JP2000230163A - Adhesive for forming laminate and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare an adhesive which retains a practical adhesion strength at the ordinary temperature, after treated at a high temperature, and simultaneously has such excellent heat-resistant adhesivity under high temperature as capable of preventing the interlayer peeling of a laminate, when a severe treatment such as a high temperature charging treatment or a high temperature retort treatment is carried out. SOLUTION: This adhesive for forming laminates comprises a vinylic compound-modified olefinic polymer which is obtained by continuously graft- polymerizing a vinylic monomer to an olefinic polymer having a specific intrinsic viscosity and a specified Mw/Mn by a bulk polymerization method, a bulk suspension polymerization method or a solution polymerization method in a plug flow type reactor. The laminate is obtained by laminating an adhesive layer comprising the adhesive to a resin layer comprising a polyamide, a polycarbonate or a polyester. The laminate has two or more layers having a structure wherein the resin layer and the adhesive layer are adjacently laminated. A packaging material for retort pouches and hot film packages comprises the above laminate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate-forming adhesive and its use, and more particularly, to a laminate-forming adhesive which does not decrease its adhesive strength even when it comes into contact with high-temperature water. And a laminate using the adhesive and having excellent gas barrier properties and capable of coping with retort treatment or hot-fill packaging.

[0002]

BACKGROUND OF THE INVENTION Polyester resins represented by polyethylene terephthalate resin have mechanical strength, rigidity,
It is excellent in heat resistance, chemical resistance, oil resistance, transparency and the like, and is widely used as a packaging material for films, sheets, containers and the like by utilizing these characteristics. However, since such a polyester resin has high permeability of gas such as oxygen, it cannot be used for packaging materials requiring high gas barrier properties (gas permeation resistance) such as foods, medicines, and cosmetics. Was.

[0003] Further, the polycarbonate resin, like the polyester resin, is excellent in transparency, heat resistance, fragrance retention and the like, but has high permeability to gases such as oxygen, and particularly has high gas barrier properties for foods and the like. It could not be used for the required packaging material.

[0004] In order to enhance the gas barrier properties of the polyester resin or the polycarbonate resin, a method of laminating on the polyester resin or the polycarbonate resin a resin having a better gas barrier property than these resins, for example, a saponified ethylene / vinyl acetate copolymer or the like. Proposed. However, the adhesiveness between the polyester resin or the polycarbonate resin and the saponified ethylene / vinyl acetate copolymer is not always sufficient, and a part of the resin peels off at the time of lamination or use, thereby deteriorating the gas barrier property or the appearance of the product. Or there was a problem that mechanical strength might fall.

[0005] Further, when these laminates are subjected to high-temperature filling (hot filling) at the time of production or heat treatment such as retort treatment, the adhesive strength may be reduced by heating, and therefore, There was also a problem that the layer was peeled off and the gas barrier property was reduced.

[0006] For this reason, there has been a demand for an adhesive for forming a laminate and a laminate thereof capable of preventing delamination of the laminate even during high-temperature filling or retort treatment.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to solve the problems associated with the prior art as described above, and to maintain the practical adhesive strength at room temperature after high-temperature treatment and to perform high-temperature filling or retort treatment. It is an object of the present invention to provide an adhesive for molding a laminate having excellent heat resistance at high temperatures so that delamination of the laminate can be prevented during severe processing.

Another object of the present invention is to provide a laminate, a retort pouch packaging material and a hot-fill packaging material which are excellent in gas barrier properties and excellent in interlayer adhesion even at high temperatures.

[0009]

The adhesive for forming a laminate according to the present invention has an intrinsic viscosity [η] of 0.01 to 10 dl / g measured in decalin at 135 ° C. in a plug flow type reaction vessel. And molecular weight distribution (Mw / M
The vinyl monomer (B) is continuously grafted to the olefin polymer (A) having n) of 4 or less by using any one of a bulk polymerization method, a bulk suspension polymerization method, and a solution polymerization method. It is characterized by comprising a vinyl compound-modified olefin polymer obtained by polymerization.

In the present invention, when the vinyl compound-modified olefin polymer is prepared, the vinyl monomer (B)
Is preferably added in portions rather than all at once to the plug flow type reaction vessel.

The olefin polymer (A) is preferably an ethylene copolymer comprising ethylene and at least one component selected from α-olefins having 3 to 20 carbon atoms and polyene. Of these, ethylene copolymers composed of ethylene and at least one selected from an α-olefin having 3 to 20 carbon atoms and a polyene having a norbornene skeleton are preferable.

The ethylene content of the ethylene copolymer is preferably 35 to 97 mol%. The olefin polymer (A) includes a transition metal complex (a) represented by the following formula (I) or (II), an ionized ionic compound (b), an organoaluminum compound (c), and an alumoxane (d). )), A copolymer prepared using a metallocene-based catalyst comprising at least one compound selected from the group consisting of:

[0013]

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In the formulas (I) and (II), M is Ti, Z
r, Hf, Rn, Nd, Sm or Ru, and Cp1
And Cp2 are cyclopentadienyl groups bound M and [pi, indenyl group, a fluorenyl group or a derivative group thereof, X ¹ and X ² are anionic ligand or a neutral Lewis base ligand Y is a nitrogen atom,
A ligand containing an oxygen atom, a phosphorus atom, or a sulfur atom, wherein Z is C, O, B, S, Ge, Si or Sn
It is an atom or a group containing these atoms. ].

The vinyl monomer (B) is preferably at least one vinyl compound selected from the group consisting of aromatic vinyl monomers, nitrile vinyl monomers and derivatives thereof. Further, at least one vinyl compound selected from the group consisting of unsaturated carboxylic acids and derivatives thereof is also preferably used.

The laminate according to the present invention comprises [I] a resin layer composed of any one of polyamide, polycarbonate and polyester, and [II] the adhesive for forming a laminate according to the present invention as described above. It is characterized by being laminated with an adhesive layer.

The laminate according to the present invention includes not only a laminate having such a two-layer structure but also a laminate having this two-layer structure, for example, the following laminates (1) to (4). There may be. (1) [I] a resin layer composed of any polymer of polyamide, polycarbonate and polyester, [II] an adhesive layer composed of the adhesive for forming a laminate according to the present invention as described above, and [I] A laminate in which a resin layer made of any one of polyamide, polycarbonate and polyester is laminated in this order. (2) [I] a resin layer made of any polymer of polyamide, polycarbonate and polyester, [II] an adhesive layer made of the adhesive for forming a laminate according to the present invention as described above, and [III] A laminate comprising a resin layer composed of an ethylene / vinyl acetate copolymer and laminated in this order. (3) [I] a resin layer made of any polymer of polyamide, polycarbonate and polyester, [II] an adhesive layer made of the adhesive for forming a laminate according to the present invention as described above, and [IV] A laminate obtained by laminating a resin layer made of a saponified ethylene / vinyl acetate copolymer in this order. (4) [I] a resin layer composed of any polymer of polyamide, polycarbonate and polyester, [II] an adhesive layer composed of the adhesive for forming a laminate according to the present invention as described above, and [III] A resin layer composed of an ethylene / vinyl acetate copolymer, [II] an adhesive layer composed of the adhesive for forming a laminate according to the present invention as described above, and [I] a polyamide;
A laminate formed by laminating a resin layer composed of any one of polycarbonate and polyester in this order.

The packaging material for retort pouches and the packaging material for hot-fill packaging according to the present invention are characterized by comprising the laminate according to the present invention as described above.

[0019]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the adhesive for forming a laminate according to the present invention and its use will be specifically described.

First, the adhesive for forming a laminate according to the present invention will be described. Laminate molding adhesive according to the present invention,
In the plug flow type reaction vessel, the intrinsic viscosity [η] measured in decalin at 135 ° C. is in the range of 0.01 to 10 dl / g, and the molecular weight distribution (Mw / M
The vinyl monomer (B) is continuously grafted to the olefin polymer (A) having n) of 4 or less by using any one of a bulk polymerization method, a bulk suspension polymerization method, and a solution polymerization method. It is composed of a vinyl compound-modified olefin polymer obtained by polymerization.

Olefin polymer (A) The olefin polymer (A) used in the present invention is 135
The intrinsic viscosity [η] measured in decalin is usually 0.0
1 to 10 dl / g, preferably 0.05 to 10 dl / g
Is desirably within the range.

The olefin polymer (A) is a GPC
Weight distribution (Mw / Mn, in terms of polystyrene, Mw: weight average molecular weight, Mn: number average molecular weight)
Is desirably 4 or less, preferably 3.0 or less.

The olefin polymer (A) used in the present invention comprises two or more components selected from ethylene, α-olefins having 3 to 20 carbon atoms, and polyenes such as non-conjugated dienes and conjugated dienes. It is desirable that the derived structural units are randomly arranged and linked.

As the α-olefin having 3 to 20 carbon atoms as described above, specifically, propylene, 1-butene, 1-hexene, 3-methyl-1-pentene, 3-ethyl-1-
Penten, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-eicosene and the like. Among them, propylene, 1-butene, 1-hexene, 4-methyl-1-
Penten and 1-octene are preferably used.

As the polyene, specifically, 1,4-
Pentadiene, 1,5-hexadiene, 1,4-hexadiene,
1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinylnorbornene, dicyclopentadiene, 7-methyl-1,6
-Non-conjugated dienes such as octadiene and 4-ethylidene-8-methyl-1,7-nonadiene; conjugated dienes such as butadiene and isoprene. Among them, a polyene having a norbornene skeleton is preferable.

The iodine value of the olefin polymer (A) using the above-mentioned polyene is usually 80 or less, preferably 5 to 60. The olefin polymer (A) used in the present invention includes ethylene and α having 3 to 20 carbon atoms.
-Ethylene copolymers comprising at least one component selected from polyenes such as olefins and dienes are preferred, especially ethylene / 1-butene copolymers, ethylene / propylene copolymers, ethylene / 1- Octene copolymers are preferred. The ethylene content of such an ethylene-based copolymer is 35 to 97 mol%, preferably 35 to 90 mol%,
More preferably, it is 35 to 75 mol%.

[ Production of Olefin Polymer (A) ] The olefin polymer (A) desirably used in the present invention is at least two kinds selected from ethylene, α-olefins having 3 to 20 carbon atoms and polyenes. Is copolymerized in the presence of the metallocene catalyst shown below.

Examples of such a metallocene-based catalyst include transition metal complexes (a) represented by the following formulas (I) and (II):

[0029]

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[In the formulas (I) and (II), M is Ti, Z
r, Hf, Rn, Nd, Sm or Ru, and Cp1
And Cp2 are cyclopentadienyl groups bound M and [pi, indenyl group, a fluorenyl group or a derivative group thereof, X ¹ and X ² are anionic ligand or a neutral Lewis base ligand Y is a nitrogen atom,
A ligand containing an oxygen atom, a phosphorus atom, or a sulfur atom, wherein Z is C, O, B, S, Ge, Si or Sn
It is an atom or a group containing these atoms. ]When,
At least one catalyst system comprising at least one compound selected from the following components (b), (c) and (d) is used. (B): a compound that reacts with the transition metal M in the component (a) to form an ionic complex (also referred to as an ionized ionic compound) (c): an organoaluminum compound (d): alumoxane.

First, the transition metal complex (a) represented by the following formula (I) used in the present invention will be described. <Transition metal complex (a)>

[0032]

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In the formula (I), M is Ti, Zr, Hf, R
n, Nd, Sm or Ru, preferably Ti, Z
r or Hf, Cp1 and Cp2 are a cyclopentadienyl group, an indenyl group, a fluorenyl group or a derivative thereof bonded to M by π, X ¹ and X ² are an anionic ligand or A neutral Lewis base ligand wherein Z is C, O, B, S, Ge, Si or S
It is an n atom or a group containing these atoms.

In the formula (I), the linking group Z is, in particular, C, O,
It is preferably one atom selected from B, S, Ge, Si, and Sn, and this atom may have a substituent such as an alkyl group or an alkoxy group, and the substituents of Z are mutually bonded. To form a ring. Of these, Z is preferably selected from O, Si and C.

Cp1 and Cp2 are ligands that coordinate to the transition metal, and include cyclopentadienyl group, indenyl group,
4,5,6,7-tetrahydroindenyl group, a ligand having a cyclopentadienyl skeleton such as a fluorenyl group,
The ligand having a cyclopentadienyl skeleton may have a substituent such as an alkyl group, a cycloalkyl group, a trialkylsilyl group, and a halogen atom.

X ¹ and X ² are anionic ligands or neutral Lewis base ligands, specifically, a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a sulfone Acid-containing groups (—SO ₃ Ra, where Ra
Is an alkyl group, an alkyl group substituted with a halogen atom,
An aryl group, an aryl group substituted with a halogen atom, or an aryl group substituted with an alkyl group. ), A halogen atom, a hydrogen atom and the like.

In the following, M is zirconium, and
A metallocene compound containing two ligands having a cyclopentadienyl skeleton is exemplified. Cyclohexylidene-bis (indenyl) dimethyl zirconium, cyclohexylidene-bis (indenyl) zirconium dichloride, isopropylidene-bis (indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylene-bis (Indenyl) zirconium dichloride, methylphenylsilylene-bis (indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-1
-Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (4,7-dimethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,4,
7-trimethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,4,6-trimethyl-1
-Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene -Bis (2-methyl-4- (α-naphthyl) -1-indenyl) zirconium dichloride, ra
c-Dimethylsilylene-bis (2-methyl-4- (β-naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (1-anthryl) -1
-Indenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) fluorenyl zirconium dichloride, isopropyl (cyclopentadienyl)
-1-fluorenyl) hafnium dichloride, isopropyl (cyclopentadienyl-1-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) fluorenylzirconium dichloride, and the like.

Further, metallocene compounds in which zirconium metal is replaced with titanium metal or hafnium metal in the above compounds can also be exemplified. The metallocene compounds as described above can be used alone or in combination of two or more.

The metallocene compound as described above is
It can also be used by being supported on a particulate carrier. like this
As a specific particulate carrier, specifically, SiO 2_Two, Al_Two
O_Three, B_TwoO_Three , MgO, ZrO_Two, CaO, TiO_Two,
ZnO, SnO_Two, BaO, ThO and other inorganic carriers, poly
Ethylene, polypropylene, poly-1-butene, poly-4-meth
Cyl-1-pentene, styrene-divinylbenzene copolymer
An organic carrier such as a body can be used. These particles
Carriers can be used alone or in combination of two or more.
it can.

In the present invention, not only the fiber metal compound (metallocene compound) represented by the above formula (I) but also the transition metal compound (metallocene compound) represented by the following formula (II)
Can also be used.

[0041]

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In the formula (II), M is a transition metal belonging to Group 4 of the periodic table or a lanthanide series.
Zr, Hf, Rn, Nd, Sm, and Ru, preferably Ti, Zr, and Hf, and Cp1 represents a cyclopentadienyl group, an indenyl group, a fluorenyl group, or a derivative thereof, which is π-bonded to M. X ¹ and X
² is an anionic ligand or a neutral Lewis base ligand, Y is a ligand containing a nitrogen atom, an oxygen atom, a phosphorus atom, or a sulfur atom, and Z is carbon, oxygen, Sulfur, boron or an element of Group 14 of the periodic table (eg, silicon, germanium or tin), preferably any of carbon, oxygen and silicon; Z may have a substituent; Y may form a condensed ring.

More specifically, Cp1 is a ligand that coordinates to a transition metal, and has a cyclopentadienyl skeleton such as a cyclopentadienyl group, an indenyl group, a fluorenyl group, or a derivative group thereof. And
The ligand having a cyclopentadienyl skeleton may have a substituent such as an alkyl group, a cycloalkyl group, a trialkylsilyl group, and a halogen atom.

Z is C, O, B, S, Ge, S
i is an atom selected from Sn, Z is an alkyl group,
There may be a substituent such as an alkoxy group, and the substituents of Z may be bonded to each other to form a ring.

X ¹ and X ² are anionic ligands or neutral Lewis base ligands, which may be the same or different from each other, are a hydrogen atom or a halogen atom, or have 20 or less carbon atoms. A hydrocarbon group, a silyl group or a germyl group containing an atom, a silicon atom or a germanium atom.

Specific examples of the compound represented by the formula (II) include (t-butylamido) dimethyl (fluorenyl) silanetitanium dimethyl, (dimethyl (t-butylamido) (tetramethyl-η ⁵ -cyclopentane) Dienyl)
(Silylene) titanium dichloride, ((t-butylamide)
(Tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl) titanium dichloride, (dimethyl (phenylamide) (tetramethyl-η ⁵ -cyclopentadienyl)
(Silylene) titanium dichloride, (dimethyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silylene) titanium dimethyl, (dimethyl (4-methylphenylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silylene) titanium dichloride, (dimethyl (t-butylamido) (eta ⁵ - cyclopentadienyl) silylene) titanium dichloride, (tetramethyl (t-butylamido)
(Tetramethyl-η ⁵ -cyclopentadienyl) disilylene) titanium dichloride.

In the present invention, the above-mentioned metallocene catalyst is preferably used as the olefin polymerization catalyst. Next, a metallocene-based catalyst is formed (b): a compound that reacts with the transition metal M in the component (a) to form an ionic complex (that is, an ionized ionic compound);
(C): an organoaluminum compound and (d): alumoxane (aluminum oxy compound) will be described.

<(B) Ionized ionic compound> (b)
The ionized ionic compound (a) is a compound that reacts with the transition metal M in the transition metal complex component to form an ionic complex. Examples of the (b) ionized ionic compound include a Lewis acid and an ionized ion. Compounds, borane compounds and carborane compounds.

As the Lewis acid, a compound represented by BR ₃ (where R is a phenyl group or a fluorine atom which may have a substituent such as a fluorine atom, a methyl group or a trifluoromethyl group). For example, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl)
Boron, tris (4-fluoromethylphenyl) boron,
Tris (pentafluorophenyl) boron, tris (p-
And tris (o-tolyl) boron and tris (3,5-dimethylphenyl) boron.

Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts. Specifically, the trialkyl-substituted ammonium salts include, for example, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) boron.
And ammonium tetra (phenyl) boron. Examples of the dialkyl ammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron. Further, examples of the ionic compound include triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate, and ferrocenium tetra (pentafluorophenyl) borate.

As the borane compound, decaborane (1
4), bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) nickelate (II
And salts of metal borane anions such as I).

Examples of the carborane compound include 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) Salts of metal carborane anions such as nickelate (IV) are exemplified.

The (b) ionized ionic compound as described above can be used alone or in combination of two or more. The (d) organic aluminum oxy compound or (b) ionized ionic compound can be used by being supported on the above-mentioned particulate carrier.

In forming the catalyst, the following (c) organoaluminum compound may be used together with (d) the organoaluminum oxy compound and / or (b) the ionized ionic compound.

<(C) Organoaluminum compound> (c)
As the organoaluminum compound, a compound having at least one Al-carbon bond in a molecule can be used. Such compounds include, for example, organoaluminum compounds represented by the following general formula.

(R ¹ ) mAl (O (R ² )) nHpXq (wherein R ¹ and R ² may be the same or different from each other and usually have 1 to 15, preferably 1 to 1 carbon atoms)
X is a halogen atom, m is 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, and q is 0
≦ q <3, and m + n + p + q
= 3. <(D) Organoaluminum oxy compound (alumoxane)> The (d) organoaluminum oxy compound may be a conventionally known aluminoxane.
It may be a benzene-insoluble organic aluminum oxy compound as exemplified in JP-A-8687.

The conventionally known aluminoxane (alumoxane) is specifically represented by the following general formula.

[0058]

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In the formula, R is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group and a butyl group, preferably a methyl group, an ethyl group, and particularly preferably a methyl group. m is an integer of 2 or more, preferably 5 to 40.

Here, the aluminoxane has the formula (OAl (R
¹⁾⁾ alkyloxy aluminum units (here represented by alkyloxy aluminum units and formula represented by (OAl (R ^2)), R ¹ and R ² are the same hydrocarbon group as R, R ¹ and R ² represents a different group.).

The (d) organic aluminum oxy compound may contain a small amount of an organic compound component of a metal other than aluminum. In the present invention, as the catalyst (olefin-based catalyst) for producing the olefin polymer (A), the above-mentioned metallocene-based catalyst is preferably used. In some cases, a conventionally known metallocene-based catalyst other than the above-mentioned metallocene-based catalyst is used. (1) A titanium-based catalyst comprising a solid titanium catalyst component and an organoaluminum compound, and (2) a vanadium-based catalyst comprising a soluble vanadium compound and an organoaluminum compound can also be used.

In the present invention, propylene, ethylene and the like are usually copolymerized in the liquid phase in the presence of the above-mentioned metallocene catalyst. In this case, a hydrocarbon solvent is generally used, but propylene may be used as the solvent. This copolymerization can be carried out by either a batch method or a continuous method.

When the copolymerization is carried out by a batch method using a metallocene catalyst, the concentration of the transition metal complex (metallocene compound) (a) in the polymerization system is usually 0.00005 to 1 / liter of polymerization volume. 1 mmol, preferably 0.
It is used in an amount from 0001 to 0.5 mmol.

(D) The organoaluminum oxy compound (alumoxane) has a molar ratio (Al / M) of the aluminum atom (Al) to the transition metal atom (M) in the metallocene compound (a) of 1 to 10,000, preferably 10-5
000 is used.

(B) The ionized ionic compound is (a)
It is used in an amount such that the molar ratio of the (b) ionized ionic compound to the metallocene compound ((b) / (a)) is 0.5 to 20, preferably 1 to 10.

When (c) an organoaluminum compound is used, the amount of polymerization is usually about 0 per liter of polymerization volume.
５5 mmol, preferably about 0-2 mmol.

The copolymerization reaction is usually carried out at a temperature of -20 to 15
0 ° C, preferably 0 to 120 ° C, more preferably 0 to
In the range of 100 ° C., the pressure exceeds 0 and is ~ 80 kg / cm
² , preferably above 0 and up to 50 kg / cm ² .

The reaction time (average residence time when the copolymerization is carried out by a continuous method) varies depending on conditions such as the catalyst concentration and the polymerization temperature, but is usually 5 minutes to 3 hours, preferably 10 minutes. ~ 1.5 hours.

The above ethylene, α-C 3 -C 20
The monomer for copolymerization of the olefin-derived component is supplied to the polymerization system in such an amount as to obtain the olefin polymer (A) as described above. At the time of copolymerization, a molecular weight regulator such as hydrogen can be used.

As described above, ethylene and carbon atoms 3
When the copolymerizing monomers of α-olefins derived from α to 20 are copolymerized, the olefin polymer (A) is usually obtained as a polymerization solution containing the same. This polymerization solution is treated by a conventional method to obtain an olefin polymer (A).

As described above, the olefin polymer (A) obtained as described above contains ethylene and C 3 carbon atoms.
And a copolymer obtained from two or more components selected from α-olefins, polyenes having a norbornene skeleton and polyenes having no norbornene skeleton.

Vinyl monomer (B) As the vinyl monomer (B) used in the present invention, specifically, an aromatic vinyl monomer such as styrene;
Vinyl naphthalene such as vinyl naphthalene; vinyl anthracene such as 9-vinyl anthracene; α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, halogenated styrene, t-butylstyrene, vinyltoluene, vinylxylene And styrene derivatives such as divinylbenzene; and nitrile vinyl monomers such as acrylonitrile; acrylonitrile derivatives such as α-chloroacrylonitrile; and unsaturated carboxylic acids or derivatives thereof such as (meth) acrylic acid; methyl methacrylate. , Ethyl methacrylate,
(Meth) acrylic acid derivatives such as methyl acrylate, ethyl acrylate and n-butyl acrylate; maleic acid and the like; maleic acid derivatives such as maleic anhydride; and a maleimide monomer such as n-phenylmaleimide;
Examples thereof include n-methylphenylmaleimide, n-cyclohexylmaleimide, and n-ethylmaleimide.

The above vinyl compounds can be used alone or in combination of two or more as a graft monomer. Among the aromatic vinyl monomers, the above-mentioned styrene or a derivative thereof is preferable, and styrene, α-methylstyrene and p-methylstyrene are more preferable, and styrene and α-methylstyrene are particularly preferable.

Among the nitrile vinyl monomers, acrylonitrile or a derivative thereof is preferred, acrylonitrile is more preferred, and among unsaturated carboxylic acids or derivatives thereof, maleic anhydride is preferred. Also,
Acrylic acid, methacrylic acid, methyl methacrylate and the like are also preferably used. Particularly preferably, an unsaturated carboxylic acid or a derivative thereof is used in combination with an aromatic vinyl monomer and / or a nitrile vinyl monomer as required.

The graft amount of the vinyl compound-modified olefin polymer is usually from 5 to 50% by weight, preferably from 50% by weight, based on 100% by weight of the olefin polymer (A) before the graft modification in terms of the vinyl monomer (B). 10 to 40% by weight.

Plug Flow Type Reaction Tank In the process for producing a vinyl compound-modified olefin polymer according to the present invention, a plug flow type reaction tank is used. Flow (the fluid state that flows into the area of interest at a certain time at the same time, without mixing with other liquid parts, continues to move as a unit afterwards ("Chemical Engineering Dictionary" edited by Chemical Engineering Association, It means a reaction tank capable of expressing a fluid state close to that of Maruzen Co., Ltd.), and does not limit the type and shape of the reaction tank.

For example, in the case of a complete mixing tank, a reaction tank in which a plurality of, preferably three or more complete mixing tanks are connected in series, a tubular reaction tank or a tower-type reaction tank closer to a plug flow than the complete mixing tank. In particular, it is desirable to use 1 to 3, preferably 1 to 2 tubular reactors or tower reactors separated into a plurality of parts by a partition plate.

As the tubular reactor and tower reactor, conventionally known tubular reactors and tower reactors can be used.
Examples of the tower-type reaction vessel include a tower-type reaction vessel described in FIG. 7.5 on page 185 of “New Polymer Production Process” (Industrial Research Council, written by Koji Saeki / Shinzo Omi). This tower-type reaction tank has an inlet for the raw material and an outlet for the produced polymer. For the reaction tank used between the inlet for the raw material and the outlet for the produced polymer, the plug flow was determined from the results of the following liquid test. Sex is tested. That is, a liquid having a viscosity of 10 poise is supplied to the reaction tank at a rate of F (liter / hour) from the inlet of the raw material, and the liquid is taken out from the outlet at a rate of F (liter / hour). When the volume is set to V (liter), F = V, and the liquid is continuously flowed in a steady state, and suddenly switched to a liquid having a density of C ₀ (%) and a viscosity of 10 poise at red at time t ₀ . At time t ₁
(T ₁ is the time two hours after t ₀ ) and the concentration C ₁ at the outlet
A polymerization apparatus in which (%) satisfies (C ₁ / C ₀ )> 0.9 is preferably used in the present invention. In the present specification, polymerization satisfying such conditions is defined as "plug flow polymerization",
The reaction tank used for this polymerization is defined as a “plug flow type reaction tank”. The plug flow type reaction vessel may be a single reaction vessel or may be composed of a plurality of reaction vessels.

In the present invention, the total amount of the vinyl monomer (B) can be added to the olefin polymer (A) charged in the plug flow type reaction vessel at a time or in portions. Addition is preferable in that the quality of the obtained vinyl compound-modified olefin polymer is excellent.

The method of dividingly adding the vinyl monomer (B) to the olefin polymer (A) in the plug flow type reaction vessel is as follows.
Although not particularly limited, one or more, preferably a plurality of monomer feed ports are provided between the main input port and the outlet of the raw material of the plug flow type reaction tank, and the vinyl monomer is continuously or intermittently provided. It is desirable to feed the monomers.
Intermittently feeding the vinyl monomer into the reaction tank at one feed port is not included in the split addition referred to in the present invention. The term "partial addition" as used in the present invention means that the vinyl monomer (B) is introduced from two or more different feed ports. When there is only one monomer feed port from the main material inlet to the outlet of the plug flow type reaction tank, part of the vinyl monomer (B) is always fed from the main material inlet. In addition, two or more different feed ports
It may be the same distance from the main feed port of the raw materials. For example, when a tower-type reaction tank is used, two feed ports are provided at different points on the same circumference of the body of the reaction tank, and vinyl feed is performed from these feed ports. The case where the monomer (B) is fed into the reaction tank is also included in the split addition according to the present invention.

In such a divided addition of the vinyl monomer (B), the vinyl monomer fed from the main input port of the plug flow type reaction tank and the vinyl monomer fed from the main input port to the outlet are used. The monomers may be the same compound or different compounds. Furthermore, when the vinyl monomer is fed from a plurality of locations between the main inlet and the outlet, the vinyl monomers fed from each location may be the same compound or different compounds. Is also good.

The ratio of the vinyl monomer fed from the main input port to the vinyl monomer fed from the main input port to the outlet of the plug flow type reaction tank, and the ratio of the vinyl monomer fed from the main input port to the outlet port When the vinyl monomer is fed from a plurality of points up to the point, the ratio of the vinyl monomer fed from each point is not particularly limited, and the entire amount of the vinyl monomer is supplied to the plug flow type reaction tank. May be fed from the main input port, or the entire amount of the vinyl monomer may be fed between the main input port and the outlet of the plug flow type reaction tank, or may be fed in an appropriately divided manner. Good.

[0083] bulk polymerization in the polymerization process the present invention, bulk suspension polymerization and solution polymerization method, a raw material olefin polymer (A) and vinyl monomer (B) was fed to the polymerization reaction step, graft polymerization reaction And the resulting polymer is taken out of the polymerization reaction step to obtain a polymer product. In the case of using 30% or more of a solvent, a solvent is usually called "solution polymerization method".
When used in an amount of less than 0% (including 0%)
It is used in an amount of less than 30%, and the case where it is in a suspended state is called "bulk suspension polymerization method".

In the present invention, an inert organic solvent can be used. For example, benzene, toluene, xylene, ethylbenzene, acetone, isopropylbenzene, methylethylketone and the like are used. Among them, toluene, ethylbenzene and xylene are preferably used. Can be

These organic solvents comprise a total amount of the olefin polymer (A), vinyl monomer (B) and organic solvent of 1
It is used in an amount of usually 400 parts by weight or less, preferably 200 parts by weight or less, more preferably 100 parts by weight or less based on 00 parts by weight.

In the present invention, when the vinyl monomer (B) is graft-polymerized to the olefin polymer (A) by employing the above polymerization method, it is preferable to use a radical initiator.

Such a radical initiator (polymerization initiator)
Although not particularly limited, for example, benzoyl peroxide, lauroyl peroxide, t-
Butylperoxypivalate, t-butylperoxybenzoate, t-butylperoxyisobutyrate, t-butylperoxyoctoate, cumylperoxyoctoate, 1,1-bis (t-butylperoxy) -3 The use of organic peroxides such as 3,3,5-trimethylcyclohexane is preferred. Among them, especially benzoyl peroxide, lauroyl peroxide, t-butyl peroxypivalate, t-
Butyl peroxyoctoate and 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane are preferably used.

These radical initiators are generally used in an amount of 0.001 to 5.0 parts by weight, preferably 0 to 5.0 parts by weight, based on 100 parts by weight of the total amount of the olefin polymer (A), vinyl monomer (B) and organic solvent. 0.00001 to 3.5 parts by weight, more preferably 0.001 to 2.0 parts by weight.

In the present invention, various chain transfer agents can be used in addition to the above-mentioned inert organic solvent in order to control the molecular weight of the target vinyl compound-modified olefin polymer. For example, α-methylstyrene dimer, t-
Known chain transfer agents such as dodecyl mercaptan, n-dodecyl mercaptan, and n-octyl mercaptan are used.

These chain transfer agents are used in a total amount of 1 to 1 of the olefin polymer (A), the vinyl monomer (B) and the organic solvent.
It is used in an amount of usually 0.001 to 5.0 parts by weight, preferably 0.001 to 3.5 parts by weight, more preferably 0.01 to 2.0 parts by weight, based on 00 parts by weight.

In the present invention, the polymerization temperature depends on whether or not a radical initiator is used, but is generally preferably 50 to 180 ° C., more preferably 60 to 150 ° C., and the residence time is preferably Is 0.2 to 6 hours, more preferably 0.5 to 4 hours.

In the present invention, the polymer solution obtained by the polymerization is dried under reduced pressure, whereby the vinyl compound-modified olefin polymer and the unreacted vinyl monomer (B), the inert organic solvent and the like are batchwise separated. The vinyl compound-modified olefin polymer may be separated from the unreacted vinyl monomer (B), an inert organic solvent, or the like. The olefin polymer may be manufactured continuously.

Laminate The laminate according to the present invention comprises [I] a resin layer comprising a polymer of any of polyamide, polycarbonate and polyester, and [II] the above-mentioned adhesive for forming a laminate according to the present invention. It is a laminate of two or more layers obtained by laminating an adhesive layer.

The above polyamide is specifically produced from aliphatic polyamides such as nylon-6, nylon-66, nylon-10, nylon-12 and nylon-46, and aromatic dicarboxylic acids and aliphatic diamines. Aromatic polyamide and the like can be mentioned. Among them, nylon-6 is particularly preferred.

As the above polycarbonate, bis (4-
Hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl)
Examples include polymers obtained from propane, 2,2-bis (4-hydroxyphenyl) butane, and the like. Among them, polycarbonate obtained from 2,2-bis (4-hydroxyphenyl) propane is particularly preferable.

As the above polyester, specifically,
Aromatic polyesters such as polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate, polycaprolactone, polyhydroxybutyrate and the like can be mentioned. Among them, polyethylene terephthalate is particularly preferred.

The laminate according to the present invention can be prepared by, for example, a conventionally known water-cooled or air-cooled coextrusion inflation method, coextrusion T-die method, dry lamination method, extrusion lamination method or the like.
And the adhesive layer [II]. In particular, from the viewpoints of laminate performance such as hygiene and economics, a water-cooled coextrusion inflation method and a coextrusion T-die method are preferred. The manufacturing conditions in the above-described method for manufacturing a laminated body are naturally set to appropriate temperatures, speeds, and the like so as not to cause deterioration of the resin.

When the laminate has a two-layer structure, the thickness of the laminate depends on the intended use. For retort packaging, for example, the total thickness of the laminate is usually from 50 to 500.
μm, preferably 50 to 400 μm, more preferably 100 to 300 μm. In this case, the thickness of the resin layer [I] constituting the laminate is generally 10 to 200 μm, preferably 10 to 150 μm, more preferably 10 to 10 μm.
0 μm, and the thickness of the adhesive layer [II] is usually 10 to 2
The thickness is 00 μm, preferably 10 to 150 μm, and more preferably 10 to 100 μm.

For hot-fill packaging, the overall thickness of the laminate is usually 50 to 700 μm, preferably 50 to 700 μm.
It is 500 μm, more preferably 50 to 400 μm. In this case, the thickness of the resin layer [I] constituting the laminate is generally 10 to 250 μm, preferably 10 to 200 μm.
m, more preferably 10 to 150 μm, and the thickness of the adhesive layer [II] is usually 10 to 250 μm, preferably 10 to 200 μm, more preferably 10 to 150 μm.
It is.

The laminate according to the present invention comprises at least a resin layer composed of any of the above-mentioned [I] polymers of polyamide, polycarbonate and polyester, and [II] a laminate composed of the adhesive for forming a laminate according to the present invention. It has a two-layer structure consisting of an agent layer.

Examples of the laminate according to the present invention include the following laminates (1) to (4) in addition to the laminate having the two-layer structure. (1) A resin layer [I] comprising a polymer of any of polyamide, polycarbonate and polyester, and an adhesive layer [II] comprising an adhesive for forming a laminate according to the present invention.
And the resin layer [I] are laminated in this order. (2) A laminate having a three-layer structure in which the resin layer [I], the adhesive layer [II], and the resin layer [III] made of an ethylene / vinyl acetate copolymer are laminated in this order. . (3) The resin layer [I], the adhesive layer [II], and the resin layer [I] comprising a saponified ethylene / vinyl acetate copolymer.
V] are laminated in this order. (4) the resin layer [I], the adhesive layer [II], a resin layer [III] made of an ethylene / vinyl acetate copolymer,
A laminate having a five-layer structure in which the adhesive layer [II] and the resin layer [I] are laminated in this order.

In the laminates (1) to (4),
Although the thickness varies depending on the intended use, for example, for retort packaging, the total thickness of the laminate is usually 50 to 500 μm.
m, preferably 50 to 400 μm, more preferably 1
It is desirable that the thickness be 00 to 300 μm. In this case, the thickness of the resin layer [I] is usually 10 to 200 μm, preferably 10 to 150 μm, more preferably 10 to 100 μm.
m, and the thickness of the adhesive layer [II] is usually 10 to 200
μm, preferably 10 to 150 μm, more preferably 10 to 100 μm. The thickness of the resin layer [III] made of an ethylene / vinyl acetate copolymer is usually 10 to 200 μm.
m, preferably 10 to 150 μm, more preferably 1
The thickness of the resin layer [IV] made of a saponified ethylene / vinyl acetate copolymer is usually 10 to 20 μm.
0 μm, preferably 10 to 150 μm, more preferably 10 to 100 μm.

For hot-fill packaging, the total thickness of the laminate is usually 50 to 700 μm, preferably 50 to 700 μm.
It is desirable that the thickness be 500 μm, more preferably 50 to 400 μm. In this case, the thickness of the resin layer [I] is usually 10 to 250 μm, preferably 10 to 200 μm, more preferably 10 to 150 μm, and the adhesive layer [I]
I] is usually 10 to 250 μm, preferably 10 to 250 μm.
To 200 μm, more preferably 10 to 150 μm, and a resin layer comprising an ethylene / vinyl acetate copolymer [II
I] is usually 10 to 250 μm, preferably 10 to 250 μm.
To 200 μm, more preferably 10 to 150 μm, and the thickness of the resin layer [IV] composed of a saponified ethylene / vinyl acetate copolymer is usually 10 to 250 μm, preferably 10 to 200 μm, and more preferably 10 to 150 μm.
It is desirable that

A polyamide for forming the resin layer [I],
About the polyamide which forms the said resin layer [V] with polycarbonate and polyester, it is as above-mentioned. The ethylene / vinyl acetate copolymer forming the resin layer [III] generally has a vinyl acetate content of 5 to 50.
%, Preferably in the range of 5 to 40% by weight. Further, the ethylene / vinyl acetate copolymer used in the present invention generally has a melt flow rate (ASTM D 1
238, 190 ° C, 2.16 kg) is 0.1 to 50 g / 10 min, preferably 0.1 to 40 g / 10 min, and has a density (ASTM D 1
505) is 0.900 to 0.980 g / cm ³ , preferably 0.91 to 0.97 g / cm ³ .

The saponified ethylene / vinyl acetate copolymer forming the resin layer [IV] may be an ethylene / vinyl acetate copolymer having an ethylene content of 15 to 60 mol%, preferably 25 to 50 mol%. Combined, the saponification degree is 50%
Above, preferably those which are saponified to 90% or more are used. When the ethylene content is within the above range, it is difficult to thermally decompose, easy to melt-mold, stretchability,
It has excellent water resistance and gas barrier properties. Further, when the saponification degree is 50% or more, the gas barrier property is excellent.

The method of lamination employed in the preparation of the above-mentioned laminate depends on the shape, size and required physical properties of the final product, and is not particularly limited. For example, the above-mentioned layers are simultaneously extruded by a multilayer extruder. And heat-sealing (co-extrusion molding).

The above-mentioned three-layer laminated body (1) to (3) is a molding method (three-layer injection molding method) in which three kinds of molten resins are injected into a mold at a different injection timing. Can also be prepared. The laminate having a five-layer structure of the above (4) can be similarly prepared by a five-layer injection molding method.

As described above, the laminate according to the present invention comprises:
It has a two-layer structure consisting of [I] a resin layer made of any polymer of polyamide, polycarbonate and polyester, and [II] an adhesive layer made of the adhesive for forming a laminate according to the present invention. The two layers may be formed from the above-described laminate having a two-layer structure according to the present invention.

That is, the surface of the adhesive layer [II] constituting the laminate having the two-layer structure is extrusion-coated with any polymer of polyamide, polycarbonate and polyester, whereby the laminate of the above (1) is obtained. can get. If an ethylene / vinyl acetate copolymer is used instead of such a polymer, the laminate of the above (2) can be obtained. If a saponified ethylene / vinyl acetate copolymer is used, the above (3) can be obtained. )) Can be obtained.

The laminate according to the present invention as described above is suitable for use as, for example, a packaging material for retort pouches and a packaging material for hot-fill packaging.

[0111]

According to the present invention, it is possible to maintain a practical adhesive strength at room temperature after a high temperature treatment and to perform a laminating process when a severe treatment such as a high temperature filling (hot fill) or a retort treatment is performed. Thus, it is possible to provide an adhesive for molding a laminate having excellent heat resistance at high temperatures so that delamination of the laminate can be prevented.

Further, according to the present invention, when a laminate having excellent interlayer adhesion even at a high temperature, especially a layer comprising a saponified ethylene / vinyl acetate copolymer is laminated, the gas barrier property is also reduced. Can provide an excellent laminate,
This laminate can be provided as a packaging material for retort pouches and a packaging material for hot-fill packaging.

[0113]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

The melting point (Tm), intrinsic viscosity [η] and Mw / Mn in Examples and the like were measured by the following methods and conditions. (1) Melting Point (Tm) The endothermic curve of DSC is determined, and the temperature at the maximum peak position is defined as the melting point (Tm).

Using a differential scanning calorimeter (DSC), the sample was packed in an aluminum pan, heated to 200 ° C. at 100 ° C./min, kept at 200 ° C. for 5 minutes, and then charged at −10 ° C./min.
It was determined from an endothermic curve when the temperature was decreased to 0 ° C. and then increased at a rate of 10 ° C./min. (2) Intrinsic viscosity [η] Intrinsic viscosity [η] was measured in decalin at 135 ° C. (3) Mw / Mn Mw / Mn was measured using GPC (gel permeation chromatography) in an orthodichlorobenzene solvent,
It was measured at 140 ° C.

[0116]

[Production Example 1] A plug flow tower type reaction tank having a volume of 1 liter ("New Polymer Production Process" (Industry Research Council, written by Koji Saeki / Shinzo Omi), page 185, described in FIG. 7.5 (b)) Acrylic acid-graft-modified ethylene / 1- was prepared by using a reaction vessel of the same type as a Mitsui Toatsu Chemical type tower-type reaction vessel, which was divided into 10 stages and exhibiting C1 / C0 = 0.955) as a continuous polymerization apparatus. A butene random copolymer (G-EBR1) was produced.

That is, an ethylene / 1-butene random copolymer having an ethylene content of 53 mol% (Mw / Mn = 2.
1, intrinsic viscosity [η] = 3 dl / g) 10.5 parts by weight, 27 parts by weight of acrylic acid and 61 parts by weight of toluene were mixed,
Prepare dissolved solution A and prepare toluene 1.5
Solution B was prepared by dissolving 0.07 parts by weight of 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane in parts by weight.

Next, the solution A and the solution B were separately supplied continuously to the plug flow tower type reaction vessel at a total of 400 g / h, and the center of the reaction vessel in the vertical direction was kept at 100 ° C.
The graft polymerization was carried out as follows.

The polymerization solution obtained as described above was mixed with 1
It was dried under reduced pressure at 10 kPaabs. At 90 ° C. for 30 minutes to obtain a target polymer (G-EBR1). To 5 g of the obtained polymer, 500 cc of methyl ethyl ketone was added, and the mixture was separated into a soluble part and an insoluble part at room temperature, and each component was dried in vacuum. The obtained methyl ethyl ketone insoluble part was subjected to elemental analysis, and the oxygen content was measured. As a result, the oxygen content was 11.3% by weight, and the acrylic acid content was 25.2.
% By weight.

[0120]

Production Example 2 The same procedure as in Production Example 1 was repeated except that maleic anhydride was used in place of acrylic acid, and the target polymer, ie, maleic anhydride graft-modified ethylene / 1-butene random, was used. Copolymer (G-
EBR2) was obtained.

To 5 g of the obtained polymer, 500 cc of methyl ethyl ketone was added, and the mixture was separated into a soluble part and an insoluble part at room temperature, and each component was dried under vacuum. The obtained methyl ethyl ketone insoluble part was subjected to elemental analysis, and the oxygen content was measured. As a result, the oxygen content was 12.8% by weight, and the maleic anhydride content was 26.7% by weight.

[0122]

Reference Example: An ethylene / 1-butene random copolymer having an ethylene content of 53 mol% in a pellet form (intrinsic viscosity [η] =
2.9 dl / g, Mw / Mn = 2.1) 100 parts by weight, 0.1 part by weight of Irganox 1010 (trade name; manufactured by Ciba Geigy), BHT (Takeda) [trade name: Takeda Pharmaceutical Co., Ltd. Co., Ltd.] and 0.1 part by weight of calcium stearate. To this mixture, 28 parts by weight of an acrylic acid monomer and 1 part by weight of perhexin 25B (trade name, manufactured by NOF CORPORATION, radical initiator) are added, and the mixture is mixed with a Henschel mixer at 40 ° C. for 20 minutes to absorb and impregnate. I let it.

Next, the obtained impregnated blend was fed to a co-rotating twin-screw extruder having a screw diameter of 30 mm and L / D = 48, and was melt-kneaded at a temperature of 200 ° C., pelletized, and treated with acrylic acid. A graft-modified ethylene / 1-butene random copolymer (G-EBR3) was obtained.

To 5 g of the obtained pellet-shaped polymer was added 500 cc of methyl ethyl ketone, and the mixture was separated into a soluble portion and an insoluble portion at room temperature, and each component was dried under vacuum. The obtained methyl ethyl ketone insoluble part was subjected to elemental analysis, and the oxygen content was measured. As a result, the oxygen content was 9.5% by weight.
And the acrylic acid content was 21.1% by weight.

[0125]

Example 1 Acrylic graft-modified ethylene / 1-butene random copolymer (G-EBR) obtained in Production Example 1
1), polycarbonate (trade name Teijin Panlite L-1)
250, manufactured by Teijin Chemicals Limited, hereinafter referred to as "PC"), and saponified ethylene / vinyl acetate copolymer [MFR (ASTM
D 1238, 190 ° C, 2.16 kg load) = 1.3 g / 10 min, density = 1.19 g / cm ³ , ethylene content = 32 mol%, trade name Kuraray Eval EP-F, manufactured by Kuraray Co., Ltd. "EVOH") under the following conditions:
A layer sheet was formed. <Lamination conditions> Layer configuration of sheet: PC / G-EBR1 / EVOH / G-EBR1 / PC Film thickness of each layer (μm): 80/50/50/50/80 Extruder: 40 mmφ extruder 280 ° C. (for PC ) 30 mmφ extruder 230 ° C. (for G-EBR1) 30 mmφ extruder 210 ° C. (for EVOH) 30 mmφ extruder 230 ° C (for G-EBR1) 40 mmφ extruder 280 ° C. (for PC) PC layer of the obtained five-layer sheet And G-EBR1 layer (FPC, g / 15 mm) and the EVOH layer and G-EBR1 layer (FEVOH, g /
15 mm) by T-type peeling at a peeling atmosphere temperature of 23 ° C. and 80 ° C. and a peeling speed of 300 mm / min. The size of the test piece used is 15 mm in width and 100 mm in length.

Further, after the sheet was subjected to a retort treatment at 131 ° C. for 30 minutes, the sheet was subjected to T
A mold release test was performed. The results are shown below. <Results>-Interfacial adhesive strength between the PC layer and the G-EBR1 layer (FP
C); 23 ° C .; 810 g / 15 mm 80 ° C .; 720 g / 15 mm After retort treatment; 410 g / 15 mm
23 ° C .; 850 g / 15 mm 80 ° C .; 700 g / 15 mm After retorting; 380 g / 15 mm Next, the above-mentioned G-EBR1, the above EVOH, polyethylene terephthalate (J135 (trade name) manufactured by Mitsui Pet Co., Ltd. "PET") under the following conditions:
A layer sheet was formed. <Lamination conditions> Layer configuration of sheet: PET / G-EBR1 / EVOH / G-EBR1 / PET Film thickness (μm) of each layer: 80/50/50/50/80 Extruder: 40 mm extruder 280 ° C. (for PET) ) 30 mm extruder 230 ° C. (for G-EBR1) 30 mm extruder 210 ° C. (for EVOH) 30 mm extruder 230 ° C. (for G-EBR1) 40 mm extruder 280 ° C. (for PET) Interfacial adhesive strength (FPET, g / 15 mm) with G-EBR1 layer and EVO
Interfacial adhesion strength between H layer and G-EBR1 layer (FEVOH,
g / 15 mm) under the same conditions as above. The results are shown below. <Results>-Interfacial adhesive strength between the EVOH layer and the G-EBR1 layer (FE
VOC); 23 ° C .; 840 g / 15 mm 80 ° C .; 620 g / 15 mm After retort treatment; 320 g / 15 mm ・ Interfacial adhesive strength (FPE
T); 23 ° C; 800 g / 15 mm 80 ° C; 710 g / 15 mm After retorting; 440 g / 15 mm

[0127]

EXAMPLE 2 The procedure of Example 1 was repeated, except that the acrylic graft-modified ethylene / 1-butene random copolymer (G-EBR1) obtained in Production Example 1 was replaced with a maleic anhydride graft-modified product obtained in Production Example 2. Two kinds of laminates were produced in the same manner as in Example 1 except that an ethylene / 1-butene random copolymer (G-EBR2) was used. About the obtained laminated body, each interface adhesive strength was measured like Example 1. FIG. The results are shown below. <Results> Layer configuration PC / G-EBR2 / EVOH / G-EBR2 /
Interfacial adhesive strength (FPC) between PC laminate and PC and G-EBR2 layer; 23 ° C; 950 g / 15 mm 80 ° C; 800 g / 15 mm After retort treatment; 400 g / 15 mm ・ Interface between EVOH layer and G-EBR2 layer Adhesive strength (FE
VOH); 23 ° C; 970 g / 15 mm 80 ° C; 820 g / 15 mm After retort treatment; 380 g / 15 mm Layer composition PET / G-EBR2 / EVOH / G-EBR2
/ PET laminate・ Interfacial adhesive strength between EVOH layer and G-EBR2 layer (FE
VOH); 23 ° C .; 950 g / 15 mm 80 ° C .; 800 g / 15 mm After retort treatment; 400 g / 15 mm ・ Interfacial adhesive strength between PET layer and G-EBR2 layer (FPE)
T); 23 ° C; 930 g / 15 mm 80 ° C; 750 g / 15 mm After retorting; 340 g / 15 mm

[0128]

Comparative Example In Example 1, the acrylic graft-modified ethylene / 1-butene random copolymer (G-EBR1) obtained in Production Example 1 was replaced with the acrylic acid-grafted modified ethylene / 1 -Two types of laminates were produced in the same manner as in Example 1 except that a butene random copolymer (G-EBR3) was used. About the obtained laminated body, each interface adhesive strength was measured like Example 1. FIG. The results are shown below. <Results> Layer configuration PC / G-EBR3 / EVOH / G-EBR3 /
Interfacial adhesive strength (FPC) between PC laminate and PC and G-EBR3 layer; 23 ° C; 710 g / 15 mm 80 ° C; 600 g / 15 mm After retort treatment; 290 g / 15 mm ・ Interface between EVOH layer and G-EBR3 layer Adhesive strength (FE
VOC); 23 ° C .; 540 g / 15 mm 80 ° C .; 470 g / 15 mm After retorting; 210 g / 15 mm Layer composition PET / G-EBR3 / EVOH / G-EBR3
/ PET laminate・ Interfacial adhesive strength between EVOH layer and G-EBR3 layer (FE
VOH); 23 ° C; 690 g / 15 mm 80 ° C; 530 g / 15 mm After retorting; 210 g / 15 mm ・ Interfacial adhesive strength between PET layer and G-EBR3 layer (FPE
T); 23 ° C; 600 g / 15 mm 80 ° C; 480 g / 15 mm After retorting; 180 g / 15 mm

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Akira Todo 1-2-1, Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Chemicals, Inc. (72) Inventor Masaaki Ogizawa 1-chome Takasago, Takaishi-shi, Osaka 6 Mitsui Chemicals Co., Ltd. (72) Inventor Ryuichi Sugimoto 1-6 Takasago, Takaishi-shi, Osaka Mitsui Chemicals Co., Ltd. F-term (reference) 4F100 AK03B AK03D AK11B AK11D AK42A AK42C AK42E AK45A AK45C AK45E AK46C AK46C AK46C AK69C AK80B AK80D AL04B AL04D AL06B AL06D BA03 BA05 BA06 BA07 BA10A BA10C BA10E CB03B CB03D EH23 GB23 JA06B JA06D JD02 JJ03 YY00B YY00D 4J040 DL041 DL061 DL071 HD41 HD43 LA01 QA08 MA10 NA06

Claims (14)

[Claims] 1. In a plug flow type reaction vessel, 135 ° C.
Of intrinsic viscosity [η] measured in decalin of 0.01 to 1
An olefin polymer (A) having a molecular weight distribution (Mw / Mn) of 4 or less in the range of 0 dl / g and a vinyl monomer (B) is added to the olefin polymer (A) by a bulk polymerization method or a bulk suspension polymerization method. And an adhesive for molding a laminate, comprising a vinyl compound-modified olefin polymer obtained by continuous graft polymerization using any one of the polymerization methods of solution polymerization and solution polymerization. 2. The olefin polymer (A) is an ethylene copolymer comprising ethylene and one or more components selected from α-olefins having 3 to 20 carbon atoms and polyenes. The adhesive for forming a laminate according to claim 1, wherein: 3. An ethylene copolymer wherein the olefin polymer (A) comprises ethylene and at least one selected from an α-olefin having 3 to 20 carbon atoms and a polyene having a norbornene skeleton. The adhesive for forming a laminate according to claim 2, wherein: 4. The adhesive for forming a laminate according to claim 2, wherein the ethylene content of the ethylene-based copolymer is 35 to 97 mol%. 5. The transition metal complex (a) wherein the olefin polymer (A) is represented by the following formula (I) or (II):
And a metallocene-based catalyst comprising an ionized ionic compound (b), one or more compounds selected from an organoaluminum compound (c) and an alumoxane (d). The adhesive for forming a laminate according to any one of claims 1 to 4, characterized by the following: [In the formulas (I) and (II), M is Ti, Zr, Hf, R
n, Nd, Sm or Ru; Cp1 and Cp2 are a cyclopentadienyl group, an indenyl group, a fluorenyl group or a derivative group thereof bonded to M by π, X ¹ and X ² are anionic groups A ligand or a neutral Lewis base ligand; Y is a ligand containing a nitrogen, oxygen, phosphorus, or sulfur atom; Z is C, O, B, S, Ge , Si or Sn atom or a group containing these atoms. ]. 6. The vinyl monomer (B) is at least one vinyl compound selected from the group consisting of aromatic vinyl monomers, nitrile vinyl monomers and derivatives thereof. The adhesive for forming a laminate according to claim 1. 7. A method according to claim 1, wherein said vinyl monomer (B) is at least one vinyl compound selected from the group consisting of unsaturated carboxylic acids and derivatives thereof.
3. The adhesive for forming a laminate according to item 1. 8. An adhesive layer comprising: [I] a resin layer comprising a polymer of any one of polyamide, polycarbonate and polyester; and [II] an adhesive layer comprising the adhesive according to any one of claims 1 to 7. A laminate characterized in that: 9. [I] a resin layer comprising a polymer of any one of polyamide, polycarbonate and polyester, [II] an adhesive layer comprising the adhesive according to any one of claims 1 to 7, and [I] The laminate according to claim 8, wherein a resin layer made of any one of polyamide, polycarbonate and polyester is laminated in this order. 10. [I] a resin layer comprising a polymer of any of polyamide, polycarbonate and polyester, [II] an adhesive layer comprising the adhesive according to any one of claims 1 to 7, and [III] The laminate according to claim 8, wherein a resin layer made of an ethylene / vinyl acetate copolymer is laminated in this order. [11] [I] a resin layer comprising a polymer of any of polyamide, polycarbonate and polyester, [II] an adhesive layer comprising the adhesive according to any one of [1] to [7], and [IV] The laminate according to claim 8, wherein a resin layer made of a saponified ethylene / vinyl acetate copolymer is laminated in this order. 12. [I] a resin layer comprising a polymer of any one of polyamide, polycarbonate and polyester; [II] an adhesive layer comprising the adhesive according to any one of claims 1 to 7; A resin layer comprising an ethylene / vinyl acetate copolymer; [II] an adhesive layer comprising the adhesive according to any one of claims 1 to 7; and [I] a polymer selected from the group consisting of polyamide, polycarbonate and polyester. 9. The laminate according to claim 8, wherein the resin layers are laminated in this order. 13. A packaging material for a retort pouch, comprising the laminate according to any one of claims 8 to 12. 14. A packaging material for hot-fill packaging, comprising the laminate according to any one of claims 8 to 12.