JPS59184251A - Resin composition - Google Patents

Abstract

PURPOSE:To provide a resin compsn. giving moldings which do not suffer delamination and have excellent thermal resistance, mechanical properties and tension of dissolution, by blending a polyether ester block copolymer, an ionomer resin and an olefin copolymer. CONSTITUTION:100pts.wt. polyether ester block copolymer (A) (the ratio of polyether soft segment to polyester hard segment being 80/20-5/95) composed of terephthalic acid, 1,4-butanediol and 5-80wt% polyoxyalkylene glycol having a number-average MW of 300-6,000, 1-25pts.wt. ionomer resin (B), such as Himiran 1,707 (a product of Mitsui Polychemical K.K.), obtd. by adding a monovalent to trivalent metallic ion to a copolymer of an alpha-olefin with a 3-8C alpha,beta- unsaturated carboxylic acid, and 1-25pts.wt. olefin copolymer (C) obtd. by reacting an alpha-olefin with an alpha,beta-unsaturated acid glycidyl ester, are blended together.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resin composition which has excellent heat aging resistance, mechanical properties and melt tension, and which can provide a molded article without delamination.

A polyether ester block copolymer (hereinafter abbreviated as polyether ester) containing a polyester hard segment such as polybutylene lenticulate and a polyether soft segment such as poly(tetramethylene oxide) glycol in its molecule is elastic. Because of its excellent mechanical properties such as recovery and flexibility, it is increasingly being used in automotive applications and electrical parts.

However, polyether esters are usually produced by the melt polymerization method, but the obtained polymer has a considerably low melt sacrificial viscosity, so it is difficult to apply it to melt molding such as profile extrusion and extrusion blowing. There is a problem in that the molding method is limited. Moreover, molded products made of polyether ester have a significant decline in mechanical properties during heat aging, and cannot withstand long-term use in high-temperature atmospheres.The development of applications that require such properties is hindered by layered products. It is.

Conventional methods for increasing the melt viscosity of polyether esters include (1) blending an ionomer resin (Japanese Patent Application Laid-Open No. 143055/1982) and (2) using a jepoxy compound, Periodic Table of the Elements 1-a, [-a A method of blending metal salts of the group metal salts and ionomer resins (Japanese Patent Application Laid-Open No. 57-4
7347), but in method (1), the phase and solubility of the polyether ester and ionomer resin are poor, so molded products obtained by injection blow molding, extrusion blow molding, etc. are prone to delamination. In addition, method (2) has the disadvantage that the heat aging resistance further deteriorates due to the inclusion of metal salts.

Therefore, the present inventors conducted extensive research with the aim of obtaining a polyetherester resin composition that has an excellent balance of heat aging resistance, mechanical properties, and melt tension, and can provide molded products without delamination. The inventors have discovered that the above object can be effectively achieved by blending the ionomer resin with other specific olefin polymers into the polyether ester, and have thus arrived at the present invention.

That is, the present invention provides (A) terephthalic acid, 1,4-butanediol, and a number average molecular weight of about 300 to 6,00'.
0 polyoxyalkylene glycol as an essential ingredient,
and 5 to 80% by weight of polyoquine alkylene glycol
Polyether ester block copolymer containing 100
parts by weight (for this, (E) α-olefin/and carbon! copolymer of α, β-unsaturated carboxylic acid having 3 to B atoms;
~ Ionomer resins 1 to 25 with self-valent metal ions added
and (C) 1 to 25 parts by weight of an olefin copolymer consisting of an a-olefin and glynodyl ester of σ, β-unsaturated acid to provide a resin composition C.

The (Δ) polyether ester used in the present invention has a node segment consisting of a polyester containing terephthalate and 1,4-butanediol as essential components and a number average molecular weight of about 600 to 6. It is a block J9 polymer composed of soft segments consisting of -000 polyoxy/alkylene glycol. The polyester serving as the polyether ester σ, ) node segment contains terephthalic acid and 1,4-butanediol as essential components, and may further contain other dicarboxylic acids and/or other diol components as minor components. Dicarboxylic acids other than terephthalic acid include inophthalic acid, phthalic acid, naphthalene-2゜6-dicarboxylic acid, naphthalene-2
, 7-dicarboxylic acid, diphenyl-4,4'-)carboxylic acid, diphenoethane dicarboxylic acid, aromatic dicarboxylic acids such as sodium 5-sulfoinophthalate, and alicyclic acids such as 1,4-cyclohexanedicarboxylic acid. Examples include aliphatic dicarboxylic acids such as cono-phosphoric acid, oxalic acid, adipic acid, quinone dicarboxylic acid, dodecanedioic acid, dimer acid, and the like.

Of course, ester-forming derivatives of dicarboxylic acids, such as lower alkyl esters, esters of 71J-oles, and furthermore, esters of 1,4-butanediol F, can be used.As diol components other than 1,4-butanediol F, for example, J Tylene glycol, tritylene glycol, pentamethylene glycol, hexamethylene L/
7 RIJ: Aliphatic diol such as I-ru, neopentyl glycol, decamethine glycol, 1,1-
Cycloaliphatic diols such as 7-chlorohexanedimethanol, 1,4-cyclohexanedimetatool, trinoclodecanedimethanol and quinorylene glycol, bis(p
-Hydroxy)diphenyl, bis(p-hydroquinphenyl)pronokne, 212-bis(4-(2-hydroquinethoquino)phenyl)propane, bis[:4-(2-
hydroxy/phenyl] sulfone, 11-bis(4-(
Examples include diols containing aromatic groups such as 2-hydroquinethoquino)phenylcocyclohexane. Such diols can also be used in the form of ester-forming derivatives such as acetyl derivatives and alkali metal salts.

= 100 to 40 mol%, preferably 100 to 50 mol% of the node segment made of 6-self polyester is composed of polybutylene terephthalate units, and the polybutylene terephthalate position is However, if the polybutylene terephthalate unit content is less than 40 mol %, the melting point will be low and the high temperature properties will be deteriorated, which is not preferable.

The polyetherester soft segment of the present invention is
It is composed of the same dicarboxylic acid as the hard segment and polyoxy/alkylene glycol having a number average molecular weight of about 300 to 6,000. The polyoxy/alkylene glycols mentioned here include polyethylene glycol, poly(1,2- and 1,3-propylene glycol) glycol, poly(terametherene oxide) glycol,
Examples include copolymers of ethylene oxide and propylene oxide, and copolymers of ethylene oxide and tetrahydrofuran. Among these, poly(tetramethylene oxide) is particularly suitable for applications that require high-temperature elastic recovery properties.
Glycols are preferred. The number average molecular weight of polyoxy/alkylene glycol is 300-6. OOO1 is preferably 500 to 4.500; if the molecular weight is too large, the polyoxy/alkylene glycol unit itself becomes crystalline, which not only loses its elastic recovery function but also reduces compatibility. On the other hand, if the molecular weight is less than 300, the length of the polyester block serving as a hard segment becomes too short, and elastic recovery properties are also lost in this case, which is not preferable.

The harmful interaction between polyether soft segment and polyester hard segment in polyether ester is 8.
0/20 to 5/95, particularly preferably 70/30 to +5/85; above 8o/20, the properties of the hard segment of the polymer will almost disappear and excellent elastic recovery will not be exhibited; If it is less than /95, the flexibility and elastic recovery under normal use conditions or at low temperatures will decrease, which is not preferable.

A method for producing a polyether ester consisting of each of the above-mentioned components includes, for example, transesterifying a lower alcohol diester of a dicarboxylic acid, an excess amount of a low saturation glycol, and a polyoxyalkylene glycol in the presence of a catalyst, and producing the resulting reaction product. A method of polycondensing a dicarboxylic acid, a glycol, and a polyoxyalkylene glycol in the presence of a catalyst, and a method of polycondensing the obtained product. A known method can be employed, such as adding another dicarboxylic acid or diol or another copolymerized polyester and polyoxene alkylene glycol, and then randomizing the mixture by transesterification.

As a common catalyst for transesterification or esterification reactions and polycondensation reactions, titanium catalysts give good results.

Particularly preferred are tetraalkyl titanates such as tetrabutyl titanate and tetramethyl titanate, and metal salts of titanium oxalate and potassium titanium oxalate. Other catalysts include tin compounds such as dibutyltin oxide and dibutyltin laurate;
Lead compounds such as lead acetate are used.

Further, polycarboxylic acids, polyfunctional mono-finger hydroxy compounds, oxic acid, and the like may be copolymerized as part of the dicarboxylic acids and glycols. The polyfunctional component effectively acts as a viscosity increasing component, and its copolymerization range is 6 mol % or less.

Some of the polyfunctional components that can be present include trimellitic acid, trimesic acid, pyromellitic acid, benzophenonetetracarboxylic acid, butanetetracarboxylic acid, glycerin, pentaerythritol, tolls and their esters, acid anhydrides, etc. can be mentioned.

The logarithmic viscosity of the polyether ester used in the present invention is preferably at least 0.35 or higher, particularly preferably in the range of O,SO to 40.

(B) A copolymer of a-olefin and a, β-unsaturated carbon having 3 to 8 carbon atoms used in the present invention contains 1 to 3
The a-olefin in the ionomer resin to which valence metal ions have been added (hereinafter abbreviated as ionomer resin) is:
Examples include ethylene, propylene, butene-1, and among these, ethylene is preferred. In addition, the α,β-unsaturated carboxylic acid must have 3 to 8 carbon atoms, such as acrylic acid, methacrylic acid, ethacrylic acid, itaconic acid, and maleic acid. Alkyl esters may be copolymerized. Among these, acrylic acid and methacrylic acid are preferably used. α in the copolymer,
The transfer of β-unsaturated carboxylic acid component is 02 to 25 mol%,
Preferably it is 1 to 10 mol%. The ionomer resin is an ionic copolymer in which a monovalent to pentavalent metal ion is added to a copolymer consisting of the above components to cause ionic crosslinking with the carboxylic acid groups in the copolymer. Mono- to trivalent metals/r-ones suitable for the formation of -1-one crosslinks include sodium, potassium, lithium, magnesium 7ium, carnoum, zinc, aluminum, ferrous and ferric ions, and the like. Ionic crosslinking can be introduced into the copolymer by reacting the copolymer with hydroxides, methoxides, ethkinds, hydroxides, nitrates, acetates, chlorates, oxides, etc. of mono- to pentavalent metals. achieved. Generally it is necessary that at least 10% of the carboxylic acid groups in the copolymer be neutralized with metal ions.

The blending amount of the above ionomer resin is 1 part polyether ester.
00 parts by weight, preferably 1 to 25 parts by weight, especially 2 to 20 parts by weight; if it is less than 1 part by weight, excellent melt tension cannot be obtained, and if it is more than 25 parts by weight, the mechanical Undesirable because it impairs its properties.

Examples of the α-olefin in the olefin copolymer consisting of a glyc/dyl ester of an a-olefin and an a,β-unsaturated acid used in the invention include ethylene, propylene, butene-1, etc. Among them, ethylene is preferably used.Gly/dyl esters of a,β-unsaturated acids have the general formula (wherein R is a hydrogen atom or a lower alkyl group).
It is a compound represented by
Examples include glycidyl ester, glycidyl methacrylate and glycidyl ethacrylate.
Among them, methacrylic acid glycidyl ester is preferably used. The amount of copolymerized glyc/dyle ester of a, β-unsaturated acid is suitably in the range of 0.1 to 20 mol%. Furthermore, if it is 40 mol% or less, unsaturated monomers copolymerizable with the above copolymers, such as esters of acrylic acid and methacrylic acid such as hahinyl ether 6R, vinyl acetate, vinyl ester tyl propionate, and propyl; Acrylonitrile, styrene, etc. may be copolymerized.

The blending amount of the above olefin copolymer is 1 to 25 parts by weight, especially 2 to 25 parts by weight, per 100 parts by weight of polyetherester.
20 parts by weight is preferred; if it is less than 1 part by weight, the effect of improving heat aging resistance and delamination of molded products is small;
Moreover, if it exceeds 25 parts by weight, it is not preferable because the excellent mechanical properties of the polyether ester are impaired.

Although there are no particular limitations on the method for producing the composition of the present invention, the king of (A) polyether ester, (B) ionomer resin, and (C) olefin copolymer is produced using an extruder, roll, Panbury mixer, etc. A method of melt blending is simple.

The composition of the present invention contains various additives, for example, forming aids such as known crystal nucleating agents and lubricants, known antioxidants, antioxidants for soil heat and light resistance such as ultraviolet absorbers, and anti-hydrolysis agents. Modifiers, colorants (pigments, east side), antistatic agents, conductive agents, flame retardants, reinforcing agents, fillers, adhesion aids, plasticizers, mold release agents, etc. can optionally be included. The heat aging resistance can be further improved by using a known heat-resistant stabilizer such as a phenolic stabilizer or an amine stabilizer.

The composition of the present invention has excellent heat aging resistance properties, mechanical properties, and melt tension, and can be extrusion blow molding and profile extrusion molding, and the molded product obtained does not cause delamination. It can be expected to be used in applications that require special characteristics.

The present invention will be explained in detail with reference to Examples below.

In the examples, all items indicated as "1 part" are expressed in weight ratios. Further, the logarithmic viscosity shown in the text and examples is a value measured in orthochlorophenol at 30° C. and a concentration of 0.5%.

In the heat aging test, the sample was left in a gear oven for a certain period of time, and then the elongation at break was determined according to ASTMm+-65B, and the retention rate was determined according to the following formula.

Elongation retention at break (final) - (elongation after treatment/elongation before treatment)
Measured according to The melt tension was measured using a melt tension measuring device manufactured by Toyo Seiki Co., Ltd., and the melt tension was measured using a melt tension measuring device manufactured by Toyo Seiki Co., Ltd..
Evaluation was made from the melt ten/yon when cutting the gut when pulled at an acceleration of 1 minute rpm. At this time, a pulley of 50 mm was used for the pulling machine.

In addition, for the JG peel test, the sample was
A molded product was formed by -70A injection molding at a molding temperature of about 200° C., and the appearance of the molded product was visually inspected to see if any delamination occurred.

Examples 1 to 6, Comparative Examples 1 to 4 945 parts of dimethyl terephthalate, 415 parts of dimethyl inophthalate, 585 parts of poly(tetramethylene oxide) glycol having a number average molecular weight of about +, 000, and 1.
945 parts of 4-butanediol were charged together with 010 parts of titanium tetrabutoxide catalyst in a reaction vessel equipped with a helical ribbon stirring blade, and heated at 210°C for 2 hours]! l
! 95% of the total amount of methanol was distilled out of the system. Reaction mixture (・Irganox 1010”
After adding 10 parts, the temperature was raised to 245° C., and then the pressure in the system was reduced to 0.2 [Hg] over 50 minutes, and polymerization was carried out under these conditions for 2 hours.

The melting point of the obtained polyether ester was 169°C, and the logarithmic viscosity was 095.

Predetermined amounts of various compounding agents shown in Table 1 were mixed with j O' 0 parts of this polyether ester pellet, and the mixture was melt-blended at 240° C. using a 30111+1φ extruder and then pelletized. The melting properties of this pellet were evaluated. The resulting sheet was formed into a press sheet at 240° C., and then a tensile test piece was punched out from the sheet and subjected to a heat aging test at 150° C.

These evaluation results are shown in Table 1.1-0 As is clear from the results in Table 1, the compositions of Examples 1 to 50 of the present invention have excellent melt tension and thermal aging properties, and also have excellent delamination. It is possible to obtain a molded product that does not occur.

In contrast, polyester elastomer alone (Comparative Example 1)
The conventional composition (Comparative Example 2) consisting only of a polyester elastomer and an ionomer resin was unsatisfactory in bath melt tension and 1) heat aging properties, and although the melt tension and other properties were improved to some extent, the molded product suffered from delamination. wake up,
Undesirable. Further, even if a glycidyl compound (Comparative Example 5) or polyethylene (Comparative Example 4) is used instead of the ethylene-glycidyl methacrylate copolymer, the effects of the present invention cannot be obtained.

Then, the pennodes of Example 1 and Comparative Example 1 were heated at 200'C.
Table 2 shows the results of molding various test pieces using an injection molding machine with the following settings and measuring their mechanical properties.
.

Table 2 *1 Sampsin was tested at 100°C x 16H'R after annealing.

As shown in Table 2, the molded products obtained from the pellets of the present invention (Example 1) retain excellent mechanical properties.

Claims (1)

[Claims] (A171/Polyether containing phthalic acid, 1,4-butanediol, and polykey/alkylene glycol with a number average molecular weight of about 30.Q to 6.000 as essential components, and containing 5 to 80% by weight of polyoxyalkylene glycol. For 103 parts by weight of the ester block copolymer, f
1 to 25 parts by weight of an ionomer resin prepared by adding monovalent to trivalent metal ions to a copolymer of Blα-olefin and α7β-unsaturated carboxylic acid having 3 to 8 carbon atoms;
- A resin composition containing 1 to 25 parts by weight of an olefin copolymer consisting of olefin 7, Q, and glycidyl ester of β to unsaturated acids.