JPWO2015093525A1 - Polyester elastomer - Google Patents

Abstract

The present invention is a polyester elastomer composed of 20 to 85% by mass of a hard segment component and 80 to 15% by mass of a soft segment component, the hard segment component comprising a dicarboxylic acid component and a glycol component, When the total dicarboxylic acid component constituting is 100% by mass, the polyester elastomer contains 20% by mass or more of the flange carboxylic acid component, and is a polyester elastomer excellent in impact resistance and adhesion to other materials.

Description

  The present invention relates to a polyester elastomer excellent in impact resistance and adhesion to other materials.

  In recent years, biodegradable resins and resins using biomass-derived materials have been developed and put to practical use as environmentally friendly or environmentally sustainable materials. However, these resins are currently inferior in thermal properties and mechanical properties to conventional general-purpose resins and engineering plastics. This is because one of the raw materials derived from biomass has an aliphatic structure, and one of the causes is that a polymer containing them has a disadvantage in thermal properties. Under such circumstances, furandicarboxylic acid is known as a biomass-derived raw material capable of polymerizing a thermoplastic resin having excellent heat resistance, but sufficient mechanical properties cannot be obtained due to low polymerization degree. That was a challenge.

  In order to solve such a problem, a technique for achieving a high molecular weight by using an ester of furandicarboxylic acid as a monomer has been developed (for example, see Patent Document 1). As a result, although some of the thermal properties and mechanical properties were improved, there was a problem inferior in impact resistance.

  In order to improve impact resistance, a copolymer resin having a skeleton structure containing a furan ring has been invented (see, for example, Patent Documents 2 and 3). However, the impact resistance of the resin obtained by these methods is not always sufficient, and further improvement in impact resistance is required in order to develop into various applications.

  While there is a need for highly practical resins using biomass-derived raw materials, that is, resins with excellent impact resistance, in recent years, there are increasing uses for composite materials with other materials such as two-color molding and insert molding. It has increased. Under such circumstances, a resin having high surface energy is more advantageous for development in various applications because it has higher adhesion to other materials.

Japanese Patent No. 5233390 JP 2007-146153 A JP 2010-254827 A

  The present invention has been made against the background of such prior art problems. That is, an object of the present invention is to provide a polyester elastomer having a high impact resistance and excellent adhesion to other materials by including a predetermined amount or more of a flange carboxylic acid component in a polyester elastomer comprising a hard segment and a soft segment. It is in.

That is, the present invention has the following configuration.
[1] A polyester elastomer composed of 20 to 85% by mass of a hard segment component and 80 to 15% by mass of a soft segment component, the hard segment component consisting of a dicarboxylic acid component and a glycol component, constituting the hard segment component A polyester elastomer comprising 20% by mass or more of a flanged carboxylic acid component, based on 100% by mass of the total dicarboxylic acid component.
[2] The polyester elastomer according to [1], wherein 70% by mass or more of the glycol component constituting the hard segment component is 1,4-butanediol.
[3] The soft segment component constituting the polyester elastomer is at least one selected from a polyalkylene ether component, an aliphatic polyester component, and a polyalkylene carbonate component [1] to [2] ] The polyester elastomer in any one of.
[4] The polyester elastomer according to any one of [1] to [2], wherein the soft segment component constituting the polyester elastomer is polytetramethylene glycol.
[5] The polyester elastomer according to any one of [1] to [2], wherein the soft segment component constituting the polyester elastomer is poly-ε-caprolactone.
[6] The polyester elastomer according to any one of [1] to [2], wherein the soft segment component constituting the polyester elastomer is polyhexamethylene carbonate diol.

  According to the present invention, a polyester elastomer excellent in impact resistance and adhesion to other materials can be obtained. Here, the excellent adhesion is due to the high surface energy, but this can be realized by containing a predetermined amount or more of the flanged carboxylic acid component. Further, the impact resistance can be improved by including a predetermined amount or more of the flanged carboxylic acid component. Impact strength and surface energy depend on the type of soft segment that constitutes the polyester elastomer. Even if any type of soft segment is used, impact resistance is achieved by including a predetermined amount or more of the flanged carboxylic acid component. It becomes possible to improve the adhesiveness between and other materials.

The present invention is described in detail below.
The polyester elastomer used in the present invention needs to have a hard segment amount of 20 to 85% by mass and a soft segment amount of 80 to 15% by mass. When the soft segment amount is less than 15% by mass, impact resistance is lowered and good surface energy cannot be obtained. When the soft segment amount exceeds 80% by mass, the melting point of the polyester elastomer is remarkably lowered, so that heat resistance becomes a problem. Considering the mechanical strength, surface energy, and heat resistance of the polyester elastomer, the upper limit of the soft segment amount is preferably 75%, more preferably 70% by mass, and the lower limit is preferably 20% by mass, more preferably 25% by mass. It is.

Here, the polyester elastomer is a thermoplastic polyester elastomer (block copolymer) composed of a hard segment component and a soft segment component. The hard segment component refers to a high melting point polyester segment composed of a dicarboxylic acid component and a glycol component and having crystallinity as typified by polybutylene terephthalate and polybutylene naphthalate. The soft segment component refers to a low-melting polymer segment such as polyoxyalkylene glycols such as polytetramethylene glycol, poly-ε-caprolactone, and polybutylene adipate.
When expressing the ratio of the hard segment and the soft segment, the molecular weight of the different soft segment species is greatly different, or the substantial molecular weight in the polyester elastomer (block copolymer) is not known depending on the soft segment species (or Since it is difficult to calculate, it is necessary to consider in mass% instead of mol%. Therefore, the ratio of the hard segment component and the soft segment component is described in mass%.

The mass% of the soft segment component of the polyester elastomer is calculated as follows.
For example, when the hard segment component constituting the polyester elastomer is a butylene terephthalate unit and the soft segment component is polytetramethylene glycol, the mass% of the polytetramethylene glycol residue in the elastomer is the mass% of the soft segment component. Further, the total of each mass% of the terephthalic acid residue and 1,4-butanediol residue in the elastomer is defined as mass% of the hard segment component.
When other components are used for the hard segment component and the soft segment component, the mass% of the soft segment component is calculated by the same method.

As a soft segment component constituting the polyester elastomer, one or two types selected from a polyalkylene ether component, an aliphatic polyester component, and a polyalkylene carbonate component are considered in consideration of an improvement effect of mechanical properties and surface energy. The above is desirable. In addition, when low temperature characteristics and hydrolysis resistance are required as characteristics other than mechanical characteristics and surface energy, it is preferable to use a polyalkylene ether component, and when heat resistance is required, an aliphatic polyester component It is preferable to use a polyalkylene carbonate component when heat resistance and hydrolysis resistance are required.
When handling property etc. are considered, a polyalkylene ether component is preferable as a soft segment component.
In the present invention, since the soft segment component is often composed of a long-chain glycol component, the soft segment component is considered as a glycol component for convenience. For example, even if the soft segment component is made of polylactone, it is considered as a glycol component.

  Examples of the polyalkylene ether component include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly (ethylene oxide / propylene oxide) copolymer, poly (ethylene oxide / tetrahydrofuran) copolymer, poly (ethylene oxide / propylene oxide / tetrahydrofuran). ) Copolymers and the like. When the total of the glycol components of the polyester elastomer (the total of the glycol components and soft segment components constituting the hard segment component) is 100% by mass, the polyalkylene ether component is preferably 25% by mass or more, more preferably It is 30% by mass or more, more preferably 35% by mass or more. In consideration of handling properties such as heat resistance and blocking, the upper limit is preferably 95% by mass or less, and more preferably 90% by mass or less.

  Polytetramethylene glycol is desirable as the polyalkylene ether component. The number average molecular weight of polytetramethylene glycol is preferably 400 or more, more preferably 500 or more, still more preferably 600 or more, particularly preferably 700 or more, and the upper limit is preferably 4000 or less, more preferably 3500 or less, More preferably, it is 3000 or less. If the number average molecular weight of the polytetramethylene glycol is less than 400, it may be difficult to develop the elasticity inherent to the elastomer, and the impact resistance may decrease. On the other hand, when it exceeds 4000, compatibility with the polyester portion constituting the hard segment component may be lowered, and it may be difficult to maintain the block property.

Examples of the aliphatic polyester component include polylactones, polyesters composed of an aliphatic dicarboxylic acid having 2 to 10 carbon atoms and an aliphatic glycol having 2 to 10 carbon atoms. Considering the use of a copolymer component of a polyester elastomer, polylactones are preferred. Examples of polylactones include polycaprolactone, polyenane lactone, and polycaprylolactone. When the total of the glycol components of the polyester elastomer (the total of the glycol component and soft segment component constituting the hard segment component) is 100% by mass, the polylactone is preferably 40% by mass or more, more preferably 45% by mass. % Or more, more preferably 50 mass% or more. In consideration of handling properties such as heat resistance and blocking, the upper limit is preferably 80% by mass or less, more preferably 70% by mass or less.
These polylactones can be used alone or in admixture of two or more, and poly-ε-caprolactone is most preferred in view of balance between physical properties, handling properties and the like. The polyester elastomer is preferably polymerized using ε-caprolactone as a raw material in consideration of reactivity and productivity.

  A polyester type block copolymer is obtained by reacting a crystalline high melting point polyester constituting the hard segment component with the lactone. The reaction is usually carried out by carrying out a melt reaction at a temperature of 200 ° C. to 250 ° C. for 0.5 to 3 hours in a nitrogen atmosphere and then removing unreacted lactones under vacuum.

Examples of the polyalkylene carbonate component include aliphatic polycarbonate diol composed of 1,6-hexanediol, 1,9-nonanediol, and 3-methyl-1,5-pentanediol. When the total of the glycol components of the polyester elastomer (the total of the glycol components and soft segment components constituting the hard segment component) is 100% by mass, the polyalkylene carbonate component is preferably 20% by mass or more, more preferably It is 25% by mass or more, more preferably 30% by mass or more. In consideration of handling properties such as heat resistance and blocking, the upper limit is preferably 80% by mass or less, more preferably 70% by mass or less.
These polyalkylene carbonate components can be used alone or in admixture of two or more, and polyhexamethylene carbonate diol is most preferred in view of balance between physical properties and handling properties. The polyester elastomer is preferably polymerized using a polyalkylene carbonate diol having a molecular weight increased to some extent in order to maintain the block property.

  The molecular weight of the polyalkylene carbonate diol used as the raw material is preferably 2000 to 80000 in terms of number average molecular weight. The higher the molecular weight, the higher the block property. The polycarbonate diol has a molecular weight of preferably 2000 or more, more preferably 3000 or more, and still more preferably 5000 or more. The upper limit of the molecular weight of the polycarbonate diol is preferably 80000 or less, more preferably 70000 or less, and even more preferably 60000 or less, from the viewpoint of compatibility between the hard segment and the soft segment. If the molecular weight of the polycarbonate diol is too large, the compatibility is lowered and phase separation occurs, which may adversely affect the mechanical properties.

  When the total of the dicarboxylic acid components constituting the hard segment component is 100% by mass, it is necessary to contain 20% by mass or more of the furandicarboxylic acid component. The methyl ester derivative may be used as the dicarboxylic acid component. In view of reactivity, the three-dimensional structure of the polymer chain and the like, 2,5-furandicarboxylic acid or its methyl ester derivative is particularly preferable as a furan carboxylic acid as a raw material monomer. More preferably, it is 40 mass% or more, More preferably, it is 60 mass% or more. If it is less than 20% by mass, a good surface energy improvement effect cannot be obtained.

  As the dicarboxylic acid component other than the furandicarboxylic acid component constituting the hard segment component, known copolymerizable components can be used. Examples of the component include aromatic dicarboxylic acids having 8 to 22 carbon atoms, aliphatic dicarboxylic acids having 4 to 12 carbon atoms, and carboxylic acids such as alicyclic dicarboxylic acids having 8 to 15 carbon atoms and ester derivatives thereof. Among these, one type or two or more types can be copolymerized.

Specifically, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, 4,4′-dicarboxybiphenyl, 5-sodium sulfoisophthalic acid, 1,4-cyclohexanedicarboxylic acid, Alicyclic dicarboxylic acids such as 3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 2,5-norbornenedicarboxylic acid, tetrahydrophthalic acid, oxalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, sebacic acid And aliphatic dicarboxylic acids such as undecanedioic acid, dodecanedioic acid, octadecanedioic acid, fumaric acid, maleic acid, itaconic acid, mesaconic acid, citraconic acid and dimer acid. The dicarboxylic acid component other than the furandicarboxylic acid component constituting the hard segment component is preferably an aromatic dicarboxylic acid from the viewpoint of hydrolysis resistance, and in particular, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 4 4'-dicarboxybiphenyl is preferred. As the dicarboxylic acid component constituting the hard segment component, the total of the furandicarboxylic acid component and the aromatic dicarboxylic acid component is preferably 90% by mass or more, and more preferably 95% by mass or more.
In a small amount, p-hydroxybenzoic acid, m-hydroxybenzoic acid, o-hydroxybenzoic acid, lactic acid, oxirane, β-propiolactone, β-butyrolactone, γ-butyrolactone, δ-valerolactone, ε- Caprolactone, glycolic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxyisobutyric acid, 2-hydroxy-2-methylbutyric acid, 2-hydroxyvaleric acid, 3-hydroxyvaleric acid, 4-hydroxy Hydroxycarboxylic acids such as valeric acid, 5-hydroxyvaleric acid, 6-hydroxycaproic acid, 10-hydroxystearic acid and their ester-forming derivatives may be used as the copolymerization component.

When the glycol component constituting the hard segment component is 100% by mass, 70% by mass or more is preferably 1,4-butanediol from the viewpoints of crystallinity, moldability, and heat resistance.
More preferably, it is 80 mass% or more, More preferably, it is 90 mass% or more. If it is less than 70% by mass, the mechanical strength and heat resistance tend to decrease.

  As glycol components other than 1,4-butanediol component constituting the hard segment component, compounds having 2 to 20 carbon atoms and having two hydroxyl groups in the molecule, 6 to 40 carbon atoms, Examples of the aromatic compound include compounds having two hydroxyl groups in the molecule, and one or more of them can be copolymerized.

  Specifically, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 2,2 -Diethyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, 2-ethyl-2-methyl-1, 3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,5-pentanediol, 1,6-hexanediol, 1 , 7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, dimethyloltricyclodecane, diethylene Ethylene oxide adducts or propylene oxide adducts of aliphatic glycols such as recall, triethylene glycol, dipropylene glycol, tripropylene glycol, bisphenol A, bisphenol S, bisphenol C, bisphenol Z, bisphenol AP, 4,4'-biphenol And alicyclic glycols such as 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol and 1,4-cyclohexanedimethanol. Of these, versatile ethylene glycol, 1,2-propanediol, neopentyl glycol, and 1,6-hexanediol are preferable. As the glycol component constituting the hard segment component, 1,4-butanediol and a total of one or more of ethylene glycol, 1,2-propanediol, neopentyl glycol, and 1,6-hexanediol, It is preferably 90% by mass or more, and more preferably 95% by mass or more.

If the amount is small, a tri- or higher functional carboxylic acid component or an alcohol component may be added as a copolymerization component. Examples of the trifunctional or higher functional carboxylic acid components include trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, and trimesic acid. Examples include aliphatic carboxylic acids such as 1,2,3,4-butanetetracarboxylic acid. Examples of the tri- or higher functional alcohol component include glycerol, trimethylolpropane, trimethylolethane, pentaerythritol, α-methylglucose, mannitol, and sorbitol.
These copolymerization ratios are preferably 0.1% by mass or more and 5% by mass or less in the hard segment component. By copolymerization in this range, the resin skeleton is branched, the terminal is increased, and the reaction The effect which promotes is demonstrated. If the copolymerization ratio of the tri- or higher functional compound is too high, gelation occurs and a problem arises in moldability and the like.

  The reduced viscosity of the polyester elastomer is not particularly limited, but is desirably 0.5 to 3.5 dl / g. If it is less than 0.5 dl / g, the mechanical strength is significantly reduced. If it exceeds 3.5 dl / g, the melt viscosity becomes high and the handling property becomes worse, and the polymerization time becomes longer, which may adversely affect the productivity. Preferably it is 0.7-3.0 dl / g, More preferably, it is 0.8-2.8 dl / g.

  As a method for producing the polyester elastomer of the present invention, a known method can be used. For example, after the above dicarboxylic acid and glycol components are esterified at 150 to 250 ° C., the pressure is reduced at 200 to 280 ° C. under reduced pressure. The desired polyester can be obtained by condensation. Alternatively, the target polyester can be obtained by polycondensation at 200 ° C. to 280 ° C. under reduced pressure after a transesterification reaction at 150 ° C. to 250 ° C. using a derivative such as dimethyl ester of dicarboxylic acid and a glycol component. Can do.

  When producing a polyester elastomer, a known catalyst can be used. For example, acetate, carbonate such as lead, zinc, manganese, calcium, cobalt, magnesium, sodium, or metal oxide such as magnesium, zinc, lead, antimony, germanium, or organometallic compound such as tin, lead, titanium, etc. Can be used singly or in combination depending on the reaction system.

When producing a polyester elastomer, it is preferable to add an antioxidant for the purpose of suppressing thermal deterioration, oxidative deterioration, etc., and it may be added before, during or after the reaction. For example, known hindered phenol-based, phosphorus-based, and thioether-based antioxidants can be used.
These antioxidants can be used alone or in combination. The addition amount is preferably 0.1% by mass or more and 5% by mass or less based on the polyester elastomer. If it is less than 0.1% by mass, the effect of preventing thermal deterioration may be poor. If it exceeds 5% by mass, other physical properties may be adversely affected.

  Furthermore, in the present invention, by adding a polyfunctional compound selected from the group of an epoxy compound having at least two reactive groups, an organic carboxylic acid and / or an anhydride thereof, an oxazoline compound, an isocyanate compound, and the like, This copolymer can be obtained in a relatively short time, and is useful from the viewpoint of the thermal stability of the polyester elastomer.

  There is no restriction | limiting in particular in the method of adding the said polyfunctional compound, A normal method is utilized. For example, a method of adding at an arbitrary stage before the end of polycondensation, a method of adding in an inert gas atmosphere after the end of polycondensation, an addition after taking out the copolymer into pellets, flakes, or powders And a method of melt mixing with an extruder or a kneader.

  In order to make the polyester elastomer of the present invention have higher performance, generally well-known stabilizers, lubricants, mold release agents, plasticizers, flame retardants, flame retardant aids, ultraviolet absorbers, light stabilizers, Pigments, dyes, antistatic agents, conductivity-imparting agents, dispersants, compatibilizing agents, antibacterial agents, various fillers, and the like can be added alone or in combination of two or more.

  Since the polyester elastomer of the present invention has better impact resistance and adhesion to other materials than conventional well-known resins, it is a molded product in a wide range of fields such as fibers, films, sheets, and various molded products. Can be mentioned. For example, a container such as a bottle, a pipe, a tube, a sheet, a plate, or a film. Particularly preferable molded articles include constituent materials such as an ink tank of an ink jet printer, an electrophotographic toner container, a packaging resin, a copying machine, a business machine such as a printer, or a camera casing.

  The method for molding the polyester elastomer of the present invention is not particularly limited. For example, molding methods generally used for thermoplastic resins, such as injection molding (including two-color molding, insert molding, etc.), hollow molding (various types) Blow molding), extrusion molding (including coextrusion molding, etc.), vacuum molding, press molding, calendar molding, and the like can be used.

  In addition, these molded articles are provided with chemical functions, electrical functions, magnetic functions, mechanical functions, friction / wear / lubricating functions, optical functions, surface functions such as thermal functions, etc. Various secondary processing can also be performed. Examples of secondary processing include embossing, painting, adhesion, printing, metalizing (plating, etc.), machining, surface treatment (antistatic treatment, corona discharge treatment, plasma treatment, photochromism treatment, physical vapor deposition, chemical vapor deposition, Coating, etc.).

  The polyester elastomer of the present invention has better impact resistance and adhesion to other materials than other well-known resins, and is useful as a component in the above applications, particularly as a composite material with other materials. It has characteristics.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the examples. In addition, each measured value described in the Example is measured by the following method.

Example 1
In a reaction vessel equipped with a stirrer, a thermometer, and a condenser for distillation, 184 parts by mass of dimethyl 2,5-furandicarboxylate, 175 parts by mass of 1,4-butanediol, polytetramethylene glycol having a number average molecular weight of 1000 60 parts by mass of “PTMG1000” (manufactured by Mitsubishi Chemical Corporation) and 0.25 parts by mass of tetrabutyl titanate were added, and a transesterification reaction was performed at 170 to 220 ° C. for 2 hours. After completion of the transesterification reaction, the temperature was raised to 245 ° C., while the pressure in the system was slowly reduced to 665 Pa at 245 ° C. over 40 minutes. Further, a polycondensation reaction was performed at 133 Pa or less for 50 minutes to obtain a polyester elastomer. The composition and physical properties of this polyester elastomer were as shown in Table 1. In the table, each component name is represented by the raw material used, but the composition (% by mass) is a value obtained from the residue of each component calculated by the method described below.

(Examples 2-5, Comparative Examples 1-6)
The synthesis was performed in the same manner as in Example 1 except that the raw materials used and the composition were changed. The composition and physical properties were as shown in Table 1.

  Comparative Examples 1-6 are compositions which do not contain a soft segment and / or furandicarboxylic acid.

(Example 6)
In a reaction vessel equipped with a stirrer, a thermometer, and a condenser for distillation, 210 parts by mass of polybutylene furandicarboxylate (PBF: polymer obtained in Comparative Example 2), ε-caprolactone (manufactured by Daicel Chemical Industries, Ltd.) ) 115 parts by mass were charged, and after purging with nitrogen gas, the mixture was melt-reacted for 120 minutes with stirring at 230 ° C. Thereafter, unreacted ε-caprolactone was removed under vacuum to obtain a polyester elastomer whose soft segment component was poly-ε-caprolactone. The composition and physical properties of this polyester elastomer were as shown in Table 2.

(Example 7)
210 parts by weight of polybutylene furandicarboxylate (PBF: polymer obtained in Comparative Example 2) and 115 parts by weight of polyhexamethylene carbonate diol having a number average molecular weight of 10,000 are stirred at 245 ° C. and 130 Pa for 1 hour, and the resin is transparent. The contents were taken out and cooled to obtain a polyester elastomer. The composition and physical properties of this polyester elastomer were as shown in Table 2.

(Comparative Example 7)
The synthesis was performed in the same manner as in Example 6 except that the raw materials used were changed. The composition and physical properties were as shown in Table 2. The polymer obtained in Comparative Example 1 was used as polybutylene terephthalate (PBT).

(Comparative Example 8)
The synthesis was performed in the same manner as in Example 7 except that the raw materials used were changed. The composition and physical properties were as shown in Table 2. The polymer obtained in Comparative Example 1 was used as polybutylene terephthalate (PBT).

  Comparative Examples 7 and 8 are compositions containing no furandicarboxylic acid.

[Evaluation method]
Determination of composition, reduction viscosity, melting point, surface energy (contact angle), and impact strength were evaluated as follows.

(composition)
The composition of the polyester elastomer was determined by ¹ H-NMR measurement (proton nuclear magnetic resonance spectroscopy) with a resonance frequency of 400 MHz. The measuring apparatus used was an NMR apparatus 400-MR manufactured by VARIAN, and deuterated chloroform was used as the solvent. When not dissolved in deuterated chloroform, deuterated chloroform / trifluoroacetic acid = 85/15 (mass ratio) was used.
(Reduced viscosity)
0.05 g of a sufficiently dried sample was dissolved in 25 ml of a mixed solvent of phenol / tetrachloroethane (mass ratio 6/4) and measured at 30 ° C. using an Ubbelohde viscosity tube.
(Melting point)
Using a differential scanning calorimeter “X-DSC7000” manufactured by Hitachi High-Tech Science Co., Ltd., 5.0 mg of a polyester elastomer sample is placed in an aluminum pan, sealed with a lid, and 20 ° C./minute from 20 ° C. to 250 ° C. After the sample was completely melted by holding for 2 minutes, the temperature was lowered to 50 ° C. at 20 ° C./min. After holding for 2 minutes, the endothermic peak from the thermogram curve obtained by raising the temperature again to 250 ° C. at 20 ° C./min was taken as the melting point.

(Preparation of impact strength sheet sample)
The sheet sample used for impact strength measurement was prepared using a heat press machine SA-302-I manufactured by Tester Sangyo Co., Ltd. Place a 0.1 mm thick mold frame and polyester elastomer in it between two Teflon (registered trademark) sheets, and sandwich the Teflon (registered trademark) sheet between two stainless steel plates. Installed in the press. After melting for 2 minutes under the temperature condition of the melting point of polyester elastomer + 50 ° C., a load of 50 kgf / cm ² was applied, and after 1 minute, it was immersed in water and rapidly cooled to obtain a sheet sample having a thickness of 0.1 mm. Depending on the level, it may become amorphous at the time of rapid cooling, but in that case, it was allowed to stand for a while at room temperature or near the crystallization temperature, and after confirming whitening due to crystallization, the impact strength was measured.

(Impact strength)
A sheet sample having a thickness of 0.1 mm obtained by heat pressing was prepared, and the impact strength was measured with an impact tester manufactured by Toyo Seiki Co., Ltd. The impact sphere used was a 14 mm hemisphere.
The higher the value is, the better the impact strength is, preferably 0.5 J or more, more preferably 0.7 J or more, and particularly preferably nondestructive (non-break; NB). If it is less than 0.5 J, the brittleness is significantly deteriorated, which is not preferable.

(Preparation of sheet sample for contact angle measurement)
The sheet sample used for contact angle measurement was produced using a heat press machine SA-302-I manufactured by Tester Sangyo Co., Ltd. Between the two naflon sheets, a 0.2 mm thick mold frame and a polyester elastomer were placed and placed, and the naflon sheet was further sandwiched between two stainless plates and installed in a heat press machine. After melting for 2 minutes under a temperature condition of about + 50 ° C. of the melting point of the polyester elastomer, a load of 50 kgf / cm ² was applied, and after 1 minute, it was immersed in water and quenched to obtain a sheet sample having a smooth surface of 0.2 mm thickness.

(Contact angle measurement)
The surface energy of the polyester elastomer was calculated from the contact angle. The contact angle was measured using a contact angle meter CA-X manufactured by Kyowa Interface Chemical Co., Ltd. according to the JIS R3257 sessile drop method. Specifically, in an environment of 23 ° C. and humidity 50% RH, the sample was placed horizontally, measured 7 times each with water and methylene iodide, and the contact angle measured with n = 5 except for the upper and lower limits. Was the contact angle of each solvent. In addition, when calculating | requiring the contact angle of water, the dripping amount was 1.8 microliters and the contact angle after standing for 1 minute was read. Moreover, when calculating | requiring the contact angle of a methylene iodide, the dripping amount was 0.9 microliter and the contact angle after standing for 30 seconds was read.
The relationship between the contact angle θ and the surface energy is based on Young's equation:
γs = γsl + γlcos θ (Formula 1)
Holds. Here, γs represents the surface energy of the solid, γl represents the surface energy of the liquid, and γsl represents the interface energy between the solid and the liquid. From the extended Fowkes formula,
[gamma] sl = [gamma] s + [gamma] l-2 ([gamma] sd * [gamma] ld) < ^1/2 > -2 ([gamma] sh * [gamma] lh) < ^1/2 > (Equation 2)
Here, γsd and γsh represent a solid surface energy dispersion component and polar component, and γld and γlh represent a liquid surface energy dispersion component and polar component, respectively.
(Expression 3) is derived from (Expression 1) and (Expression 2).
1 + cos θ = 2 [(γsd × γld) ^1/2 / γl + (γsh + γlh) ^1/2 / γl] (Formula 3)
Also,
γs = γsd + γsh (Formula 4)
Can be approximated.
When water is used for contact angle measurement, the surface tension γl = 72.8, dispersion component γld = 21.8, polar component γlh = 51.0 in (Equation 3), contact angle when water is dropped on the sample ( θ (H ₂ O)) was substituted to obtain (Equation 5).
1 + cos θ (H ₂ O) = 2 [(γsd × 21.8) ^1/2 /72.8+(γsh+51.0) ^1/2 /72.8] (Formula 5)
When methylene iodide is used for contact angle measurement, surface tension γl = 50.8 in (Equation 3), dispersion component γld = 48.5, polar component γlh = 2.3, and when methylene iodide is added dropwise to the sample The contact angle (θ (CH ₂ I ₂ )) was substituted to obtain (Equation 6).
1 + cos θ (CH ₂ I ₂ ) = 2 [(γsd × 48.5) ^{1/2 /} 50.8 + (γsh + 2.3) ^{1/2 /} 50.8] (Formula 6)
The surface energy γs of the resin was calculated from (Expression 4), (Expression 5), and (Expression 6).

  The higher the surface energy value, the better the adhesiveness with other materials. As a guide, it is desirable to be 40 mN / m or more. However, as described above, since the surface energy value varies depending on the soft segment species used, the effect of including the flanged carboxylic acid component is evaluated for each same soft segment species. There is a need to.

  Each evaluation result is shown in Tables 1 and 2.

  Compared with the resin outside the scope of the present invention, it can be seen that the polyester elastomer of the present invention has a particularly excellent impact resistance and surface energy by including a flange carboxylic acid component and a specific soft segment component. For example, when comparing Example 1 (dicarboxylic acid component of the hard segment component is furandicarboxylic acid) and Comparative Example 3 (dicarboxylic acid component of the hard segment component is terephthalic acid) having substantially the same soft segment amount (% by mass), the latter It can be seen that the impact strength and surface energy of the former are much higher than In addition, Example 1 (dicarboxylic acid component of the hard segment component is furandicarboxylic acid) and Comparative Example 4 (dicarboxylic acid component of the hard segment component is terephthalic acid / isophthalic acid) having substantially the same soft segment amount (% by mass) are compared. Then, although both have close melting | fusing point (heat resistance), also in this case, it turns out that the former impact strength and surface energy are higher than the latter.

  It can be seen that the surface energy γs is higher in the polyester elastomer containing the furandicarboxylic acid component because the polar term γsh of the surface energy is very high compared to the polyester elastomer not containing it.

  The polyester elastomer of the present invention is excellent in impact resistance and adhesion to other materials, and has great industrial utility value.

Claims (6)

  A polyester elastomer composed of 20 to 85% by mass of a hard segment component and 80 to 15% by mass of a soft segment component, wherein the hard segment component is composed of a dicarboxylic acid component and a glycol component, and all dicarboxylic acids constituting the hard segment component A polyester elastomer comprising 20% by mass or more of a furancarboxylic acid component when the acid component is 100% by mass.   The polyester elastomer according to claim 1, wherein 70 mass% or more of the glycol component constituting the hard segment component is 1,4-butanediol.   The soft segment component constituting the polyester elastomer is at least one selected from a polyalkylene ether component, an aliphatic polyester component, and a polyalkylene carbonate component. The polyester elastomer described.   The polyester elastomer according to claim 1, wherein the soft segment component constituting the polyester elastomer is polytetramethylene glycol.   The polyester elastomer according to claim 1, wherein the soft segment component constituting the polyester elastomer is poly-ε-caprolactone. The polyester elastomer according to claim 1, wherein the soft segment component constituting the polyester elastomer is polyhexamethylene carbonate diol.