Polyester resin, its use, molded body, cosmetic container, and cosmetic product

Abstract

This polyester resin comprises a polymer of (A) an acid component and (B) an alcohol component. The component (A) comprises (A1) a terephthalic acid component in an amount of 72 mol% or more and (A2) an isophthalic acid component in an amount of 8 to 28 mol% both related to the whole amount of the component (A). The component (B) comprises (B1) an ethylene glycol component in an amount of 77 mol% or more, (B2) a 2,2-dimetyl-1,3-propanediol component in an amount of 4 to 18 mol% and (B3) a diethylene glycol component in an amount of 5 mol% or less all relative to the whole amount of the component (B). The total of the ratio of the content of the component (A2) to the content of the component (A) and the ratio of the content of the component (B2) to the content of the component (B) is 24 to 43 mol%.

Description

Related Applications

[0001] The present invention is based on a claim of priority from Japanese Patent Application No. 2021-80464 (filed May 11, 2021), the entire contents of which are incorporated herein by reference. [Technical Field]

[0002] The present disclosure relates to a polyester resin and a method of using the same. The present disclosure also relates to a cosmetic container having the polyester resin and a cosmetic product using the cosmetic container. [Background technology]

[0003] Polyethylene terephthalate (PET), a copolymer of terephthalic acid and ethylene glycol, is used in a variety of applications. Polyester resins are known that have polyethylene terephthalate as the main structure and are partially copolymerized with neopentyl glycol as an alcohol component (see, for example, Patent Documents 1 and 2).

[0004] The copolymer polyester resin described in Patent Document 1 contains 100 mol % of terephthalic acid as a dicarboxylic acid component, and 79 to 94.5 mol % of ethylene glycol, 3.0 to 20.0 mol % of neopentyl glycol, and 1.0 to 2.5 mol % of diethylene glycol as glycol components, and has an intrinsic viscosity of 0.77 dL / g to 0.78 dL / g. The copolymer polyester resin described in Patent Document 2 contains 100 mol % of terephthalic acid as a dicarboxylic acid component, and 79 to 94.5 mol % of ethylene glycol, 4.0 to 31.2 mol % of neopentyl glycol, and 1.9 to 2.8 mol % of diethylene glycol as glycol components, and has an intrinsic viscosity of 0.71 dL / g to 0.75 dL / g. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2011-68879 [Patent Document 2] Japanese Patent Application Laid-Open No. 2004-123984 Summary of the Invention [Problem to be solved by the invention]

[0006] The following analysis is given in light of the present disclosure.

[0007] When resin is used as a container material, a resin is selected that is suited to the contents and application. For example, a resin that is highly resistant to the contents (contents) is selected so that the container does not discolor or deteriorate due to contact with the contents (contents). To improve the aesthetic appeal of the container or increase the visibility of the contents, a resin with high transparency is selected rather than an opaque resin. To improve design, a resin with high moldability is selected so that the resin can be easily molded into complex shapes.

[0008] However, generally, when an attempt is made to increase the transparency or moldability of a resin, the resistance of the resin to contents (contact materials) containing organic compounds tends to decrease. Therefore, in order to obtain a container that can accommodate desired contents and can be used for desired purposes, a resin with improved resistance to the contents, moldability, and transparency is required.

[0009] When the intrinsic viscosity is increased, as in the copolymer polyester resins described in Patent Documents 1 and 2, the molding temperature, i.e., the temperature required to achieve a melt viscosity suitable for molding, increases. High molding temperatures make the polyester resin more susceptible to degradation and also reduce production efficiency. Furthermore, the copolymer polyester resins described in Patent Documents 1 and 2 have a high proportion of PET structure, which makes crystalline portions prone to occur, resulting in cloudiness when thick sections are formed. Furthermore, it is difficult to improve moldability, transparency, and resistance to contact objects simply by adjusting the alcohol content, as is the case with the copolymer polyester resins described in Patent Documents 1 and 2.

[0010] Therefore, there is a demand for a polyester resin that has high moldability, can be molded at low temperatures, has transparency in molded products, and has improved resistance to contact with objects.

[0011] There is also a demand for cosmetic containers and cosmetic products that use such polyester resins. [Means for solving the problem]

[0012] According to a first aspect of the present invention, there is provided a polyester resin containing a polymer of (A) an acid component and (B) an alcohol component, wherein the component (A) is present in an amount of: 75mol%~88mol% (A1) a terephthalic acid component; 12mol%~25mol% and (A2) an isophthalic acid component of the formula: 81mol%~91mol% (B1) an ethylene glycol component; 6mol%~16mol% and (B2) 2,2-dimethyl-1,3-propanediol component. The sum of the content of the component (A2) relative to the component (A) and the content of the component (B2) relative to the component (B) is 27mol%~40mol% When the polyester resin contains the diethylene glycol component (B3), the content of the diethylene glycol component (B3) is 5 mol % or less relative to the total amount of the component (B). The melt viscosity at 180°C is 100 Pa·s to 180 Pa·s, The intrinsic viscosity is 0.48 dl / g~0.67 dl / g.

[0013] According to a second aspect of the present invention, there is provided a molded article containing the polyester resin according to the first aspect. The molded article has a container shape with a portion having a thickness of 2 mm or more and a maximum thickness of 10 mm or less. According to a third aspect of the present invention, A polyester resin comprising a polymer of an (A) acid component and a (B) alcohol component, wherein the (A) component comprises, relative to the total amount of the (A) component, 72 mol % or more of an (A1) terephthalic acid component and 8 mol % to 28 mol % of an (A2) isophthalic acid component; the (B) component comprises, relative to the total amount of the (B) component, 77 mol % or more of an (B1) ethylene glycol component and 4 mol % to 18 mol % of a (B2) 2,2-dimethyl-1,3-propanediol component; the sum of the content of the (A2) component relative to the (A) component and the content of the (B2) component relative to the (B) component is 24 mol % to 43 mol %; the (B3) diethylene glycol component is 5 mol % or less relative to the total amount of the (B) component; and the intrinsic viscosity is 0.48 dl / g to 0.67 dl / g. A cosmetic container having a polyester resin is provided.

[0014] The present invention 4 From the viewpoint of cosmetics and a second container for containing the cosmetics. 3 A cosmetic container according to the present invention; of A cosmetic product comprising:

[0015] According to a fifth aspect of the present invention, A polyester resin comprising a polymer of an (A) acid component and a (B) alcohol component, wherein the (A) component comprises, relative to the total amount of the (A) component, 72 mol % or more of an (A1) terephthalic acid component and 8 mol % to 28 mol % of an (A2) isophthalic acid component; the (B) component comprises, relative to the total amount of the (B) component, 77 mol % or more of an (B1) ethylene glycol component and 4 mol % to 18 mol % of a (B2) 2,2-dimethyl-1,3-propanediol component; the sum of the content of the (A2) component relative to the (A) component and the content of the (B2) component relative to the (B) component is 24 mol % to 43 mol %; the (B3) diethylene glycol component is 5 mol % or less relative to the total amount of the (B) component; and the intrinsic viscosity is 0.48 dl / g to 0.67 dl / g. The polyester resin is applied to a cosmetic container, and a method for using the polyester resin is applied. [Effects of the Invention]

[0016] The polyester resin of the present disclosure has high moldability.

[0017] The polyester resins of the present disclosure are moldable at low temperatures.

[0018] The polyester resin of the present disclosure has high transparency in the form of a molded article.

[0019] The polyester resins of the present disclosure have high resistance to contact with materials.

[0020] By applying the polyester resin of the present disclosure to a cosmetic container, it is possible to provide a cosmetic container and a cosmetic product that are excellent in safety, visibility, and aesthetics. [Brief explanation of the drawings]

[0021] [Figure 1] FIG. 1 is a schematic diagram for explaining a stress crack test. DETAILED DESCRIPTION OF THE INVENTION

[0022] According to a preferred embodiment of the first aspect, The amount of the diethylene glycol component (B3) is 3 mol % to 5 mol % relative to the total amount of the component (B).

[0023] According to a preferred embodiment of the first aspect, the melt viscosity at 180°C is 120 Pa·s~ 170 Pa·s.

[0024] According to a preferred embodiment of the first aspect, the tensile elongation is 100% or more.

[0025] According to a preferred embodiment of the first aspect, the Charpy impact strength is 2 kJ / m 2 That's all. According to a preferred embodiment of the first aspect, the glass transition temperature is 70° C. or higher.

[0026] According to a preferred mode of the first aspect, the polyester resin has a container shape.

[0027] According to a preferred embodiment of the first aspect, the polyester resin is used for the cosmetic container. It is useful .

[0028] In the following description, the drawings of The reference numerals are added to facilitate understanding of the invention and are not intended to limit the invention to the illustrated embodiments. Furthermore, the illustrated shapes, dimensions, scales, etc. are not intended to limit the invention to the forms shown in the drawings. In each embodiment, the same elements are denoted by the same numerals.

[0029] The polyester resin (including molded articles) of the present disclosure will be described. In this disclosure, unless otherwise specified, the polyester resin may also include molded articles. The polyester resin of the present disclosure is a polyester resin that is a copolymer of an acid component (polycarboxylic acid) and an alcohol component (polyol, polyhydroxy compound). In this disclosure, polycarboxylic acid refers to a compound having multiple carboxy groups. Furthermore, polyol or polyhydroxy compound refers to a compound having multiple hydroxy groups.

[0030] The acid component mainly contains a terephthalic acid component. The content of the terephthalic acid component is preferably 72 mol% or more, more preferably 75 mol% or more, relative to the total amount of the acid components. The content of the terephthalic acid component can be, for example, 77 mol% or more, 80 mol% or more, 82 mol% or more, 83 mol% or more, 84 mol% or more, or 86 mol% or more, relative to the total amount of the acid components. If the terephthalic acid component is less than 72 mol%, the physical strength of the polyester resin will decrease. The content of the terephthalic acid component is preferably 92 mol% or less, more preferably 90 mol% or less, and more preferably 88 mol% or less, relative to the total amount of the acid components. Furthermore The content of the terephthalic acid component relative to the total amount of the acid components can be, for example, 86 mol% or less, 85 mol% or less, 84 mol% or less, 82 mol% or less, 80 mol% or less, 79 mol% or less, or 77 mol% or less. If the terephthalic acid component exceeds 92 mol%, the melt viscosity becomes too high.

[0031] The acid component further includes an isophthalic acid component. The content of the isophthalic acid component is preferably 8 mol% or more, and more preferably 10 mol% or more, relative to the total amount of the acid components. The content of the isophthalic acid component can be, for example, 12 mol% or more, 14 mol% or more, 15 mol% or more, 16 mol% or more, 18 mol% or more, 20 mol% or more, 21 mol% or more, or 23 mol% or more, relative to the total amount of the acid components. If the isophthalic acid component is less than 8 mol%, low-temperature molding becomes difficult and the transparency of the molded product decreases. The content of the isophthalic acid component is preferably 28 mol% or less, and more preferably 25 mol% or less, relative to the total amount of the acid components. The content of the isophthalic acid component can be, for example, 23 mol% or less, 20 mol% or less, 18 mol% or less, 17 mol% or less, 16 mol% or less, or 14 mol% or less, relative to the total amount of the acid components. If the isophthalic acid content exceeds 28 mol %, the mechanical strength decreases.

[0032] The total amount of the terephthalic acid component and the isophthalic acid component is preferably 90 mol % or more, more preferably 95 mol % or more, based on the total amount of the acid components. The total amount of the terephthalic acid component and the isophthalic acid component can be 100 mol % based on the total amount of the acid components.

[0033] The acid component may contain other acid components as long as the essential properties of the polyester resin of the present disclosure are not changed. Examples of other acid components include orthophthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, succinic acid, dimer acid, 1,4-cyclohexyl 2,6-dicarboxylic acid, and the like. hmm Dicarboxylic acids, dimethyl terephthalate, dimethyl isophthalate, trimellitic acid , or These other acid components may be contained alone or in any combination of two or more kinds in any ratio.

[0034] The alcohol component mainly contains an ethylene glycol component. The content of the ethylene glycol component is preferably 77 mol% or more, and more preferably 81 mol% or more, relative to the total amount of the alcohol components. The content of the ethylene glycol component can be, for example, 82 mol% or more, 84 mol% or more, 85 mol% or more, 86 mol% or more, 87 mol% or more, 88 mol% or more, or 90 mol% or more, relative to the total amount of the alcohol components. If the ethylene glycol component is less than 77 mol%, the resistance to contact materials will decrease. The content of the ethylene glycol component is preferably 96 mol% or less, and more preferably 92 mol% or less, relative to the total amount of the alcohol components. The content of the ethylene glycol component can be, for example, 90 mol% or less, 88 mol% or less, 86 mol% or less, or 84 mol% or less, relative to the total amount of the alcohol components. If the ethylene glycol component exceeds 96 mol%, the melt viscosity will be too high.

[0035] The alcohol component further contains a 2,2-dimethyl-1,3-propanediol component (hereinafter also referred to as a "neopentyl glycol component"). The content of the neopentyl glycol component is preferably 4 mol% or more relative to the total amount of the alcohol components. The content of the neopentyl glycol component can be, for example, 6 mol% or more, 8 mol% or more, 10 mol% or more, or 12 mol% or more relative to the total amount of the alcohol components. If the neopentyl glycol component is less than 4 mol%, the mechanical strength of the polyester resin tends to be low. The content of the neopentyl glycol component is preferably 18 mol% or less, more preferably 16 mol% or less, relative to the total amount of the alcohol components. The content of the neopentyl glycol component can be, for example, 15 mol% or less, 14 mol% or less, 13 mol% or less, 12 mol% or less, or 10 mol% or less relative to the total amount of the alcohol components. If the neopentyl glycol component exceeds 18 mol%, the resistance of the polyester resin to contact materials decreases.

[0036] The total amount of the ethylene glycol component and the neopentyl glycol component is preferably 90 mol% or more, more preferably 95 mol% or more, based on the total amount of the alcohol component, and can be 100 mol% based on the total amount of the alcohol component.

[0037] The alcohol component may contain a diethylene glycol component. The diethylene glycol component may be generated as a by-product. The content of the diethylene glycol component is preferably 5 mol % or less, more preferably 4 mol % or less, and most preferably 3 mol % or less, based on the total amount of the alcohol component. Furthermore Preferably, it is 2 mol% or less. especially Preferably, 0 mol % It is okay If the diethylene glycol content exceeds 5 mol%, 、The polyester resin will have reduced resistance to substances it comes into contact with and reduced heat resistance. The total amount of the ethylene glycol component, neopentyl glycol component, and diethylene glycol component can be 95 mol % or more, preferably 100 mol %, based on the total amount of the alcohol components.

[0038] The alcohol component may contain other alcohol components as long as the essential properties of the polyester resin of the present disclosure are not changed. Examples of other alcohol components include 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,2-propanediol, 1,4-butanediol, and 1,3-butanediol. 、1 ,4-cyclohexanediol, 1,4-cyclohexanedimethanol, or These other alcohol components may be contained alone or in any combination of two or more kinds in any ratio.

[0039] The sum of the content of isophthalic acid components based on the total amount of acid components and the content of neopentyl glycol components based on the total amount of alcohol components is preferably 24 mol% or more. This sum can be, for example, 26 mol% or more, 30 mol% or more, or 35 mol% or more. If this sum is less than 24 mol%, the melt viscosity will be high and transparency will be reduced. This sum is preferably 43 mol% or less. This sum can be, for example, 40 mol% or less, 38 mol% or less, or 35 mol% or less. If this sum exceeds 43 mol%, resistance to contact materials will be reduced.

[0040] The intrinsic viscosity (IV value) of the polyester resin of the present disclosure is 0.48 dL / g (10 2 cm 3The intrinsic viscosity (IV value) of the composition of the present disclosure is preferably 0.67 dL / g or less, more preferably 0.65 dL / g or less. The intrinsic viscosity of the polyester resin of the present disclosure can be, for example, 0.62 dL / g or less, 0.60 dL / g or less, or 0.58 dL / g or more. If the intrinsic viscosity is less than 0.48 dL / g, sufficient mechanical properties cannot be obtained. The intrinsic viscosity (IV value) of the composition of the present disclosure is preferably 0.67 dL / g or less, more preferably 0.65 dL / g or less. The intrinsic viscosity of the polyester resin of the present disclosure can be, for example, 0.62 dL / g or less, 0.60 dL / g or less, or 0.58 dL / g or less. If the intrinsic viscosity exceeds 0.67 dL / g, the melt viscosity becomes high. If the melt viscosity is high, it is necessary to increase the heating temperature to reduce the melt viscosity. As a result, the cooling time becomes longer, productivity decreases, and the polyester resin deteriorates. On the other hand, if you try to force molding without increasing the heating temperature and while the melt viscosity is still high, the polyester resin will not flow properly into the mold, resulting in molding defects, or shear heat will occur, leading to deterioration of the polyester resin.

[0041] The above-mentioned intrinsic viscosity is the intrinsic viscosity at 20°C, measured by dissolving 0.5000±0.0005 g of a sample in a mixed solvent of phenol:tetrachloroethane = 60:40 (mass ratio) using an automatic viscosity measuring device equipped with an Ubbelohde viscometer.

[0042] The melt viscosity of the polyester resin of the present disclosure at 180°C is preferably 100 Pa·s or more, and more preferably 110 Pa·s or more. The melt viscosity of the polyester resin of the present disclosure at 180°C can be, for example, 120 Pa·s or more, 130 Pa·s or more, or 140 Pa·s or more. If the melt viscosity is less than 100 Pa·s, sufficient mechanical properties cannot be obtained. The melt viscosity of the composition of the present disclosure at 180°C is more preferably 200 Pa·s or less, and even more preferably 190 Pa·s or less. The melt viscosity of the polyester resin of the present disclosure at 180°C can be, for example, 180 Pa·s or less, 170 Pa·s or less, or 160 Pa·s or less. If the melt viscosity exceeds 200 Pa·s, problems similar to those occurring when the intrinsic viscosity is high will occur.

[0043] The melt viscosity at 180°C was measured using a melt viscosity measuring device at a temperature of 180°C and a shear rate of 6080 s for 20.0±5.0 g of each dried polyester resin. -1 The method for drying the polyester resin is not particularly limited, and for example, the polyester resin can be dried using a dehumidifying dryer at 60°C for 48 hours.

[0044] The tensile elongation of the polyester resin of the present disclosure is preferably 160% or more, and more preferably 180% or more. If the tensile elongation is less than 160%, sufficient mechanical properties cannot be obtained. The tensile elongation can be measured in accordance with ISO 527.

[0045] The Charpy impact strength of the polyester resin of the present disclosure is 2 kJ / m 2 The Charpy impact strength of the polyester resin of the present disclosure is preferably 2.1 kJ / m or more. 2 or more than 2.2 kJ / m 2 Charpy impact strength of 2 kJ / m or more can be achieved. 2 If the hardness is less than this, sufficient mechanical properties cannot be obtained. The Charpy impact strength can be measured in accordance with ISO179.

[0046] The glass transition temperature of the polyester resin according to the present disclosure is preferably not less than 65° C., and more preferably not less than 70° C. The glass transition temperature can be measured, for example, using a differential scanning calorimetry (DSC) device.

[0047] The polyester resin of the present disclosure is preferably one in which no melting point peak is confirmed when DSC measurement is carried out by increasing the temperature from 40° C. to 270° C. at a temperature increase rate of 10° C. / min.

[0048] The polyester resin of the present disclosure may further contain a polymerization catalyst, such as a germanium compound or a titanium compound.

[0049] The polyester resin of the present disclosure may contain known additives, such as antistatic agents, ultraviolet absorbers, heat stabilizers, release agents, antioxidants, etc., as long as the essential properties of the composition of the present disclosure are not changed.

[0050] For example, the polyester resin of the present disclosure may further contain a phosphorus compound. Examples of phosphorus compounds include phosphoric acid, phosphorous acid, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trimethyl phosphite, triethyl phosphite, and tributyl phosphite. Among these, trimethyl phosphate is particularly preferred. The content of the phosphorus compound is preferably 5 ppm to 1000 ppm, and more preferably 20 ppm to 100 ppm, relative to the mass of the polyester resin.

[0051] The polyester resin of the present disclosure may also include polyester resins obtained by the manufacturing method described below. Regarding characteristics of the polyester resin of the present disclosure other than those described above, it may be difficult or impractical to directly identify the structure, etc., by the composition. In such cases, the polyester resin of the present disclosure should be allowed to be identified by its manufacturing method.

[0052] The polyester resin of the present disclosure can be used in a wide range of molding materials, for example, containers, electric and electronic parts, and automotive materials.

[0053] The polyester resin of the present disclosure can be molded at a low temperature. For example, the molding temperature can be set to 170°C to 220°C, preferably 180°C to 200°C. This reduces the energy required for molding. Furthermore, the cooling time can be particularly shortened, thereby improving production efficiency. Therefore, molding costs can be reduced.

[0054] Furthermore, by keeping the molding temperature low, it is possible to suppress the decomposition of the polyester resin in a molten state, which in turn prevents deterioration in the quality of the molded product. Furthermore, by keeping the intrinsic viscosity low, it is possible to suppress the occurrence of temperature variations due to shear heat in a molten state, which in turn allows for uniform quality of molded products.

[0055] Furthermore, by keeping the molding temperature low, the mold cooling temperature can be increased, which reduces the cost of cooling energy and also suppresses condensation on the mold.

[0056] The polyester resin of the present disclosure has high transparency even when molded. For example, clouding is suppressed even when molded into a thick-walled container. This allows molded articles of the polyester resin of the present disclosure to have a good appearance. Furthermore, the polyester resin of the present disclosure can increase the diversity of the design of molded articles.

[0057] The polyester resin of the present disclosure has high moldability. For example, the polyester resin of the present disclosure facilitates injection molding into a mold, thereby preventing short shots. As a result, the polyester resin of the present disclosure can be used to produce molded articles having complex shapes.

[0058] The polyester resin of the present disclosure has high moldability, low-temperature moldability, and transparency, while also having high resistance to contact substances such as organic compounds. For example, even when the polyester resin comes into contact with an organic compound-containing product, discoloration and deterioration of the polyester resin are suppressed. As a result, the polyester resin of the present disclosure can be used, for example, as a container for cosmetics.

[0059] The polyester resin of the present disclosure can be applied to a container body that contains a cosmetic product. The polyester resin of the present disclosure can also be applied to a lid that is detachably attached to the container body. The cosmetic container preferably contains, for example, 70% by mass or more, 80% by mass or more, 90% by mass or more, or or The cosmetic container may contain 95% by mass or more of the polyester resin of the present disclosure. The entire cosmetic container (100% by mass) may be made of the polyester resin of the present disclosure. Because the polyester resin of the present disclosure has high transparency, when the container body is made of the polyester resin of the present disclosure, the contents (cosmetics) can be seen from the outside.

[0060] The polyester resin of the present disclosure has sufficient mechanical properties.

[0061] A method for producing the polyester resin of the present disclosure will be described.

[0062] The polyester resin of the present disclosure can be produced by a known method based on the above-mentioned monomers and additives. For example, an ester prepolymer may be produced by direct esterification using an unsubstituted polycarboxylic acid as a starting material, or an ester prepolymer may be produced by transesterification using an esterified product such as dimethyl ester as a starting material. From the viewpoint of production efficiency, direct esterification is preferred.

[0063] The addition rates of the monomers and additives may be the rates set forth above in the description of the polyester resin of the present disclosure.

[0064] The direct esterification reaction or transesterification reaction can be carried out, for example, by charging raw materials into a reaction vessel equipped with a heater, a stirrer, and a distillation tube, adding a reaction catalyst, and raising the temperature while stirring under an inert gas atmosphere at atmospheric pressure, and allowing the reaction to proceed while distilling off by-products such as methanol produced by the reaction. The reaction temperature can be, for example, 150°C to 270°C, and preferably 160°C to 260°C. The reaction time is, for example, about 3 to 7 hours.

[0065] As a catalyst for the transesterification reaction, at least one metal compound can be used. Preferred metal elements include, for example, sodium, potassium, calcium, titanium, lithium, magnesium, manganese, zinc, tin, and cobalt. Among these, titanium and manganese are particularly preferred. N This is preferred because it has high reactivity and the color tone of the resulting resin is good. Reaction The amount of catalyst added is usually preferably 5 ppm to 1000 ppm, more preferably 10 ppm to 100 ppm, based on the polyester resin produced.

[0066] To suppress the production of diethylene glycol as a by-product, it is preferable to reduce the amount of ethylene glycol in the reaction system. For example, it is preferable to set the molar ratio of the alcohol component to the acid component (alcohol component / acid component) to 1.3 or less. Furthermore, the production of diethylene glycol can be suppressed by adding, for example, 5 ppm of sodium hydroxide.

[0067] Furthermore, it is desirable to add a phosphorus compound after the completion of the direct esterification reaction or the transesterification reaction to further promote the esterification reaction. Examples of phosphorus compounds include phosphoric acid, phosphorous acid, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trimethyl phosphite, triethyl phosphite, and tributyl phosphite. Of these, trimethyl phosphate is particularly preferred. The amount of the phosphorus compound used is preferably 5 ppm to 1000 ppm, and more preferably 20 ppm to 100 ppm, based on the mass of the polyester resin produced.

[0068] In this disclosure alcohol Among the ingredients, neopentyl glycol ,acid It may be added during the direct esterification reaction of the component with ethylene glycol, or after the esterification reaction is completed. Acid It is preferable to prepare a slurry by mixing the components with ethylene glycol and neopentyl glycol at room temperature, and then proceed with the esterification reaction in an esterification reaction tank, since this can prevent the neopentyl glycol from scattering. In the present disclosure, the entire amount of ethylene glycol can be added before the esterification reaction, and it is not necessary to add a portion of it after the esterification reaction.

[0069] Following the transesterification and esterification reactions, a polymerization catalyst can be added to the ester prepolymer, and a polycondensation reaction can be further carried out until the desired molecular weight is achieved. For example, germanium dioxide can be used as the catalyst in the polymerization reaction. The catalyst addition rate can be, for example, 180 ppm to 220 ppm relative to the amount of resin produced. The polycondensation reaction can be carried out, for example, by gradually increasing the temperature and reducing the pressure inside the reaction vessel after adding the polymerization catalyst. The pressure inside the vessel is preferably reduced to, for example, 0.4 kPa or less, preferably 0.2 kPa or less. The temperature inside the vessel is preferably increased to, for example, 250°C to 290°C. The polymerization reaction can be carried out, for example, under reduced pressure until the desired melt viscosity is achieved, with the final vessel pressure being 150 Pa or less. Thereafter, the vessel pressure can be increased to, for example, 0.5 MPa, and the reaction product can be extruded and recovered from the bottom of the vessel. For example, the reaction product can be extruded into water in the form of strands, cooled, and then cut to obtain pelletized polyester resin. In the present disclosure, the obtained pellets do not need to be subjected to an infrared irradiation step.

[0070] As the polymerization catalyst, a catalyst other than germanium dioxide can also be used. For example, titanium dioxide can be used as the polymerization catalyst. When titanium dioxide is used, the catalyst addition rate can be, for example, 1 ppm to 10 ppm relative to the amount of resin produced.

[0071] The polyester resin of the present invention can be appropriately blended with various additives, such as antioxidants, heat stabilizers, lubricants, antistatic agents, plasticizers, UV absorbers, and pigments, depending on the application and molding purpose. These additives may be blended in either the polymerization reaction step or the processing and molding step. Examples of antioxidants include hindered phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants, with hindered phenol-based antioxidants being particularly preferred. The amount added is preferably approximately 100 ppm to 5000 ppm. Furthermore, when molding into a melt-extrusion film, metal salts such as magnesium acetate, calcium acetate, and magnesium chloride may be added to stabilize the electrostatic adhesion of the cooling roll.

[0072] According to the method for producing a polyester resin of the present disclosure, a composition having the above-described properties can be produced.

[0073] A method for producing a molded article of the polyester resin of the present disclosure will now be described. As a method for producing a molded article of the polyester resin, for example, injection molding can be adopted.

[0074] First, the polyester resin of the present disclosure is melted. The set temperature of the heating device (e.g., a cylinder) for melting the polyester resin is a temperature that does not cause the composition to become unmelted. The set temperature of the heating device is preferably 220°C or lower, more preferably 200°C or lower, and can be 180°C or lower depending on the polyester resin. By lowering the heating temperature, the cooling time can be shortened, production efficiency can be improved, and quality degradation can be suppressed. The set temperature of the heating device can be 170°C or higher, or 180°C or higher. The polyester resin of the present disclosure has a low intrinsic viscosity, so it is possible to suppress the temperature of the polyester resin from significantly deviating from the set temperature due to shear heat. In addition, it is possible to suppress the occurrence of temperature unevenness in the melt.

[0075] Second, the molten polyester resin is filled into a mold. The mold can be maintained at a predetermined temperature. The mold temperature can be set, for example, to 20°C to 60°C, preferably 30°C to 50°C. If the mold temperature is lower than 20°C, particularly lower than room temperature, a large amount of energy is required for cooling. In addition, condensation occurs in the mold, accelerating mold deterioration. The mold is preferably cooled with water.

[0076] Third, the polyester resin filled into the mold is molded while being held in the mold for a predetermined time. After molding, the molded body is released from the mold. The holding time from when the resin is poured into the mold until it is released is the cooling time (molding time). The cooling time depends on the size of the molded body, especially its thickness.

[0077] According to the method for producing a polyester resin molded article of the present disclosure, it is possible to reduce production costs by reducing energy consumption and improving production efficiency, and to produce molded articles with high and uniform quality.

[0078] The molded article of the polyester resin of the present disclosure will be described.

[0079] The polyester resin molded article of the present disclosure is a molded article produced by the above-mentioned manufacturing method. For example, the polyester resin molded article of the present disclosure can be a molded article obtained by melting and molding a polyester resin at a set temperature of 160°C or higher, preferably 180°C or higher and 200°C or lower. The molded article of the present disclosure preferably has a part with a thickness of 2 mm or higher, more preferably has a part with a thickness of 3 mm or higher, and more preferably has a part with a thickness of 5 mm or higher. Furthermore This is preferable. Having a portion with a thickness of 2 mm or more allows the cooling time to be shortened more effectively. For example, if the molded article has a thickness of 5 mm, it can be molded at a heating temperature of 180°C and in a mold at 20°C to 60°C for a cooling time of about 20 seconds. Furthermore, the thickest portion of the molded article of the present disclosure can be 10 mm or less in thickness. If the molded article has a thickness of 10 mm, it can be molded at a heating temperature of 180°C and in a mold at 20°C to 60°C for a cooling time of about 75 seconds.

[0080] The composition and properties of the molded body may change from those of the polyester resin before molding depending on the heat-melting conditions during production of the molded body. It may be difficult to directly identify the composition and properties of the molded body. In such cases, it is useful to identify the molded body based on the manufacturing method of the polyester resin before molding into the molded body.

[0081] The polyester resin molded article of the present disclosure is molded at a low temperature, allowing it to have quality with minimal deterioration from the polyester resin before molding. Furthermore, the polyester resin molded article of the present disclosure is not affected by uneven heat generation due to shear heat, allowing it to have uniform quality. The polyester resin molded article of the present disclosure can have the desired dimensions even with a short cooling time.

[0082] Molded articles of the polyester resin of the present disclosure can be designed in a variety of designs. For example, the molded articles can be designed into containers with thick, transparent bottoms. Such containers can have a luxurious feel. Furthermore, the molded articles can be designed into containers with complex shapes.

[0083] A molded article of the polyester resin of the present disclosure has moldability, low-temperature moldability, and transparency, yet has high resistance to contact with substances (e.g., organic compounds) with reduced discoloration and deformation.

[0084] According to the present disclosure, the polyester resin of the present disclosure can be molded into a cosmetic container for containing a cosmetic.

[0085] The cosmetic container and cosmetic product of the present disclosure will be described.

[0086] The cosmetic product of the present disclosure includes a cosmetic and a cosmetic container that contains the cosmetic. The body A cosmetic container containing the polyester resin of the present disclosure is preferably a cosmetic container, particularly a container for storing cosmetics. The bodyPreferably, the polyester resin is a molded article of the present disclosure.

[0087] The cosmetic may be in any form, such as an aqueous composition, an oil-based composition, an emulsion composition (such as an oil-in-water composition or a water-in-oil composition), etc. Examples of the cosmetic include sunscreen cosmetics, lotions, foundations, lipsticks, moisturizers, nail polish, mascara, and hair cosmetics.

[0088] By applying the polyester resin of the present disclosure to a cosmetic container, it is possible to provide a cosmetic container and a cosmetic product that are excellent in safety, visibility, and aesthetics.

[0089] In this disclosure, the term "or greater than" may be read as "greater than," where appropriate. Additionally, the term "or less than" may be read as "less than," where appropriate.

[0090] The polyester resin (including molded articles) and its use, as well as the cosmetic container and cosmetic product of the present disclosure, are described below using examples. The polyester resin and its use, as well as the cosmetic container and cosmetic product of the present disclosure, are not limited to the following examples. [Example]

[0091] [Test Examples 1 to 15] Polyester resins were prepared, and each polyester resin was tested for intrinsic viscosity, melt viscosity, glass transition temperature, content resistance, and mechanical properties. Tables 1 and 2 show the compositions and measurement results of Test Examples 1 to 15.

[0092] [Preparation of polyester resin] In a 30 L autoclave, the composition ratios shown in Tables 1 and 2 were So that The esterification reaction was carried out at 250°C under atmospheric pressure in a nitrogen stream. compositionThe ratio is the acid component and the alcohol component. of Each composition The ratio is shown. Next, using germanium dioxide as a polymerization catalyst, the pressure inside the reaction vessel was reduced over 1 hour, and a polycondensation reaction was carried out at 270°C under a reduced pressure of 100 Pa or less until the viscosity reached a predetermined level. The reaction product was extruded from the reaction vessel into water and cut with a pelletizer to obtain resin pellets. The following measurements were carried out on the produced polyester resin.

[0093] In Test Example 15, the raw material ratio G / A of the alcohol (G) and the acid (A) was set to 1.6, thereby producing a larger amount of diethylene glycol.

[0094] [Measurement of intrinsic viscosity] For each polyester resin, 0.5000 g ± 0.0005 g of sample was dissolved in a mixed solvent of phenol:tetrachloroethane = 60:40 (mass ratio), and the intrinsic viscosity at 20 °C was measured using an automatic viscosity measuring device (ALC-6C manufactured by Sun Electronics Industries) equipped with an Ubbelohde viscosity tube.

[0095] [Melt viscosity measurement] The polyester resin samples were dried at 60°C for 48 hours using a dehumidifying dryer. 20.0g±5.0g of each dried polyester resin was weighed out and measured using a melt viscosity measuring device at a measurement temperature of 180°C and a shear rate of 6080 s -1 When the resin temperature in the furnace of the melt viscosity measuring device rose above the measurement temperature, it was judged that the melt viscosity measurement was impossible.

[0096] [Glass transition temperature] Using a differential scanning calorimeter (DSC-7 manufactured by PerkinElmer), the endothermic behavior of a polyester resin sample was observed while the temperature was raised from 30°C at a rate of 2°C / min in a nitrogen atmosphere, and the midpoint temperature of the endothermic behavior due to glass transition was taken as the glass transition temperature (Tg).

[0097] [Whether or not whitening occurs during molding] The polyester resin of each test example was molded into a 9 mm thick plate at a molding temperature of 180°C and a cooling temperature of 40°C, and the molded body was checked for whitening. However, the polyester resins of test examples 9 and 12, which could not be molded at 180°C, were molded at 220°C. None: No whitening occurred in the molded product; Yes: Whitening occurred on the molded product.

[0098] [Content resistance test] Assuming that polyester resins would be used in containers, tests were conducted to determine whether they would be resistant to the contents to be contained. Specifically, the stress crack test and appearance change test described below were conducted. Test specimens were prepared by molding polyester resin into plates measuring 80 mm in length, 10 mm in width, and 2 mm in thickness. Assuming that the contents to be contained would be topical skin preparations, commercially available sunscreen cosmetics (cream and gel) and beauty serum (cream) were used as test agents applied to the test specimens. [Stress crack test] Figure 1 shows the equipment used for the stress crack test. Approximately half of the test piece 1 in the longitudinal direction protruded from the base 3 to form the fulcrum 1b. One end of the test piece 1 was fixed to the base 3 with a fixture 4. A 200g weight 2 was hung from the other end of the test piece 1, so that a load of approximately 6.9 N·cm was applied to the fulcrum 1b. The test agent was applied to the top surface of the area including the fulcrum 1b (application area 1a), and the test piece was left to stand for 24 hours at 23°C and a relative humidity of 50%. After 24 hours, the test piece 1 was checked for the presence of cracks. The evaluation criteria are as follows: A: No cracks occurred in the specimen; B: Microcracks occurred in the specimen; C: Large cracks occurred in the specimen; D: The test piece broke.

[0099] [Appearance change test] A test drug was applied to one side of the test specimen. With the test drug applied, the test specimen was left to stand for 7 days in an environment of 23°C or 37°C and a relative humidity of 50%RH. After 7 days, the appearance of the test specimen was checked. A: There was no change in the appearance of the test specimen; B: The specimen was thinly whitened; C: The test piece was whitened or the surface of the test piece was rough.

[0100] [Mechanical property measurements] The tensile elongation of each polyester resin was measured in accordance with ISO 527. Five samples were measured for tensile elongation, and the average value was calculated. The Charpy impact strength of each polyester resin was also measured in accordance with ISO 179. Ten samples were measured for Charpy impact strength, and the average value was calculated.

[0101] In Test Examples 1 to 8, good evaluations were obtained for all evaluation items.

[0102] It was found that the containers produced in Test Examples 1 to 8 could be used as cosmetic containers.

[0103] On the other hand, Test Examples 10 to 12, which contained 20 mol% or more of neopentyl glycol, received low evaluations in the stress crack test. From this, it is considered that the content of neopentyl glycol is preferably 18 mol% or less, and more preferably 16 mol% or less, relative to the total amount of alcohol components.

[0104] In addition, in Test Example 12, which did not contain isophthalic acid, the intrinsic viscosity increased and the melt viscosity became so high that it could not be measured. Furthermore, whitening occurred during container molding. Therefore, it is considered preferable that the content of isophthalic acid is 8 mol% or more relative to the total amount of acid components.

[0105] In Test Example 14, in which the isophthalic acid content was 30 mol %, sufficient mechanical strength was not obtained. From this, it is considered that the content of isophthalic acid is preferably 28 mol % or less relative to the total amount of acid components.

[0106] Test Example 15, which contained 7 mol% diethylene glycol, not only received a low score in the stress crack test but also received a low score in the appearance change test at 37° C. This suggests that the diethylene glycol content is preferably 5 mol% or less relative to the total amount of alcohol components.

[0107] In Test Example 13, which had a high total content of isophthalic acid and neopentyl glycol, the evaluation of the appearance change test, particularly the resistance to contents at high temperatures, was low. Therefore, it is considered preferable that the total content be 43 mol% or less.

[0108] In Test Example 9, where the total content of isophthalic acid and neopentyl glycol was low, the melt viscosity was too high to be measured. In Test Example 12, the transparency of the molded article was low. Therefore, it is considered preferable that the total content be 24 mol% or more.

[0109] [Table 1]

[0110] [Table 2]

[0111] The polyester resin (including molded articles), its manufacturing method, its use, and the cosmetic container and cosmetic product of the present invention have been described based on the above embodiments and examples, but are not limited to the above embodiments and examples and can include various modifications, changes, and improvements to each disclosed element (including elements described in the claims, specification, and drawings) within the scope of the present invention and based on the basic technical idea of ​​the present invention. Furthermore, various combinations, substitutions, and selections of each disclosed element are possible within the scope of the claims of the present invention.

[0112] Further objects, purposes and modes (including modifications) of the present invention will become apparent from the entire disclosure of the present invention including the claims.

[0113] With respect to numerical ranges set forth herein, unless otherwise specified, any numerical value or range falling within that range should be construed as being specifically set forth herein. [Industrial Applicability]

[0114] The polyester resin of the present disclosure has excellent moldability and mechanical properties, and therefore the polyester resin and molded articles thereof can be used in a wide range of molding materials, such as containers, electrical and electronic components, and automotive materials. [Explanation of symbols]

[0115] 1 test piece 1a Application area 1b fulcrum 2 weights 3. Pedestal 4 Fixtures

Claims

1. A polyester resin containing a polymer of (A) an acid component and (B) an alcohol component, The component (A) contains, relative to the total amount of the component (A), 75 mol % to 88 mol % of an (A1) terephthalic acid component and 12 mol % to 25 mol % of an (A2) isophthalic acid component; The component (B) contains, relative to the total amount of the component (B), 81 mol % to 91 mol % of an ethylene glycol component (B1) and 6 mol % to 16 mol % of a 2,2-dimethyl-1,3-propanediol component (B2); the sum of the content of the component (A2) relative to the component (A) and the content of the component (B2) relative to the component (B) is 27 mol % to 40 mol %, The content of the diethylene glycol component (B3) is 5 mol % or less relative to the total amount of the component (B), The melt viscosity at 180°C is 100 Pa s to 180 Pa s, A polyester resin having an intrinsic viscosity of 0.48 dl / g to 0.67 dl / g.

2. A polyester resin as described in claim 1, wherein the (B3) diethylene glycol component is 3 mol% to 5 mol% relative to the total amount of the (B) component.

3. 2. The polyester resin according to claim 1, having a melt viscosity at 180°C of 120 Pa·s to 170 Pa·s.

4. The polyester resin according to claim 1, which has a tensile elongation of 100% or more.

5. Charpy impact strength is 2 kJ / m ２ The polyester resin according to claim 1 .

6. A polyester resin described in claim 1, having a glass transition temperature of 70°C or higher.

7. The polyester resin according to any one of claims 1 to 6, which has a container shape.

8. A polyester resin described in any one of claims 1 to 6, for use in a cosmetic container.

9. A molded article comprising the polyester resin according to any one of claims 1 to 6, A molded article having a container shape with a portion having a thickness of 2 mm or more and the thickest portion being 10 mm or less.

10. A polyester resin comprising a polymer of (A) an acid component and (B) an alcohol component, The component (A) contains, relative to the total amount of the component (A), 72 mol % or more of an (A1) terephthalic acid component and 8 mol % to 28 mol % of an (A2) isophthalic acid component, The component (B) contains, relative to the total amount of the component (B), 77 mol % or more of an ethylene glycol component (B1) and 4 mol % to 18 mol % of a 2,2-dimethyl-1,3-propanediol component (B2), the sum of the content of the component (A2) relative to the component (A) and the content of the component (B2) relative to the component (B) is 24 mol % to 43 mol %, The content of the diethylene glycol component (B3) is 5 mol % or less relative to the total amount of the component (B), A cosmetic container comprising a polyester resin having an intrinsic viscosity of 0.48 dl / g to 0.67 dl / g.

11. Cosmetics and A cosmetic product comprising: the cosmetic container according to claim 10 that contains the cosmetic.

12. A polyester resin for use in a cosmetic container, comprising a polymer of (A) an acid component and (B) an alcohol component, The component (A) contains, relative to the total amount of the component (A), 72 mol % or more of an (A1) terephthalic acid component and 8 mol % to 28 mol % of an (A2) isophthalic acid component, The component (B) contains, relative to the total amount of the component (B), 77 mol % or more of an ethylene glycol component (B1) and 4 mol % to 18 mol % of a 2,2-dimethyl-1,3-propanediol component (B2), the sum of the content of the component (A2) relative to the component (A) and the content of the component (B2) relative to the component (B) is 24 mol % to 43 mol %, The content of the diethylene glycol component (B3) is 5 mol % or less relative to the total amount of the component (B), A method for using a polyester resin having an intrinsic viscosity of 0.48 dl / g to 0.67 dl / g.

Images