JPS58501327A - polyester composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] The invention is particularly useful for injection molding operations conducted at relatively low mold temperatures. The present invention relates to a thermoplastic polyester composition for use.

Polyethylene terephthalate (PET) has excellent physical properties, such as resistance to chemical attacks. has long been known to have desirable mechanical and electrical properties. It is. Despite these excellent physical properties, PET does not necessarily require injection molding. It is not the material of choice. This is because the relatively high This is because it is necessary to use a high mold temperature, for example from 120°C to 140°C. be. Trying to use a lower mold temperature, e.g. 100°C or less. One of the problems is that the molded product sticks to the inside of the mold and can only be removed with great difficulty. This results in an injection material that cannot be molded and has a lot of To avoid this processing defect, C (When poly(alkylene terephthalate) is used at a low mold temperature of 60'C Molders can use polybutyrephthalate (PBT) as long as it can be easily molded into It is necessary to choose more expensive materials such as . Lower mold temperature for PBT The ability to cool the injection molded product to a temperature that allows it to be removed from the mold The time required to remove the PET article from the initially hotter mold is This is significantly shorter than the standard cooling time. This shorter cooling time of PET results in faster Its higher speeds result in shorter process cycles and faster article production speeds. Despite its high unit price (C), its use is economical ((Correct.

Can be injection molded at relatively low mold temperatures (e.g. 100°C and below) vL. , yielding articles exhibiting good molding properties, such as good mold release and desirable physical properties. PET compositions would be a welcome contribution to the technology.

According to the present invention, (a) polyethylene terephthalate, and (b) epoxidized plasticizer, and Beauty (c) Epoxidized plasticizer of (b) Injection molded articles from the composition at a low mold temperature of at least 936C in conjunction with A thermoplastic injection moldable composition containing a homogeneous mixture of adjuvants that improves its release from the mold. products are provided.

Because of this synergistic action between earlier components (o) and (C), the composition Relatively low mold temperatures (e.g. from about 50°C to about 100°C) without It can be molded up to ).

Of course, if desired, the compositions of the present invention can be used at higher mold temperatures (e.g., about 100°C or higher). It should be understood that injection molding can also be performed at temperatures up to about 150'C).

A further aspect of the invention is that the composition further comprises a reinforcing filler, such as a glass fiber. fibers, alone or in combination with granular mineral fillers, in reinforcing amounts. be. Other additives such as flame retardants, impact modifiers, etc. can also be used in the composition.

Although crystalline PET copolymers can also be used, the polyethylene Nterephthalate is preferably homopolymer PET. References to useful PET copolymers The type is a repeating copolymer derived from terephthalic acid and ethylene glycol at least 80 mol% of the units from other known acid and/or glycol components A copolymer containing a derivatized remainder (20 moles or less).

Substitute acid components include phthalic acid, inphthalic acid, naphthalene-1,4- or naphthalene. Phosphorus-2,6-dicarboxylic acid, diphenyl-4,4/-dicarboxylic acid, diphenyl Nyl ether-4,4'-dicarboxylic acid, adipic acid, sepa7anoic acid and the like The rodanized (preferably brominated) counterpart of The glycol component is diethyl Ren glycol, neopentyl glycol, cyclohexanedimethanol, 2. 2-bis(4-hydroxyphenyl)propa7.1,3-propanediol, 1 ．． 4-butanediol, dibromoneopentyl glycol, tetrabromobisulfate bis(2-hydroxy-ethyl A/)ether of phenol A, tetrapromo p - It may also be Kinryleng υ Fool, etc.

The polyethylene terephthalate used in this specification is virgin PET or or recycled PET. Furthermore, the PET used in the composition of the present invention is Must be injection moldable and therefore generally contains 60% by weight phenol and tetra 0.0, measured at 25°C in a solvent consisting of 40% by weight of chloroethane. 6, preferably between about 0.4 and 1.2, more preferably between about 0.5 and 1.0 Many injection molding applications have an intrinsic viscosity i(1,V,)'(r) between I, Polyethylene terephthalate with a V of from 0.4 to 0.9 is most preferred. Yes.

The compositions of the present invention can be made from the epoxidized plasticizers described herein (also known in the art). (sometimes called ``epoxy plasticizer'') per 100 parts of PET 0.5 parts' to about 12 parts (i.e., from about 0.5 phr to about 12 phr) ) and adjuvants from about 0.05 parts to about 5 parts per 100 parts of PET. (i.e., from about 0.05 phr to about 5 phr) is preferred. Most preferably, the amounts used for the two components of the composition are PET 100 from about 2 to about 8 parts of epoxidized plasticizer and from about 0.1 to about 0.1 parts of adjuvant per part. It is within the range of up to 6 parts.

The epoxidized plasticizers described herein have an oxirane removal content of about 0.5% by weight. up to about 12.0% by weight. Preferably oxirane oxygen The content ranges from about 6.0% to about 10.0%.

Epoxidized plasticizers can be epoxidized, esterified and Can be produced by transesterification. Epoxidation, esterification and transesterification Substitutive techniques used in reactions (for example, force of Chemj, cal , Technology'Y) (2nd edition 1965), Volume 8, Page 238 and and the next page, page 613 and the next page, and page 656 and the next page. ``Epoki 7 Day 7 Yo/, Estelifike 7 Yon and Estel Interce (Epoxidation.

Esteriflcation and Ester Interchange ) can be found in each chapter of J.

The "epoxy plasticizer" used according to the present invention is a plasticizer for poly(vinyl chloride) resin. Illustrated are types of epoxy oils and esters used as plasticizer stabilizers. any type Although any epoxy plasticizer can be used in the practice of this invention, the preferred types include the following: (-L) A hydrocarbyl ester of a monoepoxidized alkenoic acid, which is Stells have from about 12 to about 50 carbon atoms (preferably about 16 or more) in the molecule. up to about 66 carbon atoms) hydrocarbyl ester of citric acid, (b) containing at least one epoxide group; an epoxy/unsaturated triglyceride with (C) Each epoxy ester has from about 7 to about 50 carbon atoms in the molecule. at least one monoepoxy aliphatic monocarboxylic acid ester containing t Epoxy containing at least one type of epoxy aliphatic monocarboxylic acid ester stell mixture There is.

Among the epoxy plasticizers of type (a) above, there are from about 16 to about 36 plasticizers in the molecule. Those containing carbon atoms are preferred for use in the compositions of the present invention.

About 7 alkenoic acids 1r'i from which epoxy esters of type (a) of the invention are derived up to 66 carbon atoms and (where R is hydrogen or an alkyl radical , R2 is an alkylene radical, and n is 0 or 1).

Typical examples of such monounsaturated acids are dece-9-enoic acid, dodec-9-dioic acid, and pallic acid. mitoleic acid, oleic acid, petroseli/acid, vaccenic acid, gadley/acid, 5- Eicosenoic acid, 5-tocosenoic acid, cetoleic acid, erucic acid, nervonic acid, 4-h Putenoic acid, Ro-methyl-7-octenoic acid, 4-methyl-5-hexenoic acid, 5-methyl methyl-4-hexenoic acid, 6-nityl-ro-pente/acid and 2-octenoic acid. Preferably, the alkenoic acid has from about 14 to about 24 carbon atoms.

Most preferably, the single bond is located internally, i.e. the double bond is located at a non-terminal carbon atom. The second group is alkenoic acids, such as oleic acid.

Epoxidized alkenoic acid esters of type (a) are alkyl, aryl, aralkyl or a cycloalkyl ester or a mixture thereof; Alkyl esters in which the group has from about 7 to about 66 carbon atoms are preferred.

Highly preferred alkyl esters have alkyl groups of from about 7 to about 12 carbons. It has atoms. For example, the alkyl radical forming the alkyl group thyl, ethyl, propyl, isopropyl, butyl, inbutyl, nibutyl, thyl Tributyl, pemethyl, hexyl, octyl, denyl, dodecyl, 4-methyloctyl methyl, 2-butyl-2-methylhexyl, eicosyl, and the like. Book The most useful esters of the invention are those in which the alkyl group contains 8 carbon atoms, e.g. For example, octyl monoepoxidized basic alkenoic acids.

Typical aryl esters are those in which the aryl radical is phenyl or lower alkyl substituted phenol. phenyl, e.g. tolyl (o-, m- or p-isomer), ethylphenyl (〇- 1m- or p-isomer), dimethylphenyl (2゜4-12.5-16.4- various isomers such as isomers such as phenyl and bromophenyl, naphthyl, and 2-methyl-5-ethylnaphthyl 2-propyl-4-; i-6-chloro-naphthyl, and 7-chloronaphthyl Alkyl or halogen-substituted naphthyl such as thyl.

The preparation of the esters of the invention follows the esterification of the selected alkenoic acids obtained Epoxidation of esters (which can thus be carried out.

Epoxidized octyl oleate with a minimum oxalane oxygen content of 6.6% by weight (also known as octyl epoxy stearate) is manufactured by Argus Chemical Co. Poration (Argus Chemical Corporation), The name D RAPEX 3.2 comes from the location of Purtzklin, New York 11231. You can purchase it below.

The epoxidized unsaturated triglycerides of type (b) usually have about 6 acid components each. up to about 60 carbon atoms, and at least one acid component is an epoxy It is a triglyceride of aliphatic monocarboxylic acid.

The acid component has one or more epoxide groups and one or more acid components are epoxidized. Please understand that it is okay to do so.

Examples of aliphatic monocarboxylic acids that may be present in triglyceride esters include: Although not specified, the following oleic acid, linoleic acid, lylunic acid, stearic acid, valmic acid phosphoric acid, myristic acid, lauric acid, eleostearic acid, lysate/acid, linol Acid, palmitoleic acid, peteroceric acid, bacefic acid, erucic acid, arachidic acid, Examples include tetracosanoic acid, capric acid, and casillonic acid.

In theory, prior to epoxidation, at least one of the acid groups acts as an epoxidation site. is understood to contain olefinic unsaturation.

Epoxidized unsaturated triglycerides of type (b) can be prepared as individual compounds or mixtures thereof. It may be a compound. The mixture of epoxidized unsaturated triglycerides is approximately 0.5 wt. % to about 12.0% by weight. No. The oxygen content of this oxirane ranges from about 6.0% to about 10.0%. is preferred.

Most preferably, the oki/ran oxygen content is from about 7.0% to about 9.5%. Also mentioned above The oxi7rane oxygen content of the individual compounds of type (b) rather than as a mixture is This also applies when used as individual compounds.

Examples of unsaturated triglycerides of type (b) which can be epoxidized but are not limited to The following are linseed oil, soybean oil, sunflower seed oil, safflower oil, hempseed oil, paulownia Oil, oil, corn oil, sesame oil, cottonseed oil, castor oil, olive oil, These include peanut oil, rapeseed oil, coconut oil, babassu oil, and palm oil.

Depending on formulation and processing conditions, relatively non-volatile epoxidized unsaturated triglycerides It is preferable to use For example, those having a molecular weight of at least about 400 are easily mixed and selected. Become. Due to economic considerations, epoxies with molecular weights from about 400 to about 1000 It becomes advantageous to use unsaturated triglycerides.

However, even higher molecular weight epoxidized unsaturated triglycerides, i.e. molecules It is contemplated that one having an amount of 1000 or more can be used.

Epoxidation of vegetable oils and fats (epoxidized unsaturated triglycerides obtained by preferred. Most preferred are epoxidized soybean oil and epoxidized linseed oil. Ru.

Epoxidized unsaturated triglycerides of type (b) can be prepared by those of ordinary skill in the art. can be manufactured by known techniques. Such suitable compounds include, but are not limited to: by epoxidizing unsaturated triglycerides including linseed and soybean oils. It can be manufactured. Epoxidized soybean oil is made by converting olefin bonds into peracids such as peracetic acid. epoxides by processing by known techniques with epoxidizing agents such as It can be manufactured by introducing bonds.

Epoxidized soybean oil with a minimum oxirane oxygen content of 7.0 by weight is DRAPE It can be purchased under the name X 6.8, and the minimum oxygen content is 9.6% by weight. Epoxidized linseed oil with York 112-1, under the name DRAPEX 10.4 from Purtzklin's location. It can be purchased at

Each epoxy ester has about 7 to about 11 esters in the molecule. at least one monoepoxy aliphatic monocar containing up to 50 carbon atoms Boxylic acid ester and at least one jepoxy aliphatic monocarboxylic acid ester The epoxy ester mixture of type (c) containing Another type of poxidized plasticizer is shown.

By techniques known in the art, each epoxy ester has approximately 7 or at least one epoxy ester mixture having up to about 50 carbon atoms from a monoepoxy aliphatic monocarboxylic acid ester of 1 piece of stiff epoxy ester mixture containing cyanoaliphatic monocarboxylic acid at least one alcohol having from up to about 20 carbon atoms and about 6 at least two different aliphatic monocarboxylic compounds having up to about 30 carbon atoms. from at least two carbon acids or having from 1 to about 20 carbon atoms. different alcohols and at least one alcohol having from about 6 to about 60 carbon atoms; can also be derived from one aliphatic monocarboxylic acid. Type (C) epoxy ester The mixture also contains vegetable fats or vegetable oils, the fatty acid portion of tall oil and other aliphatic Also from monocarboxylic acid esters (containing from 1 to about 20 carbon atoms) (by transesterification with one or more alcohols). Also, The epoxy ester mixture is unfractionated tall oil, i.e. Japanese Patent Publication No. 58-5013 27 (5) From tall oil containing its resin acid (rosin or rosin acid) and fatty acid moieties It is thought that it can also be induced.

The alcohol in the epoxy ester mixture of type (C) may contain from 1 to about 20 It has carbon atoms and can be aliphatic, cyclic and aromatic. Al like this Examples of calls are alkyl, alkenyl, aryl, cycloalkyl, aralkyl Alcohol, etc. Examples include, but are not limited to, methanol, ethanol, alcohol, propanol, butanol, pentanol, hexanol, heptatool , octatool, nonanol, decanol, undecanol, dodecanol, to Ridecanol, Tetradecanol, Pentadecanol, Hexadecanol, Hep Tadecanol, octadecanol, nonadecanol, 2-zolopen-1-ol (allyl alcohol), 2-buten-1-ol (crotyl alcohol), 1- Penten-6-ol, trans-2-hexen-1-ol, 9-decene-1 -ol, 10-undecen-1-ol, (-landecylenyl alcohol), Dis-9-octatecen-1-ol (oleyl alcohol), cyclositano cyclopentanol, /clohexanol, cycloheptatool, cyclool Kutatool, cyclododecanol, cycloprogylmethylcarbinol, cyclo Proby-methanol, cyclopentylzolopanol, 1-7 clopentyletha alcohol, cyclopentylmethanol, 4-fluor 1-butanol chlorohexyl methanol, cyclohexylmethanol, cyclohexylmethanol, cyclohexylmethanol lumethanol, cycloundecylmethanol, phenol, naphthol, anoto Ranol, be/zyl alcohol, methylphenyl carbinol, dimethylphenylene Examples include ethyl carbinol (benodyl-tert-phthanol).

Type (C) The fatty acid monocarboxylic acids in the ester mixture range from about 6 to about 30. Contains carbon atoms. Examples include, but are not limited to, oleic acid, linoleic acid, Lunic acid, stearic acid, palmitic acid, myristic acid, lauric acid, eleoste Allic acid, lycanic acid, su/nolic acid, palmitoleic acid, petroselic acid, bacterium Senic acid, erucic acid, arachidic acid, tetracosanoic acid, capric acid, caproic acid, etc. There is.

In theory, it is contained in the epoxy ester mixture of type (C) by epoxidation. alcohol moiety or acid moiety to yield monoepoxy7 and diepoxy compounds. There is sufficient olefinic unsaturation in either.

That is, for example, the following epoxy esters, epoxidized octyl erucate, epoxy Oxylated octyl linoleate, epoxidized octyl erucate, epoxidized Eleos Octyl thearate, epoxidized octyl lycanate, epoxidized octyl linoleate tyl, epoxidized octyl palmitoleate, epoxidized octyl petroselate Epoxidized octyl vaccenate, epoxidized octyl erucate, and stiff Epoxidized methyl, ethyl, propyl, butyl, pentyl, hexyl, heso Tel, nonyl, tesyl, dobuflu, hexanol, octadecyl, allyl, chloro Chyl, oleyl, cyclobutyl, cyclooctyl, naphthyl, anotrile or benzyl esters, glycidyl stearate, glycidyl palmitate, Glycidyl listinate, glycidyl laurate, glycidyl arachinate, tetra Grindyl cosanate, glycidyl caprate, glycidyl caproate and this Epoxidized crotyl and oleyl esters, etc., are produced and mixed. at least one monoepoxy aliphatic monocarboxylic acid ester and at least Also, one type of jepoxy aliphatic monocarboxylic acid ester can be produced.

Examples of vegetable fats and oils from which epoxy ester mixtures of type (C) can be derived are , but not limited to, the following coconut oil, babassu oil, palm oil, castor oil, olive oil, Peanut oil, rapeseed oil, corn oil, sesame oil, cottonseed oil, soybean oil, sunflower seeds Oils include safflower oil, hempseed oil, linseed oil, tung oil, and oiticica oil.

Thus, for example, coconut oil, babassu oil, palm oil, castor oil, olive oil, peanut oil oil, rapeseed oil, corn oil, sesame oil, cottonseed oil, soybean oil, sunflower seed oil, Methyl, ethyl, propyl, butyl, pentyl, benzyl, hezotyl, etc. , octyl, nonyl, del/ru, dobuful, hexadecyl, octadecyl, allyl , crotyl, oleyl, cyclodityl, cyclooctyl, naphthyl, anthryl , or benzyl epoxy ester.

Monoepoxy aliphatic monocarboxylic acid ester and epoxy aliphatic monocarboxylic acid ester Mixtures containing phosphoric acid esters [type (C) above] are commercially available. For example, soybean Epoxidized esters of oil and linseed oil are available under the product name VIKOFLEX O. King Chemical Company 838 Baker Building, Minneapolis, MN 55402 Available from location. Such epoxidized esters are epoxy soybean oil fatty acids Methyl (VIKOFLEX 7010), epoxy soybean oil fatty acid methyl (VI KOFLEX 7020), epoxy soybean oil fatty acid propyl (VIKOFLE X 7030), epoxy soybean oil fatty acid paste fk (VIKOFLEX 704 0), epoxy soybean oil fatty acid hexyl (vrKopLEx 7060), Poxy soybean oil fatty acid off f# (VIKOFLEX 7080), eboxy Linseed oil fatty acid methyl (VIKOFLEX 9010), epoxy linseed oil Ethyl fatty acid (VIKOFLEX 9020), epoxy linseed oil fatty acid zorobi p, (VIKOFLEX 9030), Eboxia Crab Oil Fatty Acid B, (VIKOFLEX 9.040), epoxy linseed oil fatty acid hexyl (V IKOFLEX 9060) and epoxy linseed oil fatty acid octyl (v x oFLgx9080).

Epoxy of fatty acid part of tall oil with minimum oxygen content of 5.0% by weight The ester mixture is octyl epoxide oil, product name DRAPEX 4. 4 Underneath Arcus Chemical Co., Ltd. 7 Yon, New York 112 Ro 1, It is commercially available from Pultsuklin, 66 Court Street.

To date, some epoxidized plasticizers and cooperative adjuvants of the compositions of the present invention have been used. Tests show that the adjuvant is synergistic. That is, monoepoxidized a Synergistically with any of the above hydrocarbyl esters of lukenic acid [type (a) above] Without the use of adjuvants, no significant improvement in PET formability is observed. In addition, Epoxidized unsaturated triglycerides such as poxidized soy extract or epoxidized linseed oil The above type (b)]’! & synergistic aids like sodium stearate PET moldability is significantly enhanced when used in combination with PET agents.

Similarly, using any of the synergistic adjuvants listed below without these epoxidized plasticizers There are no notable effects.

Given the ineffectiveness of these epoxidized plasticizers and adjuvants when used alone; , by using these in combination, formability is greatly increased. .

Using a synergistic adjuvant with the epoxy ester mixture (type (c)) as described above As a result, the moldability is much more pronounced than in compositions without epoxy ester mixtures. will be greatly improved.

For example, sodium acetate, potassium acetate, sodium zolopionate as adjuvants , potassium propionate, sodium hexanoate, sodium octoate, deca Sodium laurate, sodium laurate, potassium laurate, tetradecanoic acid such as sodium, sodium hexadecanoate, sodium stearate, etc. The use of alkali metal salts of substantially saturated aliphatic monocarboxylic acids, and acrylic acid of unsaturated aliphatic monocarbo/acids such as sodium, potassium methacrylate, etc. A synergistic effect is observed with the use of alkali metal salts.

In addition, IPOLY soap (IVORY 5OAP) and IPOLY soap No (IVORY 5 NOW) (Broctor, Ohio, ’/7) Made by & Gamble Cumber, Ipoly Snow is made with tallow fatty acids. About 85% by weight of sodium salt and about 15% by weight of sodium salt of coconut fatty acids. Ipoly soap is thought to contain about 50% of the sodium salt of tallow fatty acids. % by weight and approximately 50M of the sodium salt of coconut fatty acids) Commercially available soaps, such as, are useful as synergistic adjuvants. Although not commercially available, there are The combination of thium, cerium and rubidium salts should provide a synergistic effect. Said Among the sodium salts, sodium stearate is most preferred.

Other effective synergistic adjuvants include sodium carbonate, talc, mica, boron nitride, Surlyn (5URLYN) 1605 (ionomer tree containing sodium ions) It is made by E.I. Dupont de Nemois & Co., Ltd.), p- Oxybenzoic acid, sodium benzoate and zinc stearate.

Without wishing to be bound by theoretical considerations, according to the present invention, as an adjuvant The working materials tend to be materials that are also effective as nucleating agents. this theory and other substances found to be effective adjuvants for use in the present invention. contains lauric acid, zinc, lead, calcium, barium and cupric and stearic acid of zinc phosphate, lead, calcium, barium and cupric and potassium benzoate Metal salts of inorganic acids such as carboxylic acids, silver nitrate and stannous chloride , m-ox7benzoic acid, tetrachlorophthalic anhydride, inositol and lid Highly polar organic compounds such as limides, olefins/and acrylic or methacrylic acids such as copolymers of lylic acid and copolymers of aromatic olefins and maleic anhydride. Sodium and potassium salts of organic polymers containing penda/tocarboxyl groups , and so on. In this regard French patent no. 2,129.162 , British Patent No. 2,015,013 and The Bulletin/U Polymer ・Journal (The Brjlsh Polymer Journal), 11, pp. 146-150 (September 1979).

To date, tests carried out with epoxy ester mixtures of type (c) have This proves that the synergistic interaction between the xyester mixture and the adjuvant is synergistic. (i.e., all necessary baselines have not been drawn) There was no). However, there is a synergistic interaction between many other combinations of the present invention. The combination of epoxy ester mixtures and adjuvants was It is considered and is indeed expected to be synergistic in the work.

To ensure uniform dispersion of epoxidized plasticizers and adjuvants in the PET, If the agent and epoxidized plasticizer are present as solids, at least 60% Preferably, the particle size is such that it passes through a 0.00 mesh US standard sieve.

A preferred epoxidized plasticizer-adjuvant combination for non-woven materials is epoxidized oleic acid. octyl and stearic acid) l) Lamb's ester-auxiliary combination, epoxy Sinic plasticizer and sodium stearate and epoxidized linseed oil and stearic acid An epoxidized unsaturated triglyceride-adjuvant combination of sodium and and epoxy esters of the fatty acid part of soybean oil, linseed oil, or tall oil. A combination of sodium stearate, epoxy soybean oil fatty acid octyl (e.g. V IKOFLEX 7080), epoxy linseed oil fatty acid octyl (e.g. VIKO FLEX9080) or octyl 7-toleate (e.g. DRAPEX A combination of 4.4) and sodium stearate is more preferred.

To improve the injection moldability of polyethylene terephthalate, stearic acid) Any standard commercial grade or any heat stable grade of IJum can be used in the compositions of the present invention. It can be used at any time. However, the sodium stearate utilized must be at least 60%. The particle size is such that it passes through a 100-meter American standard sieve. For example, this Such sodium stearate is called "Sodium Stearate T-1" or [Stearate T-1]. Storium Thearate, MILF Organic Division, New York 100 17. It can be purchased from our New York location.

As mentioned above, other additives may also be used in the compositions of the invention (e.g. There's so much stuff! (Most useful if it contains a reinforcing filler. This filler , its type can increase the strength and impact quality of PET compositions. facts, supplements The use of strong fillers is necessary for many of today's commercial uses of injection molded PET. There are many.

In general, any reinforcing material, such as fibers, whiskers or metal, such as aluminum metals, such as iron or nickel, and non-metals, such as ceramics, carbon filaments, etc. silicates, asbestos, titanate whiskers, quartz, glass flakes and fibers. Small plates such as fibers can be used.

Although only the presence of at least a reinforcing amount of reinforcing filler is required, fillers are generally from about 10 parts to about 160 parts per 100 parts of unreinforced polyethylene terephthalate resin. It consists of up to parts. Filler material, especially glass fiber, per 100 parts of unreinforced PET Amounts ranging from 0 parts to about 140 parts are preferred. Because such a group This is because the composition has particularly desirable properties. In terms of ease of injection molding usage The reinforcing compositions of the present invention, especially those using glass fibers, are particularly suitable for use when the filler component is unreinforced. from about 30 parts to about 90 parts per 100 parts by weight of polyethylene terephthalate resin. Contained in an amount within the range of .

Among the lightning reinforcing materials that can be used in the compositions of the present invention, the preferred reinforcing material is glass. It is. Relatively soda-free borosilicate lime-aluminum glass fibrous glass Most preferably, filaments are used. This is known as "E" glass There is. The length of the glass filament and the concentration of this glass filament into fibers name, then whether this fiber is focused into rovings is important to the invention isn't it. However, use glass struts that are at least about 1/8 inch long. I found it appropriate to be there. Significant fracture of the strands occurs during compounding. Moreover, it should be understood that the final injection molded product will have a decrease in length (a).

Other additives may also be utilized in the compositions of the present invention to provide certain types of final injection molded products. Desired properties can also be obtained. For example, depending on the end use of the injection molded product, slow flame agents, impact modifiers, antioxidants, ultraviolet absorbers, lubricants, antistatic agents, colorants (e.g. For example, zinc sulfide), antibacterial agents, and blowing agents.

The compositions of the invention can be used in a blender such as a tumble blender or a Hen/Elmiki blender. The various components are blended in a 28 mm extruder, such as a twin screw extruder. This mixture was compounded in a printer-'Pfleiderer extruder and then It can be produced by chopping the extrudate into pellets. The resulting product is injection molded. Suitable for use with shape manipulation. Compositions of the invention provide acceptable short cycle Physical properties that are time and commercially attractive or at least have commercial potential A molded product exhibiting This is noteworthy.

The invention is further illustrated in the following examples, which are not to be construed as limiting. be done.

The various PET compositions from Example 1 to Example 29 were prepared by mixing the ingredients to form a premix. This premix is further screened at a temperature of approximately 500'F (260°C). Compounded in a Reu extruder, then pelleted on a reciprocating screw set injection molding machine manufactured by forming into an article. The injection mold is a top view of the article. of suitable shape and dimensions to provide an article having the structure shown in the figures. use The mold to be manufactured has a fixed planar sprue side and a movable cavity side. It was a tardate mold. As can be seen from the figure, the article formed by the mold is This terminal has a number of runners labeled "A" and is equipped with various specimens. Ru.

U/A traditional tapered sprue spreads out from the center of the tea grid. 2 trials The specimens are marked with square bars and the letters rBJ. These rBJ rods are approximately 6 inches long, It is 1/2 inch wide and 1/4 inch thick. The specimens labeled with "in the figure" are , a square bar 21/2 inches long, 1/2 inch wide, and 1/8 inch thick.

The two "dog bone" shaped specimens are labeled with a "D" and are tested for tensile properties. used for testing. They are approximately 6 1/2 inches long and 1/8 inch thick, and each It is 3/4 inch wide at the ends and 1/2 inch wide at the center.

Specimens labeled with rEJ are 4 inches long, 23/4 inches wide and 1/8 inch thick. Inches. The runners and sprues have a cross-sectional width of approximately 3/8 inch. test This construction for specimens is similar to the complexity of specimens used by well-accepted standard tests. and selected for yield.

The complexity of the article structure also affects the composition of the composition when used to form a typical commercial article. It is also believed that this is sufficient to predict molding performance well.

PET, epoxidized plasticizer, glass and stearic acid used in the examples Sodium is confirmed as follows.

1.Polyethylene terephthalate (PET) Guts Doyer Tire & Rubber - Vituf 5900-phenol 60 weight and tetra Intrinsic viscosity measured at 25°C in a solvent consisting of Chlorontough 40% by weight: 05 Product name: DRAPE manufactured by Argus Chemical Corporation X 3.2 one glass fiber strand Product Name Owen Sue Corning Fiberglass 419AA (3/16 In Cicciozzotostrand), Oue/Sukoni/G Fiberglass Co. Made by Poration or product name: PPGro 540 fiberglass (1/8 inch) Chopped Stranod), P.B.G. Industries Inc. - Available from Tenwitco Chemical Cumber.

1st, 2nd and 6th cases (Examples 1 to 8, Examples 9 to 16 and Examples 1 to 8 respectively) 17 to 24) show the observed observed values of moldability of various compositions of the present invention. are doing. Compositions that do not utilize the combination of the epoxated plasticizer 2 and adjuvants of the present invention The observed values of the products are shown in Table 4 (Comparative Examples 25 to 29). The moldability was shown to be “excellent”. In this case, the molded part fell freely from the mold when the mold was opened. Highly rated “good” This shows that a large number of molded parts fell freely from the cavity side of the mold. Majority If a smaller but substantial number of items still fell freely, rate it as 'fair'. Gave. Most injection molded products are evaluated as "defective" from the cavity side of the mold. Although it had to be pulled, no adhesion was observed on the sprue side of the mold. or molding even if the main part of the article did not adhere to the sprue side of the mold. This indicates that some of the sprue was attached to the sprue side. Evaluation of “impossibility of molding” In this case, the product sticks to the sprue side of the mold and the molded part is removed from the mold with a chisel. The molding cycle must be stopped in order to remove the mold by prying it open. Indicates that the

Mold temperature was maintained at approximately 200'F (93°C) in all cases.

27 28 Special Table of Showa 5E1501327 (9) 9 As can be seen from Table 4, there is no epoxidized plasticizer or shear synergistic adjuvant. will result in a composition that is not moldable under the same molding conditions.

Except that the PET used was American Enca's T-0740. Similar results were obtained with the corresponding compositions up to Example 21.

From the data shown in Table 5, a good balance of physical properties is achieved at a mold temperature of approximately 200"F ( demonstrated by an article injection molded from the composition of the invention at 93°C) The test specimen has the following ASTM operating density - D792 - 66<1975), Tensile yield, elongation and tensile modulus - D638-77a, Bending strength and flexural modulus - 1/4 inch salary eye/l throat impact at 26°C - D256-78, Heating deflection temperature - 0648-72 (1978), Vicat softening point - D1525-7 6, and Rockwell Gorges-D785-65 (1976).

Ro1 Special table 58-5013270 From example 30 to example 52 Various PET compositions from Examples 60 to 52 were prepared as described in Examples 1 to 29. Manufactured by sea urchin.

The PET, glass and sodium stearate used in these examples This is confirmed to be the same as in Examples 1 to 29. Smell from Example 30 to Example 52 Epoxidized plasticizers used in the process are as follows.

- Epoxidized soybean oil, fully epoxidized containing 7% by weight of oxirane oxygen. Arcus Chemical Corporation's product name DRAPE is soybean oil. X 6.8 and Argus Chemical Corporation product name DRAPE X　10.4゜ Tables 6 and 7 (from Example 30 to Example 68 and from Example 39 to Example 45, respectively) ) indicates the recognized parent and subvalues of the moldability of various products of the present invention. uninvented epo Table 8 shows the values for compositions without a combination of oxygenated plasticizers and adjuvants. From Comparative Example 46 to OS Comparative Example 52, 51 and 52 are Comparative Example 28 and Comparative Example 52, respectively. and Example 27 (see Table 4). Evaluation of moldability 1 [Ill is Example 1] have the same definitions as described in Example 29.

In all of these cases, the mold temperature was maintained at approximately 200'F (93'C).

4 65 special title 58-50132701) As can be seen from Table 8, the presence of either an epoxidized 5T plasticizer or a synergistic adjuvant Not molding results in a non-moldable composition under the same molding conditions.

From the data shown in Table 9, it can be seen that at a mold temperature of approximately 200'F (96°C), the A good balance of physical properties was demonstrated by the article IC injection molded from the composition. The specimens were tested using the ASTM method described in Examples 1 through 29. It was subjected to the operation.

From Example 56 to Example 57 The various PET compositions from Example 56 to Example 57 are described in Examples 1 to 29. Manufactured like this.

The PET and sodium stearate used in these examples were from Example 1. It is confirmed that these are the same as those in Examples 29 and up. From Example 56 to Example 57 The epoxidized plasticizer and glass used were as follows.

Product name manufactured by Chemical Company VIKOFLEXProduct manufactured by Chemical Company Name: VIKOFLEX Product name: DRAPEX 4.4° manufactured by Cal Corporation - Glass fiber strand Product name Owens-Corning Fiberglass 4 19 AA (3/16 inch chopped strand), Owen Sue Cornyn Manufactured by Gu Fiberglass Corporation.

Table 5 shows various compositions of the present invention (Shiori 53 to Example 55) and non-inventive compositions. Compositions (Comparative 1+1J56 and Comparative Example 28 and Comparative Example 27, respectively) 5y and comparison (see Table 4) Observations regarding the number of shots (i.e., number of injections) and “number of demolding failures” (i.e., The molding cycle must be stopped and the molded specimen physically removed from the mold. (number of times). In severe cases, use a pry to remove the stuck part. It was necessary to scrape it off with a chisel or a chisel. If the observation is indicated as “excellent”, the molding The product fell freely from the mold when the mold was opened.

The evaluation of "defects in molding" is based on the fact that the product adheres to the streaky side of the mold and the molded product Stop the molding cycle so that it can be chiseled and pried out of the mold. Indicate that it had to be done.

At full power, the mold temperature was maintained at approximately 200'F' (93°C).

As can be seen from Table 10, Comparative Examples 56 and 57, no epoxidized plasticizer was present. Molded under the same molding conditions as in the absence of squid or epoxidized plasticizers and auxiliaries resulting in an incompetent composition.

From the data shown in Table 11, the present invention A good balance of physical properties is exhibited by articles injection molded from the composition of I understand. The specimens were subjected to the ASTM procedures described in Examples 1 through 29.

Table 11 Composition of the present invention and its physical properties Composition 53 54 55 Polyethylene terephthalate, part 100 100 100 glass fiber, phr+ 43 43 43 Epoxy linseed oil fatty acid octyl, phr6. Q--Epo Soybean oil fatty acid octyl 5, phr” ~ 3.0-Epoxidole fatty acid octyl Chill 0, phr"--3,0 Sodium stearate, phr" 0.5 0 ．． 5 0.5 Zinc sulfide 6, phr“ --2,0 Tensile 4, psi 19,900 18.600 18.500 Tensile modulus, 1 0” psj, 1,330 1,410 1,405 Yield elongation, poly<10 <10　- Bending strength, psi 32,000 28.500 27.700 Bending modulus, 1 03 psj, 1,440 1.421 1.360 Izont impact, 7 bars, ft-7b/in 1.9 2-0 1.4 Izot impact, ri 7b, :t l’o/1r11-7 1.7 - Heating deflection temperature 264 psi, 'C2392412 filter 7 heating deflection temperature 66p, 3i, 'C250249- Rockwell Nsa, R scale 123 123 -% per 100 parts of PET Department.

a VIKOFLE χ9080, manufactured by Viking Chemical Company.

b VZKOFLEχ7080, manufactured by Piking Chemical Company.

c DFLAPEX 4.4, manufactured by Argus Chemical Corporation.

d View f Zinc-Color agent.

Engraving (no changes to the content) Procedural amendment (formality) %formula% 2. Name of the invention B)) Takutoku V Kakiyari 3. Person who makes corrections Relationship to the incident: Patent applicant 4. Agent 5. Date of amendment order May 10, 1982 6. Number of inventions increased by amendment 7. Subject of correction Figure [1j□-f舊・PA文　'-1□・-(:゛2τ; 站2changeΣA) - Border investigation report Imunajio-^ppuca+autoiso, PCT/US82101121 1″lsnwllorvl　A”””””’　PCT/US82101121 Continuation of page 1 Priority claim @ June 25, 1982■United States (US)■392221 @July 26, 1982■United States (US)■401929

Claims (1)

[Claims] 1. In a thermoplastic composition that can be injection molded at a relatively low mold temperature, the above composition The thing is lal polyenalene terephthalate, and (1) l epoxidized plasticizer, call (in conjunction with epoxidized plasticizers of cl　bl), the mold temperature is at least 93 °C Nucleation that improves the mold releasability of molded articles injection-molded from the composition at high temperatures. Homogeneous mixture of ingredients? Can be injection molded at relatively low mold temperatures, characterized by thermoplastic composition. 2. The epoxidized plasticizer has an oxirane oxygen content of 360% by weight to 10.0% by weight. %. 3. The epoxidized plasticizer is monoepoxidized alkonic acid hydrocarbyl ester Tell is characterized in that it contains carbon atoms from 121 planes to 501 planes in the molecule. The composition of claim 1. 4. The hydrocarbyl ester has from 7 to 36 alkyl radicals. The composition of Range 6, which is an alkyl ester having a carbon atom. 5. Set 511 of claim 4, in which the ester is an octyl ester: WI . 6. KJ epoxidized plastic i'flJ is epoxidized octyl oleate, A composition according to claim 1. Z Epoxy in which the epoxidized plasticizer contains at least one epoxide group The composition of claim 1, which is an unsaturated triglyceride. 8. Claim No. 8, wherein the epoxidized triglyceride is epoxidized linseed oil. Composition of item 7. 9. Claim 7, wherein the epoxidized triglyceride is epoxidized soybean oil. composition of the term. 10. The epoxidized plasticizer j. ! , at least one monoepoxy aliphatic mono Carboxylic acid ester and at least one jepoxy aliphatic monocarboxylic acid ester Each epoxy ester has from 7 to 50 carbon atoms in its molecule. 2. The composition of claim 1, wherein the composition is an epoxy ester mixture. 1.1. The epoxy ester mixture has from 1 to 20 carbon atoms. (with one alcohol and 6 to 60 carbon atoms) Claims 1 and 2 are derived from at least two different aliphatic monocarboxylic acids. Composition of item 10. 12. The epoxy ester mixture described in a has a carbon atom size of 1 to 20. at least two different alcohols and about 6 to 30 carbon atoms Claim 1 derived from at least one aliphatic monocarboxylic acid having Composition of item 10. 1ro. The epoxy ester mixture is derived from vegetable oil or The composition of claim 10. 14. The epoxy ester mixture is derived from soybean oil or linseed oil. The composition of claim 1o. 15. Claim No. 1, wherein said nucleating agent is synergistically cooperative with an epoxidized plasticizer. Composition of item 1. 16. The composition of claim 15, wherein the synergistic nucleating agent is a monocarboxylic acid salt. . 1Z The synergistic nucleating agent is fa) sodium stearate, sodium acetate, plastic Sodium ropionate, sodium acrylate or benzoate) alkali-terminated monocarboxylic acid salts selected from fbl mellow fatty acids and coco homogeneous mixture containing IJium salt, or fcl sodium carbonate, Merck, mica, boron nitride, p-oxybenzoic acid, zinc stearate, or sodium The MA of claim 15, which is an ionomer resin containing thorium ions. e: Thing. 18 The epoxidized plasticizer per 100 parts of the polyethylene terephthalate present in an amount within the range of 0.5 parts to 12 parts, and the nucleating agent Present in the range of 0.05 to 5 parts per 100 parts of tylene terephthalate The composition of claim 1, comprising: 19. Claim No. 1, wherein the composition further comprises a mineral filler containing glass fibers. Composition of item 1. 20. Natsumachi plastic group F3: product that can be injection molded at relatively low mold temperature, fal A solution consisting of 60% by weight of phenol and 40% by weight of tetrachloroethane. Polyethylene having an intrinsic viscosity between 0.4 and 0.9 measured at 25°C in medium lenterephthalate, and fbl Glass fiber reinforced optical fiber per 100 parts by weight of polyethylene terephthalate from 60 parts by weight to 90 parts by weight, and fcl epoxidized plasticizer, and (DL improve the releasability of articles injection molded from said composition from injection molding molds at Injection moldable at relatively low mold temperatures, characterized by a homogeneous mixture of bale-forming agents, thermoplastic composition of 21. The epoxidized plasticizer is epoxidized octyl oleate, epoxidized soybean oil, epoxidized linseed oil, epoxy linseed oil fat modified octyl, epoxy soybean tsukuro Octyl fatty acid also (epoxidol octyl oleate, and nucleating agent) 21. The composition of claim 20, wherein is a sodium salt of a monocarboxylic acid. 22. The set of claim 21, wherein the nucleating agent is sodium stearate. A product.