JPS63501725A - Blend of polyester and imidoester - 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] Blending technology of polyester and imidoester The present invention provides a novel polyester containing 1 to 35% by weight of a specific imidoester plasticizer. Regarding Esther. When polyester is plasticized, it becomes volatile and fuming, and melt viscous. The temperature, melting point and glass transition temperature are substantially reduced and processing properties are improved. this The plasticized compositions of and useful as adhesives in the form of flexible films, and also extruded flexible It is also useful for use in flexible forms (eg, tubes).

Background technology Many polyester polymers are used as hot melt adhesives for product assembly and for textiles. Useful as adhesive for objects.

However, the molecular weight of the polyester polymer is high enough to give a strong bond. In some cases, the melt viscosity is also high, making it difficult to apply these adhesives with conventional application equipment. would be difficult, if not impossible.

Ester plasticizers improve the properties of polyvinyl chloride and cellulose esters in molded products and tubes. It is effective in modifying it so that it can be used in the form of tubes, films, sheets, etc.

However, ester plasticizers such as dioctyl phthalate are generally It is completely incompatible with esters. Other plasticizers such as benzoate esters Provides a melt viscosity low enough to allow application with normal application equipment for melt adhesives.

However, the polyester portion of these blends It has a tendency to lower the intrinsic viscosity (1, V,). U.S. Patent No. 4,172,82 No. 4, No. 4,094,721, No. 3,186,961, No. 2,044 , 612, Canadian Patent No. 919,190, British Patent No. 815,991 and and U.S. Pat. No. 4,340.625.

Plasticizers used with polyester polymers generally require relatively high processing temperatures and The plasticizer tends to volatilize and cause unacceptable conditions.

Certain imidoesters are suitable as plasticizers for certain polyesters; Adding a high boiling point plasticizer to polyester lowers the melting point of the polyester and lowers the glass Can significantly lower the transition temperature and also lower the melt viscosity value of the blend It was discovered that These high boiling point plasticizers are volatile and emissive even when processed at high temperatures. It is extremely low in smoke.

U.S. Pat. No. 4,172,824 contains adipic acid and 1,4-butanediol. certain poly(ethylene terephthalate) copolyesters with certain benzoin Blends with acid ester plasticizers are disclosed.

U.S. Pat. No. 4,450,250 describes a mixture of anhydrophthalic compounds (aromatic and aliphatic). ) Amorphous or crystallizable polyester plasticized with esters and mixed phosphate esters Disclosing the stell.

Disclosure of invention The present invention α) Amorphous with a melting point less than 230 °C and a heat of fusion less than 18 power lories/gram one or more of a crystalline or crystallizable copolyester; 6) Chemical formula for plasticization amount A plasticized polyester composition characterized by comprising a compound represented by provide products. However, in the above formula, R1 is a linear or is a branched aliphatic hydrocarbon group, and R3 is a linear group having 1 to 20 carbon atoms. or branched aliphatic hydrocarbon groups, alicyclic hydrocarbon groups having 5 to 20 carbon atoms or or an aromatic hydrocarbon group having 6 to 20 carbon atoms.

The dicarboxylic acid component of the polyester is an aliphatic dicarboxylic acid component having 4 to 12 carbon atoms. acid or alicyclic dicarboxylic acid or aromatic dicarboxylic acid having 8 to 18 carbon atoms Bonic acid or a mixture of two or more of these acids is included.

Examples of such dicarboxylic acids include succinic acid, glutaric acid, adipic acid, azelaic acid, acid, sebacic acid, 1,1°2-dodecandioic acid, 1,4-cyclohexane dicarboxylic acid acid, 1,3-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, etc. There is.

The glycol component of the polyester can be an aliphatic diol or and cycloaliphatic diols having 6 to 18 carbon atoms as well as certain poly(ethylene glycols) recall) or a mixture of two or more of these diols. Such a geo Examples of alcohols include diethylene glycol, triethylene glycol, and ethylene glycol. alcohol, phlopylene gelicol, 1,3-propanediol, 1,4-butanediol 1,5-bentanediol, 1,6-hexanediol, 1,3-cyclo Examples include hexane dimetatool and 1,4-cyclohexane dimetatool.

Polyesters are readily prepared using typical polycondensation techniques well known in the art. It will be done. Typical polycondensation catalysts include titanium alkoxide, diptyltin laurate, and and zinc, manganese or magnesium acetate or benzoate and anti-oxidized Antimony or antimony triacetate combinations are included.

Useful polymers have r,v values ranging from about 0.4 to about 1.2, with preferred 1. V, value is approximately 0.5 to 1.1.

The polymer can be amorphous or crystallizable and generally has a It has a heat of fusion (ΔHf)k less than This polymer has a melting point measured by differential scanning calorimetry. The point is generally between 80 and 230°C.

Both amorphous and crystallizable polyesters are operable. Suitable polyester has a heat of fusion of about 18 calories/dulum of polymer and has a melting point of up to about 230'C. Amorphous polyesters or relatively low melting point polyesters are included. Poly( ethylene terephthalate) and poly(1,4-cyclohexylene dimethylene terephthalate) Polymers with extremely high melting points, such as Because of the high temperature (above 250° C.), it is generally not possible to practice the present invention.

Examples of useful polyesters include cyclohexane dimetatool or diethylene Recall modified poly(ethylene terephthalate) copolyester, glutaric Poly(tetramethylene terephthalate) modified with acid and diethylene glycol, Poly(hexamethylene terephthalate) modified with glutaric acid and diethylene glycol Poly(tetramethylene glycol) modified with trimellitic acid and poly(tetramethylene glycol) 1,4-cyclohexylene dimethylene 1゜4-cyclohexanedicarboxylene g), poly(hexamethylene terephthalate) modified with 1,4-butanediol ), poly(hexamethylene diol) modified with inctaric acid and 1,4-butanediol phthalate), poly(tetramethylene terephthalate) modified with isophthalic acid ), poly(1,4-cyclohexylene dimethylene tereph) modified with isophthalic acid talates), etc.

The amount of imidoester plasticizer present in the composition of the present invention generally ranges from 1 to 35% by weight of the composition. %, preferably 5 to 25%. In the above structural formula of imidoester, R1 is 2 or A linear or branched aliphatic hydrocarbon containing up to about 20 carbon atoms. R 8 may contain an alicyclic or aromatic hydrocarbon group, but generally it is an ester group. and the methylene group adjacent to the imide group.

R2 is a linear or branched aliphatic hydrocarbon group having 1 to 20 carbon atoms; is an alicyclic group, an aromatic group, or an alkyl-substituted alicyclic or aromatic group . Such imide esters are produced using conventional techniques well known in the gastrointestinal art. .

The plasticizer is added using a mixing roll, Banbury mill, extruder, etc. It is incorporated into the polyester by heating the plasticizer and polymer at a temperature of about 250°C. It will be done.

Alternatively, the components may be dissolved in a mutual solvent and then the solvent may be evaporated.

The presence of plasticizer significantly improves the processing properties of the blend. For example, unchanged It can be extruded into fibers and films at lower temperatures than the temperatures required for polyester. Can be done. Plasticized fibers are used as binders for polyester nonwovens, and The bonding is performed at relatively low temperatures.

Plasticized films can be used for laminating woven fabrics or for bonding labels and designs with low contact. Easily used at high temperatures. Generally, plasticized films are different from unmodified films. It has good flexibility and therefore gives the bonded woven fabric a good feel. Jin The plasticizer is highly compatible with polyester, so no oozing onto the film surface is observed. I can't stand it.

Plasticized polyester blends are milled using pin mills or hammer mills. It is easily ground into powder by low-temperature grinding. This powder is applied onto a fusible comfort fabric. , or for bonding nonwoven fabrics, and bonding is achieved at relatively low temperatures. non-woven fabric For bonding, the plasticized powder can be prepared from an aqueous dispersion or the dry powder can be electrostatically It is applied to the nonwoven material by spreading it onto the fibers with a spray gun.

The dry powder can be spread by scattering (scatta), such as with a shilling roll. r) Applied with a coating roll applicator.

This polyester blend can be easily extruded into tubes; Polyester is much more flexible than unmodified polyester. Possible like this Flexible tubes are quite easy to core wind.

The following examples are presented to provide a further understanding of the invention.

Example 1゜ polyester blend Terephthalic acid, ethylene glycol (69 mole percent) and 1,4-cyclo Reed with a copolyester containing lohexane dimetatool (31 mol%), 1. V, = 0.60, Tg = 73°C, amorphous, between △Hf　O Calorizo . ) was added to 2,2-dimethyl-3-2-ethylhexanoate in a Pyrex test tube. 7-talimidopropyl (boiling point 225-300°C at three points) and 25- and mix. The mixture was heated to 160° C. with stirring. This polymer easily dissolves into a clear solution was formed. polyester! Similar results were obtained by replacing polyester (■) with polyester (■). Poly Ester ■ is 72 mol% terephthalic acid, 28 mol% glutaric acid, butanediol Copolyester containing 55 mol% and 45 mol% diethylene glycol It is.

(ΔHf = 3.6 calories/2, Z, I', = 0.85, T lightning = 110℃, TQ=2℃) 2-ethylhexanoate 3-7talimidoprobyl, 2-ethylhexanoate 12- 7-talimidododecyl, 2,2-dimethyl-3-7-talimidopropyl butyrate, do 2,2-dimethyl-3-7talimidopropyl decanoate, p-dodecylbenzoic acid 2,2-dimethyl-3-7thalimidopropyl, 2,2-di p-decylbenzoate Methyl-3-7talimidopropyl, p-decylbenzoic acid 2-7talimidoethyl benzoic acid [4-(phthalimido, methyl)cyclohexylcomethyl or 2 , 4.6-) 2,2-dimethyl-3-7-thalimidopufpyr-limethylbenzoate When used, solubility was similarly good.

Implementation example 2. (Comparative example) The solubility test of Example 1 was carried out using dioctyl phthalate plasticizer at a temperature of 200°C. Repeated for Polyester I. This polyester melts and falls to the bottom of the test tube. Although a liquid layer was completely formed, it did not dissolve or mix with dioctyl heptatalate. 23℃ When cooled to did. In this example, polyester (2) has phthalic acid in the temperature range of 23 to 200°C. It shows complete insolubility in widely used plasticizers such as dioctyl.

Polyester I (47,5P) t-Plastograph mixer 19 2゜2-dimethyl-3-phthalimidopropyl 2-ethylhexanoate (2゜2-dimethyl-3-phthalimidopropyl , 5f) for 5 minutes in the melt phase to form a blend containing 5% by weight of plasticizer. Prepared. The plasticized polyester was melted at 190°C for 5.6r710 min. index and a glass transition temperature of 71°C. 0.08mm (3 mil) The modulus of the compression molded film is 15217 H/cm” (216,000 ps i) (according to ASTM-882).

In contrast, unplasticized polyester melts at 190°C for 2.9y/10 minutes. - and its glass transition temperature was 73°C. 0 of unplasticized polyester ．． The modulus of 08xx (3 mil) film is 18599#/crILt (26 4,000 pat).

0.08 mm (3 mil) compression of unplasticized and plasticized polyester Sentinel (Sm%ti%gj) heat treatment of formed film and polyester/cotton twill fabric On the sealer, bonding time 5 seconds, gauge bonding pressure 1.06 Jc’i/Cl12 (15psi) and bonded for T-peel testing using the temperatures shown below (10x lOc7rL) (4x4 inches). Cool this joint on a stone bench top. Then cut a 1.27 C0IL (3'r inch) edge from each side and remove from each specimen. Three 1 inch (2.54 cm) 7'-shaped peel test joints were cut. Contact The compound was heated on an Instron tester at 23°C, crosshead speed 5.1 cm, for 7 minutes (2 inches per minute) with the following results.

Bonding strength during T-type peeling Junction temperature kWlCm length (lb/inch length) 140 (284) 0.23 (1 ,3) 1.11 (6,2) 160 (320) 0.79 (4,4) 2.06 (11,5) 180 (356) 2.43 (13,6) 3.54 (19,8) When the bonding temperature exceeded 204°C (400'F), the fabric burned and separated.

This example shows that when only 5% of soluble plasticizer is added to polyester, the joining temperature increases. This shows that the bonding strength decreases and the bonding strength increases. Bonding with plasticized polyester Excellent resistance to 5 cycles of commercial laundering and dry cleaning Indicated.

2,2-dimethyl-3-7 talimide 2-ethylhexanoate on polyester ■ The method of Example 3 was repeated except that 25% by weight of Lobil was mixed. This is possible Plasticized polyester has a melt index of 46.4 M'/10 minutes at 190°C. In between, its glass transition temperature was 30°C. 0 according to ASTM-882, 08 $lIm (3 mil) compression molded film modulus 1973A11/cI rL2 (28,000 psi).

Plasticized compositions require much lower pressures and much more can be easily extruded into films and tubes in short cycle times and It can be injection molded into comb-shaped articles and the plasticizer will not smoke or volatilize. do not have.

0.08 mm (3 mil) of unplasticized and plasticized polyester samples Compression molded film and polyester/cotton twill fabric are placed on a sentinel heat sealer. The temperature shown below [bonding time, 5 seconds; gauge bonding pressure 1.06 Ay/crn” ( 1s pss)), and a T-type peel test bonded material 10 x 10 cIrL (4 x 4 inch) was prepared. Immediately after bonding, place the bonded items on a stone bench top (temperature ~23℃) ) and rapidly cooled to room temperature. 127 crn (5 inch) ear cut from each side Then cut out three 2.5 cm (1 inch) T-shaped peel test joints from each specimen. did. The bonded material was heated on an Instron tester at 23°C, 5.1 cm, for 7 minutes (2 inches/ The following results were obtained.

Bonding strength during T-type peeling Bonding temperature kglCm length (lb/inch length) °C (?) Unplasticized film possible Plasticized film 140 (284) 0.23 (1,3) 4.65 (26,0) 1 60 (320) 0.79 (4,4) 3.70 (20,7) 180 (350) 2.43 (13,6) 1.93 (10,8) polyester ■ with 2-ethyl When 25% by weight of 2,2-dimethyl-3-7talimidopropyl xanoate is added, , the bond strength is 0.23 kg ZcIrL length (1.3 lb/ inch length) to 4.65 Ay/cm length (26,0 lb/inch length).

With plasticized polymers, the bonding temperature can be lower than 140°C, but with unplasticized polymers, O does not bond at such low temperatures Benzoic acid [4-(phthalimidomethyl)cyclohexylcomethyl] works equally well. The results were obtained.

Example 5゜ Polyester I (1,93 bond, 4,25 bond) and 2-ethylhexanoic acid 2,2 -dimethyl-3-7 talimidoprovil 0.34 # (0.75 lb) tl, Melt mix in a 9c7rL (5 inch) Brabender extruder at ~175°C to make pellets. I made it to This blend is processed using a micro pulverizer (Mi-kro Prblv). grizgr) using a 2ii+ (0.08 inch) sieve with liquid nitrogen. Cold ground. At 40℃ and under reduced pressure (25 inches of water column, 635 kg/rn”) This powder was dried overnight and then dry mixed with 0.1% by weight of calcium stearate. It matched. Next, using a 70 to 200 U, :E, mesh sieve, mechanical shaker The powder was classified by shaking on a motor for 15 minutes.

The polyester stable fiber was passed through a woven card machine and the web weight was 47.597. A 2 oz/square yard (m2) polyester nonwoven web was formed. Plasticization port Intermediate powder of Reester (70-200 mesh) was fluidized with nitrogen and then used with an electrostatic gun. Sprayed on the web to obtain a uniform coating. Pass this web through the heating chamber of an infrared heater. The adhesive powder was melted and then passed through calender rolls. adhesive in the web The weight was 15% by weight. This web is flexible, has a good feel, and is strong. The bonding was uniform in both the machine direction and the transverse direction. Similarly, unplasticized polyester Even if the nonwoven web is bonded with Teru's 70-200 mesh powder, this polyester gives only a very weak web, probably because the melt viscosity is too high to flow out. stomach.

Example 6゜ Polyester II'5-10% by weight of 2,2-dimethyl-2-ethylhexanoate 3-7 Repeat the procedure of Example 5, except melt-mix with talimidoprobil. did. This plasticized polyester medium grade powder (70 to 200 mesh) was used for bonding. The nonwoven web is flexible and has a good texture, and has good strength in both the machine and cross directions. It had

Example 7゜ Polyester It - 10% by weight (based on polyester weight) 2-ethylhexane Dissolved in methylene chloride with the acid 2,2-dimethyl-3-7talimidoprobyl. . The methylene chloride was evaporated and the resulting blend was granulated and granulated under reduced pressure (water It was dried overnight at a silver pillar (1351 m). 3, equipped with a gear pump and a 45-hole spinneret; This blend was melt spun at 220°C using an 8crIL (1,5 inch) extruder. did.

The fibers were air cooled and wound onto take-up rolls. Next, apply this filament to 70~ Stretched 3 times at 100°C, crimped at 23°C in a stuffer box to 4.7 cm. crimp/α, 12 crimp/inch), cut to 1.27CIrL (3A inch) into stable fibers. Add 20% by weight of this binder fiber to a polyester stave. This fiber blend is then mixed into ShirLmy woven card. machine and then through an array of infrared heaters to melt the binder fR fibers and join the web. A nonwoven web was prepared. This nonwoven web is flexible, has a good hand feel, and is easy to machine. It had good strength in both the direction and the transverse direction.

Unmodified polyester cannot be spun into fibers at temperatures below 300°C. do not have.

Example 8゜ Polyester If 1.9 c7IL (s/4 inch) Melt at ~225℃ in extruder 15% by weight of 2,2-dimethyl-3-7tali 2-ethylhexanoate at melting temperature. Melt mixed with midopropyl. This extruded blend is passed through a water cooling tower to form pellets. did. The pellets were dried under reduced pressure at 40°C overnight.

This blend has a melt index of 16.0 f710 minutes at 190°C. , T by DEC analysis was ~48°C. Ninie Preten (New Er1 Using a molding machine, spiral gold was formed at a melting temperature of 230°C. Injection molded into a mold. Plasticized polyester is 49.2 kg/cm” (700p si) flowed 85 mm under pressure, while the unplasticized polyester flowed 561 m.

The term "polyester" is used in this application in a broad sense to include copolyesters. It will be done. Also, esters of acids, rather than the acids themselves, are used to prepare polyesters. be done. For example, dimethyl terephthalate can be used in place of terephthalic acid if desired. be done.

Although not necessary for the practice of this invention, stabilizers, pigments, colorants, and flow aids may be added if desired. Small amounts of agents, anti-caking agents, fluorescent agents and other additives may also be used.

In this application, whenever we use the term "intrinsic viscosity J (1, V,)" Solvent 100-1 p0 consisting of 60% by weight and 40% by weight of tetrachloroethane ．． Viscosity measured at 25° C. using 50 grams of polymer is shown.

The melting point J (Tm) of the polymers described in this application can be easily measured with a differential scanning calorimeter. Ru.

The "heat of fusion" ΔHf of a polymer is the amount of heat absorbed when a crystalline polymer melts. . The ΔHf value was measured using a differential scanning calorimeter (Perkin-Elmer CPεTkin-E1ma r　)　)). For example, one way to measure △Hf is Josrnal of Applied Polymer 5science 2 0°1209 (1976). Measurement of △Hf is thb Po% t Thermal Analysis Es1latin 4900-8 (1 965). Qualitatively determine the crystallinity of the polymer by comparing the ΔHf values can be compared.

The strength of the bond was determined using a modified ASTM “T-peel test” (i.e. using 3 specimens). It is measured by the so-called "peel test". ASTM “T-type peel test” is th eAmerican 5octety for Testing Materi The BOOK OF ASTM 5TANDARDS to be published by als Test number Riichi 1876-61- listed on pages 63 and 64 of the 1964 edition. It is 7'.

Unless otherwise specified, all parts, percentages, ratios, etc. are by weight.

Although the invention has been described in detail with particular reference to the preferred embodiments, the spirit of the invention It will be understood that various modifications and changes within the scope and scope are possible.

Bacteria tI 1st trial report ANNEX To TdE INTERNATIONAL 5EARCHREF 'ORT 0 NINTERNATIONAL APPLICATION No. PCT/lls 86102462 (SA 15281) US-A-357 93631EI105/71 NoneUS-A-2684917None

Claims (9)

[Claims] 1. a) Amorphous with a melting point less than 230°C and a heat of fusion less than 18 calories/gram one or more of a quality copolyester or a crystallizable copolyester; b) Chemical formula for plasticization amount ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ A plasticized polyester composition characterized by consisting of a compound represented by thing. However, in the above formula, R1 is a linear or branched fatty acid having 2 to 20 carbon atoms. group hydrocarbon groups or alicyclic or aromatic hydrocarbons having 6 to 20 carbon atoms R2 is a linear or branched aliphatic carbon having 1 to 20 carbon atoms. Hydrogen group, alicyclic hydrocarbon group having 5 to 20 carbon atoms or 6 to 20 carbon atoms It is an aromatic hydrocarbon group having atoms. 2. Copolyester contains 40 mol% or more of terephthalic acid; ethylene glycol 30 and diethylene glycol and cyclohexanedimethanol Contains repeating units of about 70 to 20 mol% of other glycols selected from The composition according to claim 1, characterized in that: 3. Copolyesters include terephthalic acid, glutaric acid, 1,4-butanediol and and diethylene glycol. Composition according to item 1. 4. Copolyester is terephthalic acid, glutaric acid, 1,6-hexanediol and a repeating unit of diethylene glycol. A composition according to item 1. 5. The copolyester is 1,4-cyclohexanedicarboxylic acid, trimellitic acid , 1,4-cyclohexanedimethanol and poly(tetramethylene glycol) The composition according to claim 1, characterized in that it contains a repeating unit of ). 6. The copolyester contains terephthalic acid, isophthalic acid, 1,6-hexanediol 1,4-butanediol and 1,4-butanediol The composition according to item 1. 7. The copolyester contains terephthalic acid, isophthalic acid and 1,4-butanedioic acid. The composition according to claim 1, characterized in that it contains a repeating unit of . 8. The copolyester contains terephthalic acid, 1,4-butanediol and 1,6- Claim 1, characterized in that it contains a repeating unit of hexanediol. Compositions as described. 9. Claims characterized in that R1 is a 2,2-dimethyltrimethylene group Composition according to item 1.