JP2022144043A - laminated molded body - Google Patents

Abstract

To provide a laminated molded body including an adhesive resin layer containing a modified polyester-based elastomer and a gas barrier resin layer, and satisfying adhesiveness and solvent durability.SOLUTION: There is provided a laminated molded article containing at least an adhesive resin layer containing a modified polyester-based elastomer and a gas barrier resin layer. The modified polyester-based elastomer is a modified polyester-based elastomer obtained by modifying a polyester-based elastomer with an unsaturated carboxylic acid and/or a derivative thereof, the polyester-based elastomer being composed of a polyester-polyether block copolymer including a hard segment containing an aromatic polyester and a soft segment containing a polyalkylene ether glycol segment. A content of the polyalkylene ether glycol segment in the modified polyester-based elastomer is 36 to 53 mass%.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a laminate molded article including an adhesive resin layer containing a modified polyester-based elastomer and a gas barrier resin layer.

Laminated molded products using gas barrier resins such as ethylene-vinyl alcohol copolymers and polyamide resins and polyolefin resins have excellent mechanical properties, safety in food applications, and shielding of gases such as water vapor and oxygen. Because of its properties, it is widely used for containers such as films, bottles, cups, etc. in the food packaging field, and for industrial pipes, hoses, beverage and chemical delivery tubes, automobile parts, etc. in the non-food field. When it is desired to impart aroma preservability, rigidity, heat resistance, cold resistance, surface printability, etc. to such a laminate, a polyester resin may be used instead of a polyolefin resin, or a polyester resin may be added to this laminate. A system resin layer is laminated.

Ethylene-vinyl alcohol copolymers and polyamide resins are poor in adhesiveness with polyester resins, so a technique of providing an adhesive layer made of an adhesive resin composition for laminating them is known.
For example, Patent Document 1 describes an adhesive resin composition comprising a modified polyester-based elastomer having a polyalkylene ether glycol segment content of 58 to 73% by weight.

On the other hand, for food packaging whose contents are oily, industrial hoses that come into contact with chemicals and solvents in the usage environment, tubes for transporting chemicals, automobile parts, etc., each resin layer of the laminated molded body that constitutes them There is a problem that oil, chemicals, and solvents migrate to the interface and cause peeling. In applications where the solvent is exposed for a long period of time, the adhesive layer made of the adhesive resin composition may swell and deform due to the solvent, resulting in deformation and embrittlement of the laminate. Therefore, an adhesive resin composition having excellent solvent durability is desired.
Patent Document 2 describes that an adhesive layer made of a composition containing modified polyethylene and unmodified polyethylene having a specific melt flow rate and density is excellent in initial adhesive strength and solvent durability.

JP 2002-155135 A JP-A-2003-73506

However, although the adhesive resin composition described in Patent Document 1 is excellent in adhesiveness as shown in Comparative Examples 3 to 5 below, there is room for improvement in solvent durability. The adhesive resin composition described in Patent Document 2 is excellent in solvent durability as shown in Comparative Example 6 below, but is insufficient in adhesiveness.

An object of the present invention is to provide a laminated molded article including an adhesive resin layer containing a modified polyester elastomer and a gas barrier resin layer, which satisfies adhesiveness and solvent durability.

As a result of intensive studies in order to solve the above problems, the present inventors have found that a modified polyester-based elastomer obtained by modifying a polyester polyether block copolymer with an unsaturated carboxylic acid and/or a derivative thereof, the polyalkylene ether glycol The present inventors have found that a laminated molded article containing an adhesive resin layer containing a modified polyester elastomer containing segments in a specific proportion and a gas barrier resin layer can solve the above problems, and have completed the present invention.
That is, the gist of the present invention is as follows.

[1] A laminate molded article comprising at least an adhesive resin layer containing a modified polyester elastomer and a gas barrier resin layer, wherein the modified polyester elastomer comprises a hard segment containing an aromatic polyester and a polyalkylene ether glycol. A modified polyester-based elastomer obtained by modifying a polyester-based elastomer comprising a polyester polyether block copolymer consisting of a soft segment containing segments with an unsaturated carboxylic acid and/or a derivative thereof, and the modified polyester-based elastomer A laminated molded article, wherein the content of the polyalkylene ether glycol segment in the elastomer is 36 to 53% by mass.

[2] The laminate molded article according to [1], wherein the adhesive resin layer contains the modified polyester elastomer in an amount of 50% by mass or more based on the entire constituent components of the adhesive resin layer.

[3] The laminate molded article according to [1] or [2], wherein the gas-barrier resin layer is a resin layer containing an ethylene-vinyl alcohol copolymer as a main component.

[4] The laminate molded body further comprising a polyester resin layer, wherein the adhesive resin layer is provided between the gas barrier resin layer and the polyester resin layer according to any one of [1] to [3]. laminated molded body.

ADVANTAGE OF THE INVENTION According to this invention, the laminated molded article which is a laminated molded article containing the adhesive resin layer containing a modified polyester-type elastomer, and a gas-barrier resin layer and which has both high adhesiveness and excellent solvent durability is provided.

The present invention will be described in detail below, but the following description is an example of an embodiment of the present invention, and the present invention is not limited to the following description content as long as it does not exceed the gist of the present invention. Arbitrary modifications can be made without departing from the gist of the invention.
In addition, in the present invention, when a numerical value or a physical property value is sandwiched before and after the "~", it is used to include the values before and after it.

In the present invention, the density, melting point, hardness, melt flow rate (MFR), and polyalkylene ether glycol segment content of the resin are values measured as follows.

<Density>
Density is measured by an underwater substitution method in accordance with JIS K7112.

<Melting point>
Melting points are measured using a differential scanning calorimeter (DSC). Specifically, after the temperature was once raised to 300° C. to erase the thermal history, the temperature was lowered to 40° C. at a temperature drop rate of 10° C./min, and the temperature was raised again at a temperature rise rate of 10° C./min. Let the temperature of the endothermic peak top at the time of measurement be the melting point. The unit is °C.

<Hardness>
JIS-D hardness measured with a durometer in accordance with JIS K6253 (D hardness).

<MFR>
The MFR (melt flow rate) of the polyester-based elastomer and modified polyester-based elastomer to be described later is measured according to JIS K7210 under conditions of a temperature of 230° C., a load of 2.16 kg, and 10 minutes. At the time of measurement, the polyester elastomer and the modified polyester elastomer are vacuum-dried at 100° C. for 4 hours in a pellet state to remove contained moisture.
The MFR of modified polyethylene is measured according to JIS K7210 under conditions of a temperature of 190° C., a load of 2.16 kg, and 10 minutes.

<Content ratio of polyalkylene ether glycol segment in modified polyester elastomer>
The content of the polyalkylene ether glycol segment in the modified polyester elastomer was determined by dissolving the sample in a mixed solvent of deuterated chloroform/hexafluoroisopropanol and using a nuclear magnetic resonance spectrometer (Bruker AVANCE400 spectrometer) to obtain a ¹ H NMR spectrum at room temperature. is measured and calculated based on the chemical shift of the hydrogen spectrum.
When two or more types of modified polyester elastomers are used, each modified polyester elastomer is used as a target sample, and each is measured in the same manner as described above to calculate the polyalkylene ether glycol segment content, and the blended mass of each modified polyester elastomer. It can also be calculated by proportional calculation using a ratio.
Theoretically, the polyalkylene ether glycol segment content of the modified polyester-based elastomer and the polyalkylene ether glycol segment content of the polyester-based elastomer before modification are the same. That is, it can be considered that there is no change in the content of the polyalkylene ether glycol segment before and after modification.

The laminated molded article of the present invention is a laminated molded article comprising at least an adhesive resin layer containing a modified polyester-based elastomer and a gas barrier resin layer, wherein the modified polyester-based elastomer comprises a hard segment containing an aromatic polyester. and a soft segment containing a polyalkylene ether glycol segment. , wherein the content of the polyalkylene ether glycol segment in the modified polyester-based elastomer is 36 to 53% by mass.
Hereinafter, the modified polyester-based elastomer contained in the adhesive resin layer according to the present invention is referred to as "the modified polyester-based elastomer of the present invention", and the polyester-based elastomer before modification is simply referred to as "polyester-based elastomer" or "component (A)". sometimes referred to as
Further, the unsaturated carboxylic acid and/or its derivative used for modifying the polyester elastomer may be referred to as "component (B)", and the radical generator used for modification may be referred to as "component (C)".

The modified polyester-based elastomer of the present invention is a polyester-based elastomer that is a polyester-polyether block copolymer composed of a hard segment containing an aromatic polyester and a soft segment containing a polyalkylene ether glycol segment. / Or obtained by modifying with a derivative thereof.

The term "modification" as used in the present invention refers to graft modification of a polyester elastomer with an unsaturated carboxylic acid and/or a derivative thereof, terminal modification, modification by transesterification, modification by decomposition reaction, and the like. Specifically, the site where the unsaturated carboxylic acid and/or derivative thereof is bound may be a terminal functional group or an alkyl chain portion, particularly a terminal carboxyl group, a terminal hydroxyl group, or an ether bond of a polyalkylene ether glycol segment. Examples include carbon atoms at the α-position and β-position. In particular, it is presumed that many are bound at the α-position with respect to the ether bond of the polyalkylene ether glycol segment.

When a polyester-based elastomer is modified with an unsaturated carboxylic acid and/or a derivative thereof, a modified polyester-based elastomer modified with the polyester-based elastomer, an unmodified polyester-based elastomer, and the unsaturated carboxylic acid used for modification and/or A modified polyester-based elastomer is obtained as a composition containing a derivative thereof, a radical generator described later, and the like. The modified polyester-based elastomer of the present invention means a modified polyester-based elastomer composition containing residues such as an unmodified polyester-based elastomer and unsaturated carboxylic acids and/or derivatives thereof obtained by such a modification reaction. .
The modified polyester-based elastomer of the present invention is obtained by modifying a polyester-based elastomer as long as it satisfies the content of the polyalkylene ether glycol segment defined in the present invention, preferably the suitable acid modification rate described later. A mixture of a modified polyester-based elastomer and an unmodified polyester-based elastomer may also be used.

[mechanism]
Since the adhesive resin layer according to the present invention contains the modified polyester-based elastomer, it can have sufficient adhesiveness to the gas-barrier resin layer, particularly the ethylene-vinyl alcohol copolymer and the polyamide-based resin. Moreover, since the modified polyester-based elastomer of the present invention has a polyester as a main skeleton, it has high compatibility with polyester-based resins and high adhesion.
In addition, when the content of the polyalkylene ether glycol segment in the modified polyester-based elastomer of the present invention is 36 to 53% by mass, both adhesiveness and solvent durability can be achieved. This is presumed to be due to the fact that many unsaturated carboxylic acids and/or derivatives thereof are bound to the polyalkylene ether glycol segments in the modified polyester-based elastomer due to modification. That is, if the modified polyester-based elastomer contains a sufficient amount of polyalkylene ether glycol segment of 36% by mass or more, the degree of modification (the content of the unsaturated carboxylic acid component contained in the modified polyester-based elastomer) increases, resulting in a gas barrier. Adhesiveness to the adhesive resin can be sufficiently satisfied. On the other hand, the polyalkylene ether glycol segment content of the modified polyester-based elastomer is 53% by mass or less, and the remaining part contains a sufficient amount of highly crystalline hard segments, resulting in high crystallinity as a modified polyester-based elastomer. , excellent solvent durability.

[Polyester Elastomer]
The polyester-based elastomer according to the present invention is a polyester-polyether block copolymer composed of a hard segment containing an aromatic polyester and a soft segment containing a polyalkylene ether glycol.
The polyalkylene ether glycol segment content of the polyester-based elastomer according to the present invention is 36-53% by mass, preferably 38-50% by mass, for the same reason as for the modified polyester-based elastomer described later.
As with the modified polyester-based elastomer, when two or more polyester-based elastomers are used, even if some of the polyester-based elastomers have a polyalkylene ether glycol segment content of 35 to 53% by mass, the overall polyalkylene The ether glycol segment content may be within the range of 36 to 53% by mass.

The polyester elastomer preferably has a density of 1.00 to 1.35 g/cm ³ , more preferably 1.05 to 1.30 g/cm ³ , and more preferably 1.10 to 1.25 g/cm ³ . is more preferred. Density correlates with polyalkylene ether glycol content, with higher polyalkylene ether glycol content resulting in lower density. That is, setting the density to the lower limit of the above range or higher makes it easier to suppress deterioration of solvent durability, and setting the density to the upper limit of the above range or lower makes it easy to improve adhesion with the gas barrier resin.

The polyester elastomer preferably has a melting point of 145 to 245°C, more preferably 160 to 230°C, even more preferably 175 to 215°C. When the melting point is at least the lower limit of the above range, it becomes easier to suppress deterioration of heat resistance in the usage environment, and when it is at or below the upper limit of the above range, ethylene-vinyl alcohol copolymer, etc., can be heated at high temperatures. It becomes easier to improve the coextrusion moldability with the gas barrier resin that deteriorates.

The D hardness (JIS-D hardness) of the polyester-based elastomer is preferably 10-80, more preferably 20-70, even more preferably 40-60. When the JIS-D hardness is at least the lower limit of the above range, solvent durability tends to be excellent, and when it is at most the upper limit of the above range, the required flexibility is maintained when laminated molded articles such as films and tubes are formed. tends to be easier.

In addition, according to JIS K7210 for polyester elastomers, the MFR measured under the conditions of a temperature of 230° C., a load of 2.16 kg, and 10 minutes is preferably 0.5 to 300 g/10 minutes. It is more preferably 150 g/10 minutes, and even more preferably 2 to 75 g/10 minutes. When the MFR of the polyester-based elastomer is less than the upper limit of the above range, it is easy to increase the melt tension and suppress drawdown during molding. It becomes easier to control sexual aggravation.

A polyester-based elastomer composed of a hard segment containing an aromatic polyester and a soft segment containing a polyalkylene ether glycol is usually i) an aliphatic and/or alicyclic diol having 2 to 12 carbon atoms, and ii ) an aromatic dicarboxylic acid and/or its alkyl ester, and iii) a polyalkylene ether glycol having a number average molecular weight of 400 to 6,000 as raw materials, and an oligomer obtained by an esterification reaction or a transesterification reaction is polycondensed. can be obtained.

i) As the aliphatic and/or alicyclic diol having 2 to 12 carbon atoms, those commonly used as raw materials for polyesters, particularly polyester elastomers, can be used. Examples include ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol, with 1,4-butanediol and ethylene glycol being preferred. 1,4-Butanediol is particularly preferred. These diols can be used singly or as a mixture of two or more.

ii) As the aromatic dicarboxylic acid, those commonly used as raw materials for polyesters, particularly polyester-based elastomers, can be used. Examples include terephthalic acid, isophthalic acid, phthalic acid, and 2,6-naphthalenedicarboxylic acid. mentioned. Among these, terephthalic acid and 2,6-naphthalenedicarboxylic acid are preferred, and terephthalic acid is particularly preferred. Two or more of these dicarboxylic acids may be used in combination. When alkyl esters of aromatic dicarboxylic acids are used, dimethyl esters and diethyl esters of the above dicarboxylic acids are used. Preferred are dimethylterephthalate and 2,6-dimethylnaphthalate.

iii) Polyalkylene ether glycols such as polyethylene glycol, poly(1,2 and 1,3-propylene ether) glycol, poly(tetramethylene ether) glycol, poly(hexamethylene ether) glycol, poly(decamethylene ether) ) glycols. Among these, poly(tetramethylene ether) glycol is particularly preferably used.

As the polyalkylene ether glycol, those having a number average molecular weight of 400 to 6,000 are usually used, those having a number average molecular weight of 600 to 4,000 are preferred, and those having a number average molecular weight of 900 to 3,000 are more preferred. When the number average molecular weight is at least the lower limit of the above range, it becomes easier to control the degree of modification with the unsaturated carboxylic acid and/or its derivative within a desired range, and it tends to become easier to develop sufficient adhesiveness. On the other hand, when the number average molecular weight is equal to or less than the upper limit of the above range, phase separation in the system can be suppressed, and deterioration of physical properties of the obtained polymer tends to be suppressed. The term "number average molecular weight" used herein is measured by nuclear magnetic resonance (NMR) analysis.
The polyalkylene ether glycol is used so that the polyalkylene ether glycol segment content in the polyester elastomer is 36 to 53% by mass, preferably 38 to 50% by mass.

In addition to the above components, a small amount of a trifunctional triol or tricarboxylic acid or an ester thereof may be copolymerized in the polyester-based elastomer, and an aliphatic dicarboxylic acid such as adipic acid or a dialkyl ester thereof may also be copolymerized. May be used as an ingredient.

Commercially available products may be used as the polyester-based elastomer, and examples of commercially available products include "TEFABLOCK (registered trademark)" manufactured by Mitsubishi Chemical Corporation, "Pelprene (registered trademark)" manufactured by Toyobo Co., Ltd., and Toray DuPont Co., Ltd. The company's "Hytrel (registered trademark)" can be mentioned.

One type of polyester-based elastomer may be used, or two or more types having different monomer compositions, physical properties, etc. may be subjected to modification with an unsaturated carboxylic acid and/or a derivative thereof.
As described above, when using two or more types of polyester-based elastomers, even if some polyester-based elastomers deviate from the polyalkylene ether glycol segment content of 35 to 53% by mass, the polyalkylene ether glycol segment as a whole The content should be within the range of 36 to 53% by mass.

[Unsaturated carboxylic acid and/or derivative thereof]
The unsaturated carboxylic acid used for modifying the polyester elastomer is preferably an α,β-ethylenically unsaturated carboxylic acid, such as acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, tetrahydrofumaric acid, and itaconic acid. , citraconic acid, crotonic acid, isocrotonic acid. Examples of unsaturated carboxylic acid derivatives include acid anhydrides and carboxylic acid esters of these unsaturated carboxylic acids, and derivatives such as acid halides, amides and imides. Among these derivatives, acid anhydrides are preferred.

Among these, maleic acid and/or its anhydride are particularly suitable as the unsaturated carboxylic acid and/or its derivative. Also, a plurality of these compounds may be used in combination. Furthermore, so-called vinylsilanes such as vinyltrimethoxysilane can be used in combination with unsaturated carboxylic acids and/or derivatives thereof.

[Radical generator]
A radical generator is usually used to carry out a radical reaction in modifying a polyester elastomer with an unsaturated carboxylic acid and/or a derivative thereof.
Radical generators include peroxyesters, dialkyl peroxides, diacyl peroxides, hydroperoxides, ketone peroxides and the like. Among these diacyl peroxides, dibenzoyl peroxide and 2,5-dimethyl-2,5-di(t-butylperoxy)hexane are preferably used. These radical generators may be appropriately selected according to the type of polyester elastomer, the type of unsaturated carboxylic acid and/or its derivative, and the modification conditions, and two or more of them may be used in combination. The radical generator can also be added by dissolving it in an organic solvent or the like.

[Method for producing modified polyester elastomer]
The modified polyester-based elastomer of the present invention may be produced by any known method, and may be a melt-kneading reaction method, a solution reaction method, or a suspension dispersion reaction method. preferable.

When the melt-kneading reaction method is used, the components (A) to (C) may be uniformly mixed at a predetermined compounding ratio and then melt-kneaded. For mixing, a Henschel mixer, ribbon blender, V-type blender, etc., can be used. For melt-kneading, a single-screw or twin-screw extruder, rolls, Banbury mixer, kneader, Brabender mixer, etc. can be used.
Melt-kneading is usually carried out at a temperature of 100°C or higher, preferably 120°C or higher, more preferably 150°C or higher, and usually 300°C or lower, preferably 280°C or lower, more preferably 250°C or lower, so as not to cause thermal deterioration of the resin. is done in

The amount of unsaturated carboxylic acid and/or derivative thereof used for modification is usually 0.01 parts by mass or more, preferably 0 parts by mass, based on a total of 100 parts by mass of the polyester elastomer of component (A). 05 parts by mass or more, more preferably 0.1 parts by mass or more, and usually 10 parts by mass or less, preferably 5 parts by mass or less, more preferably 1 part by mass or less. By setting the amount of the unsaturated carboxylic acid and/or derivative thereof to the above lower limit or more, sufficient modification can be easily performed, and by setting it to the above upper limit or less, not only is it economical, but it does not contribute to modification. It becomes easy to prevent the unsaturated carboxylic acid and/or its derivative from acting as an impurity and lowering the adhesiveness.

The amount of the component (C) radical generator compounded is usually 0.001 parts by mass or more, preferably 0.005 parts by mass or more, more preferably 0 parts by mass with respect to a total of 100 parts by mass of the polyester elastomer of component (A). 01 mass parts or more and usually 4 mass parts or less, preferably 3 mass parts or less, more preferably 2 mass parts or less. When the content of the radical generator is at least the above lower limit, the modification reaction is sufficiently likely to occur. You can suppress the decline. That is, in this modification reaction, a graft polymerization reaction in which the component (B) of the unsaturated carboxylic acid and/or its derivative is added to the component (A) mainly occurs, but a decomposition reaction also occurs. The material has a lower molecular weight and a lower material strength. If the amount of the radical generator used is too large, the graft polymerization reaction tends to occur, but at the same time, the decomposition reaction that leads to such molecular weight reduction also tends to occur, which is undesirable.

The product obtained by this modification reaction can be directly used for forming an adhesive resin layer as the modified polyester elastomer of the present invention, as will be described later.

[Polyalkylene ether glycol segment content of modified polyester elastomer]
The content of the polyalkylene ether glycol segment in the modified polyester-based elastomer of the present invention is 36-53% by mass. Since the polyalkylene ether glycol segment content of the modified polyester-based elastomer is 36 to 53% by mass, when this is used as an adhesive resin layer, it is possible to satisfy adhesiveness and solvent durability. If the content of the polyalkylene ether glycol segment in the modified polyester-based elastomer exceeds the upper limit of the above range, the crystallinity tends to decrease, resulting in poor solvent durability. If the polyalkylene ether glycol segment content of the modified polyester elastomer is less than the lower limit of the above range, the low-temperature impact resistance and the adhesion to ethylene-vinyl alcohol copolymers and polyamide resins tend to decrease. Become. From this point of view, the lower limit of the polyalkylene ether glycol segment content of the modified polyester elastomer of the present invention is preferably 38% by mass or more. On the other hand, the upper limit of the polyalkylene ether glycol segment content of the modified polyester-based elastomer of the present invention is preferably 50% by mass or less.

Here, the polyalkylene ether glycol segment content of the modified polyester elastomer is the polyalkylene ether glycol segment content of the modified polyester elastomer as a whole. That is, for example, when two or more modified polyester-based elastomers are mixed and used, even if one of them deviates from the polyalkylene ether glycol segment content of 36 to 53% by mass, the modified polyester-based elastomer as a mixture can be used. The polyalkylene ether glycol segment content of is within the range of 35 to 53% by mass.

[Acid Modification Rate of Modified Polyester Elastomer]
The modified polyester-based elastomer of the present invention may be produced by using an unsaturated carboxylic acid and/or a derivative thereof and a radical generator in the above-mentioned suitable blending amounts for a polyester-based elastomer, and the acid-modified Although the ratio is not particularly limited, it is preferably from 0.01 to 8. If the acid modification rate is at least the lower limit of the above range, sufficient adhesiveness to the gas barrier resin layer can be obtained. If the acid modification rate is equal to or less than the upper limit of the above range, discoloration due to unsaturated carboxylic acid and/or its derivative can be suppressed. The lower limit of the acid modification rate is more preferably 0.1 or more, still more preferably 0.15 or more, and particularly preferably 0.16 or more. The upper limit of the acid modification rate is more preferably 4 or less, and even more preferably 0.8 or less.
The acid modification rate of the modified polyester-based elastomer is measured and calculated by the method described in Examples below.

[Adhesive resin layer]
The adhesive resin layer according to the present invention preferably contains 50% by mass or more, more preferably 55% by mass or more, and still more preferably 60% by mass or more of the modified polyester elastomer of the present invention with respect to the total constituent components of the adhesive resin layer. do. If the content of the modified polyester-based elastomer is at least the above lower limit, the adhesiveness to the gas barrier resin layer and solvent durability can be sufficiently enhanced. The upper limit of the content of the modified polyester-based elastomer is not particularly limited, and may be 100% by mass.

The adhesive resin layer according to the present invention may contain optional components (hereinafter sometimes referred to as other components) in addition to the modified polyester-based elastomer of the present invention, as long as the effects of the present invention are not significantly impaired. can be compounded. The other components may be used alone or in combination of two or more in any combination and ratio.

Specific examples of other components include resin components other than the modified polyester elastomer of the present invention and rubber components (polyethylene terephthalate, polybutylene terephthalate and other polyester resins, polystyrene and other styrene resins, polyolefin resins, and Acrylic/methacrylic resins such as polymethyl methacrylate resins, etc.), heat stabilizers, weather stabilizers (antioxidants, light stabilizers, UV absorbers, etc.), flame retardants, antiblocking agents, slip agents, antistatic agents , fillers (inorganic and/or organic fillers, etc.), processing aids, plasticizers such as paraffin oil, crystal nucleating agents, impact modifiers, compatibilizers, neutralizing agents for catalyst residues, carbon black, coloring agents (pigments , dyes, etc.), antifogging agents, cross-linking agents, cross-linking aids, chain extenders, dispersants, antibacterial agents, antiviral agents, fluorescent whitening agents and the like. Among them, it is preferable to add at least one of various antioxidants such as phenol, phosphite, thioether, and aromatic amine antioxidants. The content of these antioxidants when used is not limited, but is usually 0.01% by mass or more, preferably 0.05% by mass or more, relative to all components constituting the adhesive resin layer. It is 5% by mass or less, preferably 2% by mass or less.

[Gas barrier resin layer]
The gas-barrier resin layer according to the present invention is preferably a resin layer containing an ethylene-vinyl alcohol copolymer as a main component. Ethylene-vinyl alcohol copolymers are produced by saponifying ethylene-vinyl acetate copolymers in the presence of alcohol. As the ethylene-vinyl alcohol copolymer constituting the gas barrier resin layer, an ethylene-vinyl acetate copolymer having an ethylene content of preferably 15 to 65 mol%, more preferably 20 to 50 mol%, is saponified. Saponification to a degree of preferably 50% or more, more preferably 90% or more is preferably used.
Examples of commercially available ethylene/vinyl alcohol copolymers include "Soarnol (registered trademark)" manufactured by Mitsubishi Chemical Corporation, "Eval (registered trademark)" manufactured by Kuraray Co., Ltd., and "Evasin" manufactured by Changchun Group. mentioned.

The gas-barrier resin layer may contain only one type of ethylene-vinyl alcohol copolymer, or may contain two or more types having different saponification degrees, monomer compositions, etc. The gas barrier resin layer preferably contains an ethylene-vinyl alcohol copolymer as a main component in an amount of usually 50% by mass or more, particularly 65 to 100% by mass, particularly 75 to 100% by mass. If the content of the ethylene-vinyl alcohol copolymer in the gas barrier resin layer is at least the above lower limit, excellent gas barrier properties can be obtained.

Components other than the ethylene-vinyl alcohol copolymer that may be contained in the gas barrier resin layer are not particularly limited, but include resin components such as polyolefin resins, styrene resins, acrylic/methacrylic resins, and heat stabilizers. , weather stabilizers (antioxidants, light stabilizers, UV absorbers, etc.), flame retardants, antiblocking agents, slip agents, fillers (inorganic and/or organic fillers, etc.), processing aids, plasticizers such as paraffin oil additives such as agents, crystal nucleating agents, impact modifiers, compatibilizers, neutralizers for catalyst residues, coloring agents (pigments, dyes, etc.).

[Polyester resin layer]
The laminate molded article of the present invention may further contain a layer of a polyester-based resin in order to impart functionality such as aroma preservability, rigidity, heat resistance, cold resistance, and surface printability. The polyester resin is produced by dehydration condensation of a polycarboxylic acid and a polyalcohol, and examples thereof include those obtained by polycondensation of a dicarboxylic acid and a diol.

The carboxylic acid is not particularly limited, but examples include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether-4,4-dicarboxylic acid, naphthalene-1,4- or 2,6-dicarboxylic acid, oxalic acid, Aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and undecadicarboxylic acid, and alicyclic dicarboxylic acids such as hexahydroterephteric acid can be mentioned.

Although the diol is not particularly limited, examples include alicyclic glycols such as ethylene glycol, propylene glycol, 1,4-butanediol and neopentyl glycol; alicyclic glycols such as cyclohexanedimethanol; and aromatics such as bisphenol A. Dihydroxy compounds are mentioned.

Examples of the polyester resin include polyethylene terephthalate (PET), copolymer PET, polybutylene terephthalate, polyethylene naphthalate, polycyclohexine terephthalate, and polyester elastomer. These polyester resins may be used alone, or may be used as a mixture with a plurality of polyester resins.

[Other layers]
The laminate molded article of the present invention may further have layers other than those described above. Other layers include layers made of resins other than the constituent resins of the adhesive resin layer, the gas barrier resin layer, and the polyester-based resin layer, and the base material layers described below.

The resin constituting the layer made of other resins is not limited, and specifically, the resins listed as other components in the adhesive resin layer, polyamide resins such as nylon 66 and nylon 11, cyclic polyolefin resins, poly Thermoplastic resins such as vinyl chloride, polyvinylidene chloride, and polycarbonate resins may be mentioned, but polyolefin resins and polyamide resins are preferred from the viewpoint of excellent co-extrusion properties with the modified polyester elastomer of the present invention.

Further, since the adhesive resin layer containing the modified polyester-based elastomer of the present invention is excellent in adhesiveness and solvent durability, it is laminated with a substrate layer such as a metal and/or a resin sheet through this adhesive resin layer. can also

The form of the base material layer is not limited to a film or sheet, and may be a woven fabric or non-woven fabric. Moreover, the substrate layer may have a single-layer structure or a multilayer structure. The method for producing the substrate having a multilayer structure is not particularly limited, and examples thereof include a coextruded film method, a dry lamination method, a wet lamination method, a hot melt lamination method, an extrusion lamination method, a thermal lamination method, and the like.

In addition to the adhesive resin layer containing the modified polyester-based elastomer of the present invention, the gas-barrier resin layer, the polyester-based resin layer, the layer of other resins, and the substrate layer made of the above-mentioned metals, etc., the laminated molded article of the present invention includes: Any layer can be provided.

[Laminate molding]
The laminated molded article of the present invention is a laminated molded article comprising an adhesive resin layer containing the modified polyester-based elastomer of the present invention and a gas barrier resin layer, and is a laminated molded article laminated in two or three or more layers. is preferred. Among them, it is preferable to have a gas-barrier resin layer containing an ethylene-vinyl alcohol copolymer as a main component and, if necessary, the polyester-based resin layer described above. In particular, a laminated molded body in which a polyester-based resin layer, an adhesive resin layer containing the modified polyester-based elastomer of the present invention, and a gas-barrier resin layer are laminated in this order is preferably used. In this case, for example, it is possible to form a laminate formed by laminating two or more partial layers such as polyester resin layer/adhesive resin layer/gas barrier resin layer/adhesive resin layer/polyester resin layer.

The laminate molded article of the present invention can also be a laminate molded article laminated in three or four or more layers, which further includes the other resin and/or metal layers described above.
Examples of the form of the laminated molded article of the present invention include laminated films, laminated sheets, laminated tubes, and the like. Here, the terms "film" and "sheet" are synonymous, both of which mean planar molded articles.

The overall thickness of the laminate molded article of the present invention is not particularly limited, and can be appropriately adjusted according to the application. The overall thickness of the laminated molded body of the present invention is preferably 20 μm or more, more preferably 50 μm or more, still more preferably 100 μm or more, and preferably 10 mm or less, more preferably 6 mm or less, and even more preferably 1 mm or less. When the thickness is within the above range, it becomes easy to produce a laminated molded product free from wrinkles and cracks.

The thickness of the adhesive resin layer containing the modified polyester elastomer of the present invention is preferably 1 μm or more, more preferably 5 μm or more, still more preferably 10 μm or more, and preferably 1 mm or less, more preferably 0.5 mm or less. 0.1 mm or less is more preferable.
The thickness of the gas barrier resin layer is generally 0.002 to 1 mm.
The thickness of the polyester resin layer is generally 0.01 to 3 mm.

[Manufacturing method of laminate]
As a method for producing the laminate molded article of the present invention, conventionally known various techniques can be employed. For example, blown films, cast films, sheets, tubes, pipes, bottles, and individual melted resins by a co-extrusion method in which individual molten resins melted in an extruder are supplied to a multilayer die and laminated in the die. are sequentially injected into the same mold, or co-extrusion lamination of unstretched test tube-shaped parisons and the like may be performed.

EXAMPLES The content of the present invention will be described in more detail below using examples, but the present invention is not limited by the following examples as long as the gist thereof is not exceeded. Various production conditions and values of evaluation results in the following examples have meanings as preferred values of the upper limit or lower limit in the embodiments of the present invention, and the preferred range is the above-mentioned upper limit or lower limit value, and the following It may be a range defined by the value of the example or a combination of the values of the examples.

〔raw materials〕
The raw materials used in the production of laminated molded bodies in the following examples and comparative examples are as follows.

[Adhesive resin layer]
<Component (A)>
A-1: Polyester Elastomer A polyester-polyether block copolymer comprising polybutylene terephthalate as a hard segment and polytetramethylene ether glycol having a number average molecular weight of 1,000 as a soft segment, wherein A polyester-based elastomer (density: 1.16 g/cm ³ , melting point: 189.9° C., JIS-D hardness: 43, MFR: 21 g/10 min) with a polytetramethylene ether glycol segment content of 45% by mass is used. board.
A-2: Polyester Elastomer A polyester-polyether block copolymer containing polybutylene terephthalate as a hard segment and polytetramethylene ether glycol having a number average molecular weight of 1,000 as a soft segment, wherein A polyester-based elastomer (density: 1.20 g/cm ³ , melting point: 205.1° C., JIS-D hardness: 54, MFR: 22 g/10 min) having a polytetramethylene ether glycol segment content of 32% by mass is used. board.
A'-1: Polyester Elastomer A polyester-polyether block copolymer containing polybutylene terephthalate as a hard segment and polytetramethylene ether glycol having a number average molecular weight of 2,000 as a soft segment, comprising: A polyester elastomer (density: 1.07 g/cm ³ , melting point: 160.1° C., JIS-D hardness: 24, MFR: 20 g/10 min) having a polytetramethylene ether glycol segment content of 73% by mass. Using.
A'-2: Polyester Elastomer A polyester-polyether block copolymer containing polybutylene terephthalate as a hard segment and polytetramethylene ether glycol having a number average molecular weight of 2,000 as a soft segment, comprising: A polyester elastomer (density: 1.10 g/cm ³ , melting point: 186.1° C., JIS-D hardness: 31, MFR: 21 g/10 min) having a polytetramethylene ether glycol segment content of 64% by mass. Using.
A'-3: Polyester Elastomer A polyester-polyether block copolymer containing polybutylene terephthalate as a hard segment and polytetramethylene ether glycol having a number average molecular weight of 1,000 as a soft segment, comprising: A polyester elastomer (density: 1.10 g/cm ³ , melting point: 160.6° C., JIS-D hardness: 38, MFR: 17 g/10 min) having a polytetramethylene ether glycol segment content of 61% by mass. Using.
A'-4: Polyester Elastomer A polyester-polyether block copolymer containing polybutylene terephthalate as a hard segment and polytetramethylene ether glycol having a number average molecular weight of 1,000 as a soft segment, wherein A polyester elastomer (density: 1.26 g/cm ³ , melting point: 220.0° C., JIS-D hardness: 60, MFR: 60 g/10 min) having a polytetramethylene ether glycol segment content of 20% by mass. Using.

<Component (B)>
B: Unsaturated carboxylic acid anhydride "Maleic anhydride (reagent special grade)" (particle size 5 to 10 mm) manufactured by Wako Pure Chemical Industries, Ltd. is pulverized using a small mixer so that the particle size is 1 mm or less. Using.

<Component (C)>
C: Benzoyl Peroxide "Nyper (registered trademark) BMTK-40" manufactured by NOF Corporation was used.

<Additive>
X: A phenol-based antioxidant "Irganox 1010 (registered trademark)" manufactured by BASF was used.

[Adhesive Resin Layer Not Containing Modified Polyester Elastomer]
Acid-modified polyethylene “Modic (registered trademark) H501E” (MFR: 0.8 g/10 min, density: 0.92 g/cm ³ ) manufactured by Mitsubishi Chemical Corporation was used.

[Gas barrier resin layer]
Ethylene-vinyl alcohol copolymer (EVOH)
"EVAL (registered trademark) L171B" manufactured by Kuraray Co., Ltd. was used.

[Polyester resin]
Mitsubishi Chemical Corporation "Tefablock (registered trademark) B1921" was used.

〔Evaluation method〕
In Examples and Comparative Examples, physical properties were evaluated by the following methods.

[Polyalkylene ether glycol segment content in polyester elastomer and modified polyester elastomer]
The polyalkylene ether glycol content in the polyester-based elastomer and the modified polyester-based elastomer was measured according to the method described above.

[Acid denaturation rate]
The acid modification rate is the content of the unsaturated carboxylic acid component in the modified polyester-based elastomer when measured with an infrared spectrometer (JASCOFT/IR610, manufactured by JASCO Corporation). The rate of acid modification is the absorption (1900 to 1600 cm ^-1 ) peculiar to unsaturated carboxylic acids and/or derivatives thereof in a sample obtained by press-molding modified polyester elastomer pellets into a sheet with a thickness of 20 to 50 µm at 230°C. and the absorption (1000 to 800 cm ⁻¹ ) peculiar to the aromatic ring in the hard segment.

[Measurement of degree of swelling]
The resulting modified polyester-based elastomer or comparative acid-modified polyethylene was injection molded at a melting temperature of 240°C and a mold temperature of 40°C to obtain a test piece having a length of 80 mm, a width of 10 mm and a thickness of 4 mm. was immersed at 60° C. for 168 hours in a mixed liquid in which an equal amount (volume) of was blended, and the degree of swelling (%) was calculated by the following formula.
Degree of swelling (%) = [{W ₁ -W ₀ }/W ₀ ] × 100
Specimen weight before immersion: W ₀ (g)
Specimen weight after immersion: W ₁ (g)
If the degree of swelling is 40% or less, deformation and embrittlement of the laminated molded product can be suppressed, and it was evaluated as being practical.

[Measurement of adhesive strength of laminate]
In general, if the interlayer strength of the laminate is 2 N/15 mm or more, it is considered that the strength is sufficient for practical use.
<Adhesive strength before solvent immersion>
The 5-layer film obtained in each example was cut into strips with a width of 15 mm parallel to the molding direction to form a test piece, and a T-peel peel test was performed at a speed of 300 mm / min in a constant temperature atmosphere of 23 ° C. to determine the adhesive strength. was measured. Here, the adhesive strength in Examples 1 to 3 and Comparative Examples 1 to 5 is the adhesive strength at the interface between the ethylene-vinyl alcohol copolymer layer and the adhesive resin layer. The adhesive strength of Comparative Example 6 is the adhesive strength at the interface between the polyester-based resin layer and the adhesive resin layer.
<Adhesive strength after solvent immersion>
For the 5-layer film obtained in each example, a strip-shaped test piece prepared in the same manner as described above was immersed in a mixed solution containing equal amounts (volumes) of isooctane/toluene at 60°C for 168 hours, and taken out for 5 minutes. Within that period, a T-peel peeling test was performed at a speed of 300 mm/min under a constant temperature atmosphere of 23°C to measure the adhesive strength. As described above, the adhesive strength in Examples 1 to 3 and Comparative Examples 1 to 5 is the adhesive strength at the interface between the ethylene-vinyl alcohol copolymer layer and the adhesive resin layer. The adhesive strength of Comparative Example 6 is the adhesive strength at the interface between the polyester-based resin layer and the adhesive resin layer.

[Example 1]
<Production of Modified Polyester Elastomer>
As shown in Table 1, 100 parts by mass of polyester elastomer A-1, 0.5 parts by mass of B, 0.1 parts by mass of C, and 0.1 parts by mass of X were used, and these were dry-blended and mixed. Melt and knead using a twin-screw extruder (manufactured by Nippon Steel Corporation, TEX25αIII, D = 25 mmφ, L / D = 53) at a set temperature of 180 to 240 ° C., a screw rotation speed of 200 to 400 rpm, and an extrusion rate of 15 to 30 kg / h. , to obtain a pellet-like modified polyester elastomer by strand cutting.
The degree of swelling of this modified polyester elastomer was measured.

<Production of laminate molded body>
Using a multi-layer film molding machine (Plagiken Co., Ltd.) having a 320 mm wide 4-type, 5-layer multi-manifold T-die, a polyester-based resin layer/an adhesive resin layer made of a modified polyester-based elastomer/an ethylene-vinyl alcohol copolymer layer was formed. A 5-layer film was produced as a laminate molding of /adhesive resin layer made of modified polyester elastomer/polyester resin layer. The temperature of the T-die was set to 250° C., the molding speed was 10 m/min., the cast roll temperature was 30° C., and the thickness of each layer was 140 μm/40 μm/40 μm/40 μm/140 μm to obtain a film with a total thickness of 400 μm.
Adhesion strength was measured for the obtained 5-layer film.

Table 1 shows the above measurement results.

[Examples 2-3, Comparative Examples 1-5]
In the production of the modified polyester-based elastomer, a modified polyester elastomer was obtained in the same manner as in Example 1 except that the blends shown in Table 1 were used. Table 1 shows the results.

[Comparative Example 6]
A laminated molded body was produced in the same manner as in Example 1, except that the acid-modified polyethylene "Modic H501E" was used instead of the modified polyester-based elastomer for the adhesive resin layer, and the adhesive strength was measured. Table 1 shows the results.

From Table 1, Examples 1 to 3, which are specific examples of the modified polyester-based elastomer of the present invention, show high adhesion to the ethylene-vinyl alcohol copolymer and the polyester-based resin layer, while exhibiting good solvent durability. It can be seen that the
On the other hand, in Comparative Examples 1 and 2, in which the polyalkylene ether glycol segment content of the modified polyester-based elastomer is lower than the specified range of the present invention, the acid modification rate is low, and the adhesiveness and solvent durability are inferior.
Comparative Examples 3 to 5, in which the polyalkylene ether glycol segment content of the modified polyester-based elastomer was higher than the specified range of the present invention, were inferior in solvent durability.
Comparative Example 6 using acid-modified polyethylene does not provide adhesiveness.

Claims (4)

A laminated molded article comprising at least an adhesive resin layer containing a modified polyester-based elastomer and a gas barrier resin layer,
The modified polyester-based elastomer is a polyester-based elastomer made of a polyester-polyether block copolymer composed of a hard segment containing an aromatic polyester and a soft segment containing a polyalkylene ether glycol segment, and an unsaturated carboxylic acid and/or or a modified polyester-based elastomer modified with a derivative thereof, and a polyalkylene ether glycol segment content in the modified polyester-based elastomer is 36 to 53% by mass. 2. The laminate molded article according to claim 1, wherein the adhesive resin layer contains 50% by mass or more of the modified polyester-based elastomer with respect to the entire constituent components of the adhesive resin layer. 3. The molded laminate according to claim 1, wherein the gas-barrier resin layer is a resin layer containing an ethylene-vinyl alcohol copolymer as a main component. 4. The laminate molding according to any one of claims 1 to 3, wherein the laminated molded body further has a polyester resin layer, and the adhesive resin layer is provided between the gas barrier resin layer and the polyester resin layer. body.