JPS5863744A - Polyester resin composition - Google Patents

Abstract

PURPOSE:A composition having high crystallization speed during molding, improved surface gloss and mechanical properties, obtained by blending a polyester with a specific inorganic, organic or high polymer compound as a nucleating agent and a specified styrene-containing polymer as a promotor for crystallization. CONSTITUTION:(A) 100pts.wt. polyester having polyethylene terephthalate or a repeating unit of >=80mol% ethylene terephthalate is blended with (B) 0.01- 20pts.wt. one or more of inorganic compound having an average particle diameter of <=50mu, organic compound containing a metal salt of carboxyl group, and high polymer compound containing a metal salt of carboxyl group, and (C) 0.5-30pts.wt. one or more of polystyrene and poly(alpha-methylstyrene) having a weight-average molecular weight of <= about 30,000, and styrene-(meth)acrylate copolymer with a weight-average molecular weight of <=60,000 having neither hydroxyl, epoxy, primary nor secondary amino groups in the side chain. The composition is preferably blended with 5-150pts.wt. reinforcing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a polynisder composition which provides molded products with good moldability and excellent surface gloss and mechanical properties.
It is something to do. More specifically, the mold 11JI has a high crystallization rate and is heated to about 120°C or less during injection molding.
F also relates to a polyester composition that provides an excellent molded product.

Holly ethylene terephthalate has excellent mechanical properties, electrical properties, heat resistance, chemical resistance, etc.

It is used as a film in many industrial products.

In this way, when used as a thin fiber or film, one that has been subjected to a stretching process is usually used.1 For example, when it is intended to be used as an injection molded product for plastic purposes, the above-mentioned stretching process is used. I know that problems will arise here and there. In other words, k because the fast root of crystallization at low temperatures is small.

If the mold temperature is below about 120 U, which is normally used when injection molding other plastics, the crystallization rate is insufficient, resulting in a difference in crystallinity between the surface and the inside of the resulting molded product, which causes However, it is extremely difficult to obtain a molded product that can be put to practical use because the dimensional stability and shape stability are non-uniform.

Conventionally, as a method to solve such problems.

Many methods have been proposed, such as using a high-temperature mold and adding a crystal nucleating agent or a crystallization agent. however,
#C is not practical in the method of using a high 11 mold because the operation to raise the temperature becomes complicated, the molding cycle becomes longer, and the first operation is significantly reduced.

On the other hand, many methods of adding crystallization nucleating agents and crystallization accelerators have been investigated, but
However, the molding cycle is longer than that of other plastics, and in some cases it is necessary to add crystal nucleating agents and crystallization accelerators, which may affect the surface properties such as surface gloss of the molded product and the mechanical Various problems occur, such as a significant decrease in physical properties, thermal properties, etc., and additives in the crystallization accelerator volatilize during molding, emitting odors. The reality is that there are still many points to be considered regarding the method of adding a crystal nucleating agent and a crystallization accelerator, as in the case of nits.

Therefore, the present inventors conducted extensive research in order to obtain a polyethylene terephthalate-based composition that is useful as a molding material that has excellent moldability, that is, has a fast crystallization rate during molding, and has excellent surface gloss and mechanical properties. As a result, polyethylene terephthalate or a polyester having at least 80 molar units of ethylene terephthalate repeating units,
Gf) at least one of an inorganic compound with an average particle size of 50# 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 4t+;
-) Specific polystyrene, positive (--methylstyrene)
A specific lid of one or more polymers selected from the group consisting of 1% styrene-(meth)acrylic ester combined with 1% is added, and if necessary, a specific amount of 1#! The present invention K'jIJ was achieved by discovering that the above object can be achieved by incorporating a fibrous reinforcing agent.

That is, the present invention is based on 100 parts of polyethylene terephthalate or a polyester having ethylene terephthalate repeating units of at least 80 molar proportions (hereinafter referred to as PET).

At least one of an inorganic compound having an average particle size of 50j or less, an organic compound having a gold W4 salt of a carboxyl group, and a polymer compound having a metal salt of a carboxyl group is 0.0
1 to 20 parts by weight, ←) Polystyrene, poly(,-methylstyrene) with an average molecular weight of about 30,000 or less, 'M' average molecular weight of about 60,000 or less, hydroxyl group, epoxy group, Styrene containing no primary anno group or secondary amine group (
A polyester composition comprising 0.5 to 30 ki of one or more polymers selected from the group of meth)acrylic acid ester copolymers, and K is the polyester composition v above. ! , 10 parts by weight, and 5 to 1,501 parts of a value-structured reinforcing agent are blended into a polyester ship product.

The present invention increases the crystallization rate of PET by blending specific amounts of component B) and component ←).

In addition, the surface properties such as surface gloss are improved, and if necessary, an *a* type reinforcing agent is added.

The present invention provides a composition useful as a molding material with improved mechanical properties.

It has been known that the mechanical and thermal properties of PET can be improved by adding fibrous reinforcing agents such as PETK glass fibers. If the crystallization rate is slow and the molding cycle becomes long, and if the temperature of the mold (11 degrees Celsius) is as low as, for example, about 120 degrees Celsius or less, the dimensional stability of the molded product may deteriorate because crystallization does not proceed sufficiently. However, there is a fatal problem in that both the thermal and mechanical properties cannot fully demonstrate their inherent performance.

In order to solve these problems, is there a crystal nucleating agent or component that corresponds to the component pK? ) has been extensively considered to add a crystallization promoter equivalent to PET, but in that case, additives such as crystal nucleating agents or crystallization promoters must be uniformly mixed and dispersed in PET. , and are stably compatible with each other even when subjected to stress such as during injection molding.

It is necessary that it does not ooze out of the molded product or volatilize and escape. However, conventionally used additives, especially crystallization accelerators, are not sufficiently compatible with PET, and may ooze out through dissociation or evaporate and escape, especially when heated. There are 9 problems.

On the other hand, in the polyester composition of the present invention,
This is because specific polystyrene, poly(,-methylstyrene) or styrene-(meth)acrylic acid ester #polymer is used as component ←).

It has extremely good compatibility with PET, and does not separate from PET and ooze out or volatilize even when heated. Also, when this component ←) is blended with PETK along with the ingredient mark, it becomes the component ←). Since it has the effect of increasing the crystallization rate of PET and improving the moldability compared to when the component or component is blended alone, the mold temperature during injection molding is 120°C or less 2 For example, from 100°C to Even at an IT temperature of 70°C, a molded article with excellent surface gloss can be obtained with a short cooling time. Furthermore, % quantification of component 0) and component ←) K41 quantification of M! The polyester composition of the present invention containing fibrous reinforced U has excellent moldability, surface properties, and mechanical properties, and can provide a useful acid form material with good balance. .

The polyethylene terephthalate used in the present invention is obtained from terephthalic acid or an ester of terephthalic acid and ethylene glycol by a conventional melt polymerization method, or it is obtained by subjecting it to in-phase polymerization. The polyester having at least 80 moles or more of ethylene terephthalate repeating units means 80 moles 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, acid components and glycol components of AI can be used.

For example, the acid components are in-7 talic acid, 7-tal dicarboxylic acid, and diphenyl ether dicarboxylic acid.

Diphenylmethane dicarboxylic acid, dienyl sulfone dicarboxylic acid eI1. p-(2-human-loxethoxy)benzoic acid, 5-sodium sulfoisofumel, adipic acid, azelaic acid, sepacic acid, etc. can be suppressed. In addition, the glycol component is propylene glycol,
Diethylene glycol.

Pentyl glycol, neopentyl glycol.

Examples include polyalkylene glycols such as hexamethylene glycol and polyethylene glycol.

The polystyrene or poly(a-methylstyrene) which is one of the components (b) of the MA substance of the present invention is as follows.

Polystyrene or poly(σ-
However, if the average molecular weight of polystyrene or poly(-monomethylstyrene) is greater than about 30,000, the compatibility with PET will be poor and the mobility of the molecular chain will be reduced. As a result, its effect as a wound promoting MlI & oxidation becomes smaller. Therefore, polystyrene or poly(a-methylstyrene) having a relatively low molecular weight having a 2 weight average molecular weight of about 30,000 or less is used as the polystyrene or poly(-monomethylstyrene). In addition, as the styrene-(meth)acrylic ester copolymer which is a type of component (b), a copolymer consisting of (meth)acrylic esters of a* can be used, but in this case, When the weight average molecular weight of the copolymer is greater than about 60,000.

As with polystyrene or poly(g-methylstyrene), the compatibility with PET becomes poor. Therefore, as a styrene-(meth)acrylic acid ester copolymer, 1
Those having a weight average molecular weight of about 60,000 or less are used, and those having a weight average molecular weight of about 40,000 or less are usually used. And styrene (
When using a meth)acrylic acid ester copolymer having a hydroxyl group, an epoxy group, a falm, and a secondary 72 group in the side chain, P during melt mixing or heated acid form is used.
Since ET may be decomposed or glued, the styrene-(meth)acrylic acid ester copolymer used in the ←) component of the present invention and the copolymer that does not have a secondary Polymers are used; therefore, the ester residues of the (meth)acrylic esters of the co-electropolymer component -C
R in 0OR is 2, for example, an alkyl group such as methyl, ethyl, propyl, t-butyl, neopentyl, a residue having an ether bond such as methoxyethyl, an alicyclic alcohol residue such as hexyl, a benzyl group. Specific examples include residues having an aromatic moat such as.

The copolymerization composition ratio of the styrene component in the styrene-(meth)acrylic acid ester copolymer varies depending on the type of (meth)acrylic acid ester, but generally, if the styrene content is less than 60 mol, it becomes a crystallization promoter. Therefore, a styrene-(meth)acrylate copolymer prepared by copolymerizing 60 mol % or more of a styrene component is usually used.

The inorganic compound used as component 0) of the present invention is as follows.

Its effectiveness as a crystal nucleating agent varies depending on its particle size.

If the average particle size exceeds about 50 degrees, the effect will be reduced, so inorganic compounds with an average particle size of 50 degrees or less are generally useful. and 1 the average particle size used in the present invention 501
Specific examples of inorganic compounds of 1 or less include:

For example, carbon black, silica, calcium carbonate, synthetic silicic acid and silicates, zinc oxide, halolithic clay,
Kaolin, basic magnesium carbonate.

mica, merck, quartz powder, silica gravel, de c1 mite powder,
Examples include titanium WI, zinc M oxide, antimony oxide, barium V1 acid, calcium oxalate, alumina, calcium silicate, etc., and one or more of these inorganic compounds can be used. mica,
Kaolin, Merck, and silica are useful in the present invention.

In addition, 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 the number of carbon atoms is about 7. ~30 higher fatty acids, metal salts of aromatic acids are used, such as hemenoic acid,
pelargonic acid.

All salts of higher fatty acids such as lauric acid, electric acid, curmitic acid, suderic acid, behenic acid, cerotic acid, montanic acid, 9merisic acid, benzoic acid.

Terephthal, terephthal monomethyl ester.

Specific examples of aromatic acids such as inphthalic acid and monomethyl ester of inphthalic acid can be mentioned.

In addition, the polymer compound having a wire mesh salt of a carboxyl group is not particularly limited as long as it has a metal salt of a carboxyl group at the end of the polymer or @flAl/C. Specific examples include carboxyl group-containing polyethylene obtained by oxidizing polypropylene, carboxyl group-containing polypropylene obtained by oxidizing polypropylene, a coelectrolyte of ethyacryl acid, a comonomer of styrene and maleic anhydride, etc. Comonomer gold of olefin and (meth)acrylic acid or styrene and (meth)acrylic acid
salt is used. As metals that form salts with carboxyl groups, alkaline earth * maple, alkali metals, etc. are usually used, but alkali metals have excellent effects as crystal nucleating agents, and among them, sodium and potassium are useful. .

Specific examples of #M-shaped reinforcing agents used in the present invention include glass SL fibers, carbon fibers, aromatic boria 2-carbon fibers, silicon carbide fibers, titanate fibers, etc.; ls fibers are often used.

In addition, although there are no particular restrictions on the diameter and length k of each memo, if the In length is too long, it will be difficult to mix and disperse uniformly with PET and other compounding agents, that is, components (B) to 0). On the other hand, if the steep length is too short, the effect as a reinforcing agent will be insufficient.
Steeply elongated ones with a diameter of 1 to 10 cm are used, and special Kllem
When the shaped reinforcement is glass fiber, #slenderness is 0.
．． 1 to 7 is preferable, and K is preferably 0.3 to 4. Also, the fibrous reinforcing agent is used for the purpose of improving the bond strength with PET and reinforcing effect, if necessary. However, when using crow fiber as a fibrous reinforcing agent, surface treatment agents such as vinyltriethoxysilane, r-methacryloxypropylmethoxysilane, /-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane,
Silane-based stamping agents such as r-glycidoxypropyltrimethoxysilane, r-aminopropyltriethoxysilane, r-chlorobutobyltrimethoxysilane, r-mercapdobutibyltrimethoxysilane, methacrylate chromic chloride, etc. Those treated with a chromium-based treatment agent are used.

Regarding the formulation 1ltIIC of each component in the polyester 4f4 Ml bt of the present invention, the marked components, that is, an inorganic compound with an average particle size of 50 J or less, an organic compound having a metal salt of a carboxyl group, 1. At least a portion of the polymer composition containing gold lN4 salt of carboxyl group is PE.
If it is less than 0.01 part by weight based on 100 parts of T-pattern fat, the effect of the crystal nucleating agent will be insufficient, and conversely, even if it is mixed in more than 11 parts of 20JKi, it will not work as a crystal nucleating agent. The effect is not proportional to the amount added, and if added in excess, it only acts as a filler.

Therefore, the amount of component 0) is 0.01 to 20 parts by weight per 100 parts by weight of PET resin, preferably 0.
．． 05~101ff part, further KtFf preferably 0.1~
53i parts. Furthermore, regarding the blending amount of component #X), that is, low molecular weight polystyrene or poly(a-methylstyrene), and low molecular weight styrene-(meth)acrylate copolymer, the blending amount of component #X) is PET100.
If the amount is less than 0.5 parts by weight, the effect as a crystallization accelerator will be insufficient and a molded product with hard surface characteristics will not be obtained.On the other hand, if it is more than 30 parts by weight, heat The content of IP) component is 0.5 to 3011 parts by weight per 100 parts by weight of PET.
The amount is preferably 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight.

Furthermore, in the present invention, regarding the amount of the fibrous reinforcing agent blended as needed, the blended amount is 100% of the polyester composition consisting of PET, component (A), and component #I).
Less than 5 parts by weight.

The effect of improving mechanical properties and thermal properties is insufficient, and if the amount exceeds 150 parts by weight, it becomes difficult to mix and disperse the fibrous reinforcing agent uniformly into the composition. Therefore, the blending amount of the fibrous reinforcing agent is 5 to 150 parts by weight, preferably 25 to 100 imaginary parts per 100 parts by weight of the polyester composition before addition of the fibrous reinforcing agent.

The formation f of the present invention is J! ! 4! ? Antioxidant, ultraviolet hI & collection agent 2 coloring agent, hull form agent, filler cape each a as required.
tInorganic threads or organic compounds can be blended.

The polyester composition of the present invention can be produced by mixing in various ways, and the production method is not particularly limited.
A method in which a part of each component or additive is added and mixed during the polymerization tk period of F, after the polymerization of PET, kr K fA is added and mixed to obtain pellets, and then the remainder of each component or additive is added. PET pellets are manufactured by mixing using an extrusion method or a kneader, or by adding each component or a cooling agent to PET pellets and mixing using an extrusion method or a kneader.

The composition of the present invention can be formed into various shapes 111, such as various molded articles, films, sheets, fibrous materials, tubular materials, and the like.

Next, examples and comparative examples will be given to illustrate the present invention in detail, but the present invention is not limited to these examples.

Note that "part r" shown in Examples and Comparative Examples indicates "part by weight."

Examples 1-4. Comparative Example 1 To 100 parts of polyethylene terephthalate having an intrinsic viscosity (measured in phenol/tetrachloroethane-6/4, concentration 0.5%, i1 degree, 20°C) of 0.68, I! IK 1 part talc and low molecular weight polystyrene as shown.

5 parts of poly(--methylstyrene) or styrene-methacrylate copolymer were added and mixed.

A pellet was produced through a 65-clear extruder. The composition produced in this way and PE as a comparative example
Showing the sample of T itself! A calorimeter (DSC-IJI, manufactured by Birkin Elmer) was placed in the sample, and the temperature was raised from room temperature at a rate of 20° C./min to determine the melting point (Tffl).

From the exothermic peak in the picture, the cooling crystallization temperature (T(!e
) was measured. And crystallization]ll! Evaluation was made from the value of Tcc, the shape of its peak, and ΔTwTee-7B.

It can be evaluated that the larger the value of 'fee, the sharper the root of the 7'cc peak, and the smaller the ΔT, the higher the crystallization rate. The results are shown in Table 1.

Table 1 (1): Polysterene 2 molecular weight approximately 1060 (1(2):
xyvy-71pypWkjll) Chi e (4 to this y
o:so) Copolymer molecular weight approx. 15,000 (R): Styrene seame acrylic methyl (Soru Jt)
lill 15) Copolymer molecular weight approximately 40,000 (4) my (g-/?+x#Vy)) Ten amount leopard soo.

Examples 5-9. Comparative Example 2.3 100 parts of polyethylene terephthalate (polyethylene terephthalate with a domestic viscosity of ff 10.70) to 100 parts of glass tsumugi (product number 429 manufactured by Asahi Fiberglass ■). Chi■Tupdostondo 3■Length]
, various crystal nucleating agents, and predetermined amounts of polystyrene, poly(--methylstyrene), or styrene-acrylic acid ester copolymer (referred to as a crystal accelerator) in a tumbler, and then heated in a 65 φ extruder. Pellets were produced by melt extrusion. After drying the strung pellets at 11F, cylinder temperature 240-270-280C, mold temperature 96C, injection holding time 10 seconds, injection pressure 300-60C.
A test piece measuring 174 inches x 1/2 inches x 5 inches was molded under conditions of 0 (-).

At that time, the cooling time was carefully determined, and the minimum cooling time (minimum molding cycle) was determined from the mold releasability, and at the same time, the surface of the molded product was observed. Result fl! Shown in 2.

Expressions - Nardan 1555: published by Dae-Pong Publishing Co., Ltd., eteleshiac fenugreek acid copolymerization body t) 1 rim salt kaon: application published by Kaorishi Co., Ltd. 11. N, N-Khao Son Talay! Squid: shaving, sl light 200 HK&
! 1m: l Mori, Amorphous No.7 Toshi9 Ka procedural amendment (
(Voluntary) January 29, 1980 Commissioner of the Japan Patent Office 1. Indication of the case Patent Application No. 163822-1982 2. Name of the invention Polyester resin composition 3. Relationship with the person making the amendment Patent applicant address Amagasaki 1-50 Higashihonmachi, City Name (45
0) Detailed explanation of the invention in the Yu-Riki Co., Ltd. specification - 5. Contents of amendment (1) "Amount of low molecular weight" on page 11, line 2 of the specification
is corrected to "low molecular weight."

Claims (1)

[Scope of Claims] (1) 1 et per 100 parts by weight of polyethylene terephthalate or a polyester having ethylene terephthalate repeating units of at least 80 molar proportions.
)) At least one of an inorganic compound having an average particle size of 50- 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.
1 to 20 parts by weight, I7) Polystyrene having a weight average molecular weight of about 30,000 or less. Poly(--methylstyrene) 2 weight average molecular weight is approximately 60,000 or less, hydroxyl group and epoxy group in side chain. Styrene without primary 72 groups and tuna secondary aelectro groups
A polyester composition comprising 0.5 to 30 parts by weight of one or more polymers from the group of (meth)acrylic acid-ester polymers. (2. For the polyester composite 1001 lid f!ilK described in claim 1, the fiber-like reinforcing agent 5 to 150
A polyester composition made by blending a heavy weight. (81 As an inorganic compound with an average particle size of 50j or less, inorganic compound 3 selected from the group of Merck, mica, kaolin, and silica)
3. The polyester composite according to claims 1 and 2, characterized in that one or more of these compounds are used. 2. 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. +81 The polyester composition according to claims 1 and 2, wherein the organic compound having a metal salt of a carboxyl group is a compound having about 7 to 30 carbon atoms. (6) Claims 1 and 2 which are a polymer compound having a metal salt of a carboxyl group, a copolymer of olefin and (meth)acrylic acid, or a copolymer of styrene and (meth)acrylic acid. The polyester composition according to item (2). The polyester composition according to Claims 1 and 2, wherein the C71 styrene-(meth)acrylic acid ester copolymer is a copolymer having a styrene component of 60 moles or more. (Ill) The polyester composite according to claim 2, wherein the fibrous reinforcing agent is glass fine.