JP4774686B2 - Resin composition and laminate - Google Patents

Description

  The present invention relates to a resin composition excellent in adhesiveness to a substrate and a laminate formed by extrusion lamination of the resin composition.

  Laminates formed by extrusion laminating a resin for extrusion lamination and a substrate are used for various packaging materials such as food or clothing, various liquid transport packaging materials, release paper, waterproof paper, paper containers, etc. Conventionally, high pressure radical polymerization polyethylene has been used as a resin for extrusion lamination. This high-pressure radical polymerization polyethylene may not have sufficient adhesion to the substrate, and as a resin with improved adhesion, for example, a resin composition of high-pressure radical polymerization polyethylene and ethylene-ethyl acrylate copolymer A thing is proposed (for example, refer to patent documents 1).

JP 63-13744 A

However, the laminate obtained by extrusion laminating the above resin composition may have a characteristic odor and is not sufficiently satisfactory in terms of odor.
Under such circumstances, the problem to be solved by the present invention is a resin composition that has a good odor and is excellent in adhesion to a base material, and an extrusion laminate obtained from the resin composition. It is in providing the laminated body formed.

That is, the first of the present invention contains the following component (A) and component (B), and the content of component (A) is 5 to 5% relative to 100% by weight of the total amount of component (A) and component (B). The resin composition is 95% by weight and the content of the component (B) is 95 to 5% by weight.
(A): High pressure radical polymerization polyethylene (B) having a melt flow rate of 1 to 30 g / 10 min and an expansion ratio of 1.4 to 2.0: Amorphous or low crystalline propylene polymer The second of the present invention relates to a laminate obtained by extrusion lamination of the above resin composition.

  According to the present invention, it is possible to provide a resin composition from which an extruded laminate laminate having good odor and excellent adhesion to a substrate can be obtained, and a laminate obtained by extrusion lamination of the resin composition.

  Component (A) of the present invention is high pressure radical polymerization polyethylene. The melt flow rate (hereinafter referred to as MFR) of the component (A) is 1 to 30 g / 10 minutes, preferably 2 to 25 g / 10 minutes, more preferably 3 to 20 g / 10 minutes. If the MFR is too small, the load on the extruder may increase when the resin composition of the present invention is extruded. If the MFR is too large, neck-in may occur when the resin composition of the present invention is extruded. May grow. In addition, MFR of a component (A) is measured on condition of temperature 190 degreeC and load 21.18N according to JISK7210.

The expansion ratio of component (A) (hereinafter referred to as SR) is 1.4 to 2.0, preferably 1.5 to 1.9, more preferably 1.6 to 1.8. . If the SR is too small, the neck-in may increase when the resin composition of the present invention is extruded. If the SR is too large, the ear may be cut off when the resin composition of the present invention is processed. is there. Here, SR means the outer diameter (d (mm)) of the strand extruded with a load of 21.18 N using the melt flow rate measuring device specified in JIS K7210, and the inner diameter (d ₀ (mm) of the orifice. ) Divided by (d / d ₀ ). In the case of the component (A) having an MFR of less than 10 g / 10 minutes, the measurement temperature is 190 ° C., and in the case of the component (A) having an MFR of 10 g / 10 minutes or more, the measurement temperature is 150 ° C.

The density of the component (A) is usually 930 Kg / m ³ or less, and preferably from 910 to 925 Kg / m ³ from the viewpoint of increasing the adhesive strength with the substrate.

  Component (A) is produced by a known method. For example, an organic peroxide or oxygen is used as a polymerization initiator, and ethylene is usually radicalized under conditions of a polymerization pressure of about 100 to 300 MPa and a polymerization temperature of about 130 to 300 ° C. It is obtained by polymerizing.

  The amorphous or low crystalline propylene polymer of the component (B) of the present invention is a polymer having a propylene monomer unit. The polymer may contain an olefin monomer unit other than the propylene monomer unit, and examples of the olefin of the olefin monomer unit include α-olefins having 4 or more carbon atoms. Examples of the α-olefin having 4 or more carbon atoms include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nanodecene, 1-eicocene, 3-methyl-1-butene, 3-methyl-1-pentene, 4- Examples thereof include methyl-1-pentene, 2-ethyl-1-hexene, 2,2,4-trimethyl-1-pentene, and preferably 1-butene, 1-pentene, 1-hexene, 1-octene, 1 -Decene, more preferably 1-butene and 1-hexene, and still more preferably 1-butene.

  The component (B) may contain a monomer unit other than the olefin monomer unit, and examples of the monomer of the unit include a polyene compound, a cyclic olefin, and a vinyl aromatic compound. .

  Examples of the polyene compound include conjugated polyene compounds and non-conjugated polyene compounds. Examples of the conjugated polyene compound include an aliphatic conjugated polyene compound and an alicyclic conjugated polyene compound, which may have an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group, and the like. .

  Examples of the cyclic olefin include norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, 1-methylnorbornene, 7-methylnorbornene, 5,5,6-trimethylnorbornene. 5-phenylnorbornene, 5-benzylnorbornene, 5-ethylidenenorbornene, 5-vinylnorbornene, 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1 , 2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimeta -1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a -Octahydronaphthalene, 2-ethylidene-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8 Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,5-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5 , 8,8a-octahydronaphthalene, 2-cyclohexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dichloro -1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydride Naphthalene, 2-isobutyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,2-dihydrodicyclopentadiene, 5-chloronorbornene, 5,5-dichloronorbornene, 5-fluoronorbornene, 5,5,6-trifluoro-6-trifluoromethylnorbornene, 5-chloromethylnorbornene, 5-methoxynorbornene, 5,6-dicarboxylnorbornene anhydrate, 5-dimethylaminonorbornene, 5-cyanonorbornene, cyclopentene, 3-methylcyclopentene, 4-methylcyclopentene, 3,4-dimethylcyclopentene, 3,5-dimethylcyclopentene, 3-chlorocyclopentene, cyclohexene, 3-methylcyclohexene Xene, 4-methyl Examples include lucyclohexene, 3,4-dimethylcyclohexene, 3-chlorocyclohexene, cycloheptene and the like.

  Examples of the vinyl aromatic compound include styrene, α-methylstyrene, p-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p-tert-butylstyrene, Examples thereof include ethyl styrene and vinyl naphthalene.

  Examples of the component (B) include propylene homopolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-1-butene-1-hexene copolymer, and the like. A polymer may be used by 1 type and may be used in combination of 2 or more type. The component (B) is preferably a propylene homopolymer, a copolymer of an α-olefin having 4 or more carbon atoms and propylene, more preferably, from the viewpoint of enhancing the appearance of the extruded laminate surface of the laminate. Are propylene-1-butene copolymers and propylene-1-hexene copolymers, more preferably propylene-1-butene copolymers.

  The component (B) is preferably a polymer having a propylene monomer unit content exceeding 50 mol%. However, the content of all monomer units of the polymer is 100 mol%.

  The amount of heat of fusion of component (B) is preferably 10 J / g or less, more preferably 5 J / g or less, and even more preferably 1 J / g or less, from the viewpoint of increasing the adhesive strength with the substrate. The amount of crystallization heat of component (B) is preferably 10 J / g or less, more preferably 5 J / g or less, and even more preferably 1 J / g or less, from the viewpoint of increasing the adhesive strength with the substrate. is there.

  The intrinsic viscosity [η] of the component (B) is preferably 0.1 dl / g or more, more preferably 0.7 dl / g or more, and further preferably 1.5 dl, from the viewpoint of increasing the strength of the laminate. From the viewpoint of increasing the adhesive strength with the substrate, it is preferably 10 dl / g or less, more preferably 7 dl / g, and even more preferably 5 dl / g or less. The intrinsic viscosity [η] is measured in tetralin at 135 ° C.

As a method for producing the polymer of component (B), a known polymerization method using a known olefin polymerization catalyst is used. Among these, a slurry polymerization method, a solution polymerization method, a bulk polymerization method, a gas phase polymerization method and the like using a complex catalyst such as a metallocene complex or a nonmetallocene complex are preferable. For example, JP-A-58-19309, JP-A-60-35005, JP-A-60-35006, JP-A-60-35007, JP-A-60-35008, JP-A-61. No. 130314, JP-A-3-16388, JP-A-4-268307, JP-A-9-12790, JP-A-9-87313, JP-A-11-80233, JP-A-10- Metallocene catalysts described in Japanese Patent No. 508055; Japanese Patent Laid-Open No. 10-316710, Japanese Patent Laid-Open No. 11-1000039, Japanese Patent Laid-Open No. 11-80228, Japanese Patent Laid-Open No. 1-80227, JP Kohyo 10-513489, JP-A No. 10-338706, JP-can be exemplified non-metallocene complex catalysts described in, JP table 11-71420. Among these, metallocene catalysts are preferable from the viewpoint of availability, and examples of suitable metallocene catalysts include at least one cyclopentadiene-type anion skeleton and a periodic table group 3 having a C ₁ symmetric structure. To Group 12 transition metal complexes are preferred. Further, as a particularly preferred example of the production method using a metallocene catalyst, the method of EP-A-1211287 can be exemplified.

  The content of the component (A) and the component (B) in the resin composition of the present invention is such that the content of the component (A) is 5 to 95 with respect to 100% by weight of the total amount of the component (A) and the component (B). The content of component (B) is 95-5 parts by weight, preferably the content of component (A) is 40-94% by weight, and the content of component (B) is 60- The content of component (A) is 60 to 93% by weight, and the content of component (B) is 40 to 7% by weight. If the component (A) is too small (the component (B) is too much), the neck-in may increase when the resin composition of the present invention is extruded, and the component (A) is too large (the component (B). ) Is too small), the adhesive strength with the substrate may be lowered.

  The resin composition of the present invention may contain other components such as a neutralizing agent, a dispersant, an antioxidant, a lubricant, a weather resistance improver, an antistatic agent, a pigment, and a filler as necessary.

  There is no restriction | limiting in particular as the adjustment method of the resin composition of this invention, A well-known method, for example, using a tumbler blender, a Henschel mixer, a Banbury mixer, an extruder etc., a component (A), a component (B), and necessity The method of mixing the other component contained according to it is mention | raise | lifted.

The resin composition of the present invention is used as a material for a single layer or a multilayer film, but is preferably used as a material for a multilayer film, more preferably as a material for extrusion lamination. A known extrusion laminating method is used as a method for producing a laminate obtained by extrusion laminating the resin composition of the present invention. For example, the resin composition of the present invention is formed into a single-layer film by extrusion molding such as T-die casting, or is formed into a multilayer co-extrusion film by co-extrusion with other resins, and then these single layers are formed. Or the method of laminating | stacking a multilayer film with various base materials by an extrusion coating method, a sandwich lamination method, etc. can be mention | raise | lifted.
The melt extrusion temperature of the resin composition when the resin composition of the present invention is melt-extruded is 250 to 340 ° C., preferably 260 to 330 ° C., particularly preferably, from the viewpoint of increasing the adhesive strength with the substrate. 270-300 ° C.

  Examples of the base material include polyolefin, saponified ethylene-vinyl acetate copolymer, polyester, polyamide, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, cellophane, woven fabric or nonwoven fabric or paper, metal foil such as aluminum foil, A metal vapor deposition film etc. are mentioned.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
The physical properties of the present invention were measured by the following method.
(1) Monomer unit composition of amorphous propylene polymer The monomer unit composition was calculated based on the measurement result of ¹³ C-NMR spectrum using a nuclear magnetic resonance apparatus (trade name AC-250 manufactured by Bruker). Specifically, in the ¹³ C-NMR spectrum, from the intensity ratio of the methyl carbon spectrum intensity derived from the propylene monomer unit and the methyl carbon spectrum derived from the 1-butene monomer unit, the propylene monomer unit and 1- The composition ratio of butene monomer units was calculated.
(2) Intrinsic viscosity [η]
The measurement was performed at 135 ° C. using an Ubbelohde viscometer. A tetralin solution of an amorphous propylene polymer having a concentration c of amorphous propylene polymer per unit volume of tetralin of 0.6, 1.0, 1.5 mg / ml was prepared, and the limit at 135 ° C. The viscosity was measured. The measurement was repeated three times at each concentration, the average value of the three values obtained was taken as the specific viscosity (η _sp ) at that concentration, and the value obtained by extrapolating c of η _sp / c to zero was used as the intrinsic viscosity [η ]
(3) Differential scanning calorimetry (DSC)
A differential scanning calorimeter (DSC220C manufactured by Seiko Denshi Kogyo Co., Ltd .: input compensation DSC) was used for measurement under the following conditions. Indium was used as a standard material for measurement.
(I) About 5 mg of the sample was heated from room temperature to 200 ° C. at a rate of temperature increase of 30 ° C./min, and held for 5 minutes after completion of the temperature increase.
(Ii) Next, the temperature was decreased from 200 ° C. to −100 ° C. at a rate of temperature decrease of 10 ° C./min, and held for 5 minutes after the temperature decrease was completed.
(Iii) Next, the temperature was increased from −100 ° C. to 200 ° C. at a temperature increase rate of 10 ° C./min.
(4) Melt flow rate (MFR)
According to JIS K7210 (1995), the measurement was performed under the conditions of a load of 21.18 N and a temperature of 190 ° C.
(5) Density The density was measured according to JIS K6760 (1981).
(6) Expansion ratio (SR)
Using a melt flow rate measuring device stipulated in JIS K7210 (1995), high-pressure radical polymerization polyethylene was extruded at a load of 21.18 N and a temperature of 190 ° C., and the outer diameter (d (mm)) of the extruded strand was measured. Then, a value (d / d ₀ ) divided by the inner diameter (d ₀ (mm)) of the orifice was obtained.

(7) Adhesive strength A 15-mm wide tanzaku-shaped test piece was cut out from the laminate, and then the base layer and the resin composition layer of the test piece were oriented in the direction of 180 degrees at a speed of 500 mm / min using a tensile tester. The adhesive strength between the resin composition and the substrate was determined.
(8) Odor The odor of the laminate was evaluated as follows.
○: The odor is weak.
X: Strong odor.

<Example 1>
[1] Production of amorphous propylene polymer In a 100 L SUS polymerizer equipped with a stirrer, propylene and 1-butene were continuously copolymerized by the following method using hydrogen as a molecular weight control. Thus, a propylene-1-butene copolymer corresponding to the amorphous propylene polymer of the present invention was obtained.
From the lower part of the polymerization vessel, hexane as a polymerization solvent was continuously fed at a feeding rate of 100 L / hour, propylene was fed at a feeding rate of 24.00 Kg / hour, and 1-butene was fed at a feeding rate of 1.81 Kg / hour. Supplied.
From the top of the polymerization vessel, the reaction mixture was continuously withdrawn so that the reaction mixture in the polymerization vessel maintained an amount of 100 L.
From the lower part of the polymerization vessel, as a component of the polymerization catalyst, dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride is supplied at a rate of 0.005 g / hour, Triphenylmethyltetrakis (pentafluorophenyl) borate was continuously fed at a feed rate of 0.298 g / hr and triisobutylaluminum was fed at a feed rate of 2.315 g / hr.
The copolymerization reaction was carried out at 45 ° C. by circulating cooling water through a jacket attached to the outside of the polymerization vessel.
A small amount of ethanol is added to the reaction mixture continuously withdrawn from the top of the polymerization vessel to stop the polymerization reaction, followed by demonomerization and water washing, and then the solvent is removed by steam in a large amount of water. As a result, a propylene-1-butene copolymer (hereinafter referred to as polymer (B)) was obtained and dried under reduced pressure at 80 ° C. for one day and night. The production rate of the polymer was 7.10 kg / hour.
The physical property evaluation results of the obtained polymer (B) are shown in Table 1.

[2] Preparation of resin composition for extrusion lamination As component (A), high-pressure radical polymerization polyethylene (Sumitomo Mitsui Polyolefin Co., Ltd. Sumikasen L705, MFR = 7 g / 10 min, SR = 1.77, density = 919 Kg / m ³ ) (hereinafter referred to as polyethylene (A)) 70% by weight and 30% by weight of the polymer (B) obtained in [1] above as component (B) were melt-kneaded in a twin-screw extruder. Thus, a resin composition (hereinafter referred to as resin composition (1)) was obtained.

[3] Film processing Using a 30mmφ coextrusion laminator, the resin composition (1) and polyethylene (A) are coextruded under the conditions of a processing speed of 8m / min and an extrusion temperature of 310 ° C, and extruded onto various substrates. Lamination was performed to obtain a laminate of polyethylene (A) (25 μm) / resin composition (1) (25 μm) / base material. Table 2 shows the evaluation results of the obtained laminate. In addition, the used base material is the following two types.
Base material 1: Polyester film base material having a thickness of 25 μm (Ester film E5100 manufactured by Toyobo Co., Ltd.) (hereinafter referred to as PET base material)
Base material 2: Biaxially stretched nylon film base material having a thickness of 15 μm (Emblem ON manufactured by Unitika Ltd.) (hereinafter referred to as NY base material)

<Example 2>
50% by weight of polyethylene (A) and 50% by weight of the resin composition (1) are melt-kneaded at 180 ° C. using an extruder having a screw diameter of 30 mm to obtain a resin composition (hereinafter referred to as resin composition (2)). .) As calculated values of the content of polyethylene (A) and polymer (B) in the resin composition (2), the content of polyethylene (A) = 85 wt%, the content of polymer (B) = 15 wt. (However, the total amount of polyethylene (A) and polymer (B) in the resin composition (2) is 100% by weight). Next, film processing was performed in the same manner as in Example 1 [3] except that the resin composition (1) of Example 1 was changed to the resin composition (2). Table 2 shows the evaluation results of the obtained laminate.

<Comparative Example 1>
Film processing was performed in the same manner as in Example 1 [3] except that polyethylene (A) was used in place of the resin composition (1) of Example 1. Table 2 shows the evaluation results of the obtained laminate.

<Comparative example 2>
90% by weight of polyethylene (A) and 10% by weight of the resin composition (1) were melt-kneaded at 180 ° C. using an extruder having a screw diameter of 30 mm to obtain a resin composition (hereinafter referred to as a resin composition (3)). .) The calculated values of the polyethylene (A) and the polymer (B) in the resin composition (3) are as follows: polyethylene (A) content = 97 wt%, polymer (B) content = 3 wt. (However, the total amount of polyethylene (A) and polymer (B) in the resin composition (3) is 100% by weight). Film processing was performed in the same manner as in Example 1 [3] except that the resin composition (1) in Example 1 was changed to the resin composition (3). Table 2 shows the evaluation results of the obtained laminate.

<Comparative Example 3>
70% by weight of polyethylene (A) and ethylene-methyl methacrylate copolymer resin (Aclift WH303 manufactured by Sumitomo Chemical Co., Ltd. (MFR = 7 g / 10 min, methyl methacrylate monomer unit content = 18% by weight)) 30% by weight was melt-kneaded at 180 ° C. using an extruder having a screw diameter of 30 mm to obtain a resin composition (hereinafter referred to as resin composition (4)). Film processing was performed in the same manner as in Example 1 [3] except that the resin composition (1) in Example 1 was changed to the resin composition (4). Table 2 shows the evaluation results of the obtained laminate.

<Example 3>
Using a 30 mmφ co-extrusion laminator, the resin composition (1) used in Example 1 and polyethylene (A) were co-extruded under the conditions of a processing speed of 8 m / min and an extrusion temperature of 280 ° C. The laminate was extruded and laminated to (paper) to obtain polyethylene (A) (30 μm) / resin composition (1) (25 μm) / base material (quality paper). The evaluation results of the obtained laminate are shown in Table 3.

<Comparative example 4>
Film processing was performed in the same manner as in Example 3 except that polyethylene (A) was used in place of the resin composition (1) of Example 3. The evaluation results of the obtained laminate are shown in Table 3.

  The laminate obtained by extrusion laminating the resin composition of the present invention is used for various packaging films, various surface protective films and the like.

Claims (5)

The following component (A) and component (B) are contained, the total amount of component (A) and component (B) is 100% by weight, the content of component (A) is 60 to 93% by weight, and component (B ) Content of 40 to 7% by weight.
(A): High pressure radical polymerization polyethylene (B) having a melt flow rate of 1-30 g / 10 min and an expansion ratio of 1.4-2.0: Propylene homopolymer and 4 carbon atoms A non-propylene polymer having at least one propylene polymer selected from the group consisting of copolymers of -20 α-olefin and propylene and having an intrinsic viscosity [η] of 1.5 dl / g or more and 5 dl / g or less. Crystalline or low crystalline propylene polymer Component (B) is a polymer content of propylene monomer units is more than 50 mol% (provided that the content of all monomer units of the polymer is. 100 mol%) according to claim 1 which is The resin composition described in 1. The resin composition according to claim 1 or 2 which is for extrusion lamination. The laminated body formed by extrusion-laminating the resin composition in any one of Claims 1-3 . Laminate the resin composition obtained by extrusion lamination by melt extrusion at 270 to 300 ° C. according to any one of claims 1-3.