JP2018204005A - Resin composition, film, multilayer film, stretched film, and packaging material - Google Patents

Abstract

To enhance gas barrier property of a resin composition containing a polyester resin (A) having a 2,5-furandicarboxylic acid unit and a 1,4-butanediol unit, as main structural units.SOLUTION: There is provided a resin composition containing a polyester resin (A) having a 2,5-furandicarboxylic acid unit and a 1,4-butanediol unit, as structural units, and having crystallization peak derived from the polyester resin (A) of 135°C or higher when measured by a differential scanning calorimeter (DSC).SELECTED DRAWING: None

Description

  The present application relates to a resin composition containing a polyester resin that can be produced from a biomass-derived raw material and its use.

  In recent years, polymers using biomass-derived 2,5-furandicarboxylic acid have attracted attention as environmentally friendly or environmentally sustainable materials. For example, as disclosed in Patent Document 1, a polyester resin having 2,5-furandicarboxylic acid units and aliphatic diol units as constituent units can be a film having excellent gas barrier properties. Moreover, as disclosed in Patent Document 2, polyester resins having a flange carboxylic acid unit having a specific viscosity and a specific terminal acid value exhibit excellent mechanical properties.

JP 2012-229395 A JP 2013-155388 A

  As disclosed in Patent Document 1, a resin composition comprising polybutylene-2,5-furandicarboxylate (PBF) having 2,5-furandicarboxylic acid units and 1,4-butanediol units as constituent units Has a problem that it is difficult to improve the gas barrier property as compared with a resin composition containing polyethylene-2,5-furandicarboxylate (PEF) having an ethylene glycol unit as a diol unit. This problem is difficult to solve even if the reduced viscosity or terminal acid value of the polyester is adjusted as disclosed in Patent Document 2.

The present application is one of the means for solving the above problems.
The polyester resin (A) contains a polyester resin (A) having 2,5-furandicarboxylic acid units and 1,4-butanediol units as constituent units, and measured by a differential scanning calorimeter (DSC). A resin composition having a crystallization peak derived from 135 ° C. or higher is disclosed.

  “When measured with a differential scanning calorimeter (DSC), the crystallization peak derived from the polyester resin (A) is 135 ° C. or higher” means that JIS K- is used using a differential scanning calorimeter (DSC). It means that a crystallization peak derived from the polyester resin (A) is confirmed at a temperature of 135 ° C. or higher when measured according to 7121. Specifically, the resin composition was charged into a DSC measurement pan, heated to 300 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere, held for 3 minutes, and then 0 ° C. at a temperature decreasing rate of 10 ° C./min. In the DSC curve obtained when the temperature is lowered to 1, the peak apex derived from the crystallization of the polyester resin (A) is present at a temperature of 135 ° C. or higher when the temperature is lowered.

  In the resin composition of the present disclosure, the total of 2,5-furandicarboxylic acid units and 1,4-butanediol units is preferably 50 mol% or more in all the structural units of the polyester resin (A).

  The resin composition of the present disclosure preferably further includes a thermoplastic resin that is compatible with the polyester resin (A) and has a crystallization temperature of 135 ° C. or higher.

  The resin composition of the present disclosure preferably further includes a polyester resin (B) having terephthalic acid units and 1,4-butanediol units as constituent units.

The present application is another means for solving the above-described problems.
A film comprising a resin composition comprising a polyester resin (A) having 2,5-furandicarboxylic acid units and 1,4-butanediol units as constituent units, the film being a differential scanning calorimeter (DSC) Disclosed is a film having a crystallization peak derived from the polyester resin (A) of 135 ° C. or higher when measured by

The present application is another means for solving the above-described problems.
A multilayer film having a layer made of a resin composition comprising a polyester resin (A) having 2,5-furandicarboxylic acid units and 1,4-butanediol units as constituent units, the multilayer film being a differential scanning type Disclosed is a multilayer film having a crystallization peak derived from the polyester resin (A) of 135 ° C. or higher when measured by a calorimeter (DSC).

  The film and the multilayer film may be a stretched stretched film. Moreover, the resin composition of this application is applicable as a packaging material containing this resin composition.

  The resin composition of the present disclosure includes a polyester resin (A) having 2,5-furandicarboxylic acid units and 1,4-butanediol units as constituent units, and is measured by a differential scanning calorimeter (DSC). In addition, the crystallization peak derived from the polyester resin (A) is 135 ° C. or higher. That is, the resin composition containing the polyester resin (A) is easily crystallized at a high temperature and exhibits high gas barrier properties. For example, in the case where a resin composition melted by a general method such as melt extrusion molding is formed into a film, even if the melted resin composition is rapidly cooled, the resin composition is appropriately crystallized to form a film. High gas barrier properties can be secured.

  The embodiment disclosed below is an example (representative example) of the embodiment of the present invention, and the present invention is not limited thereto. That is, the present invention can be implemented with any changes without departing from the scope of the invention.

1. Resin Composition The resin composition of the present disclosure includes a polyester resin (A) having 2,5-furandicarboxylic acid units and 1,4-butanediol units as constituent units, and is obtained by a differential scanning calorimeter (DSC). One characteristic is that the crystallization peak derived from the polyester resin (A) is 135 ° C. or higher when measured. By using such a resin composition, as described above, crystallization is facilitated and a film having high gas barrier properties can be provided. In order to facilitate crystallization, polyester resin (A) The crystallization peak derived from is preferably 140 ° C. or higher.

1.1. Polyester resin (A)
The polyester resin (A) has 2,5-furandicarboxylic acid units and 1,4-butanediol units as constituent units. The total of 2,5-furandicarboxylic acid units and 1,4-butanediol units in all the structural units constituting the polyester resin (A) is not particularly limited, but is usually 50 mol% or more, preferably Is 60 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more, and particularly preferably 90 mol% or more. Most preferably, the polyester resin (A) comprises only 2,5-furandicarboxylic acid units and 1,4-butanediol units. The polyester resin (A) has gas barrier properties and stretchability (when stretched).

1.1.1. Dicarboxylic acid unit The polyester resin (A) contains 2,5-furandicarboxylic acid units. Examples of monomers that can constitute the 2,5-furandicarboxylic acid unit include 2,5-furandicarboxylic acid and its derivatives. Examples of 2,5-furandicarboxylic acid derivatives include alkyl esters having 1 to 4 carbon atoms. Among them, methyl esters, ethyl esters, n-propyl esters, isopropyl esters, butyl esters and the like are preferable, and methyl esters are more preferable.

  The ratio of the 2,5-furandicarboxylic acid unit in all the dicarboxylic acid units constituting the polyester resin (A) is not particularly limited, but is usually 50 mol% or more, preferably 60 mol% or more, more preferably 70. It is at least mol%, more preferably at least 80 mol%, particularly preferably at least 90 mol%. Most preferably, all the dicarboxylic acid units constituting the polyester resin (A) are 2,5-furandicarboxylic acid units. By setting the ratio of the 2,5-furandicarboxylic acid unit to be equal to or higher than the lower limit, the crystallinity of the polyester resin (A) is maintained, and high gas barrier properties and heat resistance tend to be obtained.

  In the polyester resin (A), dicarboxylic acid units other than 2,5-furandicarboxylic acid units may be copolymerized within a range in which the above-described problems can be solved. The dicarboxylic acid unit other than the 2,5-furandicarboxylic acid unit is preferably 10 mol% or less, more preferably 5 mol% or less of the total dicarboxylic acid unit. Moreover, Preferably it is 0.1 mol% or more. By being in these ranges, the melting point can be slightly lowered without impairing the crystallinity. Thereby, the polymerization temperature and the processing temperature can be set low, and it tends to be possible to suppress the decomposition reaction and the molecular weight decrease during melting. Examples of copolymerizable dicarboxylic acids include aromatic dicarboxylic acids, aliphatic (including alicyclic) dicarboxylic acids, and derivatives obtained by esterifying these.

1.1.2. Diol Unit The polyester resin (A) contains 1,4-butanediol unit. Examples of the monomer that can constitute the 1,4-butanediol unit include 1,4-butanediol and derivatives thereof. Examples of the derivatives include alkyl esters having 1 to 4 carbon atoms. Among them, methyl esters, ethyl esters, n-propyl esters, isopropyl esters, butyl esters and the like are preferable, and methyl esters are more preferable.

  The proportion of 1,4-butanediol units in all diol units constituting the polyester resin (A) is not particularly limited, but is usually 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol%. Above, more preferably 80 mol% or more, particularly preferably 90 mol% or more. Most preferably, all diol units constituting the polyester resin (A) are 1,4-butanediol units.

  In the polyester resin (A), diol units other than 1,4-butanediol units may be copolymerized as long as the above-described problems can be solved. In that case, it is 10 mol% or less in all the diol units of the polyester resin (A), preferably 5 mol% or less. Examples of the copolymerizable diol include aliphatic dihydroxy compounds other than 1,4-butanediol, aromatic dihydroxy compounds, bisphenol, and derivatives thereof.

1.1.3. Other copolymerized units The polyester resin (A) may contain other copolymerized units in addition to the above-described units within a range in which the above-described problems can be solved. In that case, it is 10 mol% or less in all the structural units of the polyester resin (A), preferably 5 mol% or less. By setting it to the upper limit value or less, the crystallinity of the polyester resin (A) is maintained and heat resistance tends to be obtained. Examples of the monomer that can constitute a small amount of copolymerized units include hydroxycarboxylic acid, diamine, and derivatives thereof.

  In the polyester resin (A), a unit containing a trifunctional or higher functional group may be introduced as another copolymer unit other than the above-described copolymer unit within a range in which the above-described problems can be solved. As a monomer that can constitute a unit having a trifunctional or higher functional group, a trifunctional or higher polyhydric alcohol; a trifunctional or higher polyvalent carboxylic acid or its anhydride, acid chloride, or ester; and trifunctional Examples thereof include at least one trifunctional or higher polyfunctional compound selected from the group consisting of the above hydroxycarboxylic acids or anhydrides, acid chlorides or esters thereof; trifunctional or higher amines. Specific examples include glycerin, trimethylolpropane, pentaerythritol; malic acid, tartaric acid or citric acid.

  In the production of the polyester resin (A), a chain extender such as diisocyanate, diphenyl carbonate, dioxazoline, or silicate ester may be used. In particular, when carbonate compounds such as diphenyl carbonate are used, these carbonate compounds are added in an amount of not more than 20 mol%, preferably not more than 10 mol%, based on all components of the polyester resin (A) to obtain a polyester carbonate. May be.

  In the polyester resin (A), the polyester terminal group may be sealed with carbodiimide, an epoxy compound, a monofunctional alcohol or carboxylic acid.

1.1.4. Physical Properties of Polyester Resin (A) The resin composition of the present disclosure has a crystallization peak derived from the polyester resin (A) of 135 ° C. or higher when measured with a differential scanning calorimeter (DSC). The crystallization temperature (T _C ) of the polyester resin (A) required by the above can be 135 ° C. or higher. That is, the polyester resin (A) is easily crystallized at a high temperature and exhibits high gas barrier properties. For example, when a resin composition melted by a general method such as melt extrusion molding is formed into a film, the polyester resin (A) is appropriately crystallized even if the melted resin composition is rapidly cooled, A high gas barrier property can be secured for the film. A specific method for setting the crystallization temperature (T _C ) of the polyester resin (A) to 135 ° C. or higher will be described later. In addition, in order to improve gas barrier property more, it is preferable that the crystallization temperature (Tc) of a polyester resin (A) is 140 degreeC or more.
The "crystallization temperature _{(T C)"} refers to the crystallization temperature as measured according to JIS K-7121 using a differential scanning calorimeter (DSC). Specifically, the resin composition was charged into a DSC measurement pan, heated to 300 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere, held for 3 minutes, and then 0 ° C. at a temperature decreasing rate of 10 ° C./min. In the DSC curve obtained when the temperature is lowered to the temperature, the temperature at the peak apex derived from the crystallization of the resin confirmed at the time of temperature reduction.

The polyester resin (A) preferably has a reduced viscosity (ηred = ηsp / c; ηsp is a specific viscosity and c is a polymer concentration) of 0.8 dl / g or more. Thereby, the softness | flexibility requested | required of a soft packaging material, for example is securable.
The “reduced viscosity” is determined from the solution viscosity measured at 30 ° C. in a phenol / tetrachloroethane (1: 1 weight ratio) at a polyester resin concentration of 0.5 g / dl.

The polyester resin (A) preferably has a terminal acid value of 100 μeq / g or less. Thereby, for example, high thermal stability can be ensured.
The “terminal acid value” is measured by neutralization titration. Specifically, after pulverizing the sample, the sample was dried at 140 ° C. for 15 minutes in a hot air dryer, cooled to room temperature in a desiccator, 0.1 g was accurately weighed and collected in a test tube, and benzyl alcohol was collected. Add 3 ml and dissolve in 195 ° C. for 3 minutes while blowing dry nitrogen gas, then slowly add 5 ml of chloroform and cool to room temperature. Add 1 to 2 drops of phenol red indicator to this solution, and titrate with a 0.1N sodium hydroxide benzyl alcohol solution with stirring while blowing dry nitrogen gas, and finish when the color changes from yellow to red. Further, as a blank, the same operation is performed without dissolving the sample, and the terminal acid value is calculated by the following formula (I).
Terminal acid value (μeq / g) = (ab) × 0.1 × f / w (I)
(Where a is the amount of 0.1N sodium hydroxide in benzyl alcohol solution required for titration of the sample (μl), b is 0.1N sodium hydroxide benzyl alcohol required for titration with a blank) The amount of solution (μl), w is the amount of polyester resin sample (g), and f is the titer of 0.1N sodium hydroxide in benzyl alcohol.)

In the above formula (I), the titer (f) of a benzyl alcohol solution of 0.1N sodium hydroxide is determined by the following method. That is, 5 ml of methanol was collected in a test tube, and 1-2 drops of phenol red ethanol solution was added as an indicator. Titrate with 0.4 ml of 1N sodium hydroxide in benzyl alcohol to the color change point, then add 0.2 ml of 0.1N aqueous hydrochloric acid solution with known titer as a standard solution, and add 0.1N hydroxide again. Titrate to the discoloration point with sodium benzyl alcohol solution (the above operation is performed under dry nitrogen gas blowing). The titer (f) is calculated by the following formula (II).
Titer (f) = Titer of 0.1N aqueous hydrochloric acid × Amount of collected 0.1N aqueous hydrochloric acid (μl) / Titration of 0.1N sodium hydroxide in benzyl alcohol (μl) (II)

1.1.5. Manufacturing method of polyester resin (A) As a manufacturing method of a polyester resin (A), the manufacturing method of a general polyester resin is employable. For example, the description in Japanese Patent No. 5233390 can be exemplified.

1.2. Components other than the polyester resin (A) The resin composition of the present disclosure includes at least the polyester resin (A), and may optionally include other resins, additives, and the like.

1.2.1. Polyester resin (B)
According to the new knowledge of the present inventors, as described later, for example, in a resin composition containing a polyester resin (A), a polyester resin (B) having a crystallization temperature (T _C ) of 135 ° C. or higher is used. By further including, when measured with a differential scanning calorimeter (DSC), the resin composition can have a crystallization peak derived from the polyester resin (A) of 135 ° C. or higher. In this case, although the mechanism will be described later, the crystallization temperature (T _C ) of the polyester resin (A) can be set to 135 ° C. or higher, and the crystallization of the polyester resin (A), which is difficult to crystallize by itself. And the gas barrier property can be improved. Here, a polyester resin (B) having a crystallization temperature of 135 ° C. or higher will be described as a preferred form. However, as described above, the polyester resin (A) is included, and a differential scanning calorimeter (DSC) is used. As long as the crystallization peak derived from the polyester resin (A) can be 135 ° C. or higher when measured, a compound different from the polyester resin (B) is used instead of the polyester resin (B). Also good.

  As long as the polyester resin (B) has a crystallization temperature of 135 ° C. or higher, there is no particular limitation on the dicarboxylic acid unit. For example, aromatic dicarboxylic acid units such as terephthalic acid units and naphthalene-2,6-dicarboxylic acid units. Especially, it is preferable that a polyester resin (B) contains a terephthalic acid unit as a dicarboxylic acid unit. Examples of the monomer that can constitute the terephthalic acid unit include terephthalic acid and its derivatives. Examples of the derivatives include alkyl esters having 1 to 4 carbon atoms. Among them, methyl esters, ethyl esters, n-propyl esters, isopropyl esters, butyl esters and the like are preferable, and methyl esters are more preferable.

  When a terephthalic acid unit is adopted as the dicarboxylic acid unit, the ratio of the terephthalic acid unit in all the dicarboxylic acid units constituting the polyester resin (B) is not particularly limited, but is usually 50 mol% or more, preferably 60 mol. % Or more, more preferably 70 mol% or more, still more preferably 80 mol% or more, particularly preferably 90 mol% or more. Most preferably, all the dicarboxylic acid units constituting the polyester resin (B) are terephthalic acid units.

  In the polyester resin (B), dicarboxylic acid units other than those described above may be copolymerized as long as the above-described problems can be solved.

  As long as the polyester resin (B) has a crystallization temperature of 135 ° C. or higher, the diol unit is not particularly limited. For example, an aliphatic diol unit. Especially, it is preferable that a polyester resin (B) contains a 1, 4- butanediol unit as a diol unit. Examples of the monomer that can constitute the 1,4-butanediol unit include 1,4-butanediol and derivatives thereof. Examples of the derivatives include alkyl esters having 1 to 4 carbon atoms. Among them, methyl esters, ethyl esters, n-propyl esters, isopropyl esters, butyl esters and the like are preferable, and methyl esters are more preferable.

  When 1,4-butanediol unit is employed as the diol unit, the proportion of 1,4-butanediol unit in all diol units constituting the polyester resin (B) is not particularly limited, but is usually 50 mol%. Above, preferably 60 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more, and particularly preferably 90 mol% or more. Most preferably, all diol units constituting the polyester resin (B) are 1,4-butanediol units.

  In the polyester resin (B), diol units other than those described above may be copolymerized as long as the above-described problems can be solved.

  When employing a terephthalic acid unit as the dicarboxylic acid unit and a 1,4-butanediol unit as the diol unit, the total of the terephthalic acid unit and the 1,4-butanediol unit among all the structural units constituting the polyester resin (B) Although there is no particular limitation, it is usually 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more, and particularly preferably 90 mol% or more.

  Similarly to the polyester resin (A), the polyester resin (B) may contain a small amount of copolymer units other than those described above. Examples of the copolymerizable dicarboxylic acid include aromatic dicarboxylic acid compounds, aliphatic (including alicyclic) dicarboxylic acids, derivatives obtained by esterifying these, and the like. -Aliphatic dihydroxy compounds other than butanediol, aromatic dihydroxy compounds, bisphenols, derivatives thereof and the like. In addition, examples of monomers that can constitute a small amount of copolymerized units include hydroxycarboxylic acids, diamines, derivatives thereof, and polytetramethylene glycol units. Moreover, you may introduce | transduce the unit containing a functional group more than trifunctional as other copolymerization units other than the above-mentioned copolymerization unit. Furthermore, in the production of the polyester resin (B), a chain extender or a terminal blocking agent may be used in the same manner as in the production method of the polyester resin (A).

As described above, the polyester resin (B) has a crystallization temperature (T _C ) of 135 ° C. or higher. Preferably it is 140 degreeC or more, More preferably, it is 150 degreeC or more, More preferably, it is 160 degreeC or more, Most preferably, it is 170 degreeC or more, Most preferably, it is 180 degreeC or more. From the presumed mechanism described later, the higher the crystallization temperature of the polyester resin (B), the easier it is to produce crystal nuclei at a high temperature when the resin composition is cooled from the molten state, and the polyester resin (A) is easily formed at 135 ° C. or higher. It is thought that it can be crystallized. On the other hand, if the crystallization temperature is too high, melt mixing with the polyester resin (A) may be difficult, so the crystallization temperature (T _c ) of the polyester resin (B) is preferably 250 ° C. or less, More preferably, it is 240 degrees C or less, Most preferably, it is 230 degrees C or less.

The polyester resin (B) preferably has an intrinsic viscosity in the range of 0.6 to 2.0 (dl / g). Thereby, the softness | flexibility as a soft packaging material can be provided, and the film forming property at the time of extrusion molding becomes favorable.
The “intrinsic viscosity” is measured at a temperature of 30 ° C. using a mixed solvent of 1,1,2,2-tetrachloroethane / phenol = 1/1 (weight ratio).

  The terminal acid value of the polyester resin (B) is preferably 60 μeq / g or less. Thereby, high thermal stability is securable.

  The manufacturing method of a polyester resin (B) can employ | adopt the manufacturing method of a general polyester resin. For example, JP 2004-137455 A can be referred to. Alternatively, a commercially available PBT resin can be used. For example, NOVADURAN 5020 (homopolybutylene terephthalate resin, intrinsic viscosity 1.20 dl / g) manufactured by Mitsubishi Engineering Plastics Co., Ltd., Juranex 500FP (homopolybutylene terephthalate resin, intrinsic viscosity 0.875 dl / g g) and the like. Examples of commercially available polybutylene terephthalate copolymers include NOVADURAN 5505S (inherent viscosity 1.15 dl / g) manufactured by Mitsubishi Engineering Plastics.

  When the polyester resin (B) is included together with the polyester resin (A) in the resin composition of the present disclosure, the crystallization temperature of the polyester resin (A) is considered to be 135 ° C. or higher by the following estimation mechanism. .

  That is, when the molten resin composition is cooled, the crystal of the polyester resin (B) is precipitated at a high temperature of 135 ° C. or more, and the crystallization of the polyester resin (A) is promoted using the crystal of the polyester resin (B) as a nucleus. It is considered to be done. Here, since the polyester resin (B) has an appropriate compatibility with the polyester resin (A), the polyester resin (A) and the polyester resin (B) are uniformly in the molten state in the resin composition. It will mix, and precipitation of the crystal | crystallization of the polyester resin (B) in the whole resin composition and promotion of crystallization of the polyester resin (A) will be aimed at. As a result, it is considered that the polyester resin (A) can be rapidly crystallized. Thus, the polyester resin (B) is considered to function as a crystal nucleating agent for the polyester resin (A).

  In addition, according to the new knowledge of the present inventors, the polyester resin (A) can be obtained only by adding a conventionally known crystal nucleating agent such as talc or wax to the resin composition containing the polyester resin (A). The crystallization temperature cannot be 135 ° C. or higher. As described above, in order to set the crystallization temperature of the polyester resin (A) to 135 ° C. or higher, (1) crystal nuclei are generated at a high temperature of 135 ° C. or higher in the resin composition containing the polyester resin (A). It is considered effective to mix components satisfying the two requirements of (2) having an appropriate compatibility with the polyester resin (A). In particular, by including the polyester resin (B), not only the crystallization of the polyester resin (A) is promoted, but also various functions such as mechanical properties and heat resistance can be imparted to the resin composition.

1.2.2. Components other than the polyester resin (B) The components satisfying the above two requirements are not limited to the polyester resin (B). In place of the polyester resin (B), the crystallization temperature of the polyester resin (A) is 135 ° C. or higher even when a thermoplastic resin (for example, polyamide) other than the polyester resin that satisfies the above two requirements is included. It is thought that it can be. Thus, it is thought that a new function can be provided to the resin composition while further increasing the crystallization temperature of the polyester resin (A) by including various thermoplastic resins.

  In addition, in the resin composition of the present disclosure, in addition to the polyester resin (A) described above, various additives such as a heat stabilizer, an antioxidant, a hydrolysis inhibitor, a crystal, as long as the characteristics are not impaired. Nucleating agents, crystallization retarders, flame retardants, antistatic agents, mold release agents, lubricants, ultraviolet absorbers, coloring agents such as dyes and pigments, and the like may be added. Moreover, you may mix | blend thermoplastic resins other than the above.

1.3. Composition The content of the polyester resin (A) in the resin composition of the present disclosure is not particularly limited as long as the above-described problems can be solved. For example, the polyester resin (A) in the resin composition can be contained in an amount of 50% by mass or more and 99.9% by mass or less. When the content of the polyester resin (A) is increased, higher gas barrier properties can be secured.
As content of a polyester resin (A), More preferably, they are 60 mass% or more and 98 mass% or less, More preferably, they are 65 mass% or more and 95 mass% or less.

  When the polyester resin (B) is included in the resin composition of the present disclosure, the content thereof is not particularly limited as long as the above-described problems can be solved. For example, in the resin composition, the polyester resin (B) can be contained in an amount of 0.1% by mass to 50% by mass. The lower limit is more preferably 5% by mass or more, and the upper limit is more preferably 40% by mass or less. When the content of the polyester resin (B) is increased, higher mechanical properties and heat resistance can be secured.

When the polyester resin (B) is included in the resin composition of the present disclosure, the mass ratio between the polyester resin (A) and the polyester resin (B) is not particularly limited as long as the above-described problems can be solved. For example, it is preferable to contain 0.1% by mass or more of the polyester resin (B) based on the total mass of the polyester resin (A) and the polyester resin (B) (100% by mass), It is preferable to contain 50% by weight or less. By setting it as the said range, the balance of gas-barrier property, a softness | flexibility, and a fragrance | flavor property will become a better thing.
Moreover, as for the said mass ratio, it is more preferable to contain 2 mass% or more and 40 mass% or less of the said polyester resin (B), and it is more preferable to contain 5 mass% or more and 35 mass% or less.

  When various additives and other thermoplastic resins are included in the resin composition of the present disclosure, the content thereof is not particularly limited as long as the above-described problems can be solved. What is necessary is just to determine content suitably according to the target performance.

2. Manufacturing method of resin composition The resin composition of this indication can be easily manufactured by melt-kneading each above-mentioned component. According to the knowledge of the present inventors, even when the polyester resin (A) and the polyester resin (B) are melted and directly laminated by coextrusion or the like, the polyester resin (A) is used. A crystal in which the polyester resin (A) and the polyester resin (B) are mixed at least at the interface between the layer and the layer made of the polyester resin (B), includes the polyester resin (A), and is derived from the polyester resin (A) A layer composed of a resin composition having a conversion peak of 135 ° C. or higher is obtained. That is, the resin composition referred to in the present application includes a mixed layer formed when the molten resin is directly laminated by coextrusion or the like.

3. Use of Resin Composition The resin composition of the present disclosure can be applied to various uses after being molded. For example, a film made of the resin composition, a multilayer film having a layer made of the resin composition, a packaging material containing the resin composition, and the like.

3.1. Film The resin composition of the present disclosure can be made into a film by a general molding method such as melt extrusion molding or hot pressing. The film may or may not be stretched. In the case of a stretched film, the stretched film can be obtained by uniaxially or biaxially stretching according to a known method. Biaxial stretching may be simultaneous biaxial stretching or sequential biaxial stretching. As described above, since the polyester resin (A) contributes to stretchability in addition to gas barrier properties, the film can be easily stretched. What is necessary is just to determine the thickness etc. of a film suitably according to a use. Further, the film may be a single-layer film composed solely of the resin composition of the present disclosure, or may be a multilayer film having one or more other layers by a general molding method such as coextrusion or dry lamination.
3.2 Single layer film For example, in the case of melt extrusion, a single layer film has a simple flow path and has an advantage that it can be produced at low cost. The single layer film may be stretched or unstretched. In the case of a stretched film, the stretched film can be obtained by uniaxially or biaxially stretching according to a known method. Biaxial stretching may be simultaneous biaxial stretching or sequential biaxial stretching. What is necessary is just to determine the thickness etc. of a single layer film suitably according to a use. Since the manufacturing method of a single layer film is well-known to those skilled in the art, the detailed description beyond this is abbreviate | omitted here.

3.3. Multilayer film The multilayer film may be stretched or unstretched in the same manner as the single layer film. In the case of a stretched film, the stretched film can be obtained by uniaxially or biaxially stretching according to a known method. Biaxial stretching may be simultaneous biaxial stretching or sequential biaxial stretching. As described above, since the polyester resin (A) contributes to stretchability in addition to gas barrier properties, the multilayer film can be easily stretched. What is necessary is just to determine the thickness etc. of a multilayer film suitably according to a use. In addition, as above-mentioned, the layer which satisfy | fills the resin composition of this indication as a result by laminating | stacking polyester resin (A) and other resin (polyester resin (B) etc.) directly by coextrusion etc. It may be formed. In addition, it is preferable to form a multilayer film by coextrusion from a viewpoint of forming the mixed layer which consists of the resin composition of this invention. Of course, the resin composition of the present disclosure and other resins or resin compositions may be laminated directly or indirectly to form a multilayer film. Since the manufacturing method of a multilayer film is well-known to those skilled in the art, the detailed description beyond this is abbreviate | omitted here.

  When used for film applications, the slipperiness of the film can be improved by adding various inorganic or organic inert fine particles as necessary, and the productivity is improved. Examples of inert fine particles include aluminum oxide, silicon oxide, titanium oxide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, calcium phosphate, lithium phosphate, magnesium phosphate, fluoride Examples thereof include lithium, zeolite, celite, kaolin, talc, carbon black, and crosslinked polymer fine particles described in JP-B-59-5216. These fine particles can be used alone or in combination of two or more as required.

The average particle diameter of the inert fine particles is preferably 0.5 μm or more and 4.0 μm or less, and more preferably 0.8 μm or more and 3.0 μm. Here, the average particle diameter of the inert fine particles is a value of the average particle diameter when the cumulative weight fraction is 50% as measured using a Coulter counter (manufactured by Nippon Chemical Machinery Co., Ltd.).
Further, the addition amount of the fine particles is preferably 0.005% by weight or more and 0.5% by weight or less, and more preferably 0.01% by weight or more and 0.1% by weight or less as the content in the film.
If the average particle size of the fine particles is too small or the addition amount is too small, the effect of improving the handleability and productivity by adding the fine particles may not be sufficiently obtained. If it exceeds 4.0 μm or the amount added exceeds 0.5% by weight, the flatness and / or transparency of the film may be impaired.

  In addition, when such inert fine particles are blended in the film, it is a layered structure of three or more layers, both surface layers or only one surface layer contains inert fine particles, and the intermediate layer does not contain inert fine particles. Is preferable in terms of both transparency and handleability.

3.4. Packaging Material The resin composition of the present disclosure exhibits high gas barrier properties and is therefore suitable as a material constituting the packaging material. For example, it can be applied to packaging materials such as vegetables, fruits, fish, meat, prepared foods, retort foods, sweets, seasonings, detergents, and shampoos. Alternatively, it is also suitable for treatment bags for medical waste such as industrial waste and filth with strong odor.

  EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.

1. Raw material 1.1. Polyester resin (A)
In a reaction vessel equipped with a stirrer, a nitrogen inlet, a heating device, a thermometer, and a pressure reducing port, as raw materials, 56.07 parts by weight of dimethyl 2,5-furandicarboxylate, 42.51 parts by weight of 1,4-butanediol , And 1.42 parts by weight of a 1,4-butanediol solution in which tetraisopropyl orthotitanate was dissolved in advance by 2% by weight.
Nitrogen gas was introduced into the container while stirring the contents of the container, and the inside of the system was changed to a nitrogen atmosphere by vacuum replacement. Next, the reaction vessel was immersed in an oil bath at 160 ° C. and reacted for 3 hours while stirring the system. Next, the temperature was raised to 240 ° C. over 2 hours, and then the pressure was gradually reduced to 180 Pa or less over 1 hour 30 minutes 30 minutes after the start of temperature raising. Furthermore, after continuing superposition | polymerization for 1 hour, keeping a heating pressure reduction state at this temperature, superposition | polymerization was complete | finished and the polyester resin (A) (polybutylene-2,5-furandicarboxylate) was obtained. The polyester resin (A) obtained had a reduced viscosity of 1.3 dl / g and a terminal acid value of 86 μeq / g.

1.2. Polyester resin (B1)
A homopolyester resin of terephthalic acid and 1,4-butanediol (NOVADURAN 5008 manufactured by Mitsubishi Engineering Plastics) was used.

1.3. Polyester resin (B2)
A copolymerized polyester resin of terephthalic acid, 1,4-butanediol, and polytetramethylene glycol (PTMG) (NOVADURAN 5505S manufactured by Mitsubishi Engineering Plastics) was used.

1.4. Crystal Nucleating Agent Talc (PKP-53S manufactured by Fuji Talc Kogyo Co., Ltd.) and polyethylene wax (ACumist A6 manufactured by Honeywell) were used as the crystal nucleating agent.

2. Evaluation method 2.1. Crystallization temperature 2.1.1 DSC measurement of resin composition The crystallization temperature of each resin was measured according to JIS K-7121 using DSC-6220 manufactured by SII. That is, each sample was placed in a DSC measuring pan, heated to 300 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere, held for 3 minutes, and then cooled to 0 ° C. at a temperature decreasing rate of 10 ° C./min. And measured. The temperature at the top of the crystallization peak in the DSC curve during the temperature decrease was the crystallization temperature (T _C).
2.1.2 DSC measurement of film The DSC of the film was measured in the same manner as in 2.1.1, and the temperature at the top of the crystallization peak in the DSC curve when the temperature was lowered was defined as the crystallization temperature (Tc). In addition, about the laminated film, DSC of the whole laminated film was measured.

2.2. Gas barrier properties (oxygen permeability)
Based on JIS K7126-2, it carried out on the following conditions.
Apparatus: OX-TRAN 2/21 (manufactured by MOCON)
Temperature: 23 ° C
Humidity: 90% RH
Transmission area: 50 cm ²
The smaller the oxygen permeability, the better the gas barrier property. In addition, since oxygen permeability is in inverse proportion to film thickness, the numerical value converted into 20 μm thickness conventionally used is described below.

3. Production and Evaluation of Resin Composition [Examples 1 and 2]
The dried polyester resin (A) and the polyester resin (B1) are melt-kneaded with a composition shown in Table 1 below in a lab plast mill (Toyo Seiki Co., Ltd., Roller Mixer R60) to obtain a resin composition. Obtained. The kneading temperature was 240 ° C. and the kneading time was 3 minutes. Table 1 below shows the crystallization temperature (T _C ) of the polyester resin (A) or the polyester resin (B) contained in the obtained resin composition.

[Comparative Examples 1-4]
Using only the polyester resin (A) (Comparative Example 1), using only the polyester resin (B1) (Comparative Example 2), or the composition shown in Table 1 below instead of the polyester resin (B1) A resin composition was obtained in the same manner as in Example 1 except that talc and polyethylene wax were kneaded (Comparative Examples 3 to 5). Table 1 below shows the crystallization temperature (T _C ) of the polyester resin (A) or the polyester resin (B) contained in the obtained resin composition.

In Table 1, in Example 1 and Comparative Examples 2 to 5, only one crystallization peak was confirmed.
On the other hand, in Example 2, a crystallization peak having a peak at 145 ° C. and a crystallization peak having a peak at 189 ° C. were confirmed. 145 ° C. is the crystallization temperature derived from the polyester resin (A), and 189 ° C. is the crystallization temperature derived from the polyester resin (B).

4). Production and Evaluation of Film [Example 3]
T-die film forming machine (manufactured by Tokyu Seimitsu Kogyo Co., Ltd.) with dried polyester resin (A) and polyester resin (B2), with extruder diameters of φ20mm and φ30mm, and one T-die installed at both extruder tips. The film was formed using a take-up roll, the polyester resin (A) and the polyester resin (B2) were directly laminated, and the polyester resin (A) and the polyester resin (B2) were melt-mixed at least at the interface. An unstretched multilayer film having a layer was obtained. The resin is dried in a hot air dryer at 100 ° C. for 8 hours. The polyester resin (A) is put into a φ20 mm side and the polyester resin (B2) is put into a φ30 mm side hopper, and the resin temperature is 245 ° C. did. The film take-up speed was adjusted to 6.3 m / min, the roll temperature was adjusted to 20 ° C., and the total film thickness was adjusted to 90 μm. Moreover, the rotation speed of each extruder was adjusted so that the layer thickness ratio of polyester resin (A) and polyester resin (B1) might be set to 1: 1.
A length of 100 mm and a width of 100 mm are cut out from the obtained film and stretched by performing simultaneous biaxial stretching at a strain rate of 10 mm / min and a stretching ratio of 3.0 times with a batch-type biaxial stretching apparatus (manufactured by Island Kogyo Co., Ltd.) A multilayer film was obtained. The stretching temperature was 170 ° C.
The obtained stretched film was cut out and subjected to crystallization temperature measurement and oxygen permeability measurement. Various evaluation results are shown in Table 2.

[Comparative Example 6]
An unstretched monolayer film made of the polyester resin (A) was obtained in the same manner as in Example 1 except that the dried polyester resin (A) was charged into the hoppers of two extruders. The film thickness was adjusted to 100 μm.
A length of 100 mm and a width of 100 mm are cut out from the obtained film and stretched by performing simultaneous biaxial stretching at a strain rate of 10 mm / min and a stretching ratio of 3.0 times with a batch-type biaxial stretching apparatus (manufactured by Island Kogyo Co., Ltd.) A multilayer film was obtained. The stretching temperature was 50 ° C. Subsequent sample acquisition and various evaluations were performed in the same manner as in Example 3. The results are shown in Table 2.

[Comparative Example 7]
An unstretched monolayer film made of the polyester resin (B2) was obtained in the same manner as in Example 1 except that the dried polyester resin (B2) was charged into the hoppers of two extruders. The film thickness was adjusted to 80 μm. The film was not stretched, and the subsequent sample acquisition and various evaluations were performed in the same manner as in Example 3. The results are shown in Table 2.

In Table 2, in Example 3, a crystallization peak having an apex of 144 ° C. and a crystallization peak having an apex of 186 ° C. were confirmed. 144 ° C. is the crystallization temperature derived from the polyester resin (A), and 186 ° C. is the crystallization temperature derived from the polyester resin (B).
In Comparative Example 6, a crystallization peak was confirmed at 120 ° C. This is presumably due to the decrease in the molecular weight of the resin due to thermal decomposition during melt extrusion.
In Comparative Example 7, a crystallization peak derived from the polyester resin (B) was confirmed at 185 ° C.

[Example 4]
The dried polyester resin (A) and the polyester resin (B1) were melt-kneaded with the composition described in Example 1 using a Laboplast mill (manufactured by Toyo Seiki Co., Ltd., roller mixer R60) to obtain a resin composition. The kneading temperature was 240 ° C. and the kneading time was 3 minutes. Next, the obtained resin was hot pressed (IMC-180C, manufactured by Imoto Seisakusho Co., Ltd.) to obtain a 200 μm sheet. The hot press temperature was 240 ° C. and the time was 2 minutes. Further, a biaxially stretched film was obtained by stretching by the method described in Comparative Example 6. The resulting film had a Tc of 143 ° C. The obtained stretched film exhibits high oxygen barrier properties.

5. Discussion As shown in Tables 1 and 2, the polyester resin (A) having 2,5-furandicarboxylic acid units and 1,4-butanediol units as constituent units is amorphous without having the crystallization temperature described above. It can be seen that it is cooled as it is (Comparative Example 1), or even if it has a crystallization temperature, the temperature is very low (Comparative Example 6). In such a case, sufficient gas barrier properties cannot be ensured.
Further, as shown in Table 1, in the resin composition containing the polyester resin (A), even when a conventionally known crystal nucleating agent (talc or wax) is added (Comparative Examples 3 to 5), the resin composition is 135 ° C. It can be seen that there is no crystallization peak in the above range.
On the other hand, as shown in Table 1, when the polyester resin (B1) is mixed in the resin composition containing the polyester resin (A) (Examples 1 and 2), the resin composition has a crystallization peak in the range of 135 ° C. or higher. It can be seen that the polyester resin (A) can be crystallized at a high temperature of 135 ° C. or higher.
Moreover, as shown in Table 2, the polyester resin (A) and the polyester resin (A) are compared with the case of the polyester resin (A) alone (Comparative Example 6) and the case of the polyester resin (B2) alone (Comparative Example 7). In the case where both (B2) are used (Example 3), the resin (A) and the resin (B2) act synergistically, the crystallization temperature of the resin (A) is increased, and the gas barrier properties are dramatically increased. It can be seen that it increases.

  As described above, the resin composition contains a polyester resin (A) having 2,5-furandicarboxylic acid units and 1,4-butanediol units as constituent units, and the resin composition is in the range of 135 ° C. or higher. When it has a crystallization peak, it turned out that the gas barrier property of the film containing a resin composition and a resin composition improves significantly.

  A film made of the resin composition of the present disclosure and a multilayer film containing the resin composition have high gas barrier properties and are suitable for packaging applications. Examples include packaging applications such as vegetables, fruits, fish, meat, side dishes, retort foods, sweets, seasonings, detergents, and shampoos.

Claims (8)

The polyester resin (A) contains a polyester resin (A) having 2,5-furandicarboxylic acid units and 1,4-butanediol units as constituent units, and measured by a differential scanning calorimeter (DSC). A resin composition having a crystallization peak derived from 135 ° C. or higher. The resin composition of Claim 1 whose sum total of a 2, 5- furandicarboxylic acid unit and a 1, 4- butanediol unit is 50 mol% or more in all the structural units of the said polyester resin (A). The resin composition according to claim 1 or 2, further comprising a thermoplastic resin that is compatible with the polyester resin (A) and has a crystallization temperature of 135 ° C or higher. The resin composition according to claim 1 or 2, further comprising a polyester resin (B) having a terephthalic acid unit and a 1,4-butanediol unit as constituent units. A film comprising a resin composition comprising a polyester resin (A) having 2,5-furandicarboxylic acid units and 1,4-butanediol units as constituent units, the film being a differential scanning calorimeter (DSC) The film whose crystallization peak derived from a polyester resin (A) is 135 degreeC or more when measured by (1). A multilayer film having a layer made of a resin composition comprising a polyester resin (A) having 2,5-furandicarboxylic acid units and 1,4-butanediol units as constituent units, the multilayer film being a differential scanning type The multilayer film whose crystallization peak derived from a polyester resin (A) is 135 degreeC or more when measured with a calorimeter (DSC). The stretched film which extended | stretched the film of any one of Claim 5 or 6. The packaging material containing the resin composition of any one of Claims 1-4.