JPH07292174A - Resin composition for lamination - Google Patents

Abstract

PURPOSE:To provide a resin composition for lamination, free from mixing nonuniformity and having excellent transparency, low-temperature heat- sealability, heat-sealing strength, hot-tackiness and strength and balanced ductility and neck-in processability. CONSTITUTION:This resin composition for lamination is composed of an ethylenic resin and a copolymer of ethylene and a 4-40C alpha-olefin having the following properties of (a) to (d). (a) The density of the copolymer is 0.86-0.935g/cm<3>, (b) the melt flow rate(MFR) is 1-50g/10min, (c) the elution curve obtained by the temperature raising eluting fractionation (TREF) has a single peak at <=100 deg.C and the curve may essentially contain a fraction eluting at a temperature other than the peak elution temperature and (d) the cumulative elution amount by the temperature raising eluting fractionation(TREF) is >=90% at 90 deg.C.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a resin composition for laminating. More specifically, a laminate capable of producing a film having no resin unevenness, excellent transparency, low-temperature heat-sealing property, heat-sealing strength, hot tack property, strength, and good balance between spreadability and neck-in processability. The present invention relates to a resin composition for use.

[0002]

2. Description of the Related Art Conventionally, what has been used as a laminate material is a high-pressure low-density polyethylene (hereinafter simply referred to as "LDPE") obtained by polymerizing ethylene at high temperature and high pressure using a radical initiator. It is abbreviated). With this LDPE, a stable film is obtained during molding,
Although it was excellent in high-speed processability, it was inferior in low-temperature heat-sealing property, heat-sealing strength and hot-tack property. Therefore, as a substitute material for the LDPE, an ethylene / vinyl acetate copolymer (hereinafter simply referred to as “EV
(Hereinafter abbreviated as “A”), etc., EVA has a good low-temperature heat-sealing property, but could not improve heat-sealing strength and hot-tack property which are other defects of LDPE. Regarding the hot tack property, both LDPE and EVA were defective, and there was a problem that the heat-sealed portion was likely to peel off when the molded film was processed at high speed.

[0003]

SUMMARY OF THE INVENTION The object of the present invention is to improve the low-temperature heat-sealing property, heat-sealing strength and hot-tacking property, which are the problems of the above-mentioned prior art, and further, have excellent strength, spreadability and neck-in property. To obtain a resin composition for laminating, which has a good balance of processability, is not sticky and has a high rigidity (high rigidity), is easy to handle, and can be manufactured with good workability, and is free from uneven mixing of resins. It is in.

[0004]

[Means for Solving the Problems]

[Summary of the Invention] As a result of intensive studies to solve the above problems, the present inventors have blended a specific ethylene / α-olefin copolymer with an ethylene resin that has been conventionally used as a material for laminating. Thus, the present invention has been completed based on the finding that the above-mentioned object of the present invention can be achieved. That is, the first invention of the present application is a resin composition for laminating characterized by comprising the following components A and B. Component A: Ethylene-based resin 50 wt% over 99 wt% or less Component B: Copolymer of ethylene having the following properties (a) to (d) and an α-olefin having 4 to 40 carbon atoms 1 wt% or more Less than 50% by weight (a) Density 0.86 to 0.935 g / cm ³ (b) MFR 1 to 50 g / 10 min (c) Temperature rising elution fractionation (TREF) The peak temperature is 100
C. or less; what may be eluted at a temperature other than the elution temperature of the peak may be substantially present in the elution curve (d) When the integrated elution amount by temperature rising elution fractionation (TREF) is 90 ° C. 90% or more

In the second invention of the present application, the component A is an ethylene / vinyl acetate copolymer having the following properties (a ') to (d'), and the component B is the above ethylene / α- It is a resin composition for lamination which is an olefin copolymer. (A ') Melt flow rate (MFR) is 1 to 50 g /
10 minutes (b ') Vinyl acetate content is 3 to 30% by weight (c') Memory effect (ME)
Is 1.1 to 2.0 (d ') and the melt tension (MT: Melt Tension) is 1
g or more

In the third invention of the present application, the component A is a high-pressure low density polyethylene having the following properties (a ') to (d'), and the component B is the ethylene / α-olefin copolymer It is a resin composition for lamination which is a united body. (A ') Melt flow rate (MFR) is 1 to 50 g /
10 minutes (b ') Density 0.915-0.93g / cm ³ (c') Memory effect (ME: Memory Effect)
Is 1.3 to 2.2 (d ') and the melt tension (MT: Melt Tension) is 1
g or more

[Detailed Description of the Invention] (I) Constituents (1) Component A [Ethylene-based Resin] Specific examples of the ethylene-based resin of the component A constituting the resin composition for lamination of the present invention include so-called radicals. High-pressure low density polyethylene produced by polymerization method, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene / acrylic acid ester copolymer, ethylene / vinyl fluoride copolymer, etc. Examples thereof include polymers or copolymers containing ethylene as a main component, such as so-called linear low-density polyethylene and high-density polyethylene produced by a polymerization method. These can be appropriately selected and used, but among them, ethylene / vinyl acetate copolymer and high-pressure low-density polyethylene are preferable. These can be used alone or in combination of two or more.

[Ethylene / Vinyl Acetate Copolymer] When the ethylene resin as the component A of the present invention is an ethylene / vinyl acetate copolymer, those having the following properties are preferable. Melt Flow Rate (MFR) JI of ethylene / vinyl acetate copolymer of component A of the present invention
MFR according to SK7210 (Melt flow rate: Me
lt Flow rate: 1 to 50 g / 10 minutes, preferably 2 to 30 g / 10 minutes, particularly preferably 3 to 20
g / 10 minutes. When the MFR is too high, transparency is deteriorated when blended with the component B, which is not preferable. If the MFR is too low, molding becomes difficult, which is not preferable.

Vinyl Acetate Content The vinyl acetate content of the ethylene / vinyl acetate copolymer of the component A of the present invention is 3 to 30% by weight, preferably 4 to 20% by weight, particularly preferably 5 to 15% by weight. If the vinyl acetate content is too high, the film becomes sticky, which is not preferable. If the vinyl acetate content is too low, heat sealability becomes insufficient, which is not preferable.

Memory Effect (ME: Memory Effect) The memory effect (ME: Memory Effect) of the ethylene / vinyl acetate copolymer of the component A of the present invention.
Is 1.1 to 2.0, preferably 1.2 to 1.8, and particularly preferably 1.3 to 1.7. If the ME is too small, the molding stability becomes poor, which is not preferable. If the ME is too large, flow unevenness during molding tends to occur, which is not preferable.

Melt Tension (MT: Melt Tension) Melt Tension (MT: Melt Tension: Melt Tension at Break) of Ethylene / Vinyl Acetate Copolymer as Component A of the Present Invention
Is 1 g or more, preferably 1.5 g or more. When MT is small, moldability deteriorates, which is not preferable.

(Specific Examples of Ethylene / Vinyl Acetate Copolymer) As the ethylene / vinyl acetate copolymer used in the present invention, those having the above-mentioned physical properties can be appropriately selected from commercial products and used.

[High Pressure Low Density Polyethylene] When the ethylene resin as the component A of the present invention is a high pressure low density polyethylene, those having the following properties are preferable.

Melt Flow Rate (MFR) JIS of high-pressure low density polyethylene of component A of the present invention
MFR by K7210 (Melt flow rate: Melt F
low rate: melt flow rate) is 1 to 50 g / 10 minutes, preferably 2 to 30 g / 10 minutes, particularly preferably 3 to 20 g /
10 minutes. If the MFR is too high, the neck-in becomes large, which is not preferable. Further, if the MFR is too low, extrusion becomes difficult, which is not preferable.

Density JIS of high pressure low density polyethylene of component A of the present invention
The density according to K7112 is 0.915-0.93 g / c
m ³ , preferably 0.916 to 0.925 g / cm ³ ,
Particularly preferably, it is 0.917 to 0.923 g / cm ³ . If the density is too high, the heat sealability is deteriorated, which is not preferable. If the density is too low, the film becomes sticky, which is not preferable.

Memory effect (ME: Memory Effect) The memory effect (ME: Memory Effect: restoration effect) of the high-pressure low-density polyethylene of the component A of the present invention is
It is 1.3 to 2.2, preferably 1.5 to 2.2, and particularly preferably 1.6 to 2.2. If ME is too small, neck-in becomes large, which is not preferable. Further, if ME is too large, high-speed processing becomes difficult, which is not preferable.

Melt Tension (MT: Melt Tension) The melt tension (MT: Melt Tension: tension during melting) of the high-pressure low-density polyethylene of the component A of the present invention is 1 g.
Or more, preferably 2.5 g or more, particularly preferably 5 g or more. If MT is too small, moldability deteriorates, which is not preferable.

Activation Energy (Ea) The activation energy (Ea) at a shear rate of 24 sec ^-1 determined from the viscosity curve of the high-pressure low-density polyethylene of component A of the present invention is 4 KJ / mol or more, preferably 6 ~
20 KJ / mol, particularly preferably 8-18 KJ / mo
It is l. If the activation energy is out of the above range, the moldability is deteriorated, which is not preferable. This activation energy is described in literatures such as "Rheology" (published by Misuzu Shobo, Tsurutaro Nakagawa, Hirotaro Kobe, page 604), "Kodansha Contemporary Chemistry Series 18 Rheology" (Kodansha, published by Shizuo Hayashi, pages 160-161). The activation energy is calculated by the Arrhenius equation or the Andrade equation representing the relationship between the viscosity and the temperature.

Specifically, a shear viscosity (η) is measured at a temperature of 160 ° C. (433
K), 190 ° C. (463 K), 230 ° C. (503 K), and the shear viscosity (η) at a shear rate of 24 sec ⁻¹ is obtained from the viscosity curves (viscosity dependence curves for shear rate) measured at each temperature. . Next, 1 / T (T = measured temperature:
The intercept: logA is obtained from the graph in which K) is the horizontal axis and log η is the vertical axis. The activation energy (Ea) is calculated by substituting each obtained value into the following equation. η = Ae ^{−Ea / RT} → log η = log A−Ea / RT η: Shear viscosity (poise) A: Frequency factor Ea: Activation energy (KJ / mol) R: Gas constant (8.3145 J / K · mol) T : Absolute temperature (K)

Q value The high-pressure low-density polyethylene of the present invention has a Q value determined by size exclusion chromatography (SEC) of weight average molecular weight / number average molecular weight of 4 to 20, preferably 5 to 1.
8, particularly preferably 7 to 15. If the Q value is too large, the spreadability is insufficient, which is not preferable. If the Q value is too small, neck-in becomes large, which is not preferable.

(Specific Examples of High-Pressure Low-Density Polyethylene) The high-pressure low-density polyethylene of the component A of the present invention may be appropriately selected from commercial products having the above-mentioned physical properties.

[Linear Low-Density Polyethylene] When linear low-density polyethylene is used as all or part of the component A of the present invention (component used in combination with the above ethylene / vinyl acetate copolymer or high-pressure low-density polyethylene) It is desirable to select one having the following properties.

Melt Flow Rate (MFR) JI of linear low density polyethylene used as component A of the present invention.
MFR according to SK7210 (Melt flow rate: Me
lt Flow rate: 1 to 50 g / 10 minutes, preferably 2 to 30 g / 10 minutes, particularly preferably 3 to 20
g / 10 minutes. If the MFR is too high, the impact strength when formed into a film is poor, which is not preferable. Further, if the MFR is too low, extrusion becomes difficult, which is not preferable.

Density JI of the linear low density polyethylene used for component A of the present invention
The density according to SK7112 is 0.88 to 0.935 g
/ Cm ³ , preferably 0.90 to 0.932 g / c
m ³ , particularly preferably 0.91 to 0.93 g / cm ³ . If the density is too high, the heat sealability is deteriorated, which is not preferable. If the density is too low, the film becomes sticky, which is not preferable.

Measurement of (TREF) elution curve by temperature rising elution fractionation TR of linear low density polyethylene used for component A of the present invention
There are two or more peaks according to the EF elution curve, and at least one peak temperature is 90 ° C or higher. In addition, TRE
The F measurement method will be described later.

Such linear low-density polyethylene is a copolymer of ethylene and other α-olefin, and ethylene and, for example, propylene, 1-butene, 1-pentene, 1
It is produced by copolymerizing hexene, 1-octene, 1-heptene, 4-methylpentene-, 4-methylhexene-1,4,4-dimethylpentene-1 and the like. Among these α-olefins, those having 4 to 12 carbon atoms are preferable, and 1-hexene is particularly preferable. As a manufacturing method, a Ziegler type catalyst is used, and it is manufactured by a gas phase method, a slurry method, a solution method, a high pressure ionic polymerization method or the like.

(Specific Examples of Linear Low Density Polyethylene) As the linear low density polyethylene, those exhibiting the above physical properties can be appropriately selected from commercial products and used.

(2) Component B (Ethylene / α-Olefin Copolymer) In the present invention, the component B is an ethylene / α-olefin copolymer other than the above component A.
It is an α-olefin copolymer and has the following properties:
It is important to use those which exhibit further properties.

Density The density of the ethylene / α-olefin copolymer of component B of the present invention according to JIS K7112 is 0.86 to 0.93.
5 g / cm ³ , preferably 0.87 to 0.915 g / c
m ³ , particularly preferably 0.88 to 0.91 g / cm ³ . If the density is too high, the heat-sealing property deteriorates, which is not preferable. If the density is too low, stickiness tends to occur in the film, which is not preferable.

Melt Flow Rate (MFR) The MFR (melt flow rate) of the ethylene / α-olefin copolymer of component B of the present invention according to JIS K7210 is 1 to 50 g / 10.
Min, preferably 2 to 30 g / 10 min, particularly preferably 3
~ 20 g / 10 minutes. If the MFR is too low, extrusion becomes difficult, which is not preferable. If the MFR is too high, sagging may occur and moldability may deteriorate, which is not preferable.

Peaks in Elution Curve by Elevated Temperature Elution Fractionation (TREF) The ethylene / α-olefin copolymer of component B of the present invention has an elevated temperature elution fractionation (TREF).
re Rising Elution Fractio
The peak of the elution curve obtained by
It is preferable that the peak temperature of the peak is 100 ° C. or less, preferably 10 to 75 ° C., particularly preferably 30 to 70 ° C., and the substance that elutes at a temperature other than the elution temperature of the peak is substantially May be present in the elution curve.

Integrated Elution Amount by Elevated Temperature Elution Fractionation (TREF) The ethylene / α-olefin copolymer of component B of the present invention is an eluate at each elution temperature measured by elution curve by temperature elution fractionation (TREF). When the elution temperature is 90 ° C., the integrated elution amount is 90% or more, preferably at the elution temperature of 90 ° C., and more preferably at least 95%, and particularly preferably at the elution temperature of 90 ° C., at least 97%. is there.

Measurement of elution curve by temperature rising elution fractionation (TREF) The above temperature rising elution fractionation (Temperature Ri
sing Elution Fractionatio
n: TREF) is used to measure the elution curve by “Journ
al of Applied Polymer Sci
ence. Vol 26, 4217-4231 (198)
1) ”and“ Symposium on Macromolecules Proceedings 2P1C09 (1
1985) "and the like based on the principle described in the literature. That is, first, the target polyethylene is once completely dissolved in a solvent. It is then cooled to form a thin polymer layer on the surface of the inert carrier. In such a polymer layer, the one that is easily crystallized is formed on the inside (the side close to the surface of the inert carrier), and the one that is difficult to crystallize is formed on the outside. Next, by raising the temperature continuously or stepwise, first, the amorphous portion in the target polymer composition, that is, the one having a large degree of branching of short chain branches possessed by the polymer is first eluted at a low temperature. As the elution temperature rises, the one with less degree of branching gradually elutes, and finally the straight-chain portion without branching elutes, and the measurement ends. The composition distribution of the polymer can be seen from the graph drawn by detecting the concentration of the elution component at each temperature and drawing the elution amount and elution temperature.

Q value The Q value expressed by weight average molecular weight / number average molecular weight of the ethylene / α-olefin copolymer of the component B of the present invention measured by size exclusion chromatography (SEC) is 4 or less, preferably It is 3 or less, particularly preferably 2.5 or less.

Production Method The ethylene / α-olefin copolymer of the component B of the present invention is described in JP-A-58-19309 and 59-95292.
No. 60, No. 60-35005, No. 60-35006, No. 60-35007, No. 60-35008, No. 60-
No. 35009, No. 61-130314, JP-A 3-1
63088, European Patent Application Publication No. 42
No. 0436, U.S. Pat. No. 5,055,438 and WO 91/04257, that is, a metallocene catalyst, particularly a metallocene alumoxane catalyst, or, for example, WO 92/01723. A metallocene compound as disclosed in, for example, and a catalyst composed of a compound that reacts with the metallocene compound described below to form stable ions are used to co-produce ethylene as a main component and an α-olefin as a secondary component. It is a method of polymerizing.

The compound that reacts with the metallocene compound to form a stable ion is an ionic compound or an electrophilic compound formed from an ion pair of a cation and an anion, and reacts with the metallocene compound to form a stable ion. To form polymerization active species. Among these, the ionic compound is represented by the following general formula (I). General formula (I) [Q] ^{m +} [Y] ^m- (m is an integer of 1 or more) Q is a cation component of an ionic compound, and is a carbonium cation, tropylium cation, ammonium cation, oxonium cation, sulfonium cation. ,
Examples thereof include phosphonium cations, and further examples include metal cations and organometallic cations, which are themselves easily reduced.

These cations are listed in Table 1-5019.
Not only cations that can give a proton as disclosed in Japanese Patent No. 50, but also cations that do not give a proton may be used. Specific examples of these cations include triphenylcarbonium, diphenylcarbonium, cycloheptatrienium, indenium, triethylammonium, tripropylammonium, tributylammonium, N, N-dimethylanilinium, dipropylammonium, dicyclohexylammonium, Triphenylphosphonium, trimethylphosphonium, tri (dimethylphenyl) phosphonium, tri (methylphenyl) phosphonium, triphenylsulfonium, triphenyloxonium, triethyloxonium, pyrylium, silver ion, gold ion, platinum ion, palladium ion, Examples include mercury ions and ferrocenium ions.

Y is an anion component of the ionic compound, which is a component that reacts with the metallocene compound to form a stable ion, and is an organic boron compound anion, an organic aluminum compound anion, an organic gallium compound anion, an organic phosphorus compound. Examples thereof include anions, organic arsenic compound anions, organic antimony compound anions, and specific examples include tetraphenylboron and tetrakis (3,4,4).
5-trifluorophenyl boron, tetrakis (3,5
-Di (trifluoromethyl) phenyl) boron, tetrakis (pentafluorophenyl) boron, tetraphenylaluminum, tetrakis (3,4,5-trifluorophenyl) aluminum, tetrakis (3,5-di (trifluoromethyl) phenyl ) Aluminum, tetrakis (pentafluorophenyl) aluminum, tetraphenylgallium, tetrakis (3,4,5-trifluorophenyl) gallium, tetrakis (3,5-di (trifluoromethyl) phenyl) gallium, tetrakis (3,5) -Di (t-butyl) phenyl) gallium, tetrakis (pentafluorophenyl) gallium, tetraphenylphosphorus, tetrakis (pentafluorophenyl)
Examples thereof include phosphorus, tetraphenylarsenic, tetrakis (pentafluorophenyl) arsenic, tetraphenylantimony, tetrakis (pentafluorophenyl) antimony, decaborate, undecaborate, carbadodecaborate, decachlorodecaborate.

As the electrophilic compound, among the compounds known as Lewis acid compounds, those which react with a metallocene compound to form stable ions to form a polymerization active species, and various metal halides are used. Examples thereof include compounds and metal oxides known as solid acids. Specific examples include magnesium halides and Lewis acidic inorganic compounds.

Α-Olefin Here, the α-olefin is an α-olefin having 4 to 40 carbon atoms.
Olefin, for example 1-butene, 1-pentene, 1-
Hexene, 1-octene, 1-heptene, 4-methylpentene-1, 4-methylhexene-1,4,4-dimethylpentene-1 and the like can be mentioned. Among these α-olefins, the number of carbon atoms is preferably 4 to 12, and particularly preferably 6 to
1 to 2 or more α-olefins of 2 to 60% by weight, preferably 5 to 50% by weight, particularly preferably 10
~ 30 wt% and ethylene 40-98 wt%, preferably 50-95 wt%, particularly preferably 70-90 wt%
And is preferably copolymerized.

Examples of the copolymerization polymerization method include a gas phase method, a slurry method, a solution method and a high pressure ionic polymerization method. Among these, the solution method and the high-pressure ionic polymerization are preferable, and the high-pressure ionic polymerization method is particularly preferable. The high-pressure ionic polymerization method refers to JP-A-56-18607 and JP-A-58-
The pressure described in each publication of No. 225106 is 10
0 kg / cm ² or more, preferably 200 to 2000 kg
/ Cm ² , temperature is 125 ° C. or higher, preferably 130 to 2
It is a continuous process for producing an ethylene-based polymer, which is carried out under reaction conditions of 50 ° C., particularly 150 to 200 ° C.

(II) Amount ratio The mixing ratio of the component A and the component B is as follows: component A: component B = 99:
1 to more than 50: less than 50% by weight, preferably 90:10
-55 to 45% by weight, particularly preferably 85 to 15-6
It is 0: 40% by weight. If the blending amount of the component B is too large, the workability of the film deteriorates, which is not preferable. If the blending amount of the component B is too small, the effect of improving the transparency and heat sealability is small, which is not preferable.

(III) Manufacture of Laminating Resin Composition (1) Blending The laminating resin composition of the present invention contains the component A ethylene resin in the same manner as a usual resin composition manufacturing method.
It can be produced by mixing the component B with the ethylene / α-olefin copolymer. Specifically, Component A and Component B are melted and kneaded using an extruder, a Brabender plastograph, a Banvaloo mixer, a kneader blender, etc., and pelletized by a commonly used method, or a V blender. It is also possible to produce a resin composition by dry blending with the above.

(2) Other Additive Components In the resin composition for laminating of the present invention, generally used additive components such as an antioxidant, an antiblocking agent, a slip agent, an antistatic agent, a nucleating agent and a heat agent are used. Stabilizers, light stabilizers, ultraviolet absorbers, neutralizing agents, antifogging agents, coloring agents and the like can be added. Further, other resin components, for example, an ethylene-based polymer other than the component A and the component B can be added within a range that does not impair the effects of the present invention.

(3) Physical Properties of Composition The melt flow rate (MFR) of the resin composition for lamination of the present invention is preferably 2 to 50 g / 10 minutes, particularly preferably 3 to 30 g / 10 minutes, and the memory effect (ME) is preferably 1.2 to 2.2, particularly preferably 1.4 to 2.0.

(IV) Molding Processing A film can be manufactured by molding using the above pellets. The film is produced by a dry laminating method, an extrusion laminating method, a sandwich laminating method, a coextrusion method, or the like to obtain various laminated packaging films by extrusion coating or coextrusion with various base materials. Can be done. In particular, it is preferable to form a laminated film by laminating on a substrate by an extrusion laminating method. It can also be used as a sandwich laminate base material of various base materials and sealant base materials.

As the above-mentioned various base materials, high molecular weight polymers such as paper, metal foil such as aluminum foil, cellophane, woven cloth, non-woven cloth and film, for example, high density polyethylene, medium, low density polyethylene, ethylene・ Vinyl acetate copolymer, ethylene / acrylic ester copolymer,
Ionomer, propylene polymer, poly-1-butene, olefin polymer such as poly-4-methylpentene-1, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyacrylate, vinyl copolymer such as polyacrylonitrile, Nylon 6, Nylon 66, Nylon 7, Nylon 10, Nylon 11, Nylon 12, Nylon 610, Polyamide such as Polymethaxylylene Adipamide, Polyethylene terephthalate, Polyester terephthalate / isophthalate, Polybutylene terephthalate, Polyester, Polyvinyl alcohol, Examples thereof include ethylene / vinyl alcohol copolymer, polycarbonate and polyurethane.

[0048]

EXAMPLES The present invention will be described more specifically by showing experimental examples consisting of Examples and Comparative Examples below. [I] Measurement and Evaluation of Physical Properties Measurement and evaluation of physical properties in Examples and Comparative Examples were carried out by the following methods. (1) Measurement of physical properties (a) MFR: According to JIS K7210 (190 ° C,
2.16 kg load) (b) Density: According to JIS K7112

(C) Measurement of elution curve: Temperature rising elution fractionation (Temperature Resin) in the present invention
g Elution Fraction: T
The dissolution curve was measured by REF). Once the polymer was completely dissolved at a high temperature and then cooled, a thin polymer layer was formed on the surface of the inert carrier, and then the temperature was continuously or stepwise increased to elute. It is possible to collect the components, continuously detect the concentration thereof, and see the composition distribution of the polymer at the peak of the graph (elution curve) drawn by the elution amount and elution temperature. The elution curve was measured as follows. A cross fractionation device (CFC T150A manufactured by Mitsubishi Petrochemical Co., Ltd.) was used as a measurement device, and the measurement was performed according to the measurement method in the attached operation manual. This cross fractionation device includes a temperature-rising elution fractionation (TREF) mechanism that fractionates samples by utilizing the difference in melting temperature, and a size exclusion chromatography (Size Exclusion Chromatography) that further fractionates the fractions by molecular size.
This is a device that has an online connection of a RAP.

First, the sample to be measured is dissolved in a solvent (o-dichlorobenzene) at 140 ° C. so that the concentration becomes 4 mg / ml, and this is injected into the sample loop in the measuring device. The following measurements are automatically performed according to the set conditions. The sample solution held in the sample loop is separated by utilizing the difference in melting temperature. TREF column (inner diameter 4 m filled with glass beads as an inert carrier)
m, 150 mm long stainless steel column attached to the device)
0.4 ml is injected into. The sample is then cooled from 140 ° C. to 0 ° C. at a rate of 1 ° C./min and coated on the inert carrier. At this time, the polymer layers are formed on the surface of the inert carrier in the order of the highly crystalline component (those that are easily crystallized) to the low crystalline component (that is difficult to crystallize). TREF
After the column was kept at 0 ° C for an additional 30 minutes, 2 ml of the dissolved components at 0 ° C were treated with TR at a flow rate of 1 ml / min.
EF column to SEC column (Showa Denko AD80M /
S 3).

While the molecular size is being fractionated by SEC, the temperature is raised to the next elution temperature (5 ° C.) in the TREF column and the temperature is maintained for about 30 minutes. The measurement of each elution section by SEC was performed at 39 minute intervals. The elution temperature is raised stepwise at the following temperatures. 0, 5, 10, 15, 20, 25, 30, 35, 40,
45, 49, 52, 55, 58, 61, 64, 67, 7
0, 73, 76, 79, 82, 85, 88, 91, 9
4, 97, 100, 102, 120, 140 The solution fractionated by the SEC column according to the molecular size was measured for the absorbance in proportion to the polymer concentration with an infrared spectrophotometer attached to the device (wavelength 3.42 μ, methylene. ), And a chromatogram for each elution temperature category is obtained.

Using the built-in data processing software, the baseline of the chromatogram of each elution temperature section obtained in the above measurement is drawn and the calculation processing is performed. The area of each black tomatogram is integrated and an integrated elution curve is calculated. Further, this integrated elution curve is differentiated by temperature to calculate the differential elution curve. The plot of the calculation result is output to the printer. The output of the differential elution curve is plotted with the elution temperature of 100 on the horizontal axis.
89.3 mm per ° C, differential amount on the vertical axis (total integrated elution amount was standardized to 1.0, and change amount at 1 ° C was used as differential amount) 0.1
It was done at 76.5 mm.

(D) ME (Memory Effec)
t: Restoration effect): The melt indexer used in JIS K7210 is used, and the measurement condition is cylinder temperature 2
The setting was performed at 40 ° C. and a constant rate extrusion rate of 3 g / min. The device is filled with the sample, only the piston is placed and after 6 minutes the prescribed extrusion rate is applied. Next, a graduated cylinder containing ethyl alcohol is placed immediately below the orifice, and a straight extrudate is collected. The diameter (D) of the sampled extrudate is measured with a micrometer, and the orifice diameter of the die is D ₀ , and ME is calculated by the following equation. ME = D / D ₀

(E) MT (Melt Tension:
Melt tension at break): Toyo Seiki Capillograph 1B P
MD-C, test temperature 190 ° C., extrusion speed 1 cm /
The take-up speed at the time of taking out the extruded molten resin is gradually increased to obtain the stress when the resin filament breaks. The die diameter used was 8.00 m in length.
m, inner diameter 2.095 mm, and outer diameter 9.50 mm.

(F) Q value: size exclusion chromatography (size exclusion chromatography)
Raphy: SEC) was used under the following measurement conditions to determine the Q value from the weight average molecular weight / number average molecular weight. A universal calibration curve was prepared from monodisperse polystyrene and calculated as the molecular weight of linear polyethylene. Model: Waters Model 150C GP
C solvent: o-dichlorobenzene Flow rate: 1 ml / min Temperature: 140 ° C. Measured concentration: 2 mg / ml Injection volume: 200 μl Column: Showa Denko KK AD80M / S 3 bottles

(G) Activation energy (Ea): "Capirograph 1BPMD-C" manufactured by Toyo Seiki Seisaku-sho, Ltd. was used, and the capillary had a diameter of 1 mm and a length of 10 mm.
Extrusion speed is 2.5, 5, 10, 20, 50, 100, 2
The viscosity was measured at each temperature with an auto speed set at 00 m / min, and calculated by the activation energy (Ea) calculation method described above.

(2) Evaluation method (a) Heat sealing temperature under a load of 3 kg: Using a hot plate heat sealer manufactured by Toyo Seiki, with a sealing pressure of 2 kg / cm ² and a sealing time of 1 second, at intervals of 5 ° C. from 80 ° C. After creating a laminated film sample that was heated and heat-sealed, measure the heat-sealing strength (kg / 15mm width) of each sample with a tensile tester (pulling speed 500m / min, angle 180 °), horizontal axis A heat treatment temperature is plotted on the vertical axis, and a heat treatment strength is plotted on the vertical axis. On this graph, the temperature at which this heat-sealing strength is 3 kg / 15 mm width and when it is obtained is read and set as the 3 kg-load heat-sealing temperature.

(B) Heat seal strength: The yield point in the above heat seal strength measurement is taken as the heat seal strength.

(C) Hot tack property: As heat-sealing conditions, the seal bar size is 200 mm × 30 mm, the sealing pressure is 1 kg / cm ² , the sealing time is 0.5 seconds, and the load is 50.
g, chuck pressure 1 kg / cm ² , sealing temperature 90 ° C.
To 150 ℃ every 5 ℃ every 5 ℃, after heat-sealing, under a load of 50 g, leave until the heat-sealed part peeling completely stops, peeled length 1 mm
Read to unit. The temperature range in which the peeling distance was 1 mm to 2 mm was defined as the hot tack property.

(D) Surging: During extrusion lamination, the substrate is kraft paper, and the sample is extrusion-laminated on the kraft paper to a thickness of 20 μm.
Surging is good when L / 2 is less than 1.5 mm, where L is the width of the extrusion-laminated film,
When it fluctuates by 1.5 mm or more, it is defined as defective.

(E) Spreadability (m / min) When the number of revolutions of the extruder is 100 rpm, extrusion laminating is performed on kraft paper, and when the winding speed of the kraft paper is gradually increased, the maximum processing speed at which the laminate film breaks is set. taking measurement.

(F) Neck-in: In the same manner as in the surging evaluation, upon extrusion lamination molding, the substrate is kraft paper and the sample is extrusion-laminated on the kraft paper to a thickness of 20 μm. Neck-in, L ₀ the effective width of the die, the width of the coated film to kraft paper when is L, it is obtained from L ₀ -L.

(G) Resin pressure: Measured by a resin pressure gauge attached to the die head of the extruder during extrusion lamination.

[II] Experimental Example (1) Ethylene Resin (Component A) (Ethylene / Vinyl Acetate Copolymer) EVA MFR = 9 g / 10 min, Vinyl Acetate Content =
10% by weight, ME = 1.5, MT = 1.5 g EVA MFR = 13 g / 10 min, vinyl acetate content = 14% by weight, ME = 1.4, MT = 1.3 g EVA MFR = 8 g / 10 min, Vinyl acetate content =
7% by weight, ME = 1.6, MT = 1.8 g

(High pressure method low density polyethylene) LDPE MFR = 9 g / 10 min, density = 0.919
g / cm ³ , ME = 2.1, MT = 5 g, activation energy (Ea) = 11 KJ / mol, Q value = 14 LDPE MFR = 14 g / 10 min, density = 0.91
9 g / cm ³ , ME = 1.9, MT = 3 g, activation energy (Ea) = 14 KJ / mol, Q value = 12

Example 1 Production of Ethylene / α-Olefin Copolymer (Component B) The catalyst was prepared by the method described in JP-A-61-130314. That is, to a complex ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride of 2.0 mmol, Toyo Stoufer's methylalumoxane was added in an amount of 1000 mol times, and diluted with toluene to 10 liters. Then, a catalyst solution was prepared and polymerized by the following method. A mixture of ethylene and 1-hexene was added to a stirred autoclave-type continuous reactor having an internal volume of 1.5 liters so that the composition of 1-hexene was 8%.
The pressure in the reactor was adjusted to 160% by supplying 0% by weight.
The reaction was carried out at a temperature of 165 ° C. while maintaining 0 kg / cm ² . After the reaction was completed, the MFR was 13 g / 10 minutes and the density was 0.
Ethylene having 90 g / cm ³ , Q value of 2, TREF elution curve having one peak, peak temperature of 55 ° C., an elution amount other than the peak, and an integrated elution amount of 90 ° C. of 100% A 1-hexene copolymer (1-hexene content 20% by weight) was obtained.

Production of Resin Composition 70% by weight of EVA as component A and 30% by weight of ethylene / α-olefin copolymer as component B were melted at a temperature of 180 ° C. in a single screw 40 mmφ extruder. The mixture was kneaded to obtain a pellet-shaped resin composition. Evaluation This pellet-shaped resin composition was extruded into a film having a thickness of 30 μm at a temperature of 240 ° C. using a 40 mmφ single-screw extruder, and this was extruded with a LDPE having a thickness of 30 μm in advance from a T-die having a width of 360 mm. Extrusion laminate coating was performed on the LDPE side of the laminate laminated with a biaxially stretched nylon film having a thickness of 15 μm. Using this laminated three-layer film, heat seal strength and hot tack property were measured. In the same manner, kraft paper was used as the substrate, and the laminate film extruded and laminated to a thickness of 20 μm was evaluated for neck-in and surging. In addition, the spreadability at an extruder rotation speed of 100 rpm was evaluated. The evaluation results are shown in Table 1.

Example 2 The above EVA was used as the component A.
Molded and evaluated in the same manner as in Example 1 except that was used. The evaluation results are shown in Table 1.

Example 3 As component A, the above EVA
Molded and evaluated in the same manner as in Example 1 except that was used. The evaluation results are shown in Table 1.

[Examples 4 and 5] Molding and evaluation were carried out in the same manner as in Example 1 except that the compounding ratios of the component A and the component B were changed. The evaluation results are shown in Table 1.

[Example 6] Using LDPE as the component A, molding was carried out and evaluated in the same manner as in Example 1 except that the laminating molding temperature was changed to 280 ° C. The evaluation results are shown in Table 1.

Example 7 The same molding and evaluation as in Example 6 was carried out except that LDPE was used as the component A. The evaluation results are as shown in Table 2.

[Examples 8 and 9] LDPE as component A
Was molded and evaluated in the same manner as in Example 6 except that the blending ratio of the component A and the component B was changed. The evaluation results are as shown in Table 2.

Example 10 Production of Ethylene / α-Olefin Copolymer (Component B) The catalyst was prepared by the method described in JP-A-61-130314. That is, to a complex ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride of 2.0 mmol, Toyo Stoufer's methylalumoxane was added in an amount of 1000 mol times, and diluted with toluene to 10 liters. Then, a catalyst solution was prepared and polymerized by the following method. A mixture of ethylene and 1-hexene was fed to a stirring autoclave-type continuous reactor having an internal volume of 1.5 liters so that the composition of 1-hexene was 78% by weight, and the pressure in the reactor was 11
The reaction was carried out at a temperature of 150 ° C. while maintaining the pressure at 00 kg / cm ² . After the reaction was completed, MFR was 4 g / 10 minutes and the density was 0.9.
13 g / cm ³ , Q value is 2, there is one peak of TREF elution curve, peak temperature is 72 ° C., there is no elution amount other than the peak, and integrated elution amount at 90 ° C. is 100%. An ethylene / 1-hexene copolymer (1-hexene content 10% by weight) was obtained. EVA is used as the component A,
Molding and evaluation were performed in the same manner as in Example 1 except that the above ethylene / α-olefin copolymer was used as the component B.
The evaluation results are shown in Table 2.

[Example 11] Molding and evaluation were carried out in the same manner as in Example 6 except that LDPE was used as the component A and an ethylene / α-olefin copolymer was used as the component B. The evaluation results are shown in Table 2.

[Comparative Example 1] EVA was used as the component A without adding the component B and molded in the same manner as in Example 1 and evaluated. The evaluation results are shown in Table 3.

Comparative Example 2 Molding was carried out in the same manner as in Example 6 except that component B was not added, and LDPE was used as component A. The evaluation results are shown in Table 3.

[Comparative Example 3] Molding and evaluation were carried out in the same manner as in Example 6 except that the component A was not added. The results of the evaluation are shown in Table 3, but film formation that could evaluate the performance for all the evaluation items was not possible.

[0079]

[Table 1]

[0080]

[Table 2]

[0081]

[Table 3]

[0082]

EFFECTS OF THE INVENTION The resin composition for laminating according to the present invention is excellent in low-temperature heat-sealing property, heat-sealing strength and hot-tack property, and has a good balance between spreadability and neck-in processability. It is a thing. Therefore, snacks, dry foods such as instant noodles, miso, pickles, soups, aquatic foods such as juices, frozen foods,
Films for packing and filling foodstuffs such as meat and ham, mini packs for soy sauce, sauces, etc .; Films for packing and filling medicines such as bag-in-boxes, infusion bags; mini packs for shampoos, cosmetics, etc. Packaging / filling film: It is extremely useful as a material for laminating various packaging or filling films in a wide range of applications such as various lid materials.

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Claims (3)

[Claims] 1. A resin composition for laminating comprising a component A and a component B shown below. Ingredient A: Ethylene resin over 50% by weight 99% by weight
Component B: A copolymer of ethylene having the following properties (a) to (d) and an α-olefin having 4 to 40 carbon atoms.
1% by weight or more and less than 50% by weight (a) Density 0.86 to 0.935 g / cm ³ (b) Melt flow rate (MFR) 1 to 50 g / 1
0 min (c) The peak of the elution curve obtained by temperature rising elution fractionation (TREF) is 1; the peak temperature is 100 ° C.
The following is true; what elutes at a temperature other than the elution temperature of the peak may substantially exist in the elution curve. (D) When the integrated elution amount by temperature rising elution fractionation (TREF) is 90 ° C. 90% or more 2. The resin composition for laminating according to claim 1, wherein the component A is an ethylene / vinyl acetate copolymer having the following properties (a ′) to (d ′). (A ') Melt flow rate (MFR) is 1 to 50 g /
10 minutes (b ') Vinyl acetate content is 3 to 30% by weight (c') Memory effect (ME)
Is 1.1 to 2.0 (d ') and the melt tension (MT: Melt Tension) is 1
g or more 3. The resin composition for laminating according to claim 1, wherein the component A is a high pressure low density polyethylene having the following properties (a ′) to (d ′). (A ') Melt flow rate (MFR) is 1 to 50 g /
10 minutes (b ') Density 0.915-0.93g / cm ³ (c') Memory effect (ME: Memory Effect)
Is 1.3 to 2.2 (d ') and the melt tension (MT: Melt Tension) is 1
g or more