JPS6020954A - Polyester composition - Google Patents

Abstract

PURPOSE:To provide a polyester compsn. which has good moldability and gives moldings having excellent surface gloss and mechanical properties, by blending a specified nucleating agent, a crystallization accelerator and a reinforcing fiber with polyethylene terephthalate. CONSTITUTION:100-pts.wt. polyethylene terephthalate or polyester composed of at least 80mol% of an ethylene terephthalate repeating unit, 0.05-10pts.wt. at least one member selected from among an inorg. nucleating agent having an average particle size of 50mu or below (e.g. talc or silica) and an org. compd. (or high-molecular compd.) contg. metal carboxylate groups, 0.3-15pts.wt. ester compd. of the formula (wherein R1 is alkylene; R2, R3 are each alkyl, benzyl, etc.; m, n are each 1 or greater) derived from an aliph. dibasic acid, and 0- 150pts.wt. reinforcing fiber (e.g. glass fiber) are mixed together to obtain the desired polyester compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyester composition that has good moldability and provides molded articles with excellent surface gloss and mechanical properties. More specifically, the present invention relates to a polyester composition which has a high crystallization rate and which provides a molded article that stays hot even at a mold temperature of about 120° C. or less during injection molding.

Boryethylene terephcrate has excellent mechanical properties, electrical properties, heat resistance, chemical resistance, etc., and is used in many industrial products as fibers and films.

In this way, when used as fiber or film, 1
Fully stretched products are used, but if you want to use them as injection molded products for plastics manufacturing, for example, because they have not been subjected to the above stretching process, the molding and physical properties will be affected. It is known that various problems occur. In other words, the crystallization rate at low temperatures is low.

Since the crystallization rate is insufficient at mold temperatures below about 120°C, which are commonly used when injection molding other plastics, molded products subjected to + fU have a difference in crystallinity between the surface and the inside. arises, and therefore has a mechanical property.

The dimensional stability and shape stability become non-uniform, and it is extremely difficult to obtain a molded product that can withstand practical use.

Conventionally, as a method to solve such problems.

Many methods have been proposed, such as using a high-temperature mold and adding crystal nucleating agents or crystallization (JC promoters).
lf, which increases the length of the molding cycle and significantly reduces work efficiency, which is not practical. On the other hand, the method of adding a crystal nucleating agent and a crystallization accelerator has been tested in many studies in the past.
Although it has been done, l! I-1 The crystallization speed during molding is still not sufficient, the molding cycle is longer than that of other plastics, and in some cases, the surface of the molded product is Surface properties such as gloss, mechanical properties, thermal properties, etc. may decrease significantly,
Various problems arise, such as additives such as crystallization promoters volatilizing during molding and emitting odor. In this way, the crystal nucleating agent,
The reality is that there are still many points that need to be addressed in the method of adding crystallization promoters.

Therefore, the present inventors have developed polyethylene terephthalate, which is useful as a molding material and has excellent moldability, a fast crystallization rate during zigzag molding, and excellent surface gloss and mechanical properties.
1. i! system composition As a result of extensive research, we found that (a) an inorganic crystal nucleating agent with an average grain size of less than 50 μm, and a metal with a carboxyl group, in polyester having polyethylene terephthalate or a polyester containing 80 mol% or more of ethylene terephthalate repeating units. At least one type of organic compound having a salt, a polymer compound having a metal salt of a carboxyl group, and a 9.1 quantitative amount of a specific aliphatic nitrogen (for use), an acid Nisdel, and further as necessary. zl, +
1 amount of fiber h'11. The inventors have discovered that the above object can be achieved by incorporating a weak reinforcing agent, and have arrived at the present invention.

The present invention is based on 100 parts by weight of polyester (hereinafter abbreviated as PET) containing 1 to 80 moles of polyethylene terephthalate (both 80 mol and 9 or more) and a medium repeating ethylene terephthalate (hereinafter abbreviated as PET). (b) Average grain 1 thread 50
A non-geometric crystal nucleating agent of μ or less, a compound containing a metal salt of a carboxyl group, a polymer compound having a metal salt of a carboxyl group, etc.
~10 parts by weight, (b) aliphatic nil Ji represented by the following general LIQ (1)! >Acid caustyl compound 0.3-15
Weight part R1: Alkylene group 112, +73: Al: 1-l group, -, ndyl group,
yJ″I!2 with a group selected from shield-group substituted mono- and ndyl groups
+R+ is the same group or \Il group.

(b), n: an integer of 1 or more (c) 0 to 150 parts by weight of fibrous reinforcing fibers are added to the polyester composition.

The present invention includes specific amounts of components (() and (b)) in PUT.
The crystallization rate of PET can be improved by blending it with J.

and surface gloss etc. '1. ``ζ'' by reforming the Il nature and adding a Zen fiber-shaped strengthening shrine (if necessary).

1. The object of the present invention is to provide a white composite acid with improved mechanical properties.

Conventionally, it has been known that adding fibrous reinforcing materials such as glass fiber to PET improves the mechanical and thermal properties of PET. If the crystallization rate is low and the molding cycle becomes long, and if the mold temperature is low, for example below about 120°C, crystallization will not proceed sufficiently and the dimensional stability of the molded product will deteriorate. However, there is a fatal problem in that both thermal and mechanical properties cannot fully demonstrate their inherent performance. Problems like this? +'i
! In order to determine Additives such as crystallization accelerators are evenly mixed and dispersed in PETLI Yuko, and even during heating during injection molding, they are stably compatible and ooze out from the molded product.

It is necessary to prevent one car from starting and dissipating. However, conventionally used additives, especially crystallization accelerators, are not sufficiently compatible with PET, causing problems as they may partially separate and ooze out, or evaporate and escape, especially when heated. ing.

As a crystallization accelerator, a method of adding a low molecular weight ester-based softening agent such as diocdylphthale-1 has been proposed for a long time, and furthermore, in Japanese Patent Publication No. 55-47058'; It has been shown that oligomeric polyesters are useful in low molecular weight ester compounds such as JP-A-55-116761. However, even if low molecular weight ester compounds and oligomeric polyesters have superior ability to promote crystallization.

In particular, when heated, it has poor compatibility with polyethylene terephthalate or ethylene terephthalate polyester, and may ooze out or, in some cases, evaporate and escape, and there is a strong desire to improve this problem.

As a result of repeated studies to solve the above problems, the present inventors selected an ester compound of an aliphatic dibasic acid represented by the general formula (1) as an ester-based crystallization promoter, and added it to the component ( When used with the crystal nucleating agent shown in b), 'PE
Increase the crystallization rate of T.

Moreover, it does not ooze out or evaporate even when heated, and is t! The present invention was achieved by discovering that Ti has excellent crystallization promotion properties. Therefore, when the polyester composition of the present invention is injection molded, molded products with excellent surface gloss can be produced in a short cooling time even when the mold temperature is below 120°C, for example in the temperature range of 100°C to 70°C. Obtainable. In addition, specific amounts of ingredients (a)
and component iD] and a specific amount of fibrous reinforcing material.

It has excellent moldability, surface properties, and excellent mechanical properties, and can be used as a well-balanced and useful molding material.

The polyethylene terephthalate used in the present invention is made from terephthalic acid or an ester of terephthalic acid and ethylene glycol, and is prepared by cold cooling and commercially available.
7, or those that have been subjected to solid phase polymerization treatment. And the polyester having at least 80 mol% or more of ethylene terephthalate repeating at the Q4 position is
80 mol% or more of ethylene terephthalate repeating units and other repeating units.

In other words, it means a copolymer consisting of other copolymer components,
As the other copolymerization components mentioned above, three kinds of acid components and glycol components can be used.

For example, acid components include isophthalic acid, chic dicarboxylic acid, diphenyl etherone carboxylic acid, diphenylmethane dicarboxylic acid, diphenylsulfone dicarboxylic acid, benzoic acid, 5-sodium sulfoisophthalic acid,
Adipic acid, azelaic acid, sebacic acid, dodecane-1
, 12-dicarboxylic acid, tetosidecane-1,14-dicarboxylic acid, hexadecane-1,16-dicarboxylic acid.

Examples include octadecane-Li8-dicarboxylic acid, 6-ethyl-hexadecane-1,16-dical; 1-minic acid. Examples of glycol components include polyalkylene glycols such as pyrene glycol, diethylene glycol, butylene glycol, baytyl glycol, neopentyl glycol, xamethylene glycol, polyethylene glycol, and bolite 1 to ramethylene glycol. be able to.

The ester compound of an aliphatic dibasic acid used as component (b) in the present invention has the sulfuric acid shown in the general formula (1), and R+ represents an alkylene group, but usually has 1 to 20 carbon atoms. It is desirable to use a branched alkylene group having straight or molecular symmetry. Also '2+
R:I is a group selected from an alkyl group, a benzyl group, and an aromatic substituted benzyl group; 112. R3 is the same or different group, and examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl.

Specific examples include octyl.

Although m and n are integers of 1 or more, the larger m and n are, the greater the effect as a crystallization promoter, but conversely, the compatibility with PET is reduced (because Usually m and n are 1 to about 30.

The inorganic compound used as component (a) of the present invention is as follows.

The effect of 9) as a crystal nucleating agent differs depending on the particle size, and if the average particle size exceeds about 50 μm, the effect becomes small, so inorganic compounds with an average particle size of 5 μm or less are generally useful.

Specific examples of inorganic compounds with an average particle size of 5 μm or less used in the present invention include carbon blank, silica, calcium carbonate, synthetic silicic acid and silicates, zinc white, HaU1 zytoclay, kaolin, basic carbonate, etc. Magnesium, mica.

Talc, quartz powder, diatomaceous earth, dolomy I-J't'J
+Titanium oxide, zinc oxide, antimony oxide, barium sulfate, calcium sulfate, alumina, calcium silicate, etc. can be mentioned, and one or more of these inorganic compounds can be used.

Among them, mica, kaolin, and non-tal silica are useful in the present invention.

Further, as the organic compound having a metal salt of a carboxyl group used in the present invention, any compound having a metal salt of a carboxyl group can be used, but usually has about 7 to 7 carbon atoms. Metal salts of 30 higher fatty acids and 1 aromatic acid are used, such as hepcinic acid,
pelargonic acid.

Lauric acid, cristic acid, valmitic acid, stearic acid, hehenic acid, cerotic acid, mongkun ugliness.

Metal salts of higher fatty acids such as melisic acid, benzoic acid.

Terephthalic acid, terephculic acid monomethyl ester.

Specific examples include metal salts of aromatic acids such as isophthalic acid and monomethyl ester of isophthalic acid.

The polymer compound having a metal salt of a carboxyl group is not particularly limited as long as it has a metal salt of a carboxyl group at the end or side chain of the polymer, but for example, a carboxyl group obtained by oxidizing polypropylene can be used. polyethylene, a copolymer of olefins such as polyethylene, propylene, butene-1, etc. and (meth)acrylic acid, a copolymer of olefins and maleic anhydride, Specific examples include metal salts such as copolymers of styrene and (meth)acrylic acid and copolymers of styrene and maleic anhydride.9 Usually, olefins and (meth)acrylic acid or styrene and (meth)acrylic Copolymer metal salts of acids are used. As metals that form salts with carboxyl groups, alkaline earth metals, alkali metals, etc. are usually used, but alkali metals have excellent effects as crystal nucleating agents, and among them,
・Rium and potassium are useful.

Examples of the fibrous reinforcing phase used in the present invention include glass fibers, carbon fibers, aromatic polyamide fibers,
Specific examples include gaseous carbide fibers and titanate fibers, but glass fibers are preferred for one current application.

There are no particular restrictions on the diameter and length of the various fibers; however, if the fiber length is too long, the fibers may become uniform and resistant to PET or other compounding agents, such as the straw (a) component or the (a) component.
On the other hand, if the fiber length is too short, it will be reinforced (the effect as 1 will be insufficient, so for 1 energization, fibers with a length of 0.1 to 1Qmm are used. In particular, when the fibrous reinforcing material is glass fiber, the fiber length is preferably 0.1 to 7 mm, more preferably 0.3 mm.
~4 mm is desirable. In addition, the fibrous reinforcing material can be treated with various compounds as necessary for the purpose of improving the interfacial adhesion with PET and increasing the reinforcing effect. When using 2 various surface treatment agents, such as vinyl 1-lye 1-oxysilane, T-methacryloxypropylmethoxysilane, β-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, γ-glycid. Xypropyltrimethoxysilane, T-aminopropyltriethoxysilane,
Those treated with a silane-based treatment agent such as γ-chloropropylmethynesilane or γ-mercaptopropyltrimethine-1-xysilane, or a chromium-based treatment agent such as methacrylate chromisocchloride are used.

Regarding the blending amount of each component in the polyester composition of the present invention, component (a), an inorganic compound having an average particle size of 50 μm or less, an organic compound having a metal salt of a carboxyl group, and a metal salt of a carboxyl group. If the amount of at least one of the polymer compounds having the following is less than 0.05 parts by weight per 100 parts by weight of PET resin, the effect as a crystal nucleating agent will be insufficient; Even if they are blended, the effect as a crystal-nucleating agent is not proportional to the amount blended, and any excess blended merely acts as a filler.

Therefore, the blending amount of component (a) is 1 to 5 parts by weight per PET resin, more preferably 0.1 to 3 parts by weight. Furthermore, regarding the formulation M of the ester compound of an aliphatic dibasic acid represented by the general formula (1), the amount of the component is PYF. If the amount is less than 0.3 parts by weight per 100 parts by weight, the effect as a crystallization accelerator will be insufficient and a molded product with excellent surface properties will not be obtained; This is because other performances such as physical properties deteriorate. c) The amount of ingredients is P
E T 0.3 to 15 parts by weight, preferably 0.5 to 10 parts by weight, more preferably 1 to 7 parts by weight
It is a heavy plate part.

Furthermore, in the present invention, regarding the amount of fibrous reinforcing material added as necessary. The blending amount is PET resin 100
If it is less than 5 parts by weight, the effect of improving mechanical properties and thermal properties will be insufficient;
If the amount exceeds parts by weight, it becomes difficult to uniformly mix and disperse the fibrous reinforcing material in the composition. Therefore, the amount of the fibrous reinforcing material to be blended is 5 to 150 parts by weight, preferably 25 to 100 parts by weight, per 100 parts by weight.

The composition of the present invention may further contain an antioxidant, if necessary.
Ultraviolet absorber 1 Various inorganic or organic compounds such as colorants, mold release agents, fillers, etc. can be blended.

The polyester composition of the present invention can be manufactured by mixing in various methods, and the manufacturing method is not particularly limited.9 Usually, each component or additive is added to PIET pellets and then an extruder It is manufactured by mixing using a kneader or a kneader.

The compositions of the present invention may be available in various forms, such as molded articles, Sea 1-2 fibrous materials, etc. It can be formed into a tubular shape and used.

Next, the present invention will be specifically explained with reference to Examples and Comparative Examples.

Note that "section" shown in Examples and Comparative Examples indicates a revised section.

Examples 1 to G, Comparative Example 1.2 Zari 71555 was added to 100 parts of polyethylene terephthalate with an intrinsic viscosity of 0.68 (measured at +6 degrees 0.5% in phenol/tetrachloroethane-6/4, temperature 20 degrees Celsius).
(DuPont Co., Ltd., 2 parts of ethylene-acrylic acid co-merged sodium salt) and a predetermined amount of the following aliphatic dibasic acid ester compound 11a + IIb + Inc, lld were mixed, kneaded in an extruder, and quenched. Pellets of the composition were made.

(I[) n=4:l1a n=7:1Ib 11=12:Llc n-ta:ua Various compositions produced in this way and as a comparative example polyconyethylene terephthalate-1 itself (comparison Example 1
) and Bereso 1 (Comparative Example 2), which is a mixture of 1,100 parts of polyethylene tereph clay and 1,555.2 parts of Zarlin, were heated using differential heat (1 total (Model DSC-1, manufactured by PerkinElmer)).
The crystallization temperature at high temperatures was determined when the temperature was raised from room temperature at 20"C/min. The lower the 3T value, the higher the crystallization rate in the low temperature region.Results Table 1
Shown below.

Table 1 Example 7 Polyethylene terephthalate 70 31X with an intrinsic viscosity of 0.68 and polyconylene glycol (molecular weight 2,000
), 30 parts of ethylene terephthalate polyester copolymerized with 15% by weight, 1 part of talc, and Zarlin 1555.
1 part, adipic acid ester compound shown by the chemical formula (Ill) 3 parts 5 glass fibers (Asahi Fiberglass Co., Ltd.
J3. 3 mJ Chi Elmptotran 1. crystal t'fr
No. 429) were mixed and kneaded in an extruder to create Bereno 1. The TlIC of this composition is 98°C
This is a low value. After drying this Beleno l-, cylinder temperature 240-260-270°C1 mold temperature 9
0°C, injection time 10 seconds.

1 part 4 inch x 1/2 inch x with cooling time of 10 seconds
A 5 inch specimen was molded. The specimens have excellent surface gloss and a bending strength of 18 GO kg/cnt.

Bending elastic modulus 78.000 kg/cm, Izotsu south impact strength (with nonoji) 13.6 J-cm/cm,
Heat distortion temperature (under 18,56kg/c+ll load) 22
It showed gender 1j, 1-c.

ClI3 (-OCIh ClI2 r 8C(C11
2T 4 C-0111 + CIL2CI120su8C11300 (, lit) Example 8 Ethylene terephthalene = 1 system obtained by copolymerizing 160 parts of polyethylene terephthalate with an intrinsic viscosity of 0.68 and 20% by weight of octadecane-1,18-dicarboxylic acid. polyester 4
0 parts of Kuruk, 0.5 parts of Surlyn 1555, 4 parts of an aliphatic dibasic acid ester compound (Il, i), and 45 parts of glass fiber (same as in Example 7) were mixed and extruded into 121 parts.
Create a pellet by cutting the staff with a saw. TlI of this composition
C shows a low value of 86°C.

After drying this pellet, the cylinder temperature was 24o-2.
6o-27o°C1 Mold temperature 80°C1 Injection time 10 seconds.

1 part 4 inch x 1/2 inch x with cooling time of 10 seconds
A 5 inch specimen was molded. The test piece has a fixed surface gloss and one song has an intensity of 1700kB/c++!
.

Flexural modulus 74.000kg/cnl, isiso 1
Impact strength 9.2 kg-cm/cm, heat distortion temperature (1
8, 5G k B / cnt f::j heavy T) 20
It showed a performance of 8'C.

+1) Applicant: Unitika Co., Ltd. Continued from page 1 0 Inventor: 64, Kuseri-no-nishi, Marutani-Mujoyo-shi. -83 0 inventors Minoru Tsuji 57-1 Ujikageyama, Uji City 0 inventors Osamu Doi N12-28 Nakamukaikawa, Joyo City Procedural amendment (voluntary) Name of Polyester Composition 3, Relationship with the case of the person making the amendment Patent applicant address 1-50 Higashihonmachi, Amagasaki City, Hyogo Prefecture (1) Column 5 of "n'-item explanation of the invention" in the specification, Amendment Contents (1) Ming 8. In the 4th line of page 19 of Book IIl, "The crystallization temperature was determined during heating up." was corrected to "The temperature (TIIC') was determined."

Claims (1)

[Claims] 1. Polyethylene terephthalate or at least 80%
For 1 part of 100 mff of polyester having mol % or more of ethylene terephthalate repeating units. (b) At least one of an inorganic crystal nucleating agent with an average particle size of 50μ or less, an organic compound having a metal salt of a carboxyl group, and a polymer compound having a metal salt of a carboxyl group is added in an amount of 0.05 to 10 parts by weight. ) 0.3 to 15 parts by weight of an ester compound of an aliphatic dibasic acid represented by the following general formula (1). 122°R3 are the same or different groups. m, n: an integer of 1 or more (c) fibrous reinforcement θ ~ 150 parts by weight polyester composition 2, average particle i'f: 50μ or less Inorganic compounds include talc, mica, kaolin, silica. 2. The polyester composition according to claim 1, which contains at least one inorganic material selected from the group consisting of: 3. The polyester composition according to claim 1, wherein the metal salt of the carboxyl group is a sodium salt or potassium salt of the carboxyl group. 4. The polyester composition according to claim ff11, wherein the organic compound having a metal salt of a carboxyl group is a compound having about 7 to 30 carbon atoms. 5. The polyester composition according to claim 1, wherein the polymer compound having a metal salt of a carboxyl group is a copolymer of olefin and (meth)acrylic acid or a copolymer of styrene and (meth)acrylic acid. . 6. The polynisdel composite acid according to claim 1, wherein the fibrous reinforcing material is glass fiber or carbon fiber.