JPS60219254A - Resin composition - Google Patents

Abstract

PURPOSE:To improve the mechanical properties such as impact resistance, and flexibility, by incorporating an ethylene terpolymer consisting of ethylene, an alkoxyalkyl acrylate, and maleic anhydride, etc. into a saturated polyester resin. CONSTITUTION:55-94wt% ethylene, 5-40wt% alkoxyalkyl acrylate of the formula (where R1 is H or methyl; n is 2-6; m is 1-8) (e.g. methoxyethyl acrylate), and 0.5-15wt% maleic anhydride or glycidyl (meth)acrylate are copolymerized to prepare an ethylene terpolymer. Then, 0.5-40wt% ethylene terpolymer obtained and 99.5-60wt% saturated polyester are compounded to give an objective resin composition. This composition is suitably used for automotive parts, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to saturated polyester resin compositions with improved mechanical properties. More specifically, the present invention relates to a polyester resin composition in which mechanical properties such as impact resistance and flexibility are improved by blending a linear saturated polyester with an ethylene copolymer having a specific group &c. It is something.

Polyester resin is an engineering resin with features such as heat resistance, processability, and mechanical strength, and is widely used in the fields of automobile parts and electrical/electronic equipment parts. Further improvement in impact resistance is desired.

In the past, many proposals have been made as methods for improving the mechanical properties of polyester resins, but among these, Japanese Patent Publication No. 45-26223 and Japanese Patent Application Laid-Open No. 51-144452
The method of blending ethylene/vinyl acetate copolymer or ethylene/glycidyl methacrylate copolymer with polyester as shown in Japanese Patent Publication No. 58-47419 can be said to be a relatively excellent method. However, the molded product obtained by the above method does not have sufficient affinity between the polyester and the ethylene copolymer, and it cannot be said that the desired mechanical properties are sufficiently improved.

The inventors of the present invention made efforts to improve this drawback, and as a result, by blending polyester with an ethylene-based copolymer having a specific composition, it was possible to improve the properties and flexibility of polyester. The inventors have discovered that the mechanical properties are improved and have arrived at the present invention.

The resin composition according to the present invention provides a molded product having excellent mechanical properties, particularly excellent impact strength, and in particular, in molded products having a welded part, the appearance of the welded part and the impact strength of the welded part are significantly improved. It has the following characteristics. The impact strength of polyester resin is dramatically improved by blending the ethylene copolymer having the specific group M, * in the present invention. This is because the highly elastic ethylene copolymer is dispersed in polyester with good affinity to form a sea-island structure, and the terminal functional group in the polyester and the acid anhydride group or epoxy in the ethylene copolymer are It is thought that the reaction with the group causes a strong bond to form at the interface of both polymers.

The present invention is (A) saturated polyester resin 99.5 to 6.9
wL% and (B + ethylene copolymer 0.5-4Qw
In the thermoplastic tree strength composition consisting of The present invention relates to a thermoplastic horse chestnut resin composition characterized in that it is a copolymer of one or more of the following terpolymer copolymers.

(a) Ethylene: 55-94 wt% (1) General formula) % formula% Alkoxyalkyl acrylate = 5-4 Qwt% (where R1 is hydrogen or a methyl group, n is an integer of 2 to 6, m is An integer of 1 to 8, 1) (C) Maleic anhydride 20, 5 to 15 wt (d)
Glycidyl methacrylate and/or glycidyl acrylate - 05 to 15 wt% The saturated polyester resin in the present invention consists of a dicarboxylic acid component which is at least 40 mole of the dicarboxylic acid component or terephthalic acid, and a diol component, and the dicarboxylic acid component other than the above-mentioned terephthalic acid component. Examples include aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as adipic acid, senoacic acid and toticane dicarboxylic acid, aromatic dicarboxylic acids such as isophthalic acid and natutale dicarboxylic acid, and cyclohexane dicarboxylic acid. Examples of the diol component include ethylene glycol,
1,3-propanediol, 1,4-butanediol,
Examples include aliphatic glycols such as 1,6-hexanediol and 1,4-cyclohexanediol, and alicyclic glycols alone or as a mixture.5 Among these saturated polyesters, polyesters are particularly suitable.

Well, these saturated polyesters are solvents.

fl+1 at 25°C using 0-chlorophenol as
1 fixed 1 this Ii! It is necessary that the i17 viscosity be in the range of 0.5 to 3.0, and even if a saturated polyester having an intrinsic viscosity outside this range is used, the desired improvement in mechanical strength cannot be expected.

The ethylene copolymer in the non-invention refers to the following me(a)
, (b) and (0), or (I), (b) and (d).

-) Ethylene: 55 to 94 wt% (b) General formula B, 10 alkoxyalkyno acrylate: 5 to 4 Qwt
Rice cake (here, ILl is hydrogen or a methyl group, n is an integer of 2 to 6, and 11 is an integer of 1 to 8.) (e) Maleic anhydride: 0.5 to 15 wt% (d)
Glycidyl methacrylate rice/or cricidyl acrylate = 0.5 to 15 wt% Specific examples of component (b) include methoxyethyl acrylate, methoxyethyl methacrylate, methoxyphthyl acrylate-1-, ethoxyethyl acrylate, ethoxyethyl methacrylate, Examples include octoxyethyl methacrylate, ethoxyhexyl methacrylate, and 2-ethylhexyl methacrylate. These compounds are obtained, for example, by reaction of acrylic acid chloride or methacrylic acid chloride with terkoxyalkyl alcohol.

Furthermore, it is also illegal to include the following vinyl compounds as copolymerization components other than those produced by transesterification of methyl acrylate or methyl methacrylate with the alcohol. However, in that case, the combined content of ethylene and the vinyl compound in the copolymer must be 55 wt% or more.

(a), (b), (C), (d) Specific examples of vinyl compounds that can be copolymerized in a time other than 9 minutes include hinyl acetate, methyl methacrylate, methyl acrylate, ethyl acrylate, acrylamide, and the like.

The alkoxyalkyl acrylate content in the ethylene copolymer used in the present invention is 5 to 40 Wt, preferably 10 to 10 BQ wt, and when it is 5 wt or less, the effect of improving the compatibility of the copolymer with polyester If the amount is 40 wt% or more, there will be no further improvement in the physical properties of the resin composition, and the manufacturing cost will increase, which is not preferable. , -"if, the content of maleic anhydride, glycidyl methacrylate and/or chrycidyl acrylate in the ethylene copolymer used in the present invention is 0.5
-15 wt%, preferably 1-10 wt%. o,
If it is less than 5 wt*, the affinity between the polyester and the copolymer will not be sufficient, and if it is more than 15 w't%, the fluidity of the resin composition will decrease, resulting in poor processability, which is not preferable.

In addition, the ethylene copolymers used in the present invention are usually '(a8(b) and (C)) or IJ(
d) component in the presence of a radical initiator and a chain transfer agent at a pressure of 700 K9/(7)2 or more and 150 to 250
Preferably, those obtained by continuous copolymerization under temperature conditions of (C) and (a) and (b) Jt are
Alternatively, a copolymer obtained by graft copolymerizing component (d) using an initiator such as peroxide can also be used.

In the composition of the present invention, the content of (B) ethylene-based co-M combination is 0.5 to 4 Qwt%, preferably 3 to 3 Qwt%.
% range. , 5Qwt1 or more, the characteristic properties of polyester such as rigidity, heat resistance, and tensile strength do not necessarily decrease, but the impact strength also tends to decrease.

Moreover, if Q is less than 5 wt%, it is difficult to achieve the object of the present invention.

In addition to the above-mentioned formulations, the composition of the present invention further includes reinforced composite materials such as glass fibers, carbon W4 fibers, holamide fibers, metal whiskers, etc., silica, alumina, calcium carbonate, talc, mica, carbon fluff, Ti0
z, ZnO.

It is preferable to use it as a composite material with the addition of an inorganic photonic agent such as S11203, a flame retardant additive, other oxidizing agents, nucleating agents, plasticizers, starch ingredients, pigments, antistatic agents, weathering agents, etc. This is one of the embodiments, and when these are combined, there is virtually no decrease in impact strength at t. The preferred blending amount of the fiber reinforcing agent and inorganic photonic agent is about 5 to 7 parts by weight per 100 parts by weight of the combined polyester and ethylene copolymer.
It is 0 parts by weight. The amount of the inorganic substance used as a flame retardant aid or colorant is preferably about 0.5 to 5 parts by weight.

There are no particular limitations on the method for producing the composition of the present invention, and any conventional known method may be employed. From an industrial standpoint, a method is usually used in which polyester in the form of pellets or powder is kneaded and granulated using an extruder equipped with an automatic metering feeder. One of the 4S characteristics of the present invention is that a resin composition with sufficiently high performance can be provided using a single-screw extruder without necessarily requiring a particularly high-performance twin-screw extruder or kneader-type extruder. 1. Kneading Specific examples of the equipment include an extruder, a Banbury mixer, a roll, and a kneader.

The present invention also includes a method of triblending during injection molding or extrusion molding and directly kneading the mixture during melt processing to obtain a molded product. In any case, conditions and equipment should be selected so that each component is sufficiently mixed at the stage of the final processed molded product.

The resin composition of the present invention can be easily molded by ordinary methods such as injection molding and extrusion molding, and can be obtained by f:
Part A exhibits excellent properties.

In addition, the resin composition of the present invention can be used to mold a wide range of articles, such as various molded parts, films, sheets, plates, tubes, layered objects, containers, etc., as well as coating materials for metals, etc. , can be widely used in adhesives, etc.

The present invention will be described below with reference to Examples, but these are merely illustrative and the present invention is not limited thereto.

In addition, the Izod impact zero strength in the examples is 711 in JI8.
0 with a notch and a thickness of 6.4 words,
Tensile test is based on JISK7113, bending test is based on JISK7
This is the fco value measured according to 208. The heat distortion temperature is J
These are experimental results with a load of 18.6 Ky according to IS N7207.

Examples 1 and 2 and Comparative Example 1 Pellet-shaped polybutylene terephthalate (Mitsubishi Rayon special Toughpet PBT N1000) and pellet-shaped ethylene copolymer (ethylene H content near 0 wt%)
, quinethyl methacrylate containing j2L: 28w
t%, maleic anhydride-containing nail: 2wt%, melt index 4y-/10πiv) in the proportions shown in Table 1, and after standing in a tumbler for 20 minutes,
A polyester resin composition was obtained by pelletizing by melt mixing at a temperature of about 240° C. using a 65 mm diameter bent extruder (manufactured by Ikegai Iron Works). This composition was heated to 140℃ for 5 minutes.
After drying for 1 hour, Izot impact test was carried out using 3.5 oz injection molding P1 (manufactured by Niskin Resin - Industry σ4..l) as a molding material at a molding temperature of 240 ° o 1 and a mold temperature of 70 ° C. Test pieces for tensile tests, bending tests, and heat deformation temperature tests were molded.

The results of the Izot impact test, tensile test, bending test and heat distortion temperature test of the obtained test piece are shown in Table 1. In addition, the measured values in the case of polyethylene ethylene terephthalate-1 to j + Germany without blending the ethylene-based copolymer for comparison are also shown.

Example 3 and Comparative Example 2 Pellet-shaped polyethylene terephthalate (Unitika (
f) manufactured by MA2101. ) 95wt% ethylene copolymer in pellet form (ethylene content: 75w)
t%, containing methoxyphthyl acrylate [ffi:1
9wt; %, glycidyl methacrylate content: 5wt
%, melt index 27/10six) 5 wt
% and l., pre-prepared in a tumbler for 20 minutes, and then pelletized by bath melt kneading at a temperature of about 260°C using a 65 mm φ vent extruder (manufactured by Ikegai Tekko Q49) to obtain a polyester resin. A composition was obtained. This composition was heated to 140°C.
After drying for 5 hours, use a 3.5 oz injection molding machine (Japanese) as a molding material at a molding temperature of 26.
Test pieces for Izot impact tests, tensile tests, and bending tests were molded at 0°C and mold temperature of 130°C.

The test results of the Izot impact test, tensile test and bending test of the obtained test piece are as shown in Table 2. In addition, for comparison, the measured value when polyethylene terephthalate alone was used without blending the ethylene copolymer was D.
I write down.

Example 4 Pellet-shaped polyethylene terephthalate (Unitika ■
MA, 2101) 90 wt% and pelletized ethylene copolymer (ethylene content: 71 wt%, 2-
Ethyl to chitoxyethyl methacrylate containing i: 14w
L%, maleic anhydride-containing [i: 5 wt%, melt index 5V10 ding) lQwl, %] were blended, pre-prepared in a tumbler for 20 minutes, and then placed in a 65Mφ vent extruder (Ikegai Tetsu) x ea. > pi ), approximately 2
A polyester resin composition was obtained by pelletizing it by melt mixing at a temperature of 60°C. This composition was dried at 140°C for 5 hours. After drying, the composition was subjected to an Izot impact test using a 3.5 oz injection molding machine (Nissaya Resin Kogyo 4) at a molding temperature of 260°C and a mold temperature of 130°C. , test pieces for tensile driving and bending tests were molded.

The test results of the Izod I impact test, tensile test and bending test of the obtained test piece are shown in Table 2.

Example 5 and Comparative Example 8 Pellet-shaped polybutylene terephthalate (Tuffpet PBT N1N100O manufactured by Mitsubishi Rayon ■) 13 (i%
, pellet-shaped ethylene copolymer (ethylene content near 2 wt%, ethoxyethyl methacrylate containing ffi
: 25wt%, maleic anhydride containing [il:awi%, melt index 87/lQm+,) 4-layered fiber and chopped strand crow fiber (R manufactured by Nippon Glass Fibers)
ES 0B-'l'P60) and 80 parts by weight, pre-prepared for 20 minutes in Tanoflar, and then heated at a temperature of about 240°C using a 65 mm φ Hent extruder (manufactured by Ikegai Iron Works). The polyester resin composition was pelletized by melt-kneading to obtain one polyester resin composition. After drying this composition at 140°C for 5 hours, the molding temperature was 240°C and the mold temperature was 70°C using a 3.5 oz injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd.).
Test pieces for Izot impact tests, tensile tests, and heat deformation temperature tests were formed.

The results of the Izot impact test, tensile test, bending test, and thermal deformation test of the obtained test piece are shown in Table 8. In addition, the 1nto constant value in the case of a two-component system of polybutylene terephthalate L-t and crow W4 fiber without blending the 1-rice modified tyrene yarn copolymer for comparison is also shown.

Claims (1)

[Claims] (Saturated polyester tree IJiW 99.5-6Q w
t% and (13) ethylene copolymer 05-40 w
In the thermoplastic resin composition consisting of t%, the ethylene copolymer is
, or a thermoplastic resin composition characterized by being a copolymer of 1 (or 2f11! or more) of a ternary copolymer obtained by polymerizing (a), (b), and (d). ( a) Engineering Y-L/N: 55-94wt% (b) General formula (10% formula% Alkoxyalkyl acrylate = 5-4QwL%), R1 is hydrogen or methyl group, +1 is an integer from 2 to 6 , nl is an integer of 1 to 8.) (0) Maleic anhydride: 0.5 to 15 wt% (dJ
Glycidyl methacrylate and/or glycidyl acrylate 20.5-15 wt%