JP2019167460A - Resin composition - Google Patents

Abstract

To provide a resin composition that has both excellent cutting properties and transparency.SOLUTION: The resin composition has a polyester (A) including a constitutional unit derived from 2,2,4,4-tetramethyl-1,3-cyclobutanediol dispersed in polyethylene terephthalate (B) in which the content of the polyester (A) is more than 0.1 mass% to less than 30 mass% based on the mass of the resin composition and the polyester (A) dispersed in polyethylene terephthalate (B) has an average particle size of 50 to 800 nm in terms of circle-equivalent particle size as obtained from a cross-sectional photograph by a scanning type electron microscope.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition in which polyester is dispersed in polyethylene terephthalate, a method for producing the same, a film composed of the resin composition, a laminate comprising one or more layers comprising the resin composition, and the resin. The present invention relates to a container comprising the composition or the laminate.

  Conventionally, resin compositions containing polyethylene terephthalate (PET) have been widely used in transparent containers and the like for packaging food (Japanese Patent Laid-Open No. 10-120802).

Japanese Patent Laid-Open No. 10-120802

  The resin composition used for such a transparent container or the like is required to have cutability and transparency that can suppress generation of defects and the like during cutting. However, according to the study of the present inventor, it has been found that a conventional resin composition containing PET may not satisfy both the cutting property and the transparency.

  Accordingly, an object of the present invention includes one or more resin compositions capable of achieving both excellent cutability and transparency, a method for producing the same, a film composed of the resin composition, and a layer comprising the resin composition. It is providing the container which consists of a laminated body, this resin composition, or this laminated body.

As a result of intensive studies to solve the above problems, the present inventor has found that in the resin composition in which the polyester (A) is dispersed in the polyethylene terephthalate (B), the polyester (A) is 2,2,4,4- An average of the equivalent of yen of the polyester (A), comprising a structural unit derived from tetramethyl-1,3-cyclobutanediol, the content of the polyester (A) being more than 0.1% by mass and less than 30% by mass. When the particle size is 50 to 800 nm, it has been found that the above problems can be solved, and the present invention has been completed. That is, the present invention includes the following.
[1] A resin composition in which a polyester (A) containing a structural unit derived from 2,2,4,4-tetramethyl-1,3-cyclobutanediol is dispersed in polyethylene terephthalate (B),
The content of the polyester (A) is more than 0.1% by mass and less than 30% by mass with respect to the mass of the resin composition.
The polyester (A) dispersed in the polyethylene terephthalate (B) is a resin composition having an equivalent particle diameter in terms of a circle obtained from a cross-sectional photograph taken with a scanning electron microscope of 50 to 800 nm.
[2] The content of the structural unit derived from 2,2,4,4-tetramethyl-1,3-cyclobutanediol is based on the total number of moles of all structural units derived from the diol contained in the polyester (A). The resin composition according to [1], which is 5 to 50 mol%.
[3] The resin composition according to [1] or [2], wherein an absolute value of a difference between a refractive index of the polyethylene terephthalate (B) and a refractive index of the polyester (A) is 0.1 or less.
[4] A film composed of the resin composition according to any one of [1] to [3].
[5] A laminate comprising one or more layers comprising the resin composition according to any one of [1] to [3].
[6] At least one of the layers included in the laminate is a gas barrier layer containing a gas barrier material, and the oxygen permeability of the gas barrier layer is 10 cc. At a temperature of 20 ° C. and a relative humidity of 65%. 20 μm / m ² . atm. The laminate according to [5], which is not more than day.
[7] A container comprising the resin composition according to any one of [1] to [3] or the laminate according to [5] or [6].
[8] A process for producing a resin composition according to any one of [1] to [3], wherein the mixture is obtained by mixing at least the polyethylene terephthalate (B) and the polyester (A) (i And extruding the mixture (ii).

  The resin composition of the present invention can achieve both excellent cutability and transparency.

  In the resin composition of the present invention, polyester (A) is dispersed in polyethylene terephthalate (B).

<Polyester (A)>
Polyester (A) is a polymer having an ester bond as the main bond in the main chain, and mainly has a structural unit derived from dicarboxylic acid and a structural unit derived from diol. In the present specification, “derived structural unit” may be simply referred to as “unit”. For example, a structural unit derived from dicarboxylic acid may be referred to as a dicarboxylic acid unit, and a structural unit derived from diol may be referred to as a diol unit.

  In the polyester (A), examples of the dicarboxylic acid constituting the dicarboxylic acid unit include aliphatic dicarboxylic acids such as malonic acid, succinic acid, adipic acid, azelaic acid, and sebacic acid; cyclohexanedicarboxylic acid, norbornene dicarboxylic acid, and tricyclodecane. Alicyclic dicarboxylic acids such as dicarboxylic acids; terephthalic acid, isophthalic acid, phthalic acid, biphenyl dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenyl sulfone dicarboxylic acid, diphenyl ketone dicarboxylic acid, sodium sulfoisophthalate, 2,6-naphthalenedicarboxylic acid, Aromatic dicarboxylic acids such as 1,4-naphthalenedicarboxylic acid and 2,7-naphthalenedicarboxylic acid; and ester-forming derivatives thereof. Among these, terephthalic acid and naphthalenedicarboxylic acid are preferable, and terephthalic acid is more preferable from the viewpoint of heat resistance, stability, and productivity. Dicarboxylic acid can be used individually or in combination of 2 or more types. Of the dicarboxylic acid units constituting the polyester (A), the content of terephthalic acid units is preferably 50 mol% or more, more preferably 70 mol% or more, based on the total number of moles of all structural units derived from dicarboxylic acid. 90 mol% or more is more preferable, and 95 mol% or more is particularly preferable.

  In the resin composition of the present invention, the diol unit constituting the polyester (A) includes a structural unit derived from 2,2,4,4-tetramethyl-1,3-cyclobutanediol. By including the 2,2,4,4-tetramethyl-1,3-cyclobutanediol unit, the polyester (A) and the polyethylene terephthalate (B) become incompatible, and the adhesive strength at the interface between the two is reduced. . Since the polyester (A) is dispersed in polyethylene terephthalate, the resin composition of the present invention is likely to exhibit excellent cut properties. In addition, in this specification, cut property shows the characteristic which is easy to cut | disconnect a resin composition, and improving cut property means that a resin composition becomes easy to cut | disconnect. Further, the cut property can be measured by a known method, for example, the method of Examples.

  The content of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (sometimes referred to as TMCBD) units is based on the total number of moles of all structural units derived from the diol contained in the polyester (A). , Preferably 50 mol% or less, more preferably 40 mol% or less, still more preferably 35 mol% or less, preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 20 mol% or more. . When the content of TMCBD is in the above range, the cut property is easily improved.

  In the polyester (A), examples of the diol constituting the diol unit other than the TMCBD unit include aliphatic diols such as ethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, methylpentanediol, and diethylene glycol; Cycloaliphatic dimethanol (for example, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol), norbornene dimethanol, tricyclodecane dimethanol and the like; bisphenol compounds; Examples include aromatic diols such as hydroquinone compounds. Among these, cyclohexanedimethanol such as 1,4-cyclohexanedimethanol is preferable from the viewpoint of heat resistance, stability, and productivity. Diols can be used alone or in combination of two or more.

  The polyester (A) may contain other structural units other than the dicarboxylic acid unit and the diol unit as long as the effects of the present invention are not impaired. Examples of other structural units include hydroxycarboxylic acid units. Examples of the hydroxycarboxylic acid constituting the hydroxycarboxylic acid unit include aliphatic hydroxycarboxylic acids such as 10-hydroxyoctadecanoic acid, lactic acid, hydroxyacrylic acid, 2-hydroxy-2-methylpropionic acid, and hydroxybutyric acid; Cycloaliphatic hydroxycarboxylic acids such as acid, hydroxymethylnorbornenecarboxylic acid, hydroxymethyltricyclodecanecarboxylic acid; hydroxybenzoic acid, hydroxytoluic acid, hydroxynaphthoic acid, 3- (hydroxyphenyl) propionic acid, hydroxyphenylacetic acid, 3 -Aromatic hydroxycarboxylic acids such as hydroxy-3-phenylpropionic acid; and ester-forming derivatives thereof. These hydroxycarboxylic acids can be used alone or in combination of two or more.

  In the polyester (A), the ratio of the dicarboxylic acid unit to the diol unit is preferably 10: 1 to 1:10, more preferably 5: 1 to 1: 5, still more preferably 2: 1 to 1: 2, particularly Preferably it is 1: 1.

[Polyethylene terephthalate (B)]
The polyethylene terephthalate (B) contained in the resin composition of the present invention is a polyester having a dicarboxylic acid unit mainly composed of terephthalic acid units and a diol unit mainly composed of ethylene glycol units. The total content of terephthalic acid units and ethylene glycol units contained in polyethylene terephthalate (B) is preferably 70 mol% or more, more preferably, based on the total number of moles of all structural units constituting polyethylene terephthalate (B). It is 80 mol% or more, more preferably 90 mol% or more, preferably 100 mol% or less, more preferably 99.9 mol% or less, and still more preferably 99 mol% or less. When the total content of the terephthalic acid unit and the ethylene glycol unit contained in the polyethylene terephthalate (B) is not less than the above lower limit value, it is easy to improve the cutability of the resin composition, and the content is not more than the above upper limit value When it exists, it is easy to improve the transparency of a resin composition.

  The polyethylene terephthalate (B) may contain a structural unit derived from a bifunctional compound other than the terephthalic acid unit and the ethylene glycol unit, if necessary. Examples of the bifunctional compound unit include other dicarboxylic acid units, other diol units, and hydroxycarboxylic acid units. Examples of the dicarboxylic acid constituting the other dicarboxylic acid unit include dicarboxylic acids other than terephthalic acid exemplified in the section of [Polyester (A)]. Examples of the diol constituting the other diol unit include [ Examples include diols other than ethylene glycol exemplified in the section of “Polyester (A)”. Moreover, as a hydroxycarboxylic acid which comprises a hydroxycarboxylic acid unit, the hydroxycarboxylic acid etc. which are illustrated to the term of [polyester (A)] etc. are mentioned, for example. Among these, it is preferable to use isophthalic acid as the other dicarboxylic acid from the viewpoint of easily improving the transparency and cutability of the resin composition. A bifunctional compound unit can be used individually or in combination of 2 or more types.

  The content of the bifunctional compound unit is preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably 10 mol%, based on the total number of moles of all the structural units constituting the polyethylene terephthalate (B). Or less, preferably 0 mol% or more, more preferably 0.1 mol% or more, and even more preferably 1 mol% or more. When the content of the bifunctional compound unit is not less than the above lower limit, the transparency of the resin composition is easily improved, and when the content is not more than the above upper limit, the cutability of the resin composition is improved. It's easy to do.

  In the polyethylene terephthalate (B), the ratio of the dicarboxylic acid unit to the diol unit is preferably 10: 1 to 1:10, more preferably 5: 1 to 1: 5, still more preferably 2: 1 to 1: 2. Particularly preferred is 1: 1.

  In the resin composition of the present invention, the polyester (A) includes a structural unit derived from 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and the content of the polyester (A) is the resin composition. The polyester (A) which is more than 0.1% by mass and less than 30% by mass and dispersed in polyethylene terephthalate (B) is equivalent to a circle obtained from a cross-sectional photograph taken with a scanning electron microscope. Since the average particle diameter in terms of conversion is 50 to 800 nm, both excellent cutability and transparency can be achieved.

  The content of the polyester (A) is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass. % Or less, particularly preferably 4% by mass or less. When the content of the polyester (A) is not less than the above lower limit, the cutability of the resin composition is easily improved, and when the content is not more than the above upper limit, the transparency of the resin composition is not impaired. .

  In the resin composition of the present invention, the polyester (A) dispersed in the polyethylene terephthalate (B) preferably has an equivalent particle diameter in terms of a circle obtained from a cross-sectional photograph taken by a scanning electron microscope, preferably 50 nm or more, more preferably It is 100 nm or more, more preferably 200 nm or more, preferably 800 nm or less, more preferably 700 nm or less, still more preferably 600 nm or less, and particularly preferably 500 nm or less. When the average particle diameter in terms of yen is equal to or greater than the above lower limit value, it is easy to improve the cutability of the resin composition, and when the average particle diameter is equal to or less than the above upper limit value, the transparency of the resin composition is improved. It's easy to do. In addition, the average particle diameter in terms of yen can be calculated by measuring by the method described in the examples.

  In the resin composition of the present invention, the absolute value of the difference between the refractive index of the polyethylene terephthalate (B) and the refractive index of the polyester (A) is preferably 0.1 or less, more preferably 0.08 or less, even more preferably. Is 0.05 or less. When the absolute value of the difference in refractive index is not more than the above upper limit, whitening of the resin composition can be effectively suppressed. The lower limit of the absolute value of the difference between the refractive index of the polyethylene terephthalate (B) and the refractive index of the polyester (A) is usually 0.001. In addition, a refractive index can be measured by the method prescribed | regulated to ISO489 using an Abbe refractometer.

[Resin composition]
The resin composition of the present invention may contain additives other than the polyester (A) and the polyethylene terephthalate (B) as long as the effects of the present invention are not impaired. Other additives are not particularly limited, and other thermoplastic resins, fillers, processing stabilizers, weathering stabilizers, colorants, ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, difficulty Examples include flame retardants, lubricants, fragrances, defoamers, deodorants, extenders, release agents, mold release agents, reinforcing agents, crosslinking agents, fungicides, and preservatives. Examples of other thermoplastic resins include polyester resins other than the polyester (A) and polyethylene terephthalate (B), olefin resins, halogen-containing vinyl resins, polycarbonate resins, polythiocarbonate resins, polyacetal resins, Examples include polyamide resins, polyphenylene ether resins, polysulfone resins, polyphenylene sulfide resins, polyimide resins, polyether ketone resins, and thermoplastic elastomers. The content of the additive may be, for example, 0 to 10% by mass with respect to the mass of the resin composition.

  The resin composition of the present invention has a relatively low haze and excellent transparency. The haze of the resin composition of the present invention is preferably 20% or less, more preferably 10% or less, still more preferably 7% or less, and particularly preferably 5% or less. In addition, haze can be measured by the method as described in an Example.

  The present invention includes a film (or sheet) composed of the resin composition. The thickness of the film (or sheet) is, for example, 5 to 1000 μm, preferably 10 to 800 μm, more preferably 50 to 500 μm. The resin composition of the present invention can also be used in the form of pellets.

  In one embodiment of the present invention, the resin composition of the present invention comprises a step (i) of mixing at least the polyester (A) and the polyethylene terephthalate (B) to obtain a mixture, and a step of extruding the mixture ( It can be produced by the method comprising ii).

  Step (i) is a step of mixing at least the polyester (A) and the polyethylene terephthalate (B), and the other additives and the like can be arbitrarily mixed together.

  Step (i) is usually performed using an extruder. In the extruder, each component is subjected to shear stress by a screw, and is homogeneously mixed while being heated by applying external heat to the barrel.

  As an extruder in this invention, a normal single screw extruder or a twin screw extruder can be used. Screw diameter, extruder length (L) and screw diameter (D) ratio L / D ratio and screw rotation speed are equivalent to the circle of polyester (A) by dispersing polyester (A) in polyethylene terephthalate (B) The average particle diameter in terms of conversion is appropriately selected within a range that can be adjusted to 50 to 800 nm. In order to control the average particle diameter, it is preferable to use a twin screw extruder. The twin screw extruder may be either co-rotating or counter-rotating. For example, in one embodiment of the present invention, the screw diameter is preferably 20 to 150 mm, and the L / D ratio is preferably 20 to 50. The rotational speed of the screw is preferably 30 rpm or more, more preferably 50 rpm or more, still more preferably 80 rpm or more, particularly preferably 100 rpm or more, preferably 190 rpm or less, more preferably 180 rpm or less. When the screw rotation speed is in the above range, it is easy to adjust the average particle diameter of polyester (A) equivalent to a circle to a range of 50 to 800 nm, and it is easy to obtain a resin composition excellent in transparency and cutability. The kneading temperature is, for example, 250 to 300 ° C., and the kneading time is, for example, 20 seconds to 5 minutes. Each component contained in the resin composition may be directly introduced into the extruder, and each component is premixed using a conventional mixer such as a Brabender, open roll, kneader, tumbler mixer, etc. May be introduced into the extruder.

  Step (ii) is a step of extruding the mixture obtained in step (i). In step (ii), the molten mixture that has been pushed through the extruder while being melt-kneaded is extruded from a die. The temperature of the die is preferably 250 to 300 ° C, more preferably 260 to 285 ° C.

  In step (ii), the mixture can be extruded in the form of a film or a strand. And the resin composition of a film or a strand form is obtained by cooling the extruded mixture.

  In the case of extruding the mixture into a film, the mixture can be extruded from a film-forming die and then wound with cooling with a take-up roller. It is preferred to cool between the die and the roller to prevent the mixture from sticking to the roller. In the blow tube method, dehumidified air can be used to expand the film as it exits the die. Talc can also be entrained in the air stream to prevent film blocking.

  When extruding the mixture into a strand shape, the strand can be formed into a pellet by extruding from a strand nozzle having a plurality of holes, cooling in a water tank, and cutting with a rotary cutter. In order to prevent the sticking of the pellets, vibrations are periodically or constantly applied, and moisture on the surface of the pellets can be removed by hot air, dehumidified air or an infrared heater.

  When a known resin composition composed of polyethylene phthalate (PET) or the like is not sufficiently cut, it must be cut unless it has improved crystallinity and orientation by a method such as stretching at least a specific stretching ratio. In other words, breakage failure such as elongation of the cut portion occurs. On the other hand, since the resin composition of this invention can express the outstanding cut property, without extending | stretching, it can improve productivity.

  The present invention includes a laminate comprising one or more layers comprising the resin composition (hereinafter sometimes referred to as resin layer (I)). That is, the resin composition of the present invention may be a single layer or a laminate (multilayer). When it is a laminate, it may be composed entirely of the resin layer (I), or may be composed of the resin layer (I) and other layers. As the other layer, a layer having high transparency and cutability can be appropriately selected. For example, a layer made of a polymer such as polyethylene terephthalate (PET), biaxially stretched polypropylene (BOPP), low density polyethylene (LDPE), polylactic acid; A layer containing a gas barrier material (hereinafter sometimes referred to as a gas barrier layer); an adhesive layer, a pressure-sensitive adhesive layer, and the like. Since the laminated body of this invention is comprised by 1 or several resin layer (I) or resin layer (I), and said other layer, it can make the outstanding cut property and transparency compatible.

  In a preferred embodiment of the present invention, at least one of the layers contained in the laminate is a gas barrier layer, and more preferably, a gas barrier layer is provided on at least one surface of the resin layer (I). In this case, the gas barrier layer may be laminated or bonded to the resin layer (I) via the adhesive layer.

  In a more preferred embodiment, the laminate of the present invention has resin layer (I) / adhesive layer / gas barrier layer / adhesive layer / resin layer (I) in this order. The kind of resin composition which comprises each resin layer (I) may be the same or different.

[Gas barrier layer]
The gas barrier layer comprises a gas barrier material. The gas barrier material is not particularly limited as long as the resulting gas barrier layer has high cutability and transparency, and can exhibit gas barrier performance. For example, the gas barrier material preferably contains an ethylene-vinyl alcohol copolymer (D). From the viewpoint of imparting biodegradability to the gas barrier layer, it is preferable to contain starch and / or modified starch (C). In the present specification, starch and / or modified starch (C) is component (C), ethylene-vinyl alcohol copolymer (D) is component (D), and water-soluble resin (E) described later is component (E). ).

(Starch and / or modified starch (C))
Examples of the starch include starch derived from corn, cassava, potato, sweet potato, sago, tapioca, sorghum, beans, bracken, lotus, castor, wheat, rice, oats, kuzukon, peas and the like. Among them, starch derived from corn and cassava is preferable, and starch derived from corn having a high amylose is more preferable. Starch can be used alone or in combination of two or more.

  Examples of the modified starch include physically modified starch (for example, α-starch, fractionated amylose, wet-heat-treated starch, etc.), enzyme-modified starch (for example, hydrolyzed dextrin, enzyme-degraded dextrin, amylose, etc.), chemically-degraded modified starch (for example, acid-treated starch , Hypochlorite oxidized starch, dialdehyde starch, etc.), chemically modified starch derivatives (for example, etherified starch, esterified starch, cationized starch, cross-linked starch, etc.). Modified starch can be used individually or in combination of 2 or more types.

  Among the chemically modified starch derivatives, etherified starch includes alkyl etherified starch (such as methyl etherified starch), carboxyalkyl etherified starch (such as carboxymethyl etherified starch), hydroxyalkyl etherified starch (such as carbon atom). And etherified starch having a hydroxyalkyl group of 2 to 6). Moreover, allyl etherified starch etc. can also be used.

  The esterified starch may have other structural units, for example, structural units derived from carboxylic acids such as acetic acid; structural units derived from maleic anhydride, structural units derived from phthalic anhydride, octenyl succinic acid Examples include esterified starch having a structural unit derived from a dicarboxylic acid anhydride such as a structural unit derived from an anhydride, and esterified starch having a structural unit derived from an oxo acid such as nitric acid, phosphoric acid, and urea phosphoric acid. Other examples include xanthate esterified starch, acetoacetate esterified starch and the like.

  Examples of the cationized starch include a reaction product of starch and 2-diethylaminoethyl chloride, a reaction product of starch and 2,3-epoxypropyltrimethylammonium chloride, and the like.

  Examples of the crosslinked starch include formaldehyde crosslinked starch, epichlorohydrin crosslinked starch, phosphate crosslinked starch, and acrolein crosslinked starch.

  The modified starch is preferably an etherified starch having a hydroxyalkyl group having 2 to 6 carbon atoms, an esterified starch having a structural unit derived from dicarboxylic anhydride, or a combination thereof, and hydroxyethyl etherified starch. , Hydroxypropyl etherified starch, hydroxybutyl etherified starch, esterified starch having a structural unit derived from maleic anhydride, esterified starch having a structural unit derived from phthalic anhydride, structural unit derived from octenyl succinic anhydride More preferred are esterified starches having a combination thereof, or combinations thereof.

  The etherified starch having a hydroxyalkyl group having 2 to 6 carbon atoms may be obtained by reacting an alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide with starch. The average number of hydroxy groups used for modification is preferably 0.05 to 2 per glucose unit in starch.

  From the viewpoint of biodegradability, unmodified starch is preferred, but unmodified starch is limited in its optical transparency, moldability, tensile elasticity, and the like due to aging. For this reason, it is preferred to include modified starches that improve these properties. The content of the modified starch is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and particularly preferably 100% by mass with respect to the total mass of the component (C).

  The content of amylose in the component (C) of the starch and / or modified starch (C) is preferably 50% by mass or more, more preferably 55% by mass or more, and further preferably 60% by mass or more. When the amylose content is 50% by mass or more, it is advantageous in terms of processability. On the other hand, the starch and / or modified starch (C) usually has an amylose content of 90% by mass or less.

  What is marketed as a component (C) can be used. Examples of typical commercial products include ECOFILM (registered trademark), which is a hydroxypropyl etherified starch available from Ingredion, and National 7 (registered trademark), GELOSE (registered trademark) A939.

  When the gas barrier material contains the component (C), the content of the component (C) is preferably 20 to 100% by mass with respect to the mass of the gas barrier material.

(Ethylene-vinyl alcohol copolymer (D))
The ethylene-vinyl alcohol copolymer (D) [EVOH (D)] is a copolymer having an ethylene unit and a vinyl alcohol unit. EVOH (D) can be obtained, for example, by saponifying a copolymer composed of ethylene and vinyl ester using an alkali catalyst or the like. Examples of vinyl esters include vinyl acetate and fatty acid vinyl esters (such as vinyl propionate and vinyl pivalate).

  EVOH (D) can contain, for example, a vinylsilane compound as a copolymerization component. Examples of the vinylsilane compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (β-methoxy-ethoxy) silane, and γ-methacryloxypropylmethoxysilane. Among these, vinyltrimethoxysilane and vinyltriethoxysilane can be preferably used. EVOH (D) is an unsaturated carboxylic acid such as propylene, butylene, (meth) acrylic acid, methyl (meth) acrylate, or an ester thereof, as long as the object of the present invention is not impaired. Vinylpyrrolidone such as N-vinylpyrrolidone can be contained. EVOH (D) can be used alone or in combination of two or more.

  In EVOH (D), ethylene unit content becomes like this. Preferably it is 2-60 mol%, More preferably, it is 10-50 mol%, Furthermore, it is 20-40 mol%. When the ethylene unit content is in the above range, it is advantageous from the viewpoint of oxygen barrier properties and mechanical properties. As the ethylene unit content decreases, the oxygen permeability (OTR) tends to decrease. In the present specification, an improvement in oxygen barrier property means that oxygen permeability (OTR) is reduced, and an excellent oxygen barrier property means that oxygen permeability is low.

  In EVOH (D), the saponification degree of the vinyl alcohol unit is 90 mol% or more, preferably 95 mol% or more, more preferably 99 mol% or more, and further preferably 99.5 mol% or more. It is. When the saponification degree is within the above range, excellent oxygen barrier properties can be obtained. The degree of saponification refers to the mole fraction of hydroxyl groups relative to the total of hydroxyl groups and ester groups in vinyl alcohol units.

  When the gas barrier material contains the component (D), the content of the component (D) is preferably 5 to 100% by mass with respect to the mass of the gas barrier material.

  The gas barrier material can further contain a water-soluble resin (E) from the viewpoint of easily improving the gas barrier property.

(Water-soluble resin (E))
The water-soluble resin (E) is a resin different from EVOH (D) and is compatible with the component (C). The water-soluble resin (E) preferably has a melting point suitable for the processing temperature of the component (C), and polyvinyl alcohol is preferable from the viewpoint of excellent moldability and good elastic modulus. Polyvinyl alcohol is produced, for example, by hydrolysis of polyvinyl acetate obtained by polymerization of vinyl acetate monomers. The saponification degree of polyvinyl alcohol is preferably 80 to 99.9 mol% from the viewpoint of sufficient strength and gas barrier properties. The saponification degree is more preferably 85 mol% or more, and still more preferably 88 mol% or more. The degree of saponification refers to the mole fraction of hydroxyl groups relative to the total of hydroxyl groups and ester groups in polyvinyl alcohol.

  The polyvinyl alcohol can further contain other monomer units other than the vinyl alcohol unit. And monomer units derived from ethylenically unsaturated monomers. Examples of the ethylenically unsaturated monomer include α-olefins such as propylene, n-butene, isobutylene and 1-hexene; acrylic acid and its salt; unsaturated monomer having an acrylate group; methacrylic acid and its Salt; unsaturated monomer having methacrylic acid ester group; acrylamide, N-methylacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, diacetone acrylamide, acrylamide propanesulfonic acid and its salt, acrylamidopropyldimethylamine and Salts thereof (eg quaternary salts); methacrylamide, N-methyl methacrylamide, N-ethyl methacrylamide, methacrylamide propanesulfonic acid and salts thereof, methacrylamide propyldimethylamine and salts thereof (eg quaternary salts); Vinyl ethers such as ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, dodecyl vinyl ether, stearyl vinyl ether, 2,3-diacetoxy-1-vinyloxypropane Vinyl cyanides such as acrylonitrile and methacrylonitrile; vinyl halides such as vinyl chloride and vinyl fluoride; vinylidene halides such as vinylidene chloride and vinylidene fluoride; allyl acetate, 2,3-diacetoxy-1 -Allyl compounds such as allyloxypropane and allyl chloride; unsaturated dicarboxylic acids such as maleic acid, itaconic acid and fumaric acid and salts or esters thereof; vinyl such as vinyltrimethoxysilane Silyl compounds, isopropenyl acetate; vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl versatic acid, vinyl caproate, vinyl carlylate, vinyl laurate, vinyl palmitate, stearic acid And vinyl ester monomers such as vinyl, vinyl oleate, and vinyl benzoate. Further, monomer units derived from unsaturated monomers, which have not been saponified, are also included in the other monomer units. The content of other monomer units is preferably 10 mol% or less, and more preferably 5 mol% or less. The water-soluble resin (E) can be used alone or in combination of two or more.

  The method for producing polyvinyl alcohol is not particularly limited, but as described above, for example, vinyl acetate monomer and, if necessary, other monomers are copolymerized, and the obtained copolymer is saponified to vinyl alcohol units. The method of conversion is mentioned. Examples of the polymerization method for copolymerization include batch polymerization, semi-batch polymerization, continuous polymerization, and semi-continuous polymerization. Examples of the polymerization method include known methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. A known method can be applied to saponification of the copolymer. For example, it can be performed in a state where the copolymer is dissolved in alcohol or hydrous alcohol. The alcohol that can be used at this time is, for example, a lower alcohol such as methanol or ethanol.

  When the gas barrier material contains the component (E), the content of the component (E) is preferably 1 to 50% by mass with respect to the mass of the gas barrier material.

  The gas barrier material may further include a fatty acid having 12 to 22 carbon atoms and / or a fatty acid salt thereof. Examples of fatty acids having 12 to 22 carbon atoms and fatty acid salts thereof include stearic acid, calcium stearate, sodium stearate, palmitic acid, lauric acid, myristic acid, linolenic acid, and behenic acid. Among these, stearic acid, calcium stearate, and sodium stearate are preferable from the viewpoint of processability. The fatty acid having 12 to 22 carbon atoms and the fatty acid salt thereof can be used alone or in combination of two or more.

  When the gas barrier material contains a fatty acid having 12 to 22 carbon atoms and / or a fatty acid salt thereof, the content in the gas barrier material is preferably 0.01 to the mass of the gas barrier material. It is 3 mass%, More preferably, it is 0.03-2 mass%, More preferably, it is 0.1-1 mass%. When the content of the fatty acid having 12 to 22 carbon atoms and / or the fatty acid salt thereof is within the above range, it is advantageous in terms of processability.

  The gas barrier material may further contain a layered silicate clay. As the layered silicate clay, synthetic or natural layered silicate clays such as montmorillonite, bentonite, beidellite, mica (mica), hectorite, saponite, nontronite, soconite, vermiculite, ladykite, magadite, kenyaite, steven Sites, volconskites and mixtures thereof. Layered silicate clays can be used alone or in combination of two or more.

  When the gas barrier material contains a layered silicate clay, the content in the gas barrier material is preferably 0.1 to 5% by mass, more preferably 0.1 to 0.1% by mass with respect to the mass of the gas barrier material. It is 3 mass%, More preferably, it is 0.5-2 mass%. When the content of the layered silicate clay is in the above range, transparency and impact strength tend to be improved.

  The gas barrier material may further contain a plasticizer from the viewpoint of film formability. Examples of the plasticizer include water, sorbitol, glycerol, maltitol, xylitol, mannitol, glycerol trioleate, epoxidized linseed oil, epoxidized soybean oil, tributyl citrate, acetyl triethyl citrate, glyceryl triacetate, 2, 2 , 4-trimethyl-1,3-pentanediol diisobutyrate, polyethylene oxide, polyethylene glycol. A plasticizer can be used individually or in combination of 2 or more types.

  The content of the plasticizer is preferably 0.1% by mass, more preferably 1% by mass, and still more preferably as a lower limit with respect to the mass of the gas barrier material, from the viewpoints of film forming properties and oxygen barrier properties of the gas barrier material. Is 10% by mass, particularly preferably 15% by mass, most preferably 20% by mass, and the upper limit is preferably 50% by mass, more preferably 45% by mass, and still more preferably 40% by mass.

  The gas barrier material may contain, as necessary, those exemplified as additives other than the polyester (A) and polyethylene terephthalate (B) described in [Resin composition].

The gas barrier layer containing the gas barrier material is excellent in oxygen barrier properties. The oxygen permeability of the gas barrier layer is preferably 10 cc. At a temperature of 20 ° C. and a relative humidity of 65%. 20 μm / m ² . atm. day or less, more preferably 8 cc. 20 μm / m ² . atm. day or less, more preferably 5 cc. 20 μm / m ² . atm. day or less. When the oxygen permeability is not more than the above upper limit value, the gas barrier layer can exhibit sufficient oxygen barrier properties.

  The thickness of the gas barrier layer is, for example, from 1 to 1000 μm, preferably from 2 to 500 μm, more preferably from 5 to 200 μm, from the viewpoint of cutability of the resulting laminate.

  In one embodiment of the present invention, the gas barrier layer containing the gas barrier material includes a step (a) of mixing components constituting the gas barrier material to obtain a mixture, and a step (b) of extruding the mixture. It can be manufactured by a method.

  The step (a) is a step of mixing the components constituting the gas barrier material, for example, at least the component (C) and / or the component (D), and optionally the component (E) and the number of carbon atoms is 12-22. Fatty acids and / or fatty acid salts thereof, the layered silicate clay, the plasticizer, and the other additives can be mixed together.

  Step (a) is usually performed using an extruder. In the extruder, each component is subjected to shear stress by a screw, and is homogeneously mixed while being heated by applying external heat to the barrel.

  A twin screw extruder can be used as the extruder. The twin screw extruder may be either co-rotating or counter-rotating. The screw diameter, L / D ratio, and screw rotation speed can be selected from the same ranges as those described in the section [Resin composition].

  In the step (a), from the viewpoint of the film-forming property of the gas barrier material and the oxygen barrier property, the lower limit is preferably 0.1% by mass, more preferably 1% by mass, and still more preferably relative to the mass of the gas barrier material. 10% by weight, particularly preferably 15% by weight, most preferably 20% by weight, and the upper limit is preferably 50% by weight, more preferably 45% by weight, still more preferably 40% by weight of plasticizer, preferably water. It is preferable to mix. Here, the mass of the mixture indicates the total mass of the mixture including the plasticizer. In step (a), a plasticizer may be introduced at the initial stage of extrusion, and the plasticizer can be introduced before reaching the heating temperature, for example, at 100 ° C. or lower. The starch and / or modified starch (C) can be subjected to a cooking treatment by a combination of moisture, heat and shear stress to be gelatinized (gel). Further, by separately introducing a plasticizer, preferably water, a water-soluble polymer such as the water-soluble resin (E) can be dissolved, the gas barrier material can be softened, and the modulus and brittleness can be reduced.

  In the step (a), the cooking treatment is preferably performed by heating to a temperature of more than 100 ° C. and 150 ° C. or less, more preferably more than 115 ° C. and 140 ° C. or less. Here, a cooking process is a process which crushes starch granules and makes it gelatinize. Heating can be performed by applying heat from the outside to the barrel of the extruder. Each barrel can be heated to the target temperature by applying a stepped temperature. When the cooking process is performed at a temperature exceeding 120 ° C., it is advantageous in terms of workability.

  In order to prevent foaming, the cooked mixture is preferably pushed toward the die while lowering to a temperature of 85-120 ° C, more preferably 90-110 ° C. Further, by exhausting from the barrel, foaming can be prevented and moisture can be removed.

  The residence time in the extruder can be set according to the temperature profile and screw speed, and is preferably 1 to 2.5 minutes.

  In the step (b) of extruding the mixture, the molten mixture that has been pushed through the extruder while being melt-kneaded is extruded from a die. The temperature of the die is preferably 85 to 120 ° C, more preferably 90 to 110 ° C.

  In step (b), the mixture can be extruded in the form of a film. A gas barrier layer comprising a gas barrier material is obtained by cooling and drying the extruded mixture (melt).

  The laminate of the present invention can be obtained by laminating the resin layer (I) and a layer other than the resin layer (I), preferably a gas barrier layer, by a conventional method such as dry lamination. In a preferred embodiment, a laminate having the resin layer (I) / adhesive layer / gas barrier layer in this order by bonding a gas barrier layer to one or both sides of the resin layer (I) via an adhesive layer, or A laminate having the resin layer (I) / adhesive layer / gas barrier layer / adhesive layer / resin layer (I) in this order is obtained. The laminate may be manufactured by co-extrusion molding or co-injection molding of the resin composition and the gas barrier material.

  The present invention includes a container comprising the resin composition or the laminate. In the present invention, since the resin composition and the laminate are excellent in cutability, the resin composition or the laminate can be easily and easily cut into a predetermined shape without causing cutting failure such as elongation of a cut surface. Can be used in the container molding process. Furthermore, when the laminated body of this invention contains the said gas barrier layer, gas barrier properties, such as oxygen barrier property, can also be provided to a container. Therefore, the container of the present invention can be suitably used particularly for food packaging. Moreover, you may use the said resin composition or the said laminated body of this invention shape | molded to a tube, a bottle, a fiber, a packaging film etc. other than a container, for example.

  Examples of the cutting method include a method of cutting with a shearing force such as a punch cutter and a rotary cutter, and a method using a sharp blade such as a crash cutter. The present invention is effective in mechanical cutting including both.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

<Test method>
(1) Measurement of average particle diameter of polyester (A) Small pieces of films obtained in Examples and Comparative Examples were cut at a speed of 10 mm / min with a microtome equipped with a stainless steel blade. The cut section was observed with a scanning electron microscope (SEM).
Apparatus: “Scanning Electron Microscope SU8010” manufactured by Hitachi High-Technologies Corporation
Acceleration voltage: 1 kV
Magnification: 10,000 times

  For the dispersion derived from the polyester (A) in the microscopic image, the entire outline is shown in the photo screen using the image analysis software ("MAC-view" manufactured by MOUNTECH) (the outline is broken). No) Particles were picked up, and each cross-sectional area was calculated for 50 MD parallel sections and 50 TD parallel sections, a total of 100. In the case where the image analysis software does not automatically recognize the outline of the particle, a measure is taken to recognize the outline of the particle. With respect to the calculated cross-sectional area, the diameter (converted particle size) when the cross section was assumed to be circular was calculated, and the number average of a total of 100 converted particle sizes was defined as the equivalent particle size converted to a circle.

(2) Haze measurement The films obtained in Examples and Comparative Examples were cut into small pieces of 50 mm x 70 mm and measured with a haze meter (HR-100, manufactured by MURAKAMI) to determine the haze value.

(3) Cut property With respect to the films obtained in Examples and Comparative Examples, cut property was evaluated using a punch tool with reference to ASTM D732-02. Data was recorded with (punch moving distance) / (sample thickness) as the horizontal axis and load as the vertical axis. The load at (punch moving distance) / (sample thickness) = 6 where the punch was sufficiently cut beyond the yield point was read, and the cutability of the film was evaluated according to the following criteria.
Sample thickness: 150 μm
Punch-hole clearance: 12.5μm
Punch speed: 1000mm / min
(Evaluation criteria)
A: Good cutting property, 300N or less.
B: Cutability is poor, exceeding 300N.

(4) Material used <polyethylene terephthalate (B)>
COOL 74: Polyethylene terephthalate modified with isophthalic acid (IPA; 2 mol% based on all dicarboxylic acid units), obtained from LOTTE CHEMICAL

<Polyester (A)>
Tritan TX1001: 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCBD) modified poly (1,4-cyclohexylenedimethylene) terephthalate, available from Eastman Chemical Company Tritan TX1800: 2, 2,4,4-Tetramethyl-1,3-cyclobutanediol (TMCBD) modified poly (1,4-cyclohexylenedimethylene) terephthalate, available from Eastman Chemical Company Tritan TX2001: 2, 2, 4, 4 -Tetramethyl-1,3-cyclobutanediol (TMCBD) modified poly (1,4-cyclohexylenedimethylene) terephthalate, available from Eastman Chemical Company Ester 6863: 1,4-cyclohexanedimethanol modified polyethylene Lenterephthalate, obtained from Eastman Chemical Company Ester AN004: Poly (1,4-cyclohexylenedimethylene) terephthalate, obtained from Eastman Chemical Company

<Example 1>
980 g of polyethylene terephthalate (B) (COOL74) pellets and 20 g of polyester (A) (TritanTX1001) were mixed in a tumbler mixer for 15 minutes and dry blended. The blended pellets were fed to the hopper of a twin screw extruder (screw diameter; 25 mm, L / D ratio; 25, maximum rotation speed; 200 rpm) via a volume feeder at a speed of 2.8 kg / hour. The resin composition was kneaded at a rotation speed of 100 rpm, and a film made of the resin composition was extruded from a film forming die. The extrusion speed was set so that the extruded film had a predetermined thickness after cooling, and a film having a thickness of 150 μm was obtained. The twin-screw extruder was operated by a co-rotation (meshing self-wiping) method.

<Example 2>
A 150 μm film was obtained in the same manner as in Example 1 except that Tritan TX1800 was used as the polyester (A).

<Example 3>
A 150 μm film was obtained in the same manner as in Example 1 except that Tritan TX2001 was used as the polyester (A).

<Example 4>
A 150 μm film was obtained in the same manner as in Example 1 except that COOL 74 (995 g) and TritanTX1001 (5 g) were used as raw materials.

<Example 5>
A 150 μm film was obtained in the same manner as in Example 1 except that COOL 74 (950 g) and TritanTX1001 (50 g) were used as raw materials.

<Example 6>
A 150 μm film was obtained in the same manner as in Example 1 except that COOL 74 (900 g) and TritanTX1001 (100 g) were used as raw materials.

<Example 7>
A 150 μm film was obtained in the same manner as in Example 1 except that the rotation speed of the twin screw extruder was 180 rpm.

<Example 8>
A film having a thickness of 150 μm was obtained in the same manner as in Example 1 except that the rotational speed of the twin screw extruder was set to 50 rpm.

<Comparative Example 1>
A 150 μm film was obtained in the same manner as in Example 1 except that COOL 74 (1000 g) was used as a raw material.

<Comparative example 2>
A 150 μm film was obtained in the same manner as in Example 1 except that COOL 74 (999 g) and TritanTX1001 (1 g) were used as raw materials.

<Comparative Example 3>
A 150 μm film was obtained in the same manner as in Example 1 except that COOL 74 (700 g) and TritanTX1001 (300 g) were used as raw materials.

<Comparative example 4>
A 150 μm film was obtained in the same manner as in Example 1 except that the number of revolutions of the extruder was 200 rpm.

<Comparative Example 5>
A 150 μm film was obtained in the same manner as in Example 1 except that the number of revolutions of the extruder was 20 rpm.

<Comparative Example 6>
A 150 μm film was obtained in the same manner as in Example 1 except that Ester 6673 was used as the polyester (A).

<Comparative Example 7>
A 150 μm film was obtained in the same manner as in Example 1 except that Ester AN004 was used as the polyester (A).

  Table 1 shows the results of the average particle diameter, haze, and cutability of the films obtained in Examples 1 to 8 and Comparative Examples 1 to 7 in terms of yen equivalent. In Table 1, CHDM copolymerization amount (mol%) indicates the content of constituent units derived from 1,4-cyclohexanedimethanol (CHDM) with respect to the total number of moles of diol units contained in polyester (A), and TMCBD. The copolymerization amount (mol%) is the content of constituent units derived from 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCBD) with respect to the total number of moles of diol units contained in the polyester (A). Show. In Table 1, content (mass%) shows content of polyester (A) with respect to the mass of a resin composition.

  The resin compositions obtained in Examples 1 to 8 have low haze and good cut evaluation. That is, the resin compositions obtained in Examples 1 to 8 can achieve both excellent cutability and transparency. On the other hand, the resin compositions obtained in Comparative Examples 1, 2, 4 to 7 have poor cut evaluation. Moreover, the resin composition obtained in Comparative Example 3 has high haze and low transparency. Therefore, the film consisting of the resin composition obtained in Comparative Examples 1 to 8 cannot achieve both cutability and transparency.

Claims (8)

Polyester (A) containing a structural unit derived from 2,2,4,4-tetramethyl-1,3-cyclobutanediol is a resin composition dispersed in polyethylene terephthalate (B),
The content of the polyester (A) is more than 0.1% by mass and less than 30% by mass with respect to the mass of the resin composition.
The polyester (A) dispersed in the polyethylene terephthalate (B) is a resin composition having an equivalent particle diameter in terms of a circle obtained from a cross-sectional photograph taken with a scanning electron microscope of 50 to 800 nm.   The content of the constituent unit derived from 2,2,4,4-tetramethyl-1,3-cyclobutanediol is 5 to 5 with respect to the total number of moles of all constituent units derived from the diol contained in the polyester (A). The resin composition of Claim 1 which is 50 mol%.   The resin composition according to claim 1 or 2, wherein an absolute value of a difference between a refractive index of the polyethylene terephthalate (B) and a refractive index of the polyester (A) is 0.1 or less.   The film comprised from the resin composition in any one of Claims 1-3.   The laminated body containing one or more layers which comprise the resin composition in any one of Claims 1-3. Among the layers included in the laminate, at least one layer is a gas barrier layer containing a gas barrier material, and the oxygen permeability of the gas barrier layer is 10 cc. At a temperature of 20 ° C. and a relative humidity of 65%. 20 μm / m ² . atm. The layered product according to claim 5 which is below day.   The container which consists of the resin composition in any one of Claims 1-3, or the laminated body of Claim 5 or 6.   It is a manufacturing method of the resin composition in any one of Claims 1-3, Comprising: The process (i) which mixes at least the said polyethylene terephthalate (B) and the said polyester (A), and obtains a mixture, and this mixture A process comprising the step of extruding (ii).