Pellet-shaped melt-molding material and molded product made using the same

Abstract

The objective is to provide a polymer composition that crystallizes extremely quickly and can improve productivity and processability, such as improving release rollability in high-speed molding by extrusion lamination, as well as a polymer molded product thereof. [Solution] A pellet-shaped melt molding material containing polybutylene succinate (A) and fatty acid bisamide (B) is used, characterized in that the melt molding material is melted at 200°C and held for 3 minutes, then cooled at a rate of 100°C / min, and the semi-crystallization time of polybutylene succinate (A) in isothermal crystallization held at 80°C is 1 second or more and 44 seconds or less.

Description

[Technical Field]

[0001] This invention relates to a pelletized melt-molding material and a molded article formed using the same. [Background technology]

[0002] In recent years, concern for global environmental issues has increased, and measures are beginning to be taken in various ways. However, our lives continue to involve mass production, mass consumption, and mass disposal. As a result, the large amount of solid waste generated from consumption has become a major social problem. Currently, measures such as landfill, incineration, and recycling are being taken depending on the situation, but landfills are reaching their limits. In addition, some solid waste inevitably cannot be collected and tends to be left in the natural environment, and this tendency is even greater in oceans and forests, which are difficult for humans to reach. In this context, biodegradable aliphatic polyesters are attracting attention as polymers that minimize environmental impact from the standpoint of protecting the global environment. Due to their properties, biodegradable polymers decompose in nature into carbon dioxide and water, so even if left in nature, they have a small environmental impact.

[0003] Due to the growing awareness of environmental issues as described above, attempts are being made to develop various applications for polymer molded products using biodegradable polymers, specifically aliphatic polyester polymers such as polybutylene succinate (hereinafter sometimes abbreviated as PBS). These polymer molded products decompose in the soil even after disposal, thus reducing environmental pollution.

[0004] However, biodegradable aliphatic polyesters such as PBS have the disadvantage of slower crystallization compared to general-purpose PP and PE. Slow crystallization negatively impacts processability during molding and productivity. Specifically, in the case of extrusion lamination, it is known that poor release from the cooling roll leads to reduced adhesion to the substrate and increased product loss.

[0005] For example, Patent Document 1 describes that by adding polyethylene wax or the like as a crystal nucleating agent to PBS and controlling the semi-crystallization time at a temperature of 100°C within a certain range, it is possible to improve processing stability such as the release properties of the film while maintaining transparency, reducing roll contamination, odor and smoke during processing. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2018-162428 [Overview of the project] [Problems that the invention aims to solve]

[0007] Incidentally, the polymer composition described in Patent Document 1 is known to shorten the semi-crystallization time with an aliphatic polyester (especially PBS) and a nucleating agent, resulting in no odor in extruded laminates and improved roll release properties. However, Patent Document 1 only evaluates roll release properties at a thickness of 25 μm, and does not confirm roll release properties in high-speed molding of extruded laminates. Generally, to increase production efficiency, it is necessary to increase the take-up speed and perform high-speed molding. Increasing the take-up speed tends to worsen roll release properties, and conventionally known nucleating agents have not been able to provide sufficient effect.

[0008] This invention has been made in view of the problems of the prior art described above, and aims to provide a polymer composition that crystallizes extremely quickly and can improve productivity and processability, such as improving release rollability in high-speed molding by extrusion lamination, and a polymer molded product thereof. [Means for solving the problem]

[0009] The inventors of the present invention conducted intensive research to solve the above problems and, as a result, discovered that by using a polymer composition to which fatty acid bisamide (B) is added, crystallization is extremely fast, and processability such as release rollability during high-speed molding in extrusion lamination, as well as productivity, can be improved, leading to the completion of the present invention.

[0010] In other words, the present invention is summarized in the following [1] to [9]. [1] A pelletized melt-molding material comprising polybutylene succinate (A) and fatty acid bisamide (B), wherein the melt-molding material is characterized in that the semi-crystallization time of polybutylene succinate (A) in isothermal crystallization, which is performed by melting at 200°C and holding the molten material for 3 minutes, cooling the molten material at a rate of 100°C / min, and holding it at 80°C, is 1 second or more and 44 seconds or less.

[0011] [2] The pelletized melt-molded material according to [1], wherein the fatty acid bisamide (B) is a fatty acid bisamide having a total of 15 to 60 carbon atoms. [3] The pelletized melt-molding material according to [1], wherein the melt-molding material contains 0.01 to 10% by mass of the fatty acid bisamide (B). [4] The pelletized melt-molding material according to [3], wherein the melt-molding material contains 0.05 to 5% by mass of the fatty acid bisamide (B).

[0012] [5] The fatty acid bisamide (B) of the melt molding material is at least one selected from methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, ethylene bisstearic acid amide, ethylene bisisostearic acid amide, ethylene bishydroxystearic acid amide, ethylene bisbehenic acid amide, hexamethylene bisstearic acid amide, hexamethylene bisbehenic acid amide, hexamethylene bishydroxystearic acid amide, N,N'-distearyl adipic acid amide, N,N'-distearyl sebacic acid amide, saturated fatty acid bisamides, ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N,N'-dioleyl adipic acid amide, unsaturated fatty acid bisamide, m-xylylene bisstearic acid amide, and the pellet-like melt molding material according to [1].

[0013] [6] The fatty acid bisamide (B) of the melt molding material is at least one selected from methylene bisstearic acid amide, ethylene bislauric acid amide, ethylene bisstearic acid amide, ethylene bisisostearic acid amide, ethylene bishydroxystearic acid amide, hexamethylene bisstearic acid amide, N,N'-distearyl adipic acid amide, ethylene bisoleic acid amide, and the pellet-like melt molding material according to [1].

[0014] [7] A molded article made of the pellet-like melt molding material according to [1]. [8] The molded article according to [7] is a film molded article that is a molded article selected from a packaging film, a shopping bag, a plastic bag, a compost bag, a cup, a wrapping paper, and a multilayer film. [9] The molded article according to [7] is a sheet molded article that is a molded article selected from a coffee capsule, a seedling pot, a young tree sheet, and a tray.

[10] The molded article according to [7] is a tubular molded article that is a molded article selected from a straw, a cotton swab, and a balloon stick.

[11] The molded article according to [7] is an injection molded article that is a molded article selected from a coffee capsule, cutlery, and a tray.

[0015]

[12] A molded article of a polymer composition containing polybutylene succinate (A) and fatty acid bisamide (B), wherein the molded article is at least one molded article selected from a film molded article, a sheet molded article, a tubular molded article, and an injection molded article, and the molded article is cooled from a melt that is melted at 200 °C and held for 3 minutes at a rate of 100 °C / min, and the half-crystallization time of polybutylene succinate (A) in isothermal crystallization held at 80 °C is 1 second or more and 44 seconds or less. A resin molded article characterized by this.

[0016]

[13] The resin molded article according to

[12] , wherein the fatty acid bisamide (B) is a fatty acid bisamide having a total carbon number of 15 to 60.

[14] The resin molded article according to

[12] , wherein the polymer composition contains 0.01 to 10% by mass of the fatty acid bisamide (B).

[15] The resin molded article according to

[12] , wherein the polymer composition contains 0.05 to 5% by mass of the fatty acid bisamide (B).

[0017]

[16] The fatty acid bisamide (B) of the polymer composition is at least one selected from methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, ethylene bisstearic acid amide, ethylene bisisostearic acid amide, ethylene bishydroxystearic acid amide, ethylene bisbehenic acid amide, hexamethylene bisstearic acid amide, hexamethylene bisbehenic acid amide, hexamethylene bishydroxystearic acid amide, N,N'-distearyl adipic acid amide, N,N'-distearyl sebacic acid amide, saturated fatty acid bisamides, ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N,N'-dioleyl adipic acid amide, unsaturated fatty acid bisamide, m-xylylene bisstearic acid amide. The resin molded article according to

[12] containing at least one.

[0018]

[17] The resin molded article according to

[12] wherein the fatty acid bisamide (B) of the polymer composition comprises at least one selected from methylenebisstearate, ethylenebislaurate, ethylenebisstearate, ethylenebisisostearate, ethylenebishydroxystearate, hexamethylenebisstearate, N,N'-distearyladipamide, and ethylenebisoleamide.

[0019]

[18] The resin molded article according to

[12] , wherein the film molded article is selected from packaging film, shopping bags, plastic bags, compost bags, cups, packaging paper, and mulch film.

[19] The resin molded product according to

[12] , wherein the sheet molded product is selected from coffee capsules, seedling pots, young tree sheets, and trays.

[20] The resin molded article according to

[12] , wherein the tubular molded article is selected from a straw, a cotton swab, and a balloon stick.

[21] The resin molded article according to

[12] , wherein the injection molded article is selected from coffee capsules, cutlery, and trays. [Effects of the Invention]

[0020] According to the present invention, when a film is formed by melt extrusion, it exhibits excellent release properties, reduces roll contamination and smoke generation, and is expected to shorten the forming time, reduce the load on the equipment, and improve the film production speed. Furthermore, the resulting film also exhibits improved mechanical strength and transparency due to the nucleating agent. [Modes for carrying out the invention]

[0021] The present invention is not limited to the following description and can be modified and implemented as appropriate without departing from the spirit of the invention. In this specification, when "~" is used to enclose numerical values ​​or physical properties, it is intended to include the lower and upper limits. In this specification, “mass%”, “mass ppm”, and “parts by mass” are synonymous with “weight%”, “weight ppm”, and “parts by weight”. Furthermore, in this specification, the expression "A or B" may be interpreted as "at least one selected from the group consisting of A and B." Furthermore, although this specification describes multiple embodiments, various conditions in each embodiment can be applied to each other to the extent applicable.

[0022] The pelletized melt-molding material according to the present invention is a pelletized melt-molding material comprising a polymer composition containing polybutylene succinate (PBS) (A) and fatty acid bisamide (B).

[0023] <Aliphatic polyesters, etc.> The PBS(A) contained in the aforementioned melt-molding material is an aliphatic polyester using 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, etc. as a diol component and succinic acid as a dicarboxylic acid component. The above diol components may be used individually or in combination of two or more.

[0024] In addition to PBS(A), the melt-molding material may also contain other known aliphatic polyesters or aliphatic aromatic polyesters (hereinafter sometimes referred to as "other aliphatic polyesters, etc.") as long as they do not significantly impair the effects of the present invention. Furthermore, one type of other aliphatic polyester may be used alone, or two or more types may be used in any combination and ratio. The other aliphatic polyesters, etc. are preferably biodegradable, and even more preferably manufactured using raw materials obtained from biomass resources, in part or in whole. In the following, PBS(A) and other aliphatic polyesters will be collectively referred to as "aliphatic polyesters, etc."

[0025] The PBS(A) mentioned above is the one that has the highest molar ratio to the total melt molding material, and other aliphatic polyesters, etc., can also be used. In particular, a high ratio of PBS(A) is preferred because it has good adhesion and moldability, and it is especially preferable that it consists only of PBS(A).

[0026] Other preferred aliphatic polyesters in the present invention include aliphatic polyesters comprising a diol component consisting of an aliphatic diol represented by the following formula (I) or a derivative thereof, and an aliphatic dicarboxylic acid component consisting of an aliphatic dicarboxylic acid represented by the following formula (II), as well as aliphatic polyesters in which an aliphatic oxycarboxylic acid is the main component, such as polylactic acid and polycaprolactam. Furthermore, aliphatic aromatic polyesters comprising a diol component consisting of an aliphatic diol represented by the following formula (I) or a derivative thereof, an aliphatic dicarboxylic acid component consisting of an aliphatic dicarboxylic acid represented by the following formula (II) or a derivative thereof, and an aromatic dicarboxylic acid component consisting of an aromatic dicarboxylic acid or a derivative thereof. Furthermore, PBS(A) is not included in other aliphatic polyesters, etc., that consist of diol and dicarboxylic acid components. In addition, the aliphatic dicarboxylic acid component and aromatic dicarboxylic acid component are collectively referred to as "dicarboxylic acid component".

[0027] The diol component represented by formula (I) above has the following structure. HO-R 1 -OH (I) (In equation (I), R 1 (This represents a divalent aliphatic hydrocarbon group which may have an oxygen atom in its chain.) In equation (I), R 1 This is a divalent aliphatic hydrocarbon group which may have an oxygen atom in its chain, and may be a linear aliphatic hydrocarbon group or a cyclic aliphatic (alicyclic) hydrocarbon group. It may also have a branched chain or not.

[0028] R 1The number of carbon atoms is arbitrary as long as the effects of the present invention are not significantly impaired, but R 1 When is an aliphatic hydrocarbon group, R 1 The number of carbon atoms of is usually 2 or more, usually 10 or less, preferably 6 or less. On the other hand, when R 1 is an alicyclic hydrocarbon group, R 1 The number of carbon atoms of is usually 3 or more, usually 10 or less, preferably 8 or less. Examples of the derivative of the diol of formula (I) include ester compounds with acetic acid and the like.

[0029] Specific examples of the aliphatic diol and its derivatives represented by the above formula (I) include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like. Among them, 1,4-butanediol is particularly preferred from the viewpoint of the physical properties of the resulting aliphatic polyester and the like.

[0030] In addition, the aliphatic dicarboxylic acid component represented by the above formula (II) has the following structure. HOOC-(R 2 )n-COOH (II) (In formula (II), R 2 represents a divalent aliphatic hydrocarbon group, and n represents 0 or 1.) In formula (II), R 2 is a divalent aliphatic hydrocarbon group, which may be a linear aliphatic hydrocarbon group or an alicyclic hydrocarbon group. It may or may not have a branched chain. R 2 The number of carbon atoms of is also arbitrary as long as the effects of the present invention are not significantly impaired, but is usually 2 or more and usually 48 or less. However, when R2 is a linear aliphatic hydrocarbon group, R 2 is preferably a divalent linear aliphatic hydrocarbon group represented by -(CH2)m-. Here, m is usually an integer of 1 or more, usually 10 or less, preferably 6 or less.

[0031] Also, R 2 If R is an alicyclic hydrocarbon group, 2 The number of carbon atoms is usually 3 or more, preferably 4 or more, and usually 10 or less, preferably 8 or less. Examples of derivatives of the dicarboxylic acid of formula (II) above include lower alcohol esters and acid anhydrides of the dicarboxylic acid of formula (II) above. Among these, lower alcohol esters or acid anhydrides having 1 to 4 carbon atoms are preferred.

[0032] Specific examples of dicarboxylic acids represented by formula (II) above and their derivatives include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, heptanediic acid, octanedioic acid, nonanediic acid, decanediic acid, undecanediic acid, dodecanediic acid, tridecanediic acid, tetradecanediic acid, pentadecanediic acid, hexadecanedioic acid, octadecanediic acid, eicosanedioic acid, maleic acid, fumaric acid, 1,6-cyclohexanedicarboxylic acid, and dimer acids, which are typically linear or alicyclic dicarboxylic acids with 2 to 48 carbon atoms. Derivatives of these include esters with lower alcohols such as dimethyl esters and diethyl esters, and acid anhydrides such as succinic anhydride and adipic anhydride.

[0033] The aliphatic dicarboxylic acids and their derivatives represented by formula (II) above may be derived from petroleum or plants, but are particularly preferably derived from plants because they can contribute to reducing CO2 emissions. For example, as raw materials for dicarboxylic acids and their derivatives, succinic acid or its acid anhydride converted from plant raw materials, and esters with lower alcohols are preferred.

[0034] Furthermore, examples of aromatic dicarboxylic acid components consisting of the aforementioned aromatic dicarboxylic acid or its derivatives include terephthalic acid and its derivatives.

[0035] Furthermore, examples of the aliphatic oxycarboxylic acid component include aliphatic oxycarboxylic acids represented by the following formula (III). HO-R 3-COOH (III) (In equation (III), R 3 This is R in equation (II) above. 2 (Represents a substituent similar to the above.) Among the aliphatic oxycarboxylic acids represented by the above formula (III), the aliphatic oxycarboxylic acid represented by the following formula (IV) is preferred. HO-CHR 4 -COOH (IV) (In equation (IV), R 4 (This represents a hydrogen atom or a straight-chain or branched hydrocarbon group having 1 to 10 carbon atoms.) In particular, the aliphatic oxycarboxylic acid represented by the following formula (V) is preferred because it exhibits an effect of improving polymerization reactivity. HO-CH(C p H 2p+1 )-COOH (V) (In equation (V), p represents 0 or an integer between 1 and 10, preferably 0 or an integer between 1 and 5.)

[0036] Specific examples of oxycarboxylic acids, particularly aliphatic oxycarboxylic acids, include α,ω-hydroxycarboxylic acids and α-hydroxycarboxylic acids such as lactic acid, glycolic acid, 2-hydroxy-n-butyric acid, 2-hydroxycaproic acid, 2-hydroxy-3,3-dimethylbutyric acid, 2-hydroxy-3-methylbutyric acid, 2-hydroxyisocaproic acid, 4-hydroxycyclohexanecarboxylic acid, and 4-hydroxymethylcyclohexanecarboxylic acid, as well as derivatives of these such as lower alkyl esters and intramolecular esters (e.g., lactones, lactides, etc.) and derivatives of oxycarboxylic acid polymers. Specific examples of the aforementioned lactones include lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, and enantractone; and methylated lactones such as 4-methylcaprolactone, 2,2,4-trimethylcaprolactone, and 3,3,5-trimethylcaprolactone. Among these, lactic acid or glycolic acid is preferred, and lactic acid is particularly preferred because it exhibits a particularly significant increase in polymerization rate during use and is readily available. In terms of lactic acid form, an aqueous solution of 30-95% by mass is preferred because it is readily available. These aliphatic oxycarboxylic acid components may be used individually, or two or more may be used in any combination and ratio.

[0037] When the aliphatic polyester, etc., contains aliphatic oxycarboxylic acid units, the amount used is arbitrary as long as it does not significantly impair the effects of the present invention. However, per 100 parts by mass of the total amount of aliphatic polyester, etc., the amount is usually 0.1 parts by mass or more, preferably 1.0 part by mass or more, more preferably 2.0 parts by mass or more, and usually 100 parts by mass or less, preferably 50 parts by mass or less, more preferably 20 parts by mass or less. If the amount falls below the lower limit of the above range, the additive effect on imparting flexibility and improving polymerization reactivity may not be observed, and if it exceeds the upper limit, odor may become a problem when molding using the melt molding material of the present invention, or the release properties may worsen due to a decrease in crystallization temperature.

[0038] Furthermore, it is also preferable to include, as other aliphatic polyesters, at least one unit selected from the group consisting of aliphatic polyhydric alcohol units, aliphatic polyhydric carboxylic acid units, and aliphatic polyoxycarboxylic acid units having three or more functional groups, as a polyfunctional component unit having three or more functional groups. This improves the melt tension of the melt-molding material of the present invention and improves the processability into laminates. Note that one type of polyfunctional component unit may be used alone, or two or more types may be used in any combination and ratio.

[0039] The trifunctional aliphatic oxycarboxylic acid units that form polyfunctional component units are (i) A type having two carboxyl groups and one hydroxyl group in the same molecule, (ii) A type having one carboxyl group and two hydroxyl groups in the same molecule, They are divided into two types, but both types can be used. Specific examples of type (i) include constituent units formed from malic acid, etc., and specific examples of type (ii) include constituent units formed from glyceric acid, etc.

[0040] Similarly, the tetrafunctional aliphatic oxycarboxylic acid units that form polyfunctional component units are (i) A type that shares three carboxyl groups and one hydroxyl group in the same molecule, (ii) A type that shares two carboxyl groups and two hydroxyl groups in the same molecule, (iii) There are two types: one that shares three hydroxyl groups and one carboxyl group within the same molecule, and another that can be used. Specific examples include units formed from citric acid and tartaric acid.

[0041] When using polyfunctional component units, the amount used is arbitrary as long as it does not significantly impair the effects of the present invention. However, per 100 moles of total amount of aliphatic polyester, etc., it is usually 0.001 moles or more, preferably 0.01 moles or more, more preferably 0.1 moles or more, and usually 5 moles or less, preferably 2.5 moles or less, more preferably 1 mole or less. If the amount falls below the lower limit of this range, when manufacturing molded products such as films from the melt-molding material of the present invention by extrusion lamination (hereinafter sometimes referred to as "extrusion lamination"), problems arise such as a large neck-in of the molten film during manufacturing (referring to the phenomenon in which the width of the molten film coming out of the T-die of the extruder narrows in the space before it comes into contact with the substrate, and is indicated by the difference between the width of the molten film at the T-die exit and the width of the laminate film laminated on the substrate), or a large difference in thickness between the film thickness at the edges and the center, making it difficult to obtain a stable product. Furthermore, if the amount exceeds the upper limit, the possibility of gelation during the reaction increases, the load on the extruder motor increases significantly, and moldability may be poor.

[0042] In the melt-molding material of the present invention, the method for producing aliphatic polyesters and the like can be any known method for producing polyester. Furthermore, the polycondensation reaction in this case can be carried out under any appropriate conditions that have been used conventionally, and is not particularly limited. In addition, the degree of polymerization can usually be further increased by performing a reduced pressure operation after the esterification reaction has proceeded. When reacting a diol component with a dicarboxylic acid component during the production of aliphatic polyesters, the amounts of the diol component and the dicarboxylic acid component used should be set so that the produced aliphatic polyester has the desired composition. Typically, the diol component and the dicarboxylic acid component are used in substantially equimolar amounts. However, in this case, the amount of the diol component used is usually in excess of 1 to 20 mol% due to distillation during the esterification reaction.

[0043] When the aliphatic polyester or the like contains components other than essential components (optional components), such as aliphatic oxycarboxylic acid units or polyfunctional component units, the corresponding compounds (monomers or oligomers) are subjected to the reaction so that the aliphatic oxycarboxylic acid units and polyfunctional component units also have the desired composition. In this case, there are no restrictions on the timing or method of introducing the above optional components into the reaction system; it is arbitrary as long as an aliphatic polyester or the like suitable for the present invention can be produced.

[0044] For example, the timing and method of introducing an aliphatic oxycarboxylic acid into the reaction system are not particularly limited as long as they occur before the polycondensation reaction between the diol component and the dicarboxylic acid component. (1) A method of mixing the catalyst after it has been dissolved in an aliphatic oxycarboxylic acid solution in advance. (2) A method of introducing the catalyst into the system and mixing it at the same time as the raw materials are being charged. These are some examples. The timing of introducing the compound that forms the polyfunctional component unit may be at the same time as the other monomers and oligomers in the early stages of polymerization, or it may be introduced after the transesterification reaction but before the start of reduced pressure. However, introducing it at the same time as the other monomers and oligomers is preferable in terms of simplifying the process.

[0045] The aforementioned aliphatic polyesters are usually manufactured in the presence of a catalyst. As the catalyst, any catalyst that can be used in the manufacture of known polyesters can be arbitrarily selected as long as it does not significantly impair the effects of the present invention. For example, metal compounds such as germanium, titanium, zirconium, hafnium, antimony, tin, magnesium, calcium, and zinc are preferred. Among these, germanium compounds and titanium compounds are particularly preferred.

[0046] Examples of germanium compounds that can be used as catalysts include organic germanium compounds such as tetraalkoxygermanium, and inorganic germanium compounds such as germanium oxide and germanium chloride. Among these, germanium oxide, tetraethoxygermanium, and tetrabutoxygermanium are preferred due to their price and availability, and germanium oxide is particularly preferred.

[0047] Examples of titanium compounds that can be used as catalysts include organotitanium compounds such as tetraalkoxytitanium, tetrapropyl titanate, tetrabutyl titanate, and tetraphenyl titanate. Among these, tetrapropyl titanate and tetrabutyl titanate are preferred due to their price and availability. Furthermore, the use of other catalysts in combination is not prohibited as long as it does not impair the objective of the present invention. Note that one catalyst may be used alone, or two or more catalysts may be used in any combination and ratio.

[0048] The amount of catalyst used is arbitrary as long as it does not significantly impair the effects of the present invention, but is usually 0.0005% by mass or more, more preferably 0.001% by mass or more, and usually 3% by mass or less, preferably 1.5% by mass or less, relative to the amount of monomer used. If the amount is below the lower limit of this range, the effect of the catalyst may not be observed, and if it is above the upper limit, the manufacturing cost may increase, the resulting polymer may become significantly discolored, or its hydrolysis resistance may decrease.

[0049] The timing of catalyst introduction is not particularly limited as long as it is before polycondensation, but it may be introduced at the time of raw material charging or at the start of reduced pressure. It is preferable to introduce the catalyst at the time of raw material charging simultaneously with monomers or oligomers that form aliphatic oxycarboxylic acid units, such as lactic acid or glycolic acid, or to dissolve the catalyst in an aqueous solution of aliphatic oxycarboxylic acid and introduce it. In particular, the method of dissolving the catalyst in an aqueous solution of aliphatic oxycarboxylic acid and introducing it is preferred because it increases the polymerization rate.

[0050] The reaction conditions such as temperature, polymerization time, and pressure when producing the aliphatic polyester, etc., are arbitrary as long as they do not significantly impair the effects of the present invention. However, the reaction temperature for the esterification reaction and / or transesterification reaction between the dicarboxylic acid component and the diol component is usually 150°C or higher, preferably 180°C or higher, and the upper limit is usually 260°C or lower, preferably 250°C or lower. The reaction atmosphere is usually an inert atmosphere such as nitrogen or argon. Furthermore, the reaction pressure is usually atmospheric pressure to 10 kPa, with atmospheric pressure being preferred. The reaction time is usually 1 hour or higher at the lower limit and usually 10 hours or lower at the upper limit, preferably 6 hours or lower, more preferably 4 hours or lower. If the reaction temperature is too high, excessive formation of unsaturated bonds may occur, leading to gelation caused by these unsaturated bonds, which can make it difficult to control polymerization.

[0051] Furthermore, the esterification reaction and / or polycondensation reaction after the transesterification reaction between the dicarboxylic acid component and the diol component requires a pressure, with a lower limit of typically 0.01 × 10⁻⁶. 3 Pa or higher, preferably 0.03 × 10⁻⁶ 3 Pa or higher, with an upper limit of normally 1.4 x 10 3 Pa or less, preferably 0.4 × 10 3 It is desirable to carry out the reaction under a vacuum of Pa or less. The reaction temperature should have a lower limit of 150°C or higher, preferably 180°C or higher, and an upper limit of 260°C or lower, preferably 250°C or lower. Furthermore, the reaction time should have a lower limit of 2 hours or higher, an upper limit of 15 hours or lower, preferably 10 hours or lower. If the reaction temperature is too high, excessive formation of unsaturated bonds may occur, leading to gelation caused by these unsaturated bonds, making it difficult to control polymerization.

[0052] When manufacturing the aliphatic polyester and the like, chain extenders such as carbonate compounds and diisocyanate compounds can also be used. The amount is usually 10 mol% or less, preferably 5 mol% or less, and more preferably 3 mol% or less, of the total monomer units constituting the aliphatic polyester and the like, for carbonate bonds and urethane bonds. However, when using aliphatic polyester or other polymers in the laminate of the present invention, the presence of diisocyanates and carbonate bonds may inhibit biodegradability. Therefore, the amount used is less than 1 mol% for carbonate bonds, preferably 0.5 mol% or less, more preferably 0.1 mol% or less, and 0.55 mol% or less, preferably 0.3 mol% or less, more preferably 0.12 mol% or less, and even more preferably 0.05 mol% or less, of urethane bonds, of the total monomer units constituting the aliphatic polyester and the like. Converted to 100 parts by mass of aliphatic polyester and the like, this is 0.9 parts by mass or less, preferably 0.5 parts by mass or less, more preferably 0.2 parts by mass or less, and even more preferably 0.1 parts by mass or less. The amount of carbonate bonds and urethane bonds are 1 H-NMR and 13 The amount is calculated by NMR measurements such as 13C-NMR. If the upper limit for the amount of urethane bonding is exceeded, the decomposition of urethane bonding may cause problems such as smoke and odor from the molten film at the die exit during the manufacturing of the laminate, and film breakage due to foaming may occur in the molten film, making stable molding impossible.

[0053] Examples of the aforementioned carbonate compounds include diphenyl carbonate, ditrile carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, ethylene carbonate, diamyl carbonate, and dicyclohexyl carbonate. In addition, carbonate compounds derived from hydroxy compounds such as phenols and alcohols, consisting of the same or different hydroxy compounds, can be used.

[0054] Examples of the aforementioned diisocyanate compounds include, specifically, 2,4-tolylene diisocyanate, a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, tetramethyl xylylene diisocyanate, 2,4,6-triisopropylphenyl diisocyanate, 4,4'-diphenylmethane diisocyanate, tolidine diisocyanate, and other known diisocyanates.

[0055] The production of high molecular weight polyesters using these chain extenders (coupling agents) can be carried out using conventional techniques. After the polycondensation is complete, the chain extender is added to the reaction system in a uniform molten state without a solvent and reacted with the polyester obtained by polycondensation. In the melt-molding material of the present invention, the melting point of the aliphatic polyester, etc., is not particularly limited, but is preferably 80°C to 180°C. If the melting point is too low, the heat resistance will be insufficient when hot food or beverages are placed inside, such as in paper cups and paper trays, and there is a risk of melting. Conversely, if the melting point is too high, it is undesirable because the heat sealing temperature will need to be set high when the molded product obtained from the melt-molding material of the present invention is processed into cups, sacks, trays, bags, etc.

[0056] In the melt molding material of the present invention, the crystallization temperature of PBS(A) is preferably between 30°C and 100°C. If the temperature falls below the lower limit, problems such as adhesion to the cooling roll may occur when extruding films, and to avoid this, the temperature of the cooling roll must be set to a lower temperature. Furthermore, during secondary processing such as bag making, automatic packaging machines, and cup making machines, it may take a long time for adhesion to occur. Also, if the temperature is above 98°C, the molten film may begin to solidify in the air gap between the die exit and contact with the substrate, which may weaken the adhesion to the substrate.

[0057] In the melt molding material of the present invention, the number average molecular weight (Mn) of the aliphatic polyester, etc., is arbitrary as long as it does not significantly impair the effects of the present invention, but is usually 5,000 or more, preferably 10,000 or more, and usually 200,000 or less, preferably 150,000 or less. If the number average molecular weight falls below the lower limit of the above range, the melt film characteristics when manufacturing molded products using the melt molding material of the present invention may be inferior, for example, the neck-in may become large. On the other hand, if it exceeds the upper limit, the melt viscosity will increase, and the motor load of the extruder will increase, which may make it difficult to manufacture films by extrusion melt molding. The method for measuring the number average molecular weight (Mn) is the GPC measurement method using chloroform as the solvent and a measurement temperature of 40°C. The number average molecular weight is a converted value using monodisperse polystyrene.

[0058] In the melt molding material of the present invention, the melt flow rate (MFR; 190°C, 2.16 kg load) of the aliphatic polyester or the like, which is preferably used, is normally lower than 0.1 g / 10 min or more, preferably 0.5 g / 10 min or more, more preferably 1.0 g / 10 min or more, and even more preferably 3.0 g / 10 min or more. It is also 35 g / 10 min or less, preferably 30 g / 10 min or less. If the melt flow rate falls below the lower limit of the above range, the motor load during the manufacture of molded products using the melt molding material of the present invention increases significantly, and the processing machine may stop. On the other hand, if it exceeds the upper limit, the stability of the molten film may deteriorate (increased neck-in, occurrence of surging) when molding at high temperatures of 230°C or higher.

[0059] Furthermore, the melt flow rate (MFR; 190°C, 2.16 kg load) of the aliphatic polyester or the like that exits the die in a molten state is normally lower than 0.1 g / 10 min or more, preferably 0.5 g / 10 min or more, more preferably 1.0 g / 10 min or more, and even more preferably 3.0 g / 10 min or more. It is also 35 g / 10 min or less, preferably 30 g / 10 min or less. If the melt flow rate falls below the lower limit of the above range, the motor load in the production of films by extrusion melt molding using the melt molding material of the present invention increases significantly, and the processing machine may stop. On the other hand, if it exceeds the upper limit, the stability of the molten film may deteriorate (increased neck-in, occurrence of surging) when molding at high temperatures of 230°C or higher.

[0060] Furthermore, in the melt-molding material of the present invention, the aliphatic polyester and the like, which are preferably used, may contain unsaturated bonds, and these unsaturated bonds include not only double bonds but also triple bonds. Examples of structural units having such unsaturated bonds include unsaturated dicarboxylic acids and unsaturated diols. Representative examples of unsaturated dicarboxylic acids include maleic acid, fumaric acid, itaconic acid, citraconic acid, 3,6-endomethylene-1,2,3,6-tetrahydro-cis-phthalic acid (nadic acid), and dimer acid.

[0061] Unsaturated bonding groups generated during the polymer manufacturing process are also useful. Although the generation mechanism is not clear, possible causes include the formation of terminal vinyl groups through thermal decomposition of the main chain, and the formation of unsaturated bonds through dehydration of malic acid and other polyfunctional components added, resulting in their conversion to fumaric acid or maleic acid. These unsaturated bonds may be present individually or in any proportion of two or more types within the polymer.

[0062] In the melt molding material of the present invention, the amount of unsaturated bonds contained in the aliphatic polyester, etc. used is usually 100 μmol / g or less, preferably 80 μmol / g or less, more preferably 60 μmol / g or less, even more preferably 30 μmol / g or less, and most preferably 20 μmol / g or less. It is also usually 3 μmol / g or more, more preferably 5 μmol / g or more. If the amount of unsaturated bonds is below the lower limit, it becomes difficult to efficiently branch when branching occurs, and the melt tension cannot be increased. Conversely, if it exceeds the upper limit, significant gelation occurs, and it may become impossible to manufacture a laminate. The amount of unsaturated bonds is 1 H-NMR and 13 It is calculated by NMR measurements such as 13C-NMR.

[0063] Furthermore, in the melt-molding material of the present invention, the amount of urethane bonds in the aliphatic polyester, etc. used is preferably 0.9% by mass or less, more preferably 0.5% by mass or less, even more preferably 0.2% by mass or less, and even more preferably 0.1% by mass or less. In particular, it is preferable that the aliphatic polyester, etc. is substantially free of urethane bonds. If the amount of urethane bonds is too high, thermal decomposition of the urethane bonds tends to cause phenomena such as smoke generation and foaming, making molding difficult. For example, if we take aliphatic polyesters and other polymers as examples, we can mention PTTMCC's BioPBS® FZ series and FD series, and NatureWorks' Ingeo®.

[0064] <Other polymers> Other polymers that may be included in the melt-molding material of the present invention, in amounts that do not hinder the effects of the present invention, include, for example, the biodegradable polymer polybutylene adipate terephthalate, ultra-low density polyethylene, low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, ultra-high molecular weight polyethylene, polypropylene, ethylene-propylene rubber, polyvinyl acetate, polybutene, and the like. Furthermore, biodegradable polymers such as polyamide polymers like 4-nylon, polyamino acid polymers like polyaspartic acid, polyether polymers like polyethylene glycol and polypropylene glycol, polysaccharides like cellulose and pullulan, and polyvinyl alcohol polymers can be used. When using these other polymers, one or more polymers can be used in any combination and ratio. In particular, it is preferable to use biodegradable polymers in combination because the biodegradation rate of the laminate of the present invention is increased and the shape-disintegration after decomposition is improved.

[0065] When polymers other than the aforementioned aliphatic polyesters are used in combination, the proportion of aliphatic polyesters, etc., to 100 parts by mass of the total polymer components should be 50 parts by mass or more, preferably 70 parts by mass or more. This is because increasing the amount of aliphatic polyesters, etc., increases the biodegradation rate of the laminate of the present invention and improves its ability to disintegrate after decomposition.

[0066] <Fatty acid bisamide> The melt molding material of the present invention incorporates fatty acid bisamide (B) to control the semi-crystallization time during the production of molded products using the melt molding material and to improve processability during molding. This is expected to shorten the semi-crystallization time and improve release properties.

[0067] In the melt molding material of the present invention, a fatty acid bisamide (hereinafter sometimes referred to as "fatty acid bisamide (B)") with a total number of carbon atoms of 15 to 60 can be preferably used. By using a fatty acid bisamide with a carbon number within this range, the crystallization of the resulting melt molding material can be made extremely fast, and it is possible to improve processability such as release rollability during extrusion lamination, as well as productivity.

[0068] Specific examples of the fatty acid bisamide (B) include saturated fatty acid bisamides such as methylenebisstearate, ethylenebiscaprate, ethylenebislaurate, ethylenebisstearate, ethylenebisisostearate, ethylenebishydroxystearate, ethylenebisbehenamide, hexamethylenebisstearate, hexamethylenebisbehenamide, hexamethylenebishydroxystearate, N,N'-distearyladipamide, and N,N'-distearylsebacinamide; unsaturated fatty acid bisamides such as ethylenebisoleamide, hexamethylenebisoleamide, and N,N'-dioleyladipamide; and m-xylylenebisstearate. These may be used individually or in combination of two or more. Among these, using at least one selected from methylenebisstearamide, ethylenebislauric acidamide, ethylenebisstearamide, ethylenebisisostearate, ethylenebishydroxystearamide, hexamethylenebisstearamide, N,N'-distearyladipamide, and ethylenebisoleamide allows for even faster crystallization of the resulting melt-molded material, thereby improving processability such as release properties during extrusion lamination and increasing productivity.

[0069] <Other crystallization nucleating agents> In addition to the fatty acid bisamides mentioned above, other nucleating agents such as organic carboxylic acid metal salts, organic sulfonates, carboxylic acid amides, organic polymers, ionomers, phosphorus compound metal salts, 2,2-methylbis(4,6-di-t-butylphenyl) sodium, polyethylene wax, and inorganic nucleating agents may also be used in combination.

[0070] Examples of the aforementioned metal salts of organic carboxylates include benzoates, terephthalates, aliphatic carboxylates, salicylates, and dibenzoate compounds. Examples of the aforementioned benzoates include sodium benzoate, potassium benzoate, lithium benzoate, calcium benzoate, magnesium benzoate, barium benzoate, aluminum benzoate, sodium β-naphthalate, and sodium cyclohexanecarboxylate, while examples of the aforementioned terephthalates include lithium terephthalate, sodium terephthalate, and potassium terephthalate. Furthermore, examples of aliphatic carboxylates include calcium oxalate, sodium laurate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, sodium octacosanoate, calcium octacosanoate, sodium stearate, potassium stearate, lithium stearate, calcium stearate, magnesium stearate, barium stearate, sodium montanaate, calcium montanaate, sodium tolulate, etc. Examples of salicylates include sodium salicylate, potassium salicylate, zinc salicylate, etc. Examples of dibenzoate compounds include aluminum dibenzoate, potassium dibenzoate, lithium dibenzoate, etc.

[0071] Examples of the aforementioned organic sulfonates include sodium p-toluenesulfonate and sodium sulfisophthalate. Examples of the carboxylic acid amides include saturated fatty acid amides such as stearic acid amide, palmitic acid amide, and behenic acid amide; unsaturated fatty acid amides such as oleic acid amide, erucic acid amide, and linoleic acid amide; hydroxystearic acid amide; and tris(t-butylamide) trimesic acid. Examples of the aforementioned organic polymers include low-density polyethylene, high-density polyethylene, polypropylene, polyisopropylene, polybutene, poly-4-methylpentene, polyvinylcycloalkane, polyvinyltrialkylsilane, and high-melting-point polylactic acid. Examples of the ionomer include sodium salts or potassium salts of polymers having carboxyl groups, such as sodium salts of ethylene-acrylic acid or methacrylic acid copolymers, and sodium salts of styrene-maleic anhydride copolymers. Examples of the aforementioned phosphorus compound metal salts include benzylidene sorbitol and its derivatives, and sodium-2,2'-methylenebis(4,6-di-t-butylphenyl) phosphate.

[0072] Furthermore, specific examples of inorganic nucleating agents that may be used in combination as crystal nucleating agents in the melt-molding material of the present invention include talc, kaolin, montmorillonite, synthetic mica, clay, zeolite, silica, graphite, carbon black, zinc oxide, magnesium oxide, titanium oxide, calcium sulfide, boron nitride, calcium carbonate, barium sulfate, aluminum oxide, neodymium oxide, and metal salts of phenylphosphonate. In addition, these inorganic nucleating agents may be modified with organic substances to improve their dispersibility in the melt-molding material.

[0073] In the melt-molding material of the present invention, the average particle size of the nucleating agent can be any size within a range that does not significantly impair the effects of the present invention. It is generally desirable to have an average particle size of 50 μm or less, preferably 20 μm or less. Furthermore, from the viewpoint of secondary aggregation and handling workability, it is generally desirable to have an average particle size of 0.1 μm or more, preferably 0.5 μm or more. If the average particle size exceeds the upper limit of the above range, it is undesirable as it is ineffective in shortening the semi-crystallization time. Also, if the average particle size of the nucleating agent falls below the lower limit of the above range, it is undesirable because the manufacturing cost increases and handling becomes difficult.

[0074] The content of the fatty acid bisamide (B) in the melt-molding material of the present invention is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more. It is also preferably 10% by mass or less, more preferably 5% by mass or less, more preferably 4% by mass or less, and particularly preferably 3% by mass or less. By keeping it within this range, the crystallization of the resulting melt-molding material can be made extremely fast, and it is possible to improve processability such as the release properties of the extruded laminate and productivity. On the other hand, if it falls below the lower limit of this range, there is a risk that the effect of raising the crystallization temperature will not be observed, or that the release properties during molding will deteriorate, and if it exceeds the upper limit, there is a risk that the manufacturing cost will become too high, or that roll fouling during molding will become a problem.

[0075] Furthermore, when the crystal nucleating agent is used together with the fatty acid bisamide (B) in the melt-molding material of the present invention, the content of the crystal nucleating agent excluding the fatty acid bisamide (B) is preferably 10% by mass or less, and more preferably 5% by mass or less. In particular, the content of this crystal nucleating agent is more preferably less than that of the fatty acid bisamide (B), even more preferably 0.01% by mass or less, and particularly preferably 0.05% by mass or less. By keeping it within this range, it is possible to exhibit the characteristic of improving processability such as the release properties of the extruded lamination and productivity. On the other hand, if it exceeds the upper limit, the manufacturing cost may become too high and roll contamination during molding may become a problem.

[0076] <Method for manufacturing molten molding materials> The manufacturing of the melt-molded material of the present invention can be carried out using all conventionally known mixing / kneading techniques. As for mixers, horizontal cylindrical, V-shaped, double-cone mixers, ribbon blenders, super mixers, and various continuous mixers can be used. As for kneaders, batch kneaders such as roll or internal mixers, single-stage and double-stage continuous kneaders, twin-screw extruders, single-screw extruders, and the like can be used.

[0077] Methods of mixing include heating and melting the aliphatic polyester containing PBS (A), and then adding a nucleating agent containing fatty acid bisamide (B), various additives, fillers, and thermoplastic polymers to the mixture. Blending oils may also be used to uniformly disperse the various additives. Furthermore, the melt flow rate (MFR; 190°C, 2.16 kg load) of the melt molding material of the present invention is preferably 3 g / 10 min or more and 40 g / 10 min or less. The lower limit of the MFR of the melt molding material is more preferably 4 g / 10 min or more, and particularly preferably 5 g / 10 min or more. The upper limit of the MFR of the melt molding material is more preferably 35 g / 10 min or less, and particularly preferably 30 g / 10 min or less. Setting the MFR of the melt molding material within this range is effective in suppressing surging during processing and preventing deterioration of release rollability, thereby improving processability.

[0078] <Relationship between semi-crystallization time and nucleating agent> The semi-crystallization time of PBS(A) obtained by isothermal crystallization of a melt-molded material made from the melt-molded material of the present invention, which is melted at 200°C and held for 3 minutes, then cooled at a rate of 100°C / min and held at 80°C, is 1 second to 44 seconds, preferably 5 seconds to 35 seconds, and more preferably 9 seconds to 30 seconds. The semi-crystallization time is the time required for the melt-molded material to reach half of the final degree of crystallinity it will achieve. When a crystal nucleating agent is mixed during melt crystallization, the nucleating agent acts as a starting point for crystal nuclei, improving the crystal nucleation rate and crystal growth rate of the melt-molded material, and as a result, the semi-crystallization time can be shortened.

[0079] By setting the predetermined semi-crystallization time within the aforementioned range, the crystallization of the resulting molten molding material can be made even faster, resulting in improved processability, such as mold release during injection molding, and increased productivity. The semi-crystallization time is the time required for a molten material to reach half of its final degree of crystallinity. When a nucleating agent is mixed during molten crystallization, the nucleating agent acts as a starting point for crystal nuclei, improving the nucleation rate and crystal growth rate of the molten material, and consequently shortening the semi-crystallization time.

[0080] <Method for manufacturing polymer molded products> A method for producing polymer molded articles using the melt-molding material of the present invention is preferably an extrusion molding method (extrusion coating method) in which the melt-molding material, which is a mixture of the melt-molding material of the present invention described above, other polymers added as needed, and desired additives such as lubricants, antioxidants, and modifiers, is extruded using an extruder having a hanger-coat type T-die, or a method in which the melt-molding material of the present invention described above is formed into a film by inflation molding or T-die film molding. From the viewpoint of productivity and the physical properties of the obtained polymer molded article, the extrusion coating method is particularly preferred. When using the extrusion coating method, a melt-extrusion coating and laminating apparatus that is normally used for melt-extrusion coating and lamination of thermoplastic synthetic polymers such as polyethylene can be used. Furthermore, polymer compositions containing the polymer composition of the present invention described above, other polymers as needed, and desired additives such as lubricants, antioxidants, and modifiers can be injection molded using an injection molding machine.

[0081] <Molded products> The molten material of the present invention is used to form a film, and a film is particularly preferred as the molded product obtained from the molten material of the present invention. It can be formed into a film by various molding methods applicable to general-purpose plastics. Regarding the molding method, the effects of the present invention are particularly evident when molded by the extrusion molding or inflation molding methods described above. More specifically, examples include a method in which a film-like, sheet-like, or cylindrical material extruded to a predetermined thickness from a T-die, I-die, or round die is cooled and solidified using a cooling roll, water, compressed air, etc. When the polymer molded product of the present invention is a film, the thickness is not particularly limited, but generally 5 μm or more, more preferably 8 μm or more, and even more preferably 15 μm or more is preferred. The upper limit is 100 μm or less, preferably 50 μm or less, more preferably 30 μm or less, and even more preferably 20 μm or less. If the upper limit is exceeded, the curling of the laminated product and the release properties of the roll tend to deteriorate, and if it falls below the lower limit, although it depends on the performance of the extruder, the discharge may not be stable and thickness unevenness may occur.

[0082] Examples of film-like molded articles obtained by this method include film molded products such as packaging films, shopping bags, plastic bags, compost bags, cups, individual packaging paper, and mulch films; sheet molded products such as coffee capsules, seedling pots, young tree sheets, and trays; and tubular molded products selected from straws, cotton swabs, and balloon sticks. Furthermore, injection-molded products such as coffee capsules, cutlery, and trays can also be obtained. [Examples]

[0083] The specific embodiments of the present invention will be described in more detail below using examples, but the present invention is not limited to the following examples as long as it does not exceed its gist. The various manufacturing conditions and evaluation result values ​​in the following examples are meant as preferred upper or lower limits in the embodiments of the present invention, and the preferred range may be defined by a combination of the aforementioned upper or lower limits and the values ​​of the following examples or the values ​​of the examples themselves.

[0084] <Raw materials used> The raw materials used in the examples and comparative examples were polymers polymerized as follows or commercially available products. In the following, "PBS" refers to "polybutylene succinate".

[0085] <Commercially available product> (PBS) • PBS (FZ71PM)... "BioPBS (registered trademark) FZ71PM" manufactured by PTTMCC Biochem (MFR: 22g / 10 min, melting point: 115℃) • PBS (FZ91PM)... PTTMCC Biochem's "BioPBS (registered trademark) FZ91PM" (MFR: 5.0g / 10 min, melting point: 115℃)

[0086] <Evaluation of physical properties> The evaluation methods for various physical properties and characteristics in the examples and comparative examples are as follows. (Measurement of semi-crystallization time) 3.0 to 5.0 mg of the polyester polymer composition was placed in an aluminum pan for DSC measurement and heated and melted at 200°C for 3 minutes under a nitrogen atmosphere using a differential scanning calorimetry system (DSC8500, PerkinElmer Japan). Subsequently, it was rapidly cooled to 80°C at 100°C / min, and the time taken for half of the crystallization to be completed was calculated by performing isothermal crystallization measurements at 80°C, and this was defined as the semi-crystallization time.

[0087] (Separation properties) The processing steps and cooling stability of the extruded laminate molding process are as follows: Pellets were fed into the hopper, which is the material inlet. The fed pellets were melted in the cylinder of a single-screw extruder and extruded at 250°C using a hanger-coat type T-die. After the molten film stabilized, the molten film was passed through a cooling roll at a low speed, and the release speed was adjusted to 20 m / min, 25 m / min, and 30 m / min to check the release properties. The cooling temperature was set to 40°C, and a semi-mat type cooling roll and an air knife were used. The degree of adhesion from the cooling roll was observed according to the following criteria. ◎: The polymer is released smoothly from the cooling roll, resulting in a clean appearance. ○: The polymer is slightly difficult to separate from the cooling roll, but molding can be performed without any problems. △: The polymer is having difficulty separating from the cooling roll, resulting in a noise when it is released. Also, streaks may appear on the molded product. ×: The laminated material does not detach from the cooling roll, making operation impossible.

[0088] (Smoke and odor) In the aforementioned processing process, sensory tests were conducted on the smoke emission from the die exit and the odor. The evaluation criteria were as follows. ○: It produces little smoke and has no irritating odor that is noticeable to the nose or eyes. △: There is some smoke and a slight irritating odor that may be noticeable to the nose and eyes, but it is not at a level that would cause problems during work. ×: It emits smoke and has an irritating odor that is noticeable to the nose and eyes.

[0089] (Appearance of the molten film) In the aforementioned processing process, the stability of the molten film at the die exit and the appearance of the extruded laminated film were evaluated. The evaluation criteria were as follows: ○: No surging failures occur, and the molten film is stable with no gel and is transparent. △: There is a slight gel-like substance, but it is transparent and does not pose any problems during processing. ×: The molten film is not transparent.

[0090] (Roll stains) In the aforementioned processing process, the degree of contamination of the cooling roll after film formation was evaluated. The evaluation criteria were as follows. ○: After 1 hour of processing, only a small amount of white powdery substance was found adhering to the roll, and it did not negatively affect the processability. △: After 1 hour of processing, there is a significant amount of white powdery substance adhering to the roll, but this does not negatively affect the processability. ×: If a large amount of white powdery substance adheres to the roll after 1 hour of processing, and the white powdery substance has migrated to the film surface.

[0091] [Example 1] 93 parts by mass of PBS (FZ71PM), 2.0 parts by mass of EBS as a crystal nucleating agent, and 5.0 parts by mass of Irganox 1010 as an antioxidant were dry-blended. The mixture was extruded into strands at a mixing temperature of 160°C using a twin-screw extruder with a screw diameter of Φ30 mm, and pellets were obtained using a pelletizer. The semi-crystallization time was measured. The results are shown in Table 1.

[0092] [Example 2] 98.75 parts by mass of PBS (FZ71PM), 0.25 parts by mass of EBS as a crystal nucleating agent, and 1.0 part by mass of Irganox 1010 as an antioxidant were dry-blended. The mixture was extruded into strands at a mixing temperature of 160°C using a twin-screw extruder with a screw diameter of Φ30 mm, and pellets were obtained using a pelletizer. The semi-crystallization time was measured. The results are shown in Table 1.

[0093] [Example 3] 93 parts by mass of PBS (FZ71PM), 2.0 parts by mass of ZOA as a crystal nucleating agent, and 5.0 parts by mass of Irganox 1010 as an antioxidant were dry-blended. The mixture was extruded into strands at a mixing temperature of 160°C using a twin-screw extruder with a screw diameter of Φ30 mm, and pellets were obtained using a pelletizer. The semi-crystallization time was measured. The results are shown in Table 1.

[0094] [Example 4] 93 parts by mass of PBS (FZ71PM), 2.0 parts by mass of Slipax L as a crystal nucleating agent, and 5.0 parts by mass of Irganox 1010 as an antioxidant were dry-blended. The mixture was extruded into strands at a mixing temperature of 160°C using a twin-screw extruder with a screw diameter of Φ30 mm, and pellets were obtained using a pelletizer. The semi-crystallization time was measured. The results are shown in Table 1.

[0095] [Example 5] 100 parts by mass of PBS (FZ71PM), 0.05 parts by mass of EBS as a crystal nucleating agent, and 0.1 parts by mass of Irganox 1010 as an antioxidant were dry-blended. The mixture was extruded into strands at a mixing temperature of 160°C using a twin-screw extruder with a screw diameter of Φ30 mm, and pellets were obtained using a pelletizer. The semi-crystallization time was measured. The results are shown in Table 1.

[0096] [Example 6] 100 parts by mass of PBS (FZ71PM), 0.1 parts by mass of EBS as a crystal nucleating agent, and 0.1 parts by mass of Irganox 1010 as an antioxidant were dry-blended. The mixture was extruded into strands at a mixing temperature of 160°C using a twin-screw extruder with a screw diameter of Φ30 mm, and pellets were obtained using a pelletizer. The semi-crystallization time was measured. The results are shown in Table 1.

[0097] [Example 7] 100 parts by mass of PBS (FZ71PM), 0.1 parts by mass of ZOA as a crystal nucleating agent, and 0.1 parts by mass of Irganox 1010 as an antioxidant were dry-blended. The mixture was extruded into strands at a mixing temperature of 160°C using a twin-screw extruder with a screw diameter of Φ30 mm, and pellets were obtained using a pelletizer. The semi-crystallization time was measured. The results are shown in Table 1.

[0098] [Example 8] PBS (FZ71PM): 100 parts by mass, Slipax L: 0.1 parts by mass as a crystal nucleating agent, and Irganox 1010: 0.1 parts by mass as an antioxidant were dry-blended. The mixture was extruded into strands at a mixing temperature of 160°C using a twin-screw extruder with a screw diameter of Φ30 mm, and pellets were obtained using a pelletizer. The semi-crystallization time was measured. The results are shown in Table 1.

[0099] [Table 1]

[0100] [Comparative Example 1] 98 parts by mass of PBS (FZ71PM) and 2.0 parts by mass of Irganox 1010 as an antioxidant were dry-blended. The mixture was extruded into strands at a mixing temperature of 160°C using a twin-screw extruder with a screw diameter of Φ30 mm, and pellets were obtained using a pelletizer. The semi-crystallization time was measured. The results are shown in Table 2.

[0101] [Comparative Example 2] 91 parts by mass of PBS (FZ71PM), 4.0 parts by mass of erucic acid amide as a crystal nucleating agent, and 5.0 parts by mass of Irganox 1010 as an antioxidant were dry-blended. The mixture was extruded into strands at a mixing temperature of 160°C using a twin-screw extruder with a screw diameter of Φ30 mm, and pellets were obtained using a pelletizer. The semi-crystallization time was measured. The results are shown in Table 2.

[0102] [Comparative Example 3] 98 parts by mass of PBS (FZ71PM), 2.0 parts by mass of magnesium stearate as a crystal nucleating agent, and 0.1 parts by mass of Irganox 1010 as an antioxidant were dry-blended. The mixture was extruded into strands at a mixing temperature of 160°C using a twin-screw extruder with a screw diameter of Φ30 mm, and pellets were obtained using a pelletizer. The semi-crystallization time was measured. The results are shown in Table 2.

[0103] [Comparative Example 4] 100 parts by mass of PBS (FZ71PM), 0.1 parts by mass of erucic acid amide as a crystal nucleating agent, and 0.1 parts by mass of Irganox 1010 as an antioxidant were dry-blended. The mixture was extruded into strands at a mixing temperature of 160°C using a twin-screw extruder with a screw diameter of Φ30 mm, and pellets were obtained using a pelletizer. The semi-crystallization time was measured. The results are shown in Table 2.

[0104] [Comparative Example 5] 100 parts by mass of PBS (FZ71PM), 0.1 parts by mass of stearic acid amide as a crystal nucleating agent, and 0.1 parts by mass of Irganox 1010 as an antioxidant were dry-blended. The mixture was extruded into strands at a mixing temperature of 160°C using a twin-screw extruder with a screw diameter of Φ30 mm, and pellets were obtained using a pelletizer. The semi-crystallization time was measured. The results are shown in Table 2.

[0105] [Comparative Example 6] 100 parts by mass of PBS (FZ71PM), 0.1 parts by mass of magnesium stearate as a crystal nucleating agent, and 0.1 parts by mass of Irganox 1010 as an antioxidant were dry-blended. The mixture was extruded into strands at a mixing temperature of 160°C using a twin-screw extruder with a screw diameter of Φ30 mm, and pellets were obtained using a pelletizer. The semi-crystallization time was measured. The results are shown in Table 2.

[0106] [Comparative Example 7] 100 parts by mass of PBS (FZ71PM), 0.1 parts by mass of polyethylene wax as a crystal nucleating agent, and 0.1 parts by mass of Irganox 1010 as an antioxidant were dry-blended. The mixture was extruded into strands at a mixing temperature of 160°C using a twin-screw extruder with a screw diameter of Φ30 mm, and pellets were obtained using a pelletizer. The semi-crystallization time was measured. The results are shown in Table 2.

[0107] [Comparative Example 8] 93 parts by mass of PBS (FZ71PM), 2.0 parts by mass of polyethylene wax as a crystal nucleating agent, and 5 parts by mass of Irganox 1010 as an antioxidant were dry-blended. The mixture was extruded into strands at a kneading temperature of 160°C using a twin-screw extruder with a screw diameter of Φ30 mm, and pellets were obtained using a pelletizer. The semi-crystallization time was measured. The results are shown in Table 2.

[0108] [Table 2]

[0109] [Example 9] 50 parts by mass of PBS (FZ71PM), 50 parts by mass of PBS (FZ91PM), and 2.0 parts by mass of the pellets prepared in Example 1 were dry-blended as a masterbatch. This mixture was then extruded at 250°C using a single-screw extruder with a screw diameter of Φ50 mm and a hanger-coat type T-die with a width of 300 mm. After the molten film stabilized, smoke and odor were observed. Next, we checked the release properties. During lamination molding, the molten film was transparent, with no blemishes, bubbles, or smoke, and exhibited excellent molding stability. There was also no odor or roll contamination. Furthermore, the release properties were good. The results are shown in Table 3.

[0110] [Example 10] In Example 9, instead of using 2.0 parts by mass of the pellets prepared in Example 1 as the masterbatch, 5 parts by mass of the pellets prepared in Example 3 and 5.0 parts by mass of the pellets prepared in Comparative Example 1 were used as the masterbatch, and molding and evaluation were performed in the same manner as in Example 9. The results are shown in Table 3.

[0111] [Example 11] In Example 9, instead of using 2.0 parts by mass of the pellets prepared in Example 1 as the masterbatch, 5 parts by mass of the pellets prepared in Example 4 and 5.0 parts by mass of the pellets prepared in Comparative Example 1 were used as the masterbatch, and the molding and evaluation were carried out in the same manner as in Example 9. The results are shown in Table 3.

[0112] [Comparative Example 9] 50 parts by mass of PBS (FZ71PM), 50 parts by mass of PBS (FZ91PM), and 5.0 parts by mass of pellets prepared in Comparative Example 1 were dry-blended as a masterbatch. This mixture was extruded at 250°C using a 50mm diameter screw-screw extruder with a 300mm wide hanger-coat type T-die. After the molten film stabilized, smoke and odor were observed. As a result, the molten film was transparent during lamination, with no blemishes, bubbles, or smoke, and exhibited excellent molding stability. There was also no odor or roll contamination. The results are shown in Table 3.

[0113] [Comparative Example 10] In Comparative Example 9, instead of using 5.0 parts by mass of the pellets prepared in Comparative Example 1, 2.0 parts by mass of the pellets prepared in Comparative Example 2 were used as the masterbatch, and the molding and evaluation were performed in the same manner as in Comparative Example 9. The results are shown in Table 3.

[0114] [Comparative Example 11] In Comparative Example 9, instead of using 5.0 parts by mass of the pellets prepared in Comparative Example 1, 5.0 parts by mass of the pellets prepared in Comparative Example 1 and 5.0 parts by mass of the pellets prepared in Comparative Example 3 were used as a masterbatch, and the molding and evaluation were performed in the same manner as in Comparative Example 9. The results are shown in Table 3.

[0115] [Comparative Example 12] In Comparative Example 9, instead of using 5.0 parts by mass of the pellets prepared in Comparative Example 1, 2.0 parts by mass of the pellets prepared in Comparative Example 8 were used as the masterbatch, and the molding and evaluation were carried out in the same manner as in Comparative Example 9. The results are shown in Table 3.

[0116] [Table 3]

[0117] (result) The results shown in Tables 1 and 2 indicate that when a specific nucleating agent is mixed in, the nucleating agent acts as a starting point for crystal nuclei, improving the crystal nucleation rate and crystal growth rate of the polymer composition, thus shortening the semi-crystallization time. As a result, as shown in Table 3, the release properties can be significantly improved even at higher take-up speeds, without neck-in, molten film appearance, or roll fouling.

Claims

1. A pellet-shaped melt-molding material comprising polybutylene succinate (A) and fatty acid bisamide (B), wherein the melt-molding material is characterized in that the semi-crystallization time of polybutylene succinate (A) in isothermal crystallization, which is performed by melting at 200°C, holding the molten material for 3 minutes, cooling the molten material at a rate of 100°C / min, and holding it at 80°C, is between 1 second and 44 seconds.

2. The pelletized melt-molding material according to claim 1, wherein the fatty acid bisamide (B) is a fatty acid bisamide having a total of 15 to 60 carbon atoms.

3. The pelletized melt-molding material according to claim 1, wherein the melt-molding material contains 0.01 to 10% by mass of the fatty acid bisamide (B).

4. The pelletized melt-molding material according to claim 3, wherein the melt-molding material contains 0.05 to 5% by mass of the fatty acid bisamide (B).

5. The pelletized melt-molded material according to claim 1, wherein the fatty acid bisamide (B) of the melt-molded material comprises at least one selected from methylenebisstearate, ethylenebiscaprate, ethylenebislaurate, ethylenebisstearate, ethylenebisisostearate, ethylenebishydroxystearate, ethylenebisbehenamide, hexamethylenebisstearate, hexamethylenebisbehenamide, hexamethylenebishydroxystearate, N,N'-distearyladipamide, N,N'-distearylsebacinamide, saturated fatty acid bisamides, ethylenebisoleamide, hexamethylenebisoleamide, N,N'-dioleyladipamide, unsaturated fatty acid bisamide, and m-xylylenebisstearate.

6. The pelletized melt-molded material according to claim 1, wherein the fatty acid bisamide (B) of the melt-molded material comprises at least one selected from methylenebisstearate, ethylenebislaurate, ethylenebisstearate, ethylenebisisostearate, ethylenebishydroxystearate, hexamethylenebisstearate, N,N'-distearyladipamide, and ethylenebisoleamide.

7. A molded article made from the pelletized melt-molded material described in claim 1.

8. A film molded article, wherein the molded article described in claim 7 is selected from packaging film, shopping bags, plastic bags, compost bags, cups, packaging paper, and mulch film.

9. A sheet molded product in which the molded product described in claim 7 is selected from coffee capsules, seedling pots, young tree sheets, and trays.

10. A tubular molded article, wherein the molded article described in claim 7 is selected from a straw, a cotton swab, and a balloon stick.

11. An injection-molded product in which the molded product described in claim 7 is selected from coffee capsules, cutlery, and trays.

12. A molded article of a polymer composition comprising polybutylene succinate (A) and fatty acid bisamide (B), The aforementioned molded product is at least one type of molded product selected from film molded products, sheet molded products, tubular molded products, and injection molded products. The aforementioned molded product is a resin molded product characterized in that the semi-crystallization time of polybutylene succinate (A) in isothermal crystallization, which is performed by melting at 200°C and holding the molten material for 3 minutes, then cooling it at a rate of 100°C / min and holding it at 80°C, is between 1 second and 44 seconds.

13. The resin molded article according to claim 12, wherein the fatty acid bisamide (B) is a fatty acid bisamide having a total of 15 to 60 carbon atoms.

14. The resin molded article according to claim 12, wherein the polymer composition contains 0.01 to 10% by mass of the fatty acid bisamide (B).

15. The resin molded article according to claim 12, wherein the polymer composition contains 0.05 to 5% by mass of the fatty acid bisamide (B).

16. The resin molded article according to claim 12, wherein the fatty acid bisamide (B) of the polymer composition comprises at least one selected from methylenebisstearate, ethylenebiscaprate, ethylenebislaurate, ethylenebisstearate, ethylenebisisostearate, ethylenebishydroxystearate, ethylenebisbehenamide, hexamethylenebisstearate, hexamethylenebisbehenamide, hexamethylenebishydroxystearate, N,N'-distearyladipamide, N,N'-distearylsebacinamide, saturated fatty acid bisamides, ethylenebisoleamide, hexamethylenebisoleamide, N,N'-dioleyladipamide, unsaturated fatty acid bisamide, and m-xylylenebisstearate.

17. The resin molded article according to claim 12, wherein the fatty acid bisamide (B) of the polymer composition comprises at least one selected from methylenebisstearate, ethylenebislaurate, ethylenebisstearate, ethylenebisisostearate, ethylenebishydroxystearate, hexamethylenebisstearate, N,N'-distearyladipamide, and ethylenebisoleamide.

18. The resin molded article according to claim 12, wherein the film molded article is a molded article selected from packaging film, shopping bags, plastic bags, compost bags, cups, packaging paper, and mulch film.

19. The resin molded product according to claim 12, wherein the sheet molded product is a molded product selected from coffee capsules, seedling pots, young tree sheets, and trays.

20. The resin molded product according to claim 12, wherein the tubular molded product is a molded product selected from a straw, a cotton swab, and a balloon stick.

21. The resin molded product according to claim 12, wherein the injection molded product is a molded product selected from coffee capsules, cutlery, and trays.

Images