JP6370096B2 - Adhesive thermoplastic resin composition, method for producing the same, and laminate using the composition - Google Patents

Description

The present invention relates to an adhesive thermoplastic resin composition modified with an unsaturated carboxylic acid or a derivative thereof. More specifically, since the decrease in melt viscosity at the time of modification is suppressed, the adhesive thermoplastic resin composition has good manufacturability, excellent heat resistance and adhesiveness, and polyolefin-based adhesive with excellent film-forming properties The present invention relates to a thermoplastic resin composition.

Since the polyolefin polymer does not have a polar group in its molecular structure, it generally has a low polarity and has a problem of poor adhesion to a material having a polar group such as a hydroxyl group or a carboxyl group. One of the countermeasures for this problem is a method of graft-polymerizing a reactive monomer having a polar group such as an unsaturated carboxylic acid or a derivative thereof to a polyolefin polymer to improve its adhesion (often modified or acid-modified). Is known). In performing the modification, a catalyst such as an organic peroxide is generally used in order to perform the reaction efficiently. However, when the polypropylene polymer is modified, the main chain of the polypropylene polymer is cleaved (often called β-cleavage) by the organic peroxide, so that the resulting adhesive composition has a melt viscosity. There is a problem that it becomes extremely low.

As a method for solving this problem, it is conceivable to apply a technique (Patent Document 1) in which the modification is performed in the first half of the twin-screw extruder and the crystalline polyolefin is further side-fed in the second half. According to this technique, even if the melt viscosity is lowered in the first half, the melt viscosity of the obtained adhesive composition can be adjusted to a desired range by the crystalline polyolefin side-fed in the second half. Moreover, it is possible to apply the technique (for example, patent document 2) which mix | blends high molecular weight materials, such as a rubber substance, after modification | denaturation. However, these techniques cannot satisfy all the manufacturability of the adhesive composition and the physical properties such as heat resistance and adhesiveness of the obtained adhesive composition.

Japanese Patent Laid-Open No. 04-272950 Japanese Patent Publication No.54-040112

The problem of the present invention is that since the decrease in melt viscosity at the time of modification is suppressed, the productivity of the adhesive thermoplastic resin composition is good, the heat resistance and the adhesiveness are excellent, and the film-forming property is also excellent. An object of the present invention is to provide a polyolefin-based adhesive thermoplastic resin composition, a production method thereof, and a laminate using the composition.

As a result of intensive studies, the present inventor has found that a specific thermoplastic resin composition can achieve the above-described problem.

That is, the present invention
(Α) 100 parts by mass of a polyolefin-based polymer;
(D) one or more selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid derivatives 0.05 to 5.0 parts by mass; and (e) organic peroxides 0.05 to 5.0 parts by mass Part;
Where (α) the polyolefin polymer is
(Beta) polypropylene polymer 55-90 mass parts which consists of (a) crystalline polypropylene polymer 10-60 mass% and (b) polypropylene polymer plastomer 90-40 mass%;
(C) 45 to 10 parts by mass of a polyethylene-based polymer;
Is a thermoplastic resin composition (A).
However, the sum of the said component (a) and the said component (b) is 100 mass%, and the sum of the said polymer ((beta)) and the said component (c) is 100 mass parts.

The second invention includes 10 to 45 parts by mass of the thermoplastic resin composition (A) according to the first invention; and (f) 90 to 55 parts by mass of a polypropylene polymer; The sum of (A) and the said component (f) is a thermoplastic resin composition (B) which is 100 mass parts.

3rd invention is a manufacturing method of the composition (B) as described in 2nd invention, Comprising: The mixture containing the said component (a)-(e) is melt-kneaded, The said composition (A) is obtained. Thereafter, a mixture containing the composition (A) and the component (f) is melt-kneaded.

4th invention is the thermoplastic resin composition (B) obtained by the method as described in 3rd invention.

5th invention is a laminated body which has at least 1 layer (p) which consists of a thermoplastic resin composition (A) as described in 1st invention.

6th invention is a laminated body which has at least 1 layer (q) which consists of a thermoplastic resin composition (B) as described in 2nd invention or 4th invention.

7th invention is a laminated body as described in 5th invention by which the polypropylene-type polymer layer, the said layer (p), and an ethylene-vinyl alcohol copolymer layer are laminated | stacked directly in this order.

The eighth invention is the laminate according to the sixth invention, in which the polypropylene polymer layer, the layer (q), and the ethylene-vinyl alcohol copolymer layer are directly laminated in this order.

The polyolefin-based adhesive thermoplastic resin composition of the present invention has good manufacturability of the composition, excellent heat resistance, and excellent film formability. Also, resins having polar groups such as ethylene-vinyl alcohol copolymer (EVOH), nylon, and polyester; nonpolar resins such as polyethylene, polypropylene, poly 1-butene, and poly 4-methyl-1-pentene; and metals Excellent adhesion to Therefore, it can be suitably used as a material for forming the adhesive layer of the laminate.

Thermoplastic resin composition (A)
The thermoplastic resin composition (A) of the present invention comprises (α) 100 mass parts of a polyolefin polymer; (d) one or more selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid derivative. 05-5.0 parts by mass; and (e) 0.05-5.0 parts by mass of organic peroxide.

In this specification, the term “polymer” is used as a term including a resin mixture or a resin composition composed of two or more polymers.

The (α) polyolefin polymer comprises (a) 10 to 60% by mass of a crystalline polypropylene polymer and (b) 90 to 40% by mass of a polypropylene polymer plastomer (β) polypropylene polymer 55 And 90 parts by mass; and (c) 45 to 10 parts by mass of a polyethylene-based polymer. However, the sum of the said component (a) and the said component (b) is 100 mass%, and the sum of the said polymer ((beta)) and the said component (c) is 100 mass parts.

(A) Crystalline polypropylene-based polymer The crystalline polypropylene-based polymer used as the component (a) of the present invention is a polymer containing propylene as a main monomer, and has an isotactic fraction of propylene chain ( It is distinguished from the component (b) in that it has high stereoregularity and high crystallinity.

In this specification, crystalline polypropylene is a Diamond DSC type differential scanning calorimeter manufactured by PerkinElmer Japan Co., Ltd., maintained at 230 ° C. for 5 minutes, cooled to −10 ° C. at 10 ° C./min, and −10 In the second melting curve (melting curve measured in the last temperature rising process) measured by a program that holds at 5 ° C. for 5 minutes and raises the temperature to 230 ° C. at 10 ° C./min, the peak top melting point on the highest temperature side is It means more than 110 ° C, preferably more than 120 ° C. The melting enthalpy is usually more than 50 J / g, preferably 60 J / g or more.

As the component (a), (a1) propylene homopolymer, (a2) random copolymer of propylene and α-olefin comonomer, and (a3) block copolymer of propylene and α-olefin comonomer (crystals) And a propylene homopolymer (a copolymer composed of a propylene homopolymer or a random copolymer of propylene and an α-olefin comonomer) and a copolymer rubber component of propylene and an α-olefin comonomer). . As the component (a), one or a mixture of two or more of these can be used.

The (a1) propylene homopolymer is a polymer having a high isotactic fraction (stereoregularity) of propylene chain, but if desired, disorder of stereoregularity such as a meso racemic structure or a racemic racemic structure; The crystallinity may be adjusted by including misinsertion such as insertion or 1-3 insertion.

Examples of the α-olefin comonomer that can be used in the random copolymer of propylene and α-olefin comonomer (a2) include ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 2-methyl-1-propene, 2-methyl-1-butene, 3-methyl-1-butene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 3-methyl- Examples thereof include 1-pentene and 4-methyl-1-pentene, and one or more of these can be used.

The polymer (a2) is a polymer having a high isotactic fraction (stereoregularity) of a propylene chain, but if desired, disruption of stereoregularity such as a meso racemic structure or a racemic racemic structure; The crystallinity may be adjusted by including misinsertion such as 1-3 insertion.

The content of the α-olefin comonomer in the polymer (a2) depends on the catalyst system used for the production of the polymer (a2) (polymers having greatly different comonomer composition distribution and steric regularity of propylene chain depending on the catalyst system). For example, in the case of a metallocene catalyst, it is usually 6 mol% or less. In the case of a Ziegler-Natta catalyst, it is usually 9 mol% or less.

The (a3) block copolymer of propylene and α-olefin comonomer is composed of a crystalline polypropylene component (propylene homopolymer or random copolymer of propylene and α-olefin comonomer), propylene and α-olefin comonomer. A copolymer composed of a copolymer rubber component.

The propylene homopolymer as the crystalline polypropylene component is the same polymer as the polymer (a1). A random copolymer of propylene and an α-olefin comonomer as the crystalline polypropylene component is the same polymer as the polymer (a2). Both have been described above.

From the viewpoint of miscibility with the crystalline polypropylene component, the copolymer rubber component of propylene and an α-olefin comonomer is usually propylene as a main monomer (usually 50 mol% or more, preferably 70 mol% or more). Polymer. The stereoregularity (isotactic fraction and syndiotactic fraction) of the propylene chain is arbitrary, and may be high or low. There may also be erroneous insertion.

Examples of the α-olefin comonomer that can be used for the copolymer rubber component of propylene and α-olefin comonomer include those described above in the description of the polymer (a2), and one or two of these can be used. The above can be used.

The content of the α-olefin comonomer in the copolymer rubber component of the propylene and α-olefin comonomer depends on the catalyst system used to produce the rubber component (depending on the catalyst system, the comonomer composition distribution and the steric rule of the propylene chain). However, in the case of a metallocene catalyst, it is usually at least 7 mol%, preferably at least 8 mol%. In the case of a Ziegler-Natta catalyst, it is usually at least 10 mol%, preferably at least 12 mol%.

As said component (a), the said polymer (a2) and the said polymer (a3) are preferable from a viewpoint of suppressing the melt viscosity fall at the time of modification | denaturation. From the viewpoint of adhesiveness of the adhesive composition, the polymer (a2) is preferable. Further, from the viewpoints of manufacturability of the adhesive composition and film formability, a melt mass flow rate (hereinafter abbreviated as MFR-a) measured under the conditions of 230 ° C. and 21.18 N in accordance with JIS K 7210: 1999. Is preferably 0.1-80 g / 10 min.

(B) Polypropylene polymer plastomer The polypropylene polymer plastomer used as the component (b) of the present invention is a polymer containing propylene as a main monomer and has amorphous or low crystallinity. Is distinguished from the component (a). Component (b) functions to suppress a decrease in melt viscosity at the time of modification and to improve the adhesiveness of the resulting adhesive composition.

In this specification, an amorphous or low-crystalline polypropylene polymer is a Diamond DSC differential scanning calorimeter manufactured by PerkinElmer Japan Co., Ltd., held at 230 ° C. for 5 minutes, and at 10 ° C./min. In the second melting curve (melting curve measured in the last heating process) measured by a program that cools to −10 ° C., holds at −10 ° C. for 5 minutes, and raises the temperature to 230 ° C. at 10 ° C./min. It means that there is no clear melting peak, or the peak top melting point on the highest temperature side is 110 ° C. or lower, preferably 100 ° C. or lower, more preferably 90 ° C. or lower. The melting enthalpy is usually 50 J / g or less, preferably 40 J / g or less, more preferably 30 J / g or less.

Examples of the component (b) include (b1) a propylene homopolymer, (b2) a random copolymer of propylene and an α-olefin comonomer, and (b3) a block copolymer of propylene and an α-olefin comonomer. be able to. As the component (b), one or a mixture of two or more of these can be used.

The (b1) propylene homopolymer has a disorder of stereoregularity (meso-racemic structure or racemic racemic structure in the case of isotactic polypropylene; meso-racemic structure or meso-meso structure in the case of syndiotactic polypropylene); 1-2 insertion or 1 -3 misinsertion such as insertion; and the like, and a polymer having a low propylene chain stereoregularity.

From the viewpoint of miscibility with the component (a), the random copolymer of propylene and the α-olefin comonomer (b2) is composed of propylene as a main monomer (usually 50 mol% or more, preferably 70 mol% or more). Polymer. The stereoregularity of the propylene chain is arbitrary and may be high or low. There may also be erroneous insertion.

As an alpha olefin comonomer which can be used for the said polymer (b2), what was mentioned above in description of the said polymer (a2) can be mention | raise | lifted, These 1 type (s) or 2 or more types can be used.

The content of the α-olefin comonomer in the polymer (b2) depends on the catalyst system used for the production of the polymer (b2) (the comonomer composition distribution and the stereoregularity of the propylene chain differ greatly depending on the catalyst system). For example, in the case of a metallocene catalyst, it is usually at least 7 mol%, preferably at least 8 mol%. In the case of a Ziegler-Natta catalyst, it is usually at least 10 mol%, preferably at least 12 mol%.

The block copolymer of (b3) propylene and an α-olefin comonomer is a low crystalline polypropylene component (a propylene homopolymer or a random copolymer of propylene and an α-olefin comonomer), propylene and an α-olefin comonomer. A copolymer rubber component.

The propylene homopolymer as the low crystalline polypropylene component is the same polymer as the polymer (b1). The random copolymer of propylene and an α-olefin comonomer as the low crystalline polypropylene component is a polymer similar to the polymer (b2). The copolymer rubber component of propylene and α-olefin comonomer is a polymer similar to the copolymer rubber component of propylene and α-olefin comonomer of the polymer (a3). Both have been described above.

The component (b) is preferably the polymer (b2) from the viewpoint of suppressing a decrease in melt viscosity at the time of modification and improving the adhesion of the adhesive composition, and is a heavy polymer produced using a metallocene catalyst. Combined (b2) is more preferred.

Furthermore, from the viewpoint of manufacturability of the adhesive composition and film formability, a melt mass flow rate (hereinafter abbreviated as MFR-b) measured under the conditions of 230 ° C. and 21.18 N in accordance with JIS K 7210: 1999. Is preferably 0.1-80 g / 10 min. More preferably, it is 0.2-50 g / 10min, More preferably, it is 0.5-30 g / 10min.

The stereoregularity of the components (a), (b), and (f), and the type and content of the comonomer can be determined from a ¹³ C-NMR spectrum. JP-A-9-208629, JP-A-11-255833, JP-A-11-255834, JP-A-2002-047383, and publications cited therein can be referred to for the measurement method. .

Examples of the commercially available component (b) include “VERSIFY (trade name)” manufactured by Dow Chemical Co., “VISTAMAX (trade name)” manufactured by ExxonMobil.

(C) Polyethylene polymer The polyethylene polymer used as the component (c) of the present invention is a polymer containing ethylene as a main monomer, and reduces the melt viscosity of the thermoplastic resin composition of the present invention. It works to suppress.

Examples of the component (c) include high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, a random copolymer of ethylene and α-olefin, an ethylene-vinyl acetate copolymer, and ethylene- An acrylic ester copolymer can be used. As the component (c), one or a mixture of two or more of these can be used.

Examples of the α-olefin comonomer used in the random copolymer of ethylene and α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene and 2-methyl. -1-propene, 2-methyl-1-butene, 3-methyl-1-butene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 3-methyl-1-pentene, and 4- Examples thereof include methyl-1-pentene, and one or more of these can be used.

The component (c) is preferably a random copolymer of ethylene and an α-olefin produced using a metallocene catalyst from the viewpoint of suppressing a decrease in melt viscosity during modification, and produced using a metallocene catalyst. Random copolymer of ethylene and α-olefin having a density of 850 to 900 Kg / m ³ (based on JIS K7112: 1999, measured by an underwater substitution method) was more preferable, and was produced using a metallocene catalyst. A random copolymer of ethylene and 1-octene having a density of 850 to 900 Kg / m ³ is more preferable.

In addition, from the viewpoint of manufacturability of the adhesive composition and film formability, a melt mass flow rate (hereinafter abbreviated as MFR-c) measured under the conditions of 190 ° C. and 21.18 N in accordance with JIS K 7210: 1999. Is preferably 0.1 to 20 g / 10 min. More preferably, it is 0.3-10 g / 10min.

(Α) Polyolefin polymer The polymer (α) comprises the polymer (β) and the component (c). Here, the sum of the polymer (β) and the component (c) is 100 parts by mass. The blending ratio of the polymer (β) and the component (c) is such that molding processability such as film-forming property of the adhesive composition, and poor appearance such as blisters on the film obtained by forming the adhesive composition. From the viewpoint of preventing the occurrence of water, the polymer (β) is 55 parts by mass or more (component (c) 45 parts by mass or less). The polymer (β) is preferably 60 parts by mass or more (component (c) 40 parts by mass or less), and more preferably the polymer (β) 65 parts by mass or more (component (c) 35 parts by mass or less). Moreover, from a viewpoint of suppressing the melt viscosity fall at the time of modification | denaturation and preventing the gel generation | occurrence | production at the time of film forming of an adhesive composition, it is 90 mass parts or less (component (c) 10 mass parts or more). . The polymer (β) is preferably 85 parts by mass or less (component (c) 15 parts by mass or more). More preferably, it is 80 parts by mass or less (component (c) 20 parts by mass or more) of the polymer (β).

(Β) Polypropylene polymer The polymer (β) comprises the component (a) and the component (b). Here, the sum of component (a) and component (b) is 100% by mass. The compounding ratio of the component (a) and the component (b) is 10% by mass or more of the component (a) (90% by mass or less of the component (b)) from the viewpoints of manufacturability and adhesiveness of the adhesive composition. . Preferably it is 20 mass% or more (component (b) 80 mass% or less) of a component (a), More preferably, it is 25 mass% or more (component (b) 75 mass% or less) of a component (a). Moreover, it is a component (a) 60 mass% or less (component (b) 40 mass% or more) from a viewpoint of suppressing the melt viscosity fall at the time of modification | denaturation and preventing the gel generation at the time of film forming of the adhesive composition. Preferably it is 45 mass% or less (component (b) 55 mass% or more) of a component (a), More preferably, it is 40 mass% or less (component (b) 60 mass% or more) of a component (a).

(D) Unsaturated carboxylic acid, derivative of unsaturated carboxylic acid Component (d) of the present invention is one or more selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid derivative. Yes, a resin having a polar group such as ethylene-vinyl alcohol copolymer (EVOH), nylon, and polyester, which is graft-polymerized with the above components (a) to (c) and is added to the thermoplastic resin composition of the present invention; It works to give adhesion to metal.

Examples of the unsaturated carboxylic acid include maleic acid, itaconic acid, fumaric acid, acrylic acid, and methacrylic acid. Examples of unsaturated carboxylic acid derivatives include maleic acid monoester, maleic acid diester, maleic anhydride, itaconic acid monoester, itaconic acid diester, itaconic anhydride, fumaric acid monoester, fumaric acid diester, fumaric anhydride, acrylic acid Examples thereof include alkyl acrylates such as methyl and alkyl methacrylates such as methyl methacrylate. As said component (d), these 1 type, or 2 or more types of mixtures can be used.

As the component (d), maleic anhydride is preferable from the viewpoint of reactivity with the components (a) to (c) and the adhesiveness of the adhesive composition.

The compounding amount of the component (d) is 0.05 parts by mass or more from the viewpoint of improving the adhesiveness of the adhesive composition with respect to 100 parts by mass of the (α) polyolefin polymer. Preferably it is 0.2 mass part or more, More preferably, it is 0.5 mass part or more. In addition, from the viewpoint of preventing the component (d) from remaining unreacted in the adhesive composition at the time of modification and causing an appearance defect such as gel in an article made of the adhesive composition, 5.0 parts by mass or less. It is. Preferably it is 4.0 mass parts or less, More preferably, it is 3.0 mass parts or less.

(E) Organic peroxide The component (e) of the present invention is an organic peroxide and catalyzes the graft polymerization reaction of the components (a) to (c) with the component (d). Work.

Examples of the component (e) include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl- 2,5-di (tert-butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5- Trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert- Butyl peroxyisopropyl carbonate, diacetyl peroxide Lauroyl peroxide, etc. tert- butyl cumyl peroxide and the like. As the component (e), one or a mixture of two or more of these can be used.

As the component (e), 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2 is used from the viewpoint of manufacturability and adhesiveness of the adhesive composition. , 5-Di- (tert-butylperoxy) hexyne-3 is preferred.

The amount of the component (e) is 0 with respect to 100 parts by mass of the (α) polyolefin polymer from the viewpoint of improving the adhesiveness of the adhesive composition and preventing gel formation during film formation. .05 parts by mass or more. Preferably it is 0.2 mass part or more, More preferably, it is 0.5 mass part or more. Moreover, it is 5.0 mass parts or less from a viewpoint of suppressing the melt viscosity fall at the time of modification | denaturation. Preferably it is 4.0 mass parts or less, More preferably, it is 3.0 mass parts or less.

In the composition (A), a component other than the components (a) to (e), for example, a thermoplastic resin other than the components (a) to (c) is optionally added, as long as the object of the present invention is not adversely affected. Pigments, inorganic fillers, organic fillers, resin fillers; additives such as lubricants, antioxidants, weathering stabilizers, heat stabilizers, mold release agents, antistatic agents, and surfactants; Can do.

Production of thermoplastic resin composition (A) The thermoplastic resin composition (A) of the present invention comprises the above-mentioned components (a) to (e) and optional components used as required, and any melt kneader. It is obtained by melt-kneading using The conditions of the melt-kneading are preferably one minute and a half of the component (e) from the viewpoint that the component (d) and the component (e) react completely and do not remain unreacted in the composition (A). It is 1 minute or more at a temperature equal to or higher than the initial temperature, more preferably 2 minutes or higher at a temperature equal to or higher than the 1 minute half-life temperature of the component (e). Moreover, based on JISK7210: 1999 of a composition (A), the melt mass flow rate (henceforth abbreviated as MFR-A) measured on condition of 230 degreeC and 21.18N is 1.0 g / 10. It is preferable to select a condition that results in at least minutes. Manufacturability of the composition (A) is improved. Moreover, it is preferable to select the conditions which become 100 g / 10min or less. The moldability at the time of molding a laminate using the composition (A) and the adhesiveness of the composition (A) are improved.

Examples of the melt kneader include batch kneaders such as a pressure kneader and a mixer; extrusion kneaders such as a single screw extruder, a co-rotating twin screw extruder, and a different direction rotating twin screw extruder; a calendar roll kneader; Can give. These may be used in any combination. The obtained composition (A) can be pelletized by an arbitrary method and then formed into an arbitrary article by an arbitrary method. Alternatively, the melt-kneaded composition (A) may be formed into an arbitrary article as it is by an arbitrary method. The pelletization can be performed by methods such as hot cut, strand cut, and underwater cut.

Thermoplastic resin composition (B)
The thermoplastic resin composition (B) of the present invention comprises 10 to 45 parts by mass of the thermoplastic resin composition (A); and (f) 90 to 55 parts by mass of a polypropylene-based polymer. Here, the sum of the composition (A) and the component (f) is 100 parts by mass.

The thermoplastic resin composition (A) has been described above.

(F) Polypropylene polymer Component (f) of the present invention is a component used for the purpose of obtaining a thermoplastic resin composition (B). The component (f) is a polymer containing propylene as a main monomer, and is a crystalline polypropylene polymer (described above in the description of the component (a)) and a polypropylene polymer plastomer (description of the component (b). Any of the above can be used. As the component (f), one or a mixture of two or more of these can be used.

The polypropylene polymer used as the component (f) of the present invention may be the same polymer as the component (a) or the component (b), or may be a different polymer, and is not limited.

As said component (f), a random copolymer and a block copolymer are preferable from a viewpoint of the adhesiveness of the said composition (B), and a random copolymer is more preferable.

The blending ratio of the composition (A) to the component (f) is 10 parts by mass or more (component (f) 90 parts by mass or less) of the composition (A) from the viewpoint of adhesiveness of the composition (B). It is. Preferably it is 15 mass parts or more (component (f) 85 mass parts or less) of a composition (A), More preferably, it is 20 mass parts or more (component (f) 80 mass parts or less) of a composition (A). From the viewpoint of obtaining the effect of improving the molding processability when the component (f) is blended to form an article comprising the composition (B), the composition (A) is 45 parts by mass or less (component (f) 55 parts by mass). Above). Preferably it is 40 mass parts or less (component (f) 60 mass parts or more) of a composition (A), More preferably, it is 30 mass parts or less (component (f) 70 mass parts or more) of a composition (A).

The composition (B) may contain other components than the components (a) to (f), for example, other than the components (a) to (c) and (f), as long as it does not contradict the purpose of the present invention. Thermoplastic resins; pigments, inorganic fillers, organic fillers, resin fillers; additives such as lubricants, antioxidants, weathering stabilizers, thermal stabilizers, mold release agents, antistatic agents, and surfactants; It can be further included.

Production of thermoplastic resin composition (B) The thermoplastic resin composition (B) of the present invention comprises the above-mentioned components (a) to (f) and optional components used as required in any melt kneader. It is obtained by melt-kneading using

The composition (B) is preferably prepared by melt-kneading the components (a) to (e) and optional components used as required using an optional melt-kneader. After being obtained, the composition (A), the component (f), and an optional component used as required are obtained by melt-kneading using an optional melt-kneader. The conditions in the first melt-kneading step are that the component (d) and the component (e) react completely and do not remain unreacted in the composition (A), and the melt viscosity of the composition (B) is desired. From the viewpoint of facilitating the adjustment to the above range, it is preferably at least 1 minute half-life temperature of the component (e) for 1 minute, more preferably at least 1 minute half-life temperature of the component (e). 2 minutes or longer. The melt mass flow rate (hereinafter sometimes abbreviated as MFR-B) measured under the conditions of 230 ° C. and 21.18 N in accordance with JIS K7210: 1999 of the composition (B) is produced in the subsequent melt-kneading step. From the viewpoint of improving the properties, 0.5 g / 10 min or more is preferable. Moreover, from the viewpoint of the moldability at the time of shape | molding a laminated body using a composition (B) and the adhesiveness of a composition (B), 15 g / 10min or less is preferable.

As an apparatus used for manufacture of the said composition (B), what was mentioned above in manufacture of the said composition (A) can be used.

In the composition (A) and the composition (B), a polar group such as a carboxyl group is introduced into a polyolefin-based nonpolar material and exhibits good adhesiveness with various materials. Examples of the nonpolar material exhibiting good adhesion include nonpolar resins such as polyethylene, polypropylene, poly 1-butene, and poly 4-methyl-1-pentene. Examples of polar materials include resins having polar groups such as ethylene-vinyl alcohol copolymer (EVOH), nylon, and polyester; and metals such as iron, aluminum, copper, and tin, and oxides of the metal Materials; In particular, it is surprising that both polypropylene and ethylene-vinyl alcohol copolymer having a large amount of hydroxyl groups exhibit good adhesion. Therefore, the composition (A) or the composition (B) can be suitably used as an adhesive material.

Laminate As a preferable article using the composition (A), a laminate having at least one layer (p) composed of the composition (A) can be mentioned. As a preferable article using the composition (B), a laminate having at least one layer (q) made of the composition (B) can be mentioned. The laminated body may have both the layer (p) and the layer (q).

From the viewpoint of adhesiveness, the thickness of the layer (p) or the layer (q) is usually 1 μm or more, preferably 2 μm or more. Moreover, from a viewpoint of economical efficiency, it is 100 micrometers or less normally, Preferably it is 30 micrometers or less.

Moreover, the whole thickness of the said laminated body is 10-1000 micrometers normally from a viewpoint of the manufacturability of a laminated body, mechanical strength, and web handling property, Preferably it is 20-150 micrometers.

One example of a more preferred embodiment of the laminate is a laminate in which a polypropylene polymer layer, the layer (q), and an ethylene-vinyl alcohol copolymer layer are directly laminated in this order. Another example of a more preferred embodiment is a laminate in which a polypropylene polymer layer, the layer (q), and an ethylene-vinyl alcohol copolymer layer are directly laminated in this order. As a laminated body which has the heat-sealing property of a polypropylene-type polymer and the barrier property of ethylene-vinyl alcohol copolymerization, it can use suitably as packaging materials, such as a foodstuff and a medical instrument, for example.

The method for producing the laminate is not limited and can be produced by any method using any device. For example, a method in which the constituent materials of each layer are melted in each extruder and obtained by T-die coextrusion by a feed block method or a multi-manifold method; after at least one resin film is obtained by any method, the film Examples thereof include an extrusion laminating method in which other resin layers are melt-extruded; a method in which the resin film of each layer is obtained by an arbitrary method and then integrated by thermal lamination; and the like.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these.

Measuring method (1) Melt mass flow rate:
It measured based on JISK7210: 1999. The conditions of temperature and load are described above in the description of each component, polymer, and composition.

(2) Adhesiveness:
In accordance with JIS Z 0237: 2009, a sample was taken from the multilayer film obtained in the following (4) so that the machine direction of the film was the peeling direction, and an adhesive composition layer, an ethylene-vinyl alcohol copolymer layer, The layer was peeled 180 ° at a test speed of 300 mm / min. Although the adhesive strength depends on the application, it may be 4N / 15 mm or more, and preferably 12 N / 15 mm or more.

(3) Manufacturability of the adhesive composition:
The adhesive composition was evaluated based on whether it could be pelletized by a die cutter when granulating by a strand cut method. Those that could obtain pellets of good shape were marked with “◯”, and those that were not so were marked with “x”.

(4) Multilayer film-forming properties:
Using a multi-layer film-forming apparatus equipped with an extruder, a feed block, and a T-die, Prime Polymer Co., Ltd., a polypropylene (random copolymer of propylene and ethylene) “F-730NV (trade name)”, adhesiveness The composition, Kuraray Co., Ltd.'s ethylene-vinyl alcohol copolymer “Eval F-171B (trade name)” was directly laminated in this order, polypropylene was the extruder tip temperature 180 ° C., and the adhesive composition was Extruder tip temperature 180 ° C, ethylene-vinyl alcohol copolymer was extruded under conditions of extruder tip temperature 170 ° C, feed block set temperature 220 ° C, T-die outlet resin temperature 220 ° C, polypropylene layer thickness 20 µm, adhesive composition The film was formed under the conditions of a layer thickness of 10 μm and an ethylene-vinyl alcohol copolymer layer of 10 μm. “◯” indicates that a good film was obtained, and “x” indicates that it was not. In addition, “−” indicates that the test sample (2) could not be prepared.

Raw materials used Component (a):
(A-1) Propylene-ethylene random copolymer “EG7F (trade name)” of Nippon Polypro Co., Ltd., MFR-a 1.3 g / 10 min, ethylene content 3 mol%, peak top melting point 143 ° C., melting enthalpy 92J / G.
(A-2) Propylene-ethylene block copolymer “VB370A (trade name)” of Sun Allomer Co., Ltd., MFR-a 1.5 g / 10 min, peak top melting point 160 ° C., melting enthalpy 90 J / g.
(A-3) Propylene homopolymer “VS200A (trade name)” of Sun Allomer Co., Ltd., MFR-a 0.5 g / 10 min, peak top melting point 165 ° C., melting enthalpy 120 J / g.

Component (b):
(B-1) Propylene-ethylene random copolymer “VERSIFY 2300 (trade name)” of Dow Chemical Company, MFR-b 2.0 g / 10 min, ethylene content 12 mol%, non-crystalline (DSC second melting curve) No clear peak.), Density 867 Kg / m ³ .

Component (c):
(C-1) Ethylene-octene copolymer “ENGAGE 8150 (trade name)” manufactured by Dow Chemical Co., Ltd., density 868 Kg / m ³ , MFR-c 0.5 g / 10 min

Component (d):
(D-1) Maleic anhydride of Nippon Shokubai Co., Ltd.

Ingredient (e):
(E-1) 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane “Perhexa 25B (trade name)” manufactured by NOF Corporation, 1 minute half-life temperature 180 ° C.

Component (f):
(F-1) Propylene-ethylene random copolymer “F-730NV (trade name)” of Prime Polymer Co., Ltd., MFR-a 7.0 g / 10 min, ethylene content 5 mol%, peak top melting point 139 ° C., melting Enthalpy 88J / g.
(F-2) Propylene-ethylene random copolymer “EG7F (trade name)” of Nippon Polypro Co., Ltd., MFR-a 1.3 g / 10 min, ethylene content 3 mol%, peak top melting point 143 ° C., melting enthalpy 92J / G.
(F-3) Propylene-ethylene block copolymer “VB370A (trade name)” of Sun Allomer Co., Ltd., MFR-a 1.5 g / 10 min, peak top melting point 160 ° C., melting enthalpy 90 J / g.
(F-4) Propylene homopolymer “VS200A (trade name)” of Sun Allomer Co., Ltd., MFR-a 0.5 g / 10 min, peak top melting point 165 ° C., melting enthalpy 120 J / g.

Polymer β
Polymers β-1 to 9 having the composition shown in Table 1 were obtained.

Examples 1-13, Comparative Examples 1-8
Using the same-direction rotating twin-screw extruder, the mixture having the composition shown in any one of Tables 2 to 4 is collectively fed and melt-kneaded under the condition of the extruder outlet resin temperature of 190 ° C. Obtained. About the obtained adhesive composition, said evaluation (1)-(4) was performed. The results are shown in any one of Tables 2-4.

Examples 14 to 24, Comparative Example 9
Using the same-direction rotating twin-screw extruder, a mixture having the composition shown in Table 5 or 6 was collectively fed, and melt-kneaded under the condition of an extruder outlet resin temperature of 180 ° C. to obtain an adhesive composition. About the obtained adhesive composition, said evaluation (1)-(4) was performed. The results are shown in Table 5 or 6.

The adhesive composition according to the present invention has a suitable melt mass flow rate value, and the adhesiveness, the productivity of the adhesive composition, and the film formability of the multilayer film are all good.

On the other hand, since Comparative Example 1 had less component (a) than the predetermined range (more component (b) than the predetermined range), the result was inferior in manufacturability and adhesiveness of the adhesive composition. In Comparative Example 2, since the component (a) is larger than the predetermined range (the component (b) is smaller than the predetermined range), a drastic decrease in viscosity occurs during melt-kneading, and even a sample for evaluating adhesiveness is produced. could not. In Comparative Example 3, since the component (c) is larger than the predetermined range (the polymer (β) is smaller than the predetermined range), the melt mass flow rate of the adhesive composition is lower than the preferred range (the melt viscosity is high). ) The productivity of the adhesive composition was also poor. In Comparative Example 4, since the component (c) is less than the predetermined range (the polymer (β) is more than the predetermined range), a drastic decrease in viscosity occurs during melt-kneading, and a sample for evaluating adhesiveness is prepared. I couldn't even do it. In Comparative Example 5, since the blending amount of the component (d) was less than the predetermined range, the adhesion was poor. In Comparative Example 6, since the blending amount of the component (d) was larger than the predetermined range, a drastic decrease in viscosity occurred during melt-kneading, and it was not possible to prepare a sample for evaluating adhesiveness. Since the compounding quantity of the component (e) was less than the predetermined range, the comparative example 7 resulted in inferior adhesiveness. In Comparative Example 8, since the blending amount of the component (e) was larger than the predetermined range, a significant decrease in viscosity occurred during melt kneading, and even strand cutting was not possible. Therefore, it was not possible to create a sample for evaluating adhesiveness. The composition of Comparative Example 9 using the composition of Comparative Example 5 instead of the composition (A) resulted in poor adhesion.

Claims (7)

(Α) 100 parts by mass of a polyolefin-based polymer;
(D) one or more selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid derivatives 0.05 to 5.0 parts by mass; and (e) organic peroxides 0.05 to 5.0 parts by mass Part;
Where (α) the polyolefin polymer is
(Β) Polypropylene polymer consisting of 10 to 60% by mass and (b) 90 to 40% by mass of amorphous polypropylene polymer plastomer (b) 55 to 90 parts by mass of polypropylene polymer; ,
(C) 45 to 10 parts by mass of a polyethylene-based polymer;
A thermoplastic resin composition (A) comprising:
However, the sum of the said component (a) and the said component (b) is 100 mass%, and the sum of the said polymer ((beta)) and the said component (c) is 100 mass parts.
The thermoplastic resin composition (A) according to claim 1, 10 to 45 parts by mass; and (f) 90 to 55 parts by mass of a polypropylene-based polymer;
Here, the sum of the composition (A) and the component (f) is 100 parts by mass, and the thermoplastic resin composition (B).
It is a manufacturing method of the composition (B) of Claim 2, Comprising:
After melt-kneading the mixture containing the components (a) to (e) to obtain the composition (A),
A method of melt-kneading a mixture containing the composition (A) and the component (f).
The laminated body which has at least 1 layer (p) which consists of a thermoplastic resin composition (A) of Claim 1.
A laminate having at least one layer (q) comprising the thermoplastic resin composition (B) according to claim 2.
The laminate according to claim 4, wherein the polypropylene polymer layer, the layer (p), and the ethylene-vinyl alcohol copolymer layer are directly laminated in this order.
The laminate according to claim 5, wherein the polypropylene polymer layer, the layer (q), and the ethylene-vinyl alcohol copolymer layer are directly laminated in this order.