manufactured by Ehon Kasei ■) 1: Bisphenol A diglycidyl ether (
Epicoat 828) manufactured by Yuka Shell Co., Ltd. E2: Phenylcricidyl ether Example 3 The aromatic polyester polymer prepared in the same manner as in Example ① was used as the resin composition of pockets 4 and 5 in Table 1, and the resin compositions were processed using an extruder. Pel/tube (output end 40mm extruder, 290-3
108C).

Next, this pellet was left in a 170° C. gear oven for two weeks, and the retention rate of the initial molecular weight (ηsp/c) was measured. For comparison, commercially available aromatic polyester pellets consisting of terephthalic acid/isophthalic acid-bisphenol A) (U-100, manufactured by Unitika (Kiki)) were also prepared in the same manner. The results are shown in Table 2.

Table 2 Dry heat test results *ηsp/c (ηsp/c).

(ηSp/c). As shown in Table 2, N□5, which contains an epoxy compound, has greatly improved dry heat durability compared to Fuku4, and is superior to commercially available products. It can be seen that it is superior compared to

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

Claims (1)

Scope of Claims: (1) (a) In the formula based on 100 parts by weight of an aromatic polyester polymer having the general formulas fl) and (1), unsubstituted 2
valent hydrocarbon groups, -0-, -8-, -8O2- and -CO
A divalent group selected from -, Jt,! (,'; carbon number 1~
Monovalent group selected from 20 alkyl, allyl, aralkyl, alkoxyl, allyloxyl and hyalylalkoxyl groups and their substituents, /% rogene and mixtures thereof, p, q; p + q = integer from t to 8, m ,n;
Q or 1 However, when m == t (7) n\-0, k
, 13; 0 or 1 However, when 1(=l, l~0, and the molar ratio of (11 and (Ill) is (1)/(1) 10(I
I) = t~0.01) (b) 0.01 to 10 parts by weight of a phosphite compound, (C) 0.01 to 10 parts by weight of an aliphatic amide compound.
01 to 20 parts by weight and (d) epoxy compound 0.01-
A resin composition containing 01-1O parts. (2) The molar ratio of (11 and +1) in the polymer is medium / (1
) -1-(1) =0.99-0.01, the resin composition according to claim 1. The molar ratio of (representing bisphenol residues) is (1)
/ II) Claim 1 which is 10 m-1 to 0.9
The composition described in Section 2 or Section 2. +41 The composition according to claim 1, 2, or 3, wherein formula (1) is represented by formula (V) below. (X, m, n; same as above, n, 1 to 4; carbon number 1 to
(4) A monovalent group selected from alkyl groups and alkoxyl groups, phenyl groups, and halogen atoms) (5) A phosphite compound has the general formula! ′! The composition according to claim 1, which is expressed as a funeral. (1,5O-)-P (111) (B, 5; a monovalent group selected from alkyl, cycloalkyl, allyl, allylalkyl, and alkylaryl groups having 1 to 3 carbon atoms) (6) The phosphite compound is The composition according to claim 1 or 5, which is a cyclic phosphite compound represented by the following general formula. (In the formula, 几6, R7; a monovalent group selected from a hydrogen atom, an alkyl group, a cycloalkyl group, an allyl group, an allyl alkyl group, an alkylaryl group, a polyhydric phenol residue, and a polyhydric alcohol residue) 7) A composition according to claim 1, wherein the aliphatic amide compound is a mono- or bis-aliphatic amide containing 8 to 60 carbon atoms. (8) The composition according to claim 1, wherein the epoxy compound is a monovalent or polyvalent glycidyl derivative or oxirane derivative.