MXPA98002228A - Compositions of polyester molding improves - Google Patents

Abstract

This invention relates to molded objects prepared from a copolyester having an inherent viscosity of 0.4 to 1.1 dl / g, wherein the terephthalic acid component and 10 to 60% in molds of 1 or more of the selected dibasic acids cyclohexanedicarboxylic acid, naphthalene dicarboxylic acid, diphenyldicarboxylic acid and stilbenedicarboxylic acid, wherein the glycol component comprises repeated units of 1,4-cyclohexanedimethane

Description

IMPROVED POLYESTER MOLDING COMPOSITIONS DESCRIPTION OF THE INVENTION This invention relates to certain molded objects comprising copolyesters poly (1,4-cyclohexylenedimethylene terephthalate) which have improved hardness, transparency and resistance to stress cracking. Various polymer materials have been commonly used. the past 60 years to mold toothbrushes, tool handles, windshield wipers, hairbrushes, cutlery, lens frames and the like. In many of these applications, the molded parts must be transparent, hard, impact resistant, stress crack resistant, hydrolysis resistant, as well as a pleasant feel and appearance. The plasticized acetate propionate (CAP) cellulose compositions have been used successfully in the past for toothbrush handles. Such compositions have good transparency, gleaming appearance and overall appearance. However, changes in the designs of toothbrush handles to increase the density of bristles have led to fracture in certain brushes. Fractures which occur during the insertion of bristles are a result of insufficient resistance to the welding line. Increased plasticizer concentrations improve resistance to the weld line, but this leads to decreased strength, which can result in inadequate retention of the bristles. Certain rigid polyurethane materials have been evaluated in this application, but this polymer is difficult to mold, and the urethane bonds in the polymer chain can be hydrolyzed in the presence of moisture during molding. Polyester materials such as poly (ethylene terephthalate) (PET) and poly (1,4-cyclohexylenedimethylene terephthalate) (PCT) have many desirable properties for molded parts, but these polymers are easily crystallizable and provide turbidity or opacity to the molded parts. objects when they are molded into thick parts. The modification of PET polymers with high levels of glycol components apart from ethylene glycol provide hard, transparent molded parts but these tend to stress cracks in the presence of certain toothpaste solutions containing peppermint oil. For example, the United States Patent 2,901,466 (1959) assigned to Eastman Kodak Company discloses a common range of linear polyesters and polyesteramides derived from 1,4-cyclohexanedimethanol (CHDM). Many of the compositions are easily crystallizable and the molded parts are opaque or cloudy. In this way, they are not suitable for transparent, molded objects. There is a need in the art, therefore, for mouldable compositions which have a visual transparency and which have improved molding and appropriate physical requirements. This invention relates to molded objects prepared from a copolyester having an inherent viscosity of 0.4 to 1.1 dl / g, wherein the acid components comprise repeating units of 90 to 40 mol% terephthalic acid and 10 to 60 mol% of 1 or more additional dibasic acids selected from a group consisting of isophthalic acid, cyclohexanedicarboxylic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid and stybenedicarboxylic acid; and, wherein the glycol components comprise repeating units of 1,4-cyclohexanedimethanol. These molded objects have the advantage of having improved transparency and resistance to stress cracking. They also have good physical properties including strength, stiffness, impact resistance and resistance to hydrolysis.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 illustrates the molded plates used to determine the chemical resistance, Figure 2 illustrates the test apparatus used to determine the tensile crack resistance. It has been found that certain PCT copolyethers are highly suitable for molding transparent parts, hard, resistant parts to the tension crack. The molded articles are prepared from a copolyester having an inherent viscosity of 0.4 to 1.1 dl / g, wherein the acid component comprises repeated units of 90 to 40 mole%, preferably 85 to 52 mole%, more preferably from 83 to 52 mol% terephthalic acid and from 10 to 60 mol%, preferably 15 to 48 mol%, preferably 48 mol%, preferably 17 to 48 mol%, of 1 or more dibasic acids additional compounds selected from the group consisting of isophthalic acid, cyclohexanedicarboxylic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid and stybenedicarboxylic acid; wherein the glycol components comprise repeated 1,4-cyclohexanedimethanol units, preferably 80 to 100% by mole of 1,4-cyclohexanedimethanol, more preferably from 85 to 100% by mole, even more preferably from 90 to 100% by weight moles, and even more preferably 95 to 100 mole%. When cyclohexanedicarboxylic acids are used, they may be in the cis or trans form or as a mixture of cis / trans isomers. Lower alkyl esters, such as methyl esters, can be used in place of dibasic acids in the preparation of the casting compositions of this invention. When cyclohexanedicarboxylic acid is used, 1,3- and 1-cyclohexanedicarboxylic acid are preferred. When naphthalenedicarboxylic acid is used, the 2,6-, 2,7-, 1,4- and 1,5-naphthalenedicarboxylic acids are preferred. The molded objects of the invention can comprise up to 10 mol% of the additional dibasic acids. These dibasic acids may be selected from one or more of the groups consisting of aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and cycloaliphatic dicarboxylic acids, each preferably having from 4 to 40 carbon atoms. More specifically, these additional dibasic acids can be selected from 1 or more of the groups consisting of phthalic acid, cyclohexanediacetic acid, succinic acid, glutaric acid, adipic acid, acelaic acid, sebasic acid, isophthalic acid, cyclohexanedicarboxylic acid, naphthandicarboxylic acid, diphenyldicarboxylic acid, and eethylbendicarboxylic acid. The preferred additional carboxylic acids are selected from the group consisting of isophthalic acid, cyclohexanedicarboxylic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, and stybenedicarboxylic acid. Even more preferred are the additional dibasic acids including isophthalic acid, cyclohexanedicarboxylic acid and naphthalenedicarboxylic acid. The glycol component can contain up to 20 mole% of one or more of the additional aliphatic or alicyclic glycols preferably containing from 2 to 20 carbon atoms. These additional glycols can be selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, propandiol, butanediol, pentanediol, hexanediol, neopentyl glycol and tetramethylcyclobutanediol. Ethylene glycol is particularly preferred. Very small amounts (less than 1.5 mole%) of certain branched agents such as trimellitic anhydride, trimellitic acid, pyromellitic dianhydride, trimesic acid, hemimellitic acid, glycerol, trimethylolpropane, pentaerythritol, 1,2,4-butanediol, 1,2, 6-hexantriol, sorbitol, 1, 1, 4, 4-tetrakis (hydroxymethyl) cyclohexane, dipentaerythritol and the like can be used.The copolyesters of this invention are readily prepared using melt phase or solid state poly condensation processes, well known in the art. This can be done by continuous process or batch. Examples of these processes can be found in U.S. Patent Nos. 4,256,861, 4,539,390 and 2,901,466 and include preparation by direct condensation or by ester exchange. Specifically, the polymers of this invention can be prepared according to the methods described in U.S. Patent 2,901,466. However, the preparation of the polymers of this invention is not particularly limited to the method described in U.S. Patent 2,901,466. This patent describes the exchange reactions, as well as the processes for the formation of the polymerization. Briefly, a typical procedure consists of at least two distinct stages; The first stage, known as ester exchange or esterification, is carried out under an inert atmosphere at a temperature of 150 to 250 ° C for 0.5 to 8 hours, preferably 180 to 240 ° C for 1 to 4 hours. The glycols, depending on their reactivities and the specific experimental conditions employed, are commonly used in molar excesses of 1.05 to 2.5 per total moles of functional acidic monomers. The second stage, referred to the polycondensation, is carried out under reduced pressure at a temperature of 230 to 350 ° C, preferably 265 to 325 ° C, and more preferably 270 to 300 ° C for 0.1 to 6 hours, preferably 0.25 to 2 hours. Agitation or appropriate conditions are used in both stages to ensure adequate heat transfer and renewal of the surface of the reaction mixture. The reactions of both steps are facilitated by appropriate catalysts, especially those well known in the art, such as alkoxy titanium compounds, alkali metal hydroxides and alcoholates, salts of organic carboxylic acids, alkyltin compounds, metal oxides, and so on. . Suitable copolyesters can have inherent viscosity (I.V.) values of from about 0.4 to about 1.1 dl / g. Such values are obtained from a 60/40 phenyl / tetrachloroethane solution containing 0.5 grams (g) of the polymer in 100 milliliters (ml) of solution. It is preferred that the copolyester have an I.V. of at least 0.5 dl / g. The preferred copolyesters should have a glass transition temperature (Tg) of at least 70 ° C as determined by the Differential Scanning Calorimeter (DSC) in a mean crystallization time of at least] minute as measured by the diffusion technique of laser beam angle. The technique for determining the mean recrystallization clouding time is mainly followed by the increase in the depolarization of the plane of light polarized by the polyester. The method used in this invention is mainly that shown in "A New Method for Following Rapid Rates of Crystallization", I. Poly (hexamethylene adipamide), J. H. Magil. Polymer, Vol. 2. page 221-233 (1961) with the exception that Magil uses a polarized microscope co or light source and light collector lens. By measuring the average crystallization time of the present invention, a helium-neon laser [a small angle light diffusion technique (SALS)] was used as shown by Adams and Stein in J. Polymer Sci. A2, Vol. 6 (1962). The average crystallization times are measured at the time at which the transmittance intensity is half of the maximum intensity reached. The method used is generally as follows: (1) Melt the sample to eliminate the existing crystallinity; (2) Crystallize the polyester sample at a predetermined temperature; (3) Record the transmitted transmitted light intensity cont i to time; (4) Find the time in which the transmittance intensity is half of the maximum intensity reached. The above-mentioned process is repeated at different temperatures until a maximum value for the mean crystallization time can be reached. "The minimum value" refers to the lowest measurable point of the plot plotted using the temperature data and the corresponding data of mean crystallization time. The term "measured crystallization clouding time of the molten phase" as defined herein is the procedure described above. It is preferred that the molded objects of the invention have a mean crystallization clouding time greater than 1 minute, preferably greater than 3 minutes and more preferably greater than 5 minutes. When the molded objects of the invention have mean crystallization clouding time as described, they are generally visually transparent for regions of a molded object having a thickness of 1 to 11.5 millimeters, preferably 7.62 cm to 29.21 cm (3 to 11.5 It is also preferable that the molded objects prepared in the mixtures of the invention have a diffusion titration value of less than about 60%, more preferably less than about 40% and even more preferably less than about 20. %, as determined by ASTM Method D1003.When the diffusion transmittance value is less than about 60%, the molded objects are visually transparent.Also, the molded objects of the invention demonstrate improvements in stress crack resistance as determined in the test samples which are 0.32 centimeters wide on the friction resistance with 1.4 % of deformation and with 2.7% of deformation as is more fully demonstrated in the following examples. This stress crack resistance test is preferably performed in the presence of a flavoring. More preferably, the flavoring is a peppermint oil. Of the possible peppermint oils, it is preferable that the peppermint oil is either the peppermint oil or the spearmint oil. The strain crack resistance measurements used in the invention are also preferably performed in the presence of a toothpaste solution comprising water and a toothpaste content greater than 0.6% by weight of peppermint oil or, more specifically, in the presence of peppermint oil directly as described more fully in the following Examples. Other ingredients can be used in the toothpaste solution including glycerin, sodium bicarbonate, water, hydrated silicate, polyethylene glycol, sodium lauryl sulfate, sodium lauryl sarcosinate, sodium pyrophosphate, sodium phosphate, sorbitol, sodium benzoate, saccharin sodium, xanthan gum, cellulose gum, flavoring, sodium saccharin, blue FD &; C # 1 and yellow FD &C # 10, red FD &C 30, 1 -hydroxy-2-propanone, 3-octanol, 4-methyl-1- (1-methylethyl) cyclohexane, pulegone, dodecanol, 3-phenyl -2-propenal, dodecanol, eugenol and titanium dioxide. The flavors used in the preparation of the tests of the invention include peppermint oil, peppermint oil, anise oil, Japanese anise oil, caraway oil, eucalyptus oil, fennel oil, cinnamon oil, clove oil , geranium oil, sagebrush oil, pepper oil, thyme oil, and marjoram oil. Peppermint oil may contain several ingredients including, but not limited to: limonene, cineole, menthone, menthol and carvone. The copyl esters can be used in a transparent form or can be colored or pigmented with additives or copolymerizable dyes. Copolymerizable dyes - typically used as described in U.S. Patent 5,030,708 (1991), 5,102,980 (1992) and 5,194,571 (1993) all assigned to Eastman Kodak Company, incorporated herein by reference. Other additives such as stabilizers, antioxidants, mold release agents, fillers and the like may also be used if desired. Polymer blends can be used. The copolyesters of this invention are easily molded into desired shapes such as toothbrush handles, hairbrush handles, ice scrapers, cutlery or cutlery handles, tool handles, automobile steering wheels, lens frames and the like. This invention may further be illustrated by the following examples of preferred embodiments thereof, although it will be understood that these examples are included only for purposes of illustration and are not intended to limit the scope of the invention unless specifically indicated otherwise. The starting materials are commercially available unless otherwise indicated. Percentages are based on weight unless otherwise stated. 3. 4 I. PREPARATION OF COPOLYTHERES AND MOLDED OBJECTS Example 1 - Comparative - Preparation of Copolyesters containing terephthalate, ethylene glycol, and 3% by mole of 1,2-cyclohexanedimethanol To a 5000 ml stainless steel reactor equipped with a motor stirrer, an inlet Nitrogen and one outlet to allow removal of volatile materials and charge with 679.7 grams of dimethyl terephthalate (3.5 moles) (DMT), 427.8 grams of ethylene glycol (6.9 moles) (EG), 16.4 grams of 1,4-cyclohexanedimethanol (0.11 mol) (CHDM) (70% trans isomer / 30% cis isomer) and 1.35 ml of a solution of titanium (IV) isopropoxide 3. 30% (w / v) in n-butanol. The reactor is purged with nitrogen and heated to 200 ° C under a gentle stream of nitrogen with stirring and maintained for one hour. The temperature of the reactor is elevated to 220 ° C and maintained for two hours. The temperature is raised to 280 ° C and the nitrogen purge is eliminated by applying a vacuum of less than 0.5 mm which is maintained for a period of 30 minutes. The reactor is stirred under vacuum for 1 hour. The vacuum is then displaced with a nitrogen atmosphere and the polymer is extruded through an opening at the bottom of the reactor. The extruded bar is cooled to 5 ° C in a water bath and forming the granules. The coated polymer granules have an inherent viscosity of 0.70 deciliters (dl) / g according to ASTM D3835-79. The diol component of the polymer yielded 96% by mass of EG, 3% by mole of CHDM and 1% of mol of diethylene glycol (DEG) measured by gae chromatography in a hydrolysed sample. The glass transition temperature (T) of 78 ° C and the melting point (T) of 248 ° C are measured by the DSC analysis (differential scanning colorimetry). The mean crystallization clouding time as measured in the molten phase is 0.8 minutes. The sample is dried at 150 ° C in a dryer dehumidifier for about 4 hours and injection molding to transparent plates that are 7.5 square centimeters and 0.32 centimeters wide. Located approximately 1 centimeter from the edge of the plate is an area of 1.1 cm by 0.6 cm which contains 12 holes approximately 0.1 cm in diameter as shown in Figure 1. This area of the plate is used to simulate the head of the toothbrush in which the bristles are inserted. Example 2 - Comparative - Preparation of Copolyester containing terephthalate. EG and 31 mole% of CHDM The apparatus and method indicated in Example 1 is used. The following amounts of reagents were charged to the reactor: 679.5 grams of DMT (3.5 moles), 365.6 grams of EG (5.9 moles), 160.4 grams of CHDM (1.1 mole) and 2.05 ml of a 3.30% (w / v) solution of 36 titanium isopropoxide in n-butanol. The diol exchange step is conducted at 200 ° C for one hour and at 210 ° C for 2 hours. The polycondensation step is conducted under vacuum at 0.5 mm Hg for one hour. The polymer is extracted from the bottom of the reactor. The extruded bar is cooled in a water bath at 5 ° C and the granule is formed. The coated polymer granules have an inherent viscosity of 0.74 dl / g. The diol component of the polymer consists of 68 mol% of EG, 31 mol% of CHMD and 1 mol% of DEG. The amorphous copolymer possesses a T of 80 ° C as determined by the DSC analysis. The average crystallization time as measured by the molten phase is greater than 1 hour. The sample is dried at 65 ° C in a drying dehumidifier for approximately 16 hours. It is injection molded into transparent samples as set forth in Example 1. Example 3 - Comparative - Preparation of Copolyester containing terephthalate, EG and 62% by mole of CHDM The apparatus and method indicated in Example 1 are used. The following quantities of reagents were charged to the reactor: 679.7 grams of DMT (3.5 moles), 305.6 grams of EG (4.9 moles), 302.5 grams of CHDM (2.1 moles) and 2.06 ml of a 3.30% (w / v) solution of isopropoxide of titanium in n-butanol. The diol exchange step is conducted at 200 ° C for one hour and at 210 ° C for 2 hours. The polycondensation step is conducted under vacuum at 0.5 mm Hg for 45 minutes. The polymer is extruded from the bottom of the reactor. The extruded bar is cooled in a water bath at 5 ° C and the granule is formed. The coated polymer granules have an inherent viscosity of 0.72 dl / g. The diol component of the polymer consists of 37% by weight of EG, 62% by mole of CHDM and 1% by mole of DEG. A T of 82 ° C and a Tm of 225 ° C are obtained by the copolymer by DSC analysis. The average crystallization time as measured by the molten phase is 28 minutes. The sample is dried at 65 ° C in a drying dehumidifier for about 16 hours and injection molded into clear samples as set forth in Example 1. Example 4 - Comparative - Preparation of Copolyester containing terephthalate, EG and 81% by mole of CHDM The apparatus and method are used as indicated in Example 1. The following quantities of reagents were charged to the reactor: 679.2 grams of DMT (3.5 moles), 248.1 grams of EG (4.0 moles), 432.9 grams of CHDM (3.0 moles) ) and 2.38 ml of a 3.30% (w / v) solution of titanium isopropoxide in n-butanol. The diol exchange step is conducted at 200 ° C for one hour and at 210 ° C for 2 hours. The polycondensation step is conducted under vacuum at 0.5 mm Hg for 40 minutes. The polymer is extracted from the bottom of the reactor, cooled in a water bath at 5 ° C and the granules are formed. The coated polymer granules have an inherent viscosity of 0.76 dl / g and the diol component of the polymer consists of 18 mol% of EG, 81 mol% of CHMD and 1 mol% of DEG. A T of 87 ° C and a Tm of 257 ° C are obtained from the copolymer by DSC analysis. The mean crystallization clouding time as measured by the molten phase is 3 minutes. The sample is dried at 150 ° C in a drying dehumidifier for about 16 hours and injection molded into transparent samples as set forth in Example 1. Example 5 - Comparative - Preparation of Copolyester containing 95 mol% terephthalate, 5% in moles of isophthalate and EG and CHDM The apparatus and method are used as indicated in Example 1. The following quantities of reagents are charged to the reactor: 645.2 grams of DMT (3.3 moles), 34.1 grams of EG (0.2 moles) of dimethyl isophthalate (DMI), 555.7 grams of CHDM (3.9 moles) and 2.68 ml of a 3.30% (w / v) solution of titanium isopropoxide in n- butanol. The reactor is purged with nitrogen and heated to 300 ° C under a slight stream of nitrogen with stirring. The temperature of the reactor is maintained for 30 minutes and then the nitrogen purge is removed and vacuum is applied in such a way that the vacuum of < 0.5 mm Hg is achieved during a period of 30 minutes. The vacuum and temperature are maintained for 50 minutes. The polymer is extruded in the lower part of the reactor. The extruded bar is cooled in a water bath at 5 ° C and the granules are formed. The coated polymer granules have an inherent viscosity of 0.78 dl / g and the polymer comprises 95 mol% terephthalate and 5 mol% isophthalate measured in 1 H NMR. A T of 92 ° C and a Tm of 287 ° C are obtained by the copolymer by DSC analysis. The mean crystallization clouding time as measured from the molten phase is 0.5 minutes. The sample is dried at 150 ° C in a drying dehumidifier for about 4 hours and injection molded into clear samples as set forth in Example 1. Example 6 - Example of the Invention - Preparation of Copolyester containing 83 mol% terephthalate , 17% in moles of isophthalate and CHDM. The apparatus and method indicated in Example 1 were used. The following quantities of reagents were charged to the reactor: 577.3 grams of DMT (3.0 moles), 101.9 grams of DMI (0.5 moles), 565.4 grams of CHDM (3.9 moles) and 2.67 ml of a 3.30% (w / v) solution of titanium isopropoxide in n-butanol. The reactor is purged with nitrogen and heated to 290 ° C under a slight stream of nitrogen with stirring. The temperature of the reactor is maintained for 30 minutes and then the nitrogen purge is removed and vacuum is applied in such a way that the vacuum of < 0.5 mm Hg is achieved during a period of 30 minutes. The vacuum and temperature are maintained for 43 minutes. "The polymer is extruded into the lower part of the reactor, cooled in a water bath at 5 ° C and the granules are formed.The coated polymer granules have an inherent viscosity of 0.70 dl / g and the polymer consists of 83 mol% of terephthalate and 17 mol% of isophthalate measured in 1 H NMR, A T of 89 ° C and Tm of 262 ° C are obtained by the copolymer by DSC analysis. The mean crystallization clouding time as measured from the molten phase is 1.5 minutes.The sample is dried at 150 ° C in a drying dehumidifier for about 4 hours and injection molded into transparent samples as set forth in Example 1. Example 7 - Example of the Invention - Preparation of Copolyester containing 70 mol% terephthalate, 30 mol% isophthalate and CHDM The apparatus and method indicated in Example 1 were used. were charged to the reactor: 476.3 grams of DMT (2.5 moles), 204.1 grams of DMI (1.0 moles), 555.8 grams of CHDM (3.9 moles) and 2.67 ml of a 3.30% (w / v) solution of titanium isopropoxide in n-butanol. The reactor is purged with nitrogen and heated to 290 ° C under a slight stream of nitrogen with stirring. The temperature of the reactor is maintained for 30 minutes and then the nitrogen purge is removed and vacuum is applied in such a way that the vacuum of < 0.5 mm Hg is achieved during a period of 30 minutes. The vacuum and temperature are maintained for 53 minutes. The polymer is extruded in the lower part of the reactor. The extruded bar is cooled in a water bath at 5 ° C and the granules are formed. The coated polymer granules have an inherent viscosity of 0.70 dl / g and the polymer comprises 70 mol% terephthalate and 30 mol% isophthalate measured in 1 H NMR. An amorphous polymer having a T of 87 ° C is recovered as measured by DSC. The mean crystallization clouding time as measured by the molten phase is 6.8 minutes. The sample is dried at 65 ° C in a drying dehumidifier for about 4 hours and injection molded into clear samples as set forth in Example 1. Example 8 - Example of the Invention - Preparation of Copolyester containing 91 mol% terephthalate, 39% by mole of 1,4-cyclohexanedicarboxylate and CHDM The apparatus and method indicated in Example 1 were used. The following amounts of reagents were charged to the reactor: 404.7 grams of DMT (2.1 moles), 243.6 grams of 1,4-dimethylcyclohexanedicarboxylate (DMCD) (1.4 moles), (35% trans isomer / 65% cis isomer) 580.4 grams of CHDM (4.03 moles) and 2.65 ml of a solution at 3.30% (w / v) of titanium isopropoxide in n-butanol. The reactor is purged with nitrogen and heated at 220 ° C for 60 minutes under a slight stream of nitrogen with sufficient agitation. After reaching the temperature of 290 ° C the nitrogen purge is eliminated and vacuum is applied in such a way that the vacuum of < 0.5 mm Hg is achieved during a period of 30 minutes. The vacuum and temperature are maintained for 120 minutes to carry out the polycondensation. The vacuum is then displaced with a nitrogen atmosphere and the polymer is drained from the bottom of the reactor, cooled in a water bath at 5 ° C and the granules are formed. An inherent viscosity of 0.70 dl / g is determined by the recovered polymer. The polymer contains 61 mol% terephthalate and 39 mol% 1,4-cycloxandicarboxylate (51% trans isomer / 49% cis isomer) as measured by 1 H NMR. A T of 72 ° C and a Tm of 223 ° C is obtained from the copolymer by DSC analysis. The mean crystallization clouding time as measured by the molten phase is 15 minutes. The mixture is dried at 65 ° C in a drying dehumidifier for about 4 hours and injection molded into clear samples as set forth in Example 1.

Example 9 - Example of the Invention - Preparation of Copolyester containing 52 mol% is of terephthalate, 48 mol% of 1,4-cyclohexanedicarboxylate and CHDM The apparatus and method indicated in Example 1 were used. Amounts of reagents were charged to the reactor: 404.7 grams of dimethyl terephthalate (DMT) (2.1 moles), 243.6 grams of dimethyl 1,4-cyclohexanedicarboxylate (1.4 moles), (95% trans isomer / 5% cis isomer) 580.4 grams of CHDM (4.03 moles) and 2.68 ml of a 3.30% (w / v) solution of titanium isopropoxide in n-butanol. The reactor is purged with nitrogen and heated to 290 ° C, under a slight stream of nitrogen with stirring. The temperature of the reactor is maintained for 30 minutes and then the nitrogen purge is removed and vacuum is applied in such a way that the vacuum of < 0.5 mm Hg is achieved during a period of 30 minutes. The vacuum and temperature are maintained for 53 minutes. The polymer is extruded into the lower part of the reactor through a hole. The extruded bar is cooled in a water bath at 5 ° C and the granules are formed. An inherent viscosity of 0.74 dl / g is determined by the recovered polymer. The polymer contains 52 mol% terephthalate and 48 mol 1,4-cycloxandicarboxylate (88% trans isomer / 12% cis isomer) as measured by 1 H NMR. A vitreous transition temperature at a T of 78 ° C and a Tm of 225 ° C is obtained by the polymer by a DSC analysis. The mean crystallization clouding time as measured by the molten phase is 11.5 minutes. The mixture is dried at 65 ° C in a drying dehumidifier for about 4 hours and injection molded into transparent samples as set forth in Example 1. Example 10 - Example of the Invention - Preparation of Copolyester dream contains 70 mol% terephthalate , 30% by mole of 2, 6-naphthalenedicarboxylate and CHDM The apparatus and method indicated in Example 1 were used. The following quantities of reagents were charged to the reactor: 477.0 grams of DMT (2.5 moles), 203.9 grams of DMI , (1.0 mole) 565.4 g of CHDM (3.9 mole) and 2.67 ml of a 3.30% (w / v) solution of titanium isopropoxide in N-butanol. The reactor is purged with nitrogen and heated to 290 ° C under a slight stream of nitrogen with stirring. The temperature of the reactor is maintained for 30 minutes and then the nitrogen purge is removed and vacuum is applied in such a way that the vacuum of < 0.5 mm Hg is achieved during a period 30 minutes. The vacuum and temperature are maintained for 43 minutes. The polymer is extruded in the lower part of the reactor. The extruded bar is cooled in a water bath at 5 ° C and the granules are formed. The coated polymer granules have an inherent viscosity of 0.64 dl / g and the polymer consists of 70 mol% terephthalate and 30 mol% naphthalate measured by 1U NMR. A T of 103 ° C and a Tm of 246 ° C are obtained from the copolymer by means of the DSC analysis. The mean crystallization clouding time as measured by the molten phase is 9 minutes. The sample is dried at 85 ° C in a drying dehumidifier for about 4 hours and injection molded into clear samples as set forth in Example 1. Example 11 - Example of the Invention - Preparation of Copolyester containing 68 mol% of terephthalate, 32% by mole of 1,4-cyclohexanedicarboxylate and CHDM The apparatus and method indicated in Example 1 were used. The following amounts of reagents were charged to the reactor: 461.8 grams of dimethyl terephthalate (DMT) (2.4 moles) , 224.0 grams of dimethyl 1,4-cyclohexanedicarboxylate (1.1 moles), (95% trans isomer / 5% cis isomer) 580.4 grams of CHDM (4.03 moles) and 2.68 ml of a 3.30% solution (p. / v) of titanium isopropoxide in n-butanol. The reactor is purged with nitrogen and heated to 290 ° C under a slight stream of nitrogen with stirring. The temperature of the reactor is maintained for 30 minutes and after the nitrogen purge is removed, vacuum is applied in such a way that the vacuum of <; 0.5 mm is achieved during a period of 30 minutes. The vacuum and temperature are maintained for 50 minutes. The polymer is extruded into the lower part of the reactor through a hole. The extruded bar is cooled in a water bath at 5 ° C and the granules are formed. An inherent viscosity of 0.70 dl / g is determined for the recovered polymer. The polymer contains 68 mol% terephthalate and 32 mol% 1,4-cyclohexanedicarboxylate (89% trans isomer / 11% cis isomer) as measured by 1 H NMR. A glass transition temperature T of 82 ° C and a Tm of 245 ° C is obtained from the copolymer by DSC analysis. The mean crystallization clouding time of the molten sample is 2 minutes. The sample is dried at 65 ° C in a drying dehumidifier for about 4 hours and injection molded into transparent samples as set out in Example 1. II PREPARATION FOR AND EXECUTION OF THE METHODS OF STRENGTH RESISTANCE OF TENSION USING MINT OIL AND A TOOTHPASTE SOLUTION A. Preparation of Toothpaste Solution A toothpaste solution using toothpaste A as described in the following table is prepared using the following procedure. In a 500 ml container, 50 grams of a solid toothpaste is added to 120 ml of pure tap water. The mixture is sealed and then stirred using a magnetic stir bar and magnetically stirring the container. After 30 minutes of mixing time the dispersion is applied to the test samples using an applicator brush and observing. The same toothpaste solution is used for each test cycle. The next morning the test samples of Examples 1-10 are inspected and classified according to appearance using a fissure classification system. The fissures are precursors to the breakage which is formed due to the interaction of the solvent with the matrix polymer. The fissures are similar to breaking, but the fissures contain highly oriented fibrils of polymers which cross these surfaces. Fissures are not necessarily structural defects, but often achieve the formation of real breaks. After sorting, the test samples are moistened with the toothpaste solution. The samples are moistened with the toothpaste solution 8 hours later and observed the next morning. The resistance to stress cracking to peppermint oil is determined using the same methodology as for the toothpaste solution test. Peppermint oil has the following composition: Composition of Mint Oil Compound Percent by Weight Dimethylsulfide 0.02 2 Methylpropanal 0.03 3 methylpropanal ~ < 0.01 2 methylbutanal < 0.01 3 methylbutanal 0.15 2 ethylfuran 0.03 trans-2, 5-diethyl THF 0.02 a-pinene 0.66 Sabieno 0.42 miiceno 0.18 Qi-terpineno 0.34 Limonene 1.33 1,8 cineol 4.80 trans-ocimene 0.03 cis-ocimene 0.31 G-terpinene 0.56 trans-2-hexenal 0.07 para-cimeme 0.10 Terpenenole 0.16 Hexanol 0.13 3 octylacetate 0.03 cis-3-hexanol 0.01 3 - . 3-Octanol 0.21 trans-2-hexenol 0.02 Hydrated Sabineno 0.80 Mentona 20.48 Mentofurano 1.67 D-isomenthone 2.77 B-borjonol 0.37 Neo ethylacetate 0.21 Linalool 0.26 cis-sabineno hydrated 0.07 methyl acetate 5.02 Isopulegol 0.7 neoisomenthyl acetate 0.26 Neomentol 3.34 ß-caryophyllene 2.13 Terpinen-4-ol 0.98 Neoisoisopulegol * 0.03 Neoisomentol 0.78 Menthol 43.18 Pulegona 0.77 trans-ß farenceno 0.29 Isomentol 0.19 Humelene 0.03 a-terpineol 0.16 Germacreno-D 2.19 Piperitone 0.96 Viridiflorol 0.26 Eugenol 0.02 Thymol 0.04 B. Resistance to Peppermint Oil and Toothpaste Molding Items Check The molded plates of Examples 1 to 10 are mounted on a test kit shown in Figure 2. In Figure 2 the parts labeled with A are screws to hold the test sample, B is the curved portion of the equipment which determines the tension of the test sample that is below and C is the plate molded under tension. The test equipment is configured in such a way that the bending tension for each sample is 2.7%. The test equipment is used to simulate the final conditions such as the insertion of bristles. The samples remain in the test equipment for 7 days and are observed day after day for the formation of fissures. A classification system of 1 to 3 is used to identify the severity of the cracking in each sample, (the visual observation codes as referred to herein). In this system, the visual observation code 1 is assigned to the test plates that do not exhibit change during the test period. As the severity of cracking increases, the classifications increase in value. Table 1 illustrates the effect of the 2.7% strain on the test samples manufactured from granules of Examples 1 to 5. No effect is observed in all test samples. This indicates that the placement of the test samples in the test apparatus does not indicate the cracks. The effect of the toothpaste solution in Examples 1 to 5 under bending stress is shown in Table 2. The data in Table 2 indicate that how the CHDM content of the copolyesters is increased in relation to the EG content. , the resistance to cracking stress of the test samples is improved. At high levels of CHDM as illustrated in Examples 4 and 5 no effect is observed. The same trend is observed when peppermint oil is used as a chemical agent as seen in Table 3. The data in Table 2 and Table 3 indicate that examples 4 and 5 have a higher resistance to cracking stress when they are exposed to the toothpaste solution and peppermint oil over bending stress more than Examples 1 to 13. Examples 3, 4 and 5 are injection molded to cylindrical articles that are approximately 20 centimeters in length. The diameter of each article varies from 5 to 11.5 mm. The molded articles prepared from Example 3 are transparent. The prepared articles of examples 4 and 5 are not completely transparent. They contain opaque sections, usually in the area where the article increases the diameter. This result indicates that the copolyesters represented by examples 4 and 5 are resistant to cracking stress, however; Articles molded with wide sections of materials and Examples 4 and 5 are not preferred. In Table 4, the effect of the bending stress of 2.7% on manufactured samples of Examples 6-10 is shown. The data in Table 4 indicate that placing the test samples on the test apparatus does not induce cracking. The data and Table 5 indicate that the molded plates of Examples 6 to 10 show no effect when the sample is under bending stress in the presence of toothpaste solution. The data in Table 6 indicate that examples 6-10 all show an improvement in crack stress resistance with peppermint oil under bending stress more than examples 1-3., the granules of Examples 6-10 are injection molded into cylindrical articles of 20 centimeters in length. The diameter of each article varies between 5 and 11.5 millimeters. The molded articles prepared from Example 6 contain opaque sections particularly in the wide sections, while the prepared articles of Examples 7-10 are transparent. This result indicates that certain copolyesters can be used to produce molded articles with wide sections having excellent transparency and are resistant to crack tension by toothpaste and peppermint oil.

The granules of Example 6 are injection molded into cylindrical articles of 20 cm length. The diameter of each article varies between 5 and 7 mm. The molded articles are transparent. This finding indicates that certain copolyesters can be used to produce molded articles that have excellent transparency and are resistant to stress cracking from teeth and peppermint oil. Table 1. Effect of bending stress of 2.7% on copolyesters without the use of solution A of toothpaste or peppermint oil.

Time Example 1 Example 2 Example 3 Example 4 Example 5 (h.) 18 42 66 90 162 186 Visual Observation Codes: 1 = No effect 2 = the test sample is slightly fissured. The fissures are not very deep and are located randomly. 3 = the test sample is highly cracked. The fissures are deep and located randomly. Table 2. Effect of solution A of toothpaste in copolyesters at a bending tension of 2.7%.

Time Example 1 Example 2 Example 3 Example 4 Example 5 (h.) 18 3 3 3 42 3 3 3 66 3 3 3 90 3 3 3 162 3 3 3 186 3 3 3 Visual Observation Codes: 1 = No effect 2 = the test sample is slightly fissured. The fissures are not very deep and are located randomly. 3 = the test sample is highly cracked. The fissures are deep and located randomly.

Table 3. Effect of peppermint oil on copolyesters at a flexion tension of 2.7%.

Time Example 1 Example 2 Example 3 Example 4 Example 5 (h.) 2 3S 3S 3S 2 2 18 3S 3S 3S 2 2 42 3S 3S 3S 2 2 66 3S 3S 3S 2 2 90 3S 3S 3S 2 2 114 3S 3S 3S 2 2 Visual Observation Codes: 1 = No effect 2 = the test sample is slightly fissured. The fissures are not very deep and are located randomly. 3 = the test sample is highly cracked. The fissures are deep and located randomly. s = bulky test sample Table 4 - Effect of 2.7% Flexion Deformation on Copolyesters ein ei Use of the Toothpaste or Mint Oil Solution.

Time Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 (h.) 18 1 1 42 1 1 66 1 1 90 1 162 1 1 186 1 1 Visual observation codes: No effect the test sample is slightly fissured. The fissures are not very deep and randomly located the test sample is highly fissured. The fissures are deep and located randomly Table 5. Effect of solution A of toothpaste in copolyesters at a flexion tension of 2.7%.

Time Example 6 Exer < n. ) 18 1 i 42 1 i 66 1 1 90 1 i 162 1 i 186 1 1 Visual Observation Codes: 1 = No effect 2 = the test sample is slightly fissured. The fissures are not very deep and are located randomly. 5 = the test sample is highly cracked. The fissures are deep and located randomly. Table 6. Effect of mint oil on copolyesters at a flexion tension of 2.7%.

Time Example 6 Example 8 Example 9 Example 20 1 2 2 3S 2 2 22 2 2 3S 2 3 46 2 2 3S 2 3 70 2 2 3S 2 3 94 2 2 3S 2 3 118 2 2 3S 2 Visual Observation Codes: 1 = No effect 2 = the test sample is slightly fissured. The fissures are not very deep and are located randomly. 3 = the test sample is highly cracked. The fissures are deep and located randomly. s = bulky test sample Comparison of tensile strength of molded articles before and after exposure to a toothpaste solution In Table 7 and 8, the effect of toothpaste solutions on tensile strength retained are deployed. The granules of the Examples listed in the tables are molded to 0.32 cm wide tractile bars as the ASTM D638 method. A sample of the bars is tested by the method ASTM D638 without exposing it to the toothpaste solution to establish a standard control. In addition, the bars are maintained in a tension equipment described in the previous section at a bending tension of 1.4% and 2.7%. The toothpaste solution is applied to these bars for a week as described in the previous section. After the exhibition, the bars are removed from the equipment and tested by the ASTM D638 method. The proportion of the tensile strength of the samples exposed to the tensile strength of the standard control multiplied 100 times is the percentage of resistance retained. Any example which shows a retained strength of more than 90%, preferably more than 95%, more preferably, more than 98%, and even more preferably 100%, is considered to possess sufficient chemical resistance to toothbrush applications . The data in Table 7 confirm that examples 1-3 have a lower chemical resistance after exposing them to toothpaste A. The data in Table 8 show how increasing the level of flavor in the toothpaste affects the examples 2, 3, 6 and 11. The level of flavoring is determined as a total percentage of limonene, cineole, menthone, menthol and carvone, determined by gas chromatography combined with mass spectroscopy. The levels of these components are also listed in Table 8. There are five components with the major components present in peppermint oil and spearmint oil. The levels of other compounds are listed in Table 9.

Table 7 Percentage of Resistance Withheld * Example tS > 1.4% Resistance gj > 2.7% Flexion Resistance to Flexion 27 38 98 98 100 lOO 10O lOO lOO lOO 8 lOO lOO 100 10O 100 lOO 11 loo 100 Table 8 Percent Example 2 Example 3 Example 6 Example 11 By Weight Code VO * Code VO * Code VO * Code VO * Flavoring (% Resistance (% Resistance (% Resistance (% Resistance Retained) Withheld) Withheld) Withheld Toothpaste A * 0.800% 3 (0%) 1 (100%) 1 (100%) Toothpaste B * 0.4751 1. { 97%) 2 (98%) • 1 (100%) 1 (100%) Pasta de dènte e * 0.685% 2 (81%) 2 (98%) 1 (100%) 1 (100%) Toothpaste D * 0.480% 2 (67%) 1 (100%) 1 (100%) Toothpaste E * 0.845 * 3 (0%) 3 (0%) 1 (100%) 1 (100%) Toothpaste F * 0.740% 3 (0%) 1 (100%) 1 (100%) Percentages by Weight of Flavoring Compositions for Toothpaste A-F: Limoneno Cineol Mentona Menthol Carvona Total Toothpaste A: 0.01 0.02 0.105 0.67 0.01 0.800 Toothpaste 8: 0.02 < 0.01 0.01 0.215 0.23 0.475 Toothpaste O < 0.01 0.015 0.09 0.57 0.01 0.685 Toothpaste D: 0.01 < 0.01 0.05 0.31 o.p 0.480 Toothpaste E: 0.02 0.035 0.245 0.465 0.08 0.845 Toothpaste F: 0.02 0.035 0.19 0.485 0.01 0.-740 VO Code * = Visual Observation Code Table 9 CONCENTRATION (% BY WEIGHT) OF OTHER COMPOUNDS DETECTED IN TOOTH PASTES BY GAS CHROMATOGRAPHY / MASS SPECTROSCOPY Glycerin Compound Compound Compound Compound Compound Compound Compound Compound Compound 1 2 3 4 5 6 7 8 and i U Toothpaste A 21.62 0.01 0.025 0.025 0.085 0.27.5 0.115 0.07 Toothpaste B 18.06 0.01 0.055 0.155 0.55 0.01 Toothpaste c 9. 52 0.02 0.095 0.175 0.11 0.06 0.03 Toothpaste D 8.98 0.07 0.01 0.01 0.065 0.275 0.105 0.05 0.05 4- > Toothpaste e 21.67 0.05 0.01 O.OS 0.025 0.01 0.28 0.13 0.08 Toothpaste F 12.15 0.04 0.01 0.04 0.04 0. 14 0.065 0.01 Identification of Compound (Comp.) 1 1-HO-2-Propanone 1 3-Octanol. 4- ethyl-1- (1-methylethyl) cyclohexene 4 Putegone 5 Dodecanol (isomer 1) 6 Dodecanol (isomer 2) 3-phenyl-2-propenal 8 Dodecanol (isomer 3) 0 Eugenol The invention has been described in detail with particular reference to the preferred embodiments thereof, but it will be understood that variations and modifications can be made within the spirit and scope of the invention. In addition, all patents, patent applications (published and unpublished foreign or national), literary references or other publications mentioned in the foregoing are incorporated herein by reference for any description pertinent to the practice of this invention.

Claims (39)

1. RK1VIMDICACIOWM 1. A molded object is prepared from a copolyester having an inherent viscosity of 0.4 to 1.1 dl / g, measured in a solution of 60/40 phenol / tetrachloroethane containing 0.5 grams of polymer in 100 milliliters of solution, characterized in that the The acid component comprises repeating units of 90 to 40% by mole of terephthalic acid and 10 to 60% by mole of 1 or more additional dibáßicoß acid selected from a group consisting of isophthalic acid, cyclohexanedicarboxylic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid and acid. stybendicarboxylic; Wherein the glycol component comprises repeating units of 1,4-cyclohexanedimethanol.
2. 2. The molded object according to claim 1, characterized in that the acid component comprises repeat units of 85 to 52 mole% of terephthalic acid and 15 to 48 mole% of 1 or more of the additional dibasic acids.
3. 3. The molded object according to claim 2, characterized in that the acid component comprises repeating units of 83 to 52 mol% of terephthalic acid and 17 to 48 mol% of 1 or more of the additional dibasic acids.
4. The molded object according to claim 1, characterized in that one or more of the additional dibasic acids comprise isophthalic acid, cyclohexanedicarboxylic acid, naphthalenedicarboxylic acid.
5. 5. The molded object according to claim 4, characterized in that one or more of the additional dibasic acids comprise isophthalic acid.
6. 6. The molded object according to claim 4, characterized in that one or more of the additional dibasic acids comprise 1,3-cyclohexanedicarboxylic acid.
7. The molded object according to claim 4, characterized in that one or more of the additional dibasic acids comprise 1,4-cyclohexanedicarboxylic acid.
8. 8. The molded article according to claim 4, characterized in that one or more of the additional dibasic acids comprise naphicarboxylic acid.
9. The molded object according to claim 8, characterized in that the naphthalenedicarboxylic acid is selected from a group consisting of 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1,4-naphidendicarboxylic acid, acid 1, 5-naphthalenedicarboxylic.
10. 10. The molded object according to claim 1, characterized in that it comprises up to 10% in molds of any of the additional dibasic acids.
11. 11. The molded object according to claim 10, characterized in that the additional dibasic acids are selected from 1 or more of the groups consisting of aromatic dicarboxylic acids preferably having from 8 to 14 carbon atoms, aliphatic dicarboxylic acids preferably having 4 to 4 carbon atoms. to 12 carbon atoms, and preferably cycloaliphatic dicarboxylic acids having from 8 to 12 carbon atoms.
12. The molded object according to claim 11, characterized in that the additional dibasic acids are selected from one or more of the groups consisting of phthalic acid, cyclohexanediacetic acid, succinic acid, glutaric acid, adipic acid, azelaic acid and sebasic acid .
13. 13. The molded object according to claim 1, characterized in that the glycol component comprises 70 to 100 mol% of 1,4-cyclohexanedimethanol.
14. 14. The molded object according to claim 13, characterized in that the glycol component comprises 80 to 100 mol% of 1,4-cyclohexanedimethanol.
15. 15. The molded object according to claim 14, characterized in that the glycol component comprises 85 to 100 mol% of 1, -cyclohexanedimethanol.
16. 16. The molded object according to claim 15, characterized in that the glycol component comprises 90 to 100 mol% of 1,4-cyclohexanedimethanol.
17. 17. The molded object according to claim 16, characterized in that the glycol component comprises 95 to 100 mol% of 1,4-cyclohexanedimethanol.
18. The molded object according to claim 13, characterized in that the glycol component contains up to 30% by mole of one or more of the additional aliphatic or alicyclic glycols.
19. The molded article according to claim 18, characterized in that 1 or more of the additional glycols is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, pronanodiol, butanediol, pentanediol, hexanediol, neopentyl glycol and tetramethylcyclobutanediol.
20. The molded object according to claim 19, characterized in that one or more of the additional glycols comprises ethylene glycol.
21. 21. The molded object according to claim 1, characterized in that it has an average crystallization clouding time greater than one minute.
22. 22. The molded object according to claim 1, characterized in that it has an average crystallization clouding time of more than 3 minutes.
23. 23. The molded object according to claim 21, characterized in that it is visually transparent for portions of the objects having a thickness of 1 to 11.5 mm.
24. 24. The molded object according to claim 22, characterized in that it has an average crystallization clouding time greater than 5 minutes.
25. 25. The molded object according to claim 23, characterized in that it is visually transparent for portions of the objects having a thickness of 5 to 11.5 mm.
26. 26. The molded object according to claim 1, characterized in that it is prepared from the copolyester having a diffusion transmittance value of less than about 60% as determined by the ASTM method D1003.
27. 27. The molded object according to claim 1, characterized by having an improved fissure tension strength, on a molded object prepared from a copolyester in which the acid component comprises repeat units of more than 90% mol terephthalic acid , as determined in the test samples laß cualeß are 0.32 centimeters thick under a bending load of deformation of 2.7%.
28. 28. The molded object according to claim 13, characterized in that the molded object has an improved fissure tension strength on a molded object prepared from a copolyester in which the acid component comprises repeat units of more than 90% mol terephthalic acid as determined by the test samples which are 0.32 centimeters wide under a deformation bending load of 2.7%.
29. 29. The molded object according to claim 26, characterized in that the molded object has an improved fissure tension strength as determined for a test sample with 0.32 centimeters in width under a bending load of 2.7% strain and they are in contact with a dß paßta de dienteß solution comprising 0.6% in peßo dß ßaborizantß as determined by gaa chromatography.
30. 30. The molded article according to claim 29, characterized in that each ß solution of the paßta de dientesß comprises: (a) water and (b) a paßta dß dienteß comprising 0.6% in peppermint oil.
31. 31. The molded object according to claim 30, characterized in that the molded object is brought into contact with a toothpaste solution for 18 to 186 hours.
32. 32. The molded object according to claim 29, characterized in that the molded object is brought into contact with the flavor for 1 to 118 hours.
33. 33. The molded object according to claim 32, characterized in that the molded object is brought into contact with the flavor for 1 to 6 hours.
34. The molded object according to claim 29, characterized in that the flavor is selected from a group consisting of peppermint oil, spearmint oil, curly mint oil, anise oil, Japanese anise oil, caraway oil , eucalyptus oil, fennel oil, cinnamon oil, clove oil, geranium oil, sagebrush oil, pepper oil, thyme oil, marjoram oil.
35. 35. The molded object according to claim 34, characterized in that the flavor is selected from peppermint oil.
36. 36. The molded object according to claim 35, characterized in that the peppermint oil comprises a component selected from a group consisting of limonene, cineole, menthone, menthol and carvone.
37. 37. The molded object according to claim 35, characterized in that the mint oil comprises mint oil.
38. 38. The molded object according to claim 29, characterized in that the flavor contains synthetic ingredients.
39. 39. The molded object according to claim 38, characterized in that the synthetic ingredient is mentioned.