JPH10101868A - 4-methyl-1-pentene-based resin composition excellent in adhesive strength to substrate and laminate having the same resin composition layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a 4-methyl-1-pentane (P)-based resin composition, excellent in heat resistance, adhesive strength to a substrate, an extrusion lamination molding processability and capable of manifesting excellent mold releasability as a mold releasing layer and a laminate comprising a resin composition layer laminated to a paper substrate or a metallic substrate such as an aluminum foil. SOLUTION: This composition comprises (A) 30-95 pts.wt. P-based polymer having a melt flow rate(MFR) (at 260 deg.C temperature under 5.0kg load) within the range of 1-400g/10min, (B) 2-30 pts.wt. high-pressure-produced low-density polyethylene having the MFR within the range of 0.1-100g/10min, (C) 0.1-20 pts.wt. modified α-olefin-based polymer graft modified with an unsaturated carboxylic acid or its derivative in a grafting amount within the range of 0.01-10wt.% and (D) 2-55 pts.wt. copolymer, having 1-100g/10min MFR and comprising ethylene and at least one monomer selected from the group consisting of (meth)acrylic acid, an acrylic or a methacrylic ester and a metallic (meth) acrylate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a 4-methyl-1-pentene resin composition having excellent adhesive strength to a substrate and to laminating the resin composition layer on a substrate made of paper, metal foil or the like. And a laminate comprising: More specifically, it has excellent heat resistance, adhesive strength to the substrate, and extruded laminate molding processability, remarkably improves neck-in and ear shaking, does not cause drawdown surging, and is laminated with a substrate such as paper. 4-methyl-1 which shows excellent release properties as a release layer when used as release paper
A pentene-based resin composition, and excellent heat resistance, interlayer adhesion strength, and excellent properties such as releasability formed by laminating the resin composition layer on a metal substrate such as a paper substrate or an aluminum foil. The present invention relates to a laminate showing performance.

[0002]

2. Description of the Related Art A 4-methyl-1-pentene polymer is
Since the melting point is 220 to 240 ° C., it has high heat resistance, and is widely used as a laminated material laminated on paper or other base material as a food container such as a food cooking container, a packaging material, and the like. Various release materials such as release paper (process paper) for manufacturing synthetic leather, release film for manufacturing flexible printed circuit boards, release paper for adhesives, etc., or heat-resistant copy paper, synthetic paper It is also used for such purposes.

However, a 4-methyl-1-pentene polymer generally has a high melt viscosity temperature dependency. For example, the melt viscosity is low at a high temperature such as the temperature at which extrusion lamination is performed, and the melt viscosity is low. It is also known that the tension is low, and therefore, in extrusion lamination molding of a 4-methyl-1-pentene polymer, neck-in is larger than in the case of extrusion lamination molding of polyethylene or polypropylene, and ear turbulence tends to occur. .

Therefore, attempts have been made to suppress the occurrence of such an undesired phenomenon by using a polymer having a low melt flow rate (MFR).
Although the methyl-1-pentene polymer has a large melt viscosity at the molding temperature, it has the disadvantage that the spreadability of the molten film in the extrusion lamination molding process becomes non-uniform over time. There is a drawback that it is difficult to obtain a molded product having a large thickness, that is, drawdown surging is likely to occur.

As a measure for avoiding this inconvenience,
In a molding process of a 4-methyl-1-pentene polymer having a large MFR, heated air is blown to both ends of a web, and a resin temperature during molding is reduced. Also, 70-97 parts by weight of a 4-methyl-1-pentene polymer is a high-pressure low-density polyethylene 30.
It has already been proposed to improve lamination moldability by blending from 3 to 3 parts by weight to form a composition. However, even with the above-described countermeasures or formulation, the effects have not always been sufficiently satisfactory.

[0006] Therefore, while maintaining excellent peelability and heat resistance, the adhesive strength to substrates such as paper and aluminum foil is excellent, neck-in during extrusion lamination molding, ear shaking is small, and draw down surging is performed. There is a demand for the appearance of a material in which the occurrence of phenomena is suppressed.

[0007]

SUMMARY OF THE INVENTION The present inventors have studied the extrusion lamination of a 4-methyl-1-pentene polymer while maintaining various properties such as substrate adhesion and excellent heat resistance as much as possible. As a result of various studies for the purpose of improving the moldability, a specific 4-methyl-1-pentene polymer, a specific low-density polyethylene, a specific modified polyolefin polymer, ethylene and (meth) acrylic acid,
4- obtained by blending a copolymer with at least one monomer selected from the group consisting of (meth) acrylic acid ester and (meth) acrylic acid metal salt at a specific ratio.
The present inventors have found that a methyl-1-pentene resin composition satisfies all of the above-mentioned properties, and have completed the present invention.

Accordingly, an object of the present invention is to provide a 4-methyl-1-pentene resin composition which is excellent not only in heat resistance, adhesiveness, release property, etc., but also in extrusion lamination processability. To be. Further, another object of the present invention is to provide a layer formed of the above resin composition on a base layer such as paper, metal, and plastic, and have excellent interlayer adhesion strength, heat resistance, mold release properties, and excellent surface gloss. It is to provide a laminate.

[0009]

According to the present invention, (A)
Melt flow rate (temperature 260 ° C, load 5.0kg)
Is 4-methyl- in the range of 1 to 400 g / 10 min.
30-95 parts by weight of 1-pentene polymer, (B) melt flow rate (temperature 190 ° C., load 2.16 kg)
From 2 to 30 parts by weight of a high-pressure low-density polyethylene in the range of 0.1 to 100 g / 10 minutes, and (C) a grafting amount of 0.01 to 10% by weight using an unsaturated carboxylic acid or a derivative thereof. 0.1 to 20 parts by weight of the modified modified poly-α-olefin polymer and (D) melt flow rate (temperature 190 ° C., load 2.16 kg)
Is a copolymer of ethylene and at least one monomer selected from the group consisting of (meth) acrylic acid, (meth) acrylic acid ester and (meth) acrylic acid metal salt in an amount of 1 to 100 g / 10 min. 2 to 55 parts by weight of (A),
4 including 100 parts by weight in total of the components (B), (C) and (D)
-Methyl-1-pentene resin composition is provided. According to the present invention, there is also provided a laminate obtained by laminating a layer of the above resin composition on a base material layer.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION

[4-Methyl-1-pentene-based resin composition]
The -methyl-1-pentene-based resin composition includes the specific 4-methyl-1-pentene-based polymer (A), the specified high-pressure low-density polyethylene (B), and the graft-modified poly-α-olefin-based polymer (C). ) And a copolymer (D) of ethylene and at least one monomer selected from the group consisting of (meth) acrylic acid, (meth) acrylic acid ester, and (meth) acrylic acid metal salt as a main constituent resin Component.

The 4-methyl-1-pentene polymer (A) used in the resin composition of the present invention is a homopolymer of 4-methyl-1-pentene or 4-methyl-1-pentene.
Pentene and other α-olefins, such as ethylene, propylene, 1-butene, 1-hexene, 1-octene,
Copolymers with α-olefins having 2 to 20 carbon atoms such as 1-decene, 1-dedecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene are used.

When the component (A) is a copolymer, the copolymer may be a 4-methyl-1-pentene component unit having 8 units.
Copolymers mainly composed of 4-methyl-1-pentene units, which are contained in an amount of 0% by weight or more, are preferred. Preferred copolymerization components are 1-dedecene, 1-hexadecene, 1-octadecene or 1-eicosene. The 4-methyl-1-pentene copolymer (A) has a copolymer component unit content of 20.
If the amount is more than 10% by weight, the melting point of the 4-methyl-1-pentene polymer decreases, and the heat resistance of the resin composition slightly decreases.

The 4-methyl-1-pentene polymer (A) of the present invention has a melt flow rate (MFR) of ASTM.
According to D1238, the value measured under the conditions of a temperature of 260 ° C. and a load of 5 kg needs to be in the range of 1 to 400 g / 10 min, and preferably in the range of 10 to 300 g / 10 min. When the MFR of the 4-methyl-1-pentene polymer (A) is less than 1, the spreadability of the composition decreases during lamination at high speed to produce a laminated product such as a laminated paper having a uniform thickness. Becomes difficult. on the other hand,
If the MFR is more than 400, the molecular weight of the resin is too small, so that the wavering of the resin during lamination molding and the adhesive strength with the substrate layer, for example, in the case of lamination with a paper layer, the peel strength between the resin and paper is significantly reduced. Thus, the practical value of the laminated paper decreases.

The compounding amount of the 4-methyl-1-pentene polymer (A) is from 30 to 95 parts by weight per 100 parts by weight of the total amount of the components (A), (B), (C) and (D). Department. In particular, 45 to 95 for lamination with paper base.
The range of parts by weight is preferable from the viewpoint of adhesive strength to the substrate and lamination moldability, more preferably from 60 to 90 parts by weight, and particularly preferably from 65 to 85 parts by weight. When used for lamination with a metal, particularly an aluminum substrate, for the same reason as above, it is preferable to use one in the range of 30 to 70 parts by weight, more preferably 30 to 65 parts by weight, and more preferably 30 to 65 parts by weight. 60 parts by weight are particularly preferred. 4-
When the blending amount of the methyl-1-pentene polymer (A) is less than 30 parts by weight, the heat resistance, which is a characteristic of the 4-methyl-1-pentene resin composition of the present invention, and the case where it is used as process paper. The releasability and the like are remarkably reduced, while the compounding amount is 9
If the amount exceeds 5 parts by weight, the adhesiveness to the base paper, extrusion laminating processability, repetitive use performance when used for applications such as synthetic leather manufacturing process paper, and the like deteriorate, and all are not preferred.

As the high-pressure low-density polyethylene (B) used in the 4-methyl-1-pentene resin composition of the present invention, the temperature is 190 ° C. in accordance with ASTM D1238.
A melt flow rate (MFR) measured under a load of 2.16 kg within a range of 0.1 to 100 g / 10 minutes is used.
0.935 g / cm ³ , melting point of 1 as measured by DSC
It is preferable to use one having a melt flow rate (MFR) of from 00 to 110 ° C. and 1.0 to 100 g / 10 minutes. In particular, a density of 0.915 to 0.9
It is more preferable to use one having 30 g / cm ³ , a melting point of 100 to 110 ° C., and an MFR of 1 to 50 g / 10 min.

The compounding amount of the high-pressure low-density polyethylene (B) is as follows: (A), (B), (C) and (D)
It is 2 to 30 parts by weight, preferably 3 to 20 parts by weight, particularly preferably 5 to 15 parts by weight, per 100 parts by weight. When the compounding amount of the high-pressure method low-density polyethylene (B) is less than 2 parts by weight, the resin composition of the present invention has poor laminating processability, and neck-in and tremors are large. On the other hand, when the amount exceeds 30 parts by weight, the heat resistance is greatly reduced.

The base polymer of the graft-modified poly-α-olefin polymer as the component (C) of the present invention includes:
Although not particularly limited, usually, a homopolymer of α-olefin having 2 to 20 carbon atoms or a copolymer of those α-olefins is used, for example, polyethylene, polypropylene, polybutene, polypentene-1, polypentene, and the like. Homopolymers such as (4-methyl-1-pentene), ethylene-propylene copolymer, ethylene-butene copolymer, propylene-butene copolymer, butene-pentene-1 copolymer, 4-methyl-1-pentene And copolymers of other α-olefins having 2 to 20 carbon atoms, such as ethylene-propylene-diene copolymer, ethylene-propylene-butene copolymer, and ethylene-propylene-pentene copolymer. Can be used. Among these, polypropylene, 4-methyl-1-pentene homopolymer or a copolymer of 4-methyl-1-pentene and another α-olefin is preferred from the viewpoint of economy, adhesion, and moldability. is there. When the base polymer is a copolymer of 4-methyl-1-pentene and another α-olefin, preferred copolymerization components include 1-decene, 1-decene, and 1-decene.
-Tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene, and a copolymer mainly composed of 4-methyl-1-pentene units is preferable.

As the base polymer, (A) of the present invention
The same properties as the 4-methyl-1-pentene polymer used as the component may be used.

Examples of the unsaturated carboxylic acid or its derivative grafted onto the base polymer include maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid,
Unsaturated carboxylic acids such as citraconic acid, crotonic acid, isocrotonic acid, nadic acid, acrylic acid, methacrylic acid,
Alternatively, a derivative thereof, for example, an acid anhydride of the above-mentioned unsaturated carboxylic acid, imide, amide, ester and the like can be mentioned. Specific examples of the derivative include maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, glycidyl maleate and the like. Among these, unsaturated carboxylic acids or acid anhydrides thereof are preferred, and maleic acid, nadic acid and their acid anhydrides are particularly preferred.

In order to produce a modified product by graft-copolymerizing a graft monomer selected from such unsaturated carboxylic acids or derivatives thereof with the base polymer, a conventionally known method can be used. When using a 4-methyl-1-pentene polymer as
Use of a melt modification method in which the 4-methyl-1-pentene polymer is melted and a graft monomer is added thereto to perform graft copolymerization, or a solution modification method in which the polymer is dissolved in a solvent and the graft monomer is added to carry out graft copolymerization. Can be done.

In order to efficiently graft the modifying monomer to the base polymer to obtain the graft-modified poly-α-olefin (C) of the present invention, the reaction is preferably carried out in the presence of a radical initiator. The conversion reaction is usually performed at a temperature of 60 to 350 ° C. The usage ratio of the radical initiator is usually in the range of 0.001 to 2 parts by weight based on 100 parts by weight of the base polymer. As radical initiators, dicumyl peroxide, di-tert
-Butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3,2,
Organic peroxides such as 5-dimethyl-2,5-di (tert-butylperoxy) hexane, and 1,4-bis (tert-butylperoxyisopropyl) benzene are preferred.

The graft-modified poly-α-olefin (C) of the present invention is preferably modified in a modification amount of 0.01 to 10% by weight, especially 1 to 5% by weight as a graft monomer. If the amount of graft modification is less than the lower limit of the above range, the compatibility with other resin components in the composition becomes poor, and when a laminate is formed, the interlayer adhesion tends to decrease, and lamination molding is difficult. Is not preferred. Conversely, if the graft amount is to be higher than the upper limit amount, together with the grafting reaction,
By heat or the action of a radical initiator such as peroxide, the main chain forming skeleton of the base polymer, for example, 4-
Cleavage and cleavage reactions of the methyl-1-pentene skeleton and the like inevitably occur, and the molecular weight of the graft-modified poly-α-olefin (C) such as a graft-modified 4-methyl-1-pentene polymer becomes extremely small. , The lamination moldability of the resin composition containing the compound deteriorates, and the productivity decreases.

The graft-modified poly-α-olefin (C) of the present invention usually has an intrinsic viscosity which is an index of its average molecular weight, that is, an intrinsic viscosity at 135 ° C. in a decalin solvent of 0.1.
It is preferably from 5 to 10 dl / g, particularly preferably from 0.6 to 5 dl / g.

The poly-α-olefin (C) graft-modified with the unsaturated carboxylic acid or its derivative of the present invention
Is used in an amount of 0.1 to 20 parts by weight, preferably 0.2 to 15 parts by weight, more preferably 0.2 to 15 parts by weight, per 100 parts by weight of the total amount of the components (A), (B), (C) and (D). 1 to 10
Parts by weight. Graft-modified poly-α-olefin (C)
If the compounding amount is less than 0.1 part by weight, the compatibility of the resin component in the composition becomes poor, and when the laminate is used, the interlayer adhesion tends to decrease, and lamination molding is performed. It is not preferable because it becomes difficult. On the other hand, if the compounding amount exceeds 20 parts by weight, the peel strength is too high, and it is not suitable for use as release paper.

The copolymer of ethylene and at least one monomer selected from the group consisting of (meth) acrylic acid, (meth) acrylic acid ester and (meth) acrylic acid metal salt used in the present invention ( D) is the MFR (ASTM D1)
(Measured under the conditions of a load of 2.16 kg and a temperature of 190 ° C. according to 238) within a range of 1 to 100 g / 10 minutes. More preferably, it is 2 to 50 g / 10 min, especially 5 to 10 g / 10 min. The (meth) acrylic acid ester as a copolymer component of the copolymer (D) is not particularly limited, but an ester of (meth) acrylic acid with an aliphatic alcohol, for example, methyl acrylate , Ethyl acrylate, isobutyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, n-methacrylate
Butyl, 2-ethylhexyl methacrylate and the like are preferably used. Further, as the metal (meth) acrylate, M
Metal salts such as g, Ca, Co, Li, Ba, Na, Pb, and Zn can be exemplified. As the copolymer (D), copolymerized components such as (meth) acrylic acid, (meth) acrylic acid ester and (meth) acrylic acid metal salt are used in a total amount of 2 to 50.
What contains by weight is preferable. In the present invention, among these copolymers, the use of an ethylene / (meth) acrylic acid / (meth) acrylate ester terpolymer significantly improves adhesive strength, lamination moldability, and the like. It is preferred in that it can be used, and the (meth) acrylic acid component unit is 1 to 25% by weight, more preferably 2 to 25% by weight.
20% by weight, more preferably 5 to 15% by weight, wherein the (meth) acrylate component unit is 1 to 25%.
It is particularly preferable that the content is in the range of 2 to 20% by weight, more preferably 2 to 20% by weight, and still more preferably 5 to 15% by weight. The copolymer has a density of 0.935 to 0.945 g / c.
It is particularly preferable to use those having m ³ , more preferably around 0.940 g / cm ³ . Examples of the (meth) acrylate which is a constituent component of the terpolymer of ethylene / (meth) acrylic acid / (meth) acrylate include, for example, methyl acrylate, ethyl acrylate, isobutyl acrylate and n-acrylate. -Butyl, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, n-methacrylate
-Butyl, 2-ethylhexyl methacrylate and the like. Such an ethylene / (meth) acrylic acid / (meth) acrylate ester terpolymer itself is as follows:
It can be purchased as a commercial product.

The amount of the copolymer (D) is (A)
It is 2 to 55 parts by weight per 100 parts by weight of the total amount of the components (B), (C) and (D). In particular, the range of 2 to 30 parts by weight is preferred for lamination with a paper substrate, and 3 to 2 parts by weight.
A range of 0 parts by weight is more preferable, and a range of 5 to 15 parts by weight is particularly preferable. In addition, when used for lamination with a metal, particularly an aluminum substrate, it is preferable to use one in the range of 25 to 55 parts by weight in terms of adhesiveness with the substrate, heat resistance at higher temperatures, and the like, It is more preferably from 30 to 55 parts by weight, particularly preferably from 35 to 55 parts by weight. When the blending amount of the copolymer (D) is less than 2 parts by weight, lamination molding property when the composition of the present invention is laminated is slightly lowered, and the effect of improving neck-in and ear sway is remarkable. It cannot be obtained, and the bonding strength with the substrate is slightly reduced. On the other hand, when the compounding amount exceeds 55 parts by weight, the heat resistance, the releasability and the like of the obtained composition are reduced.

The 4-methyl-1-pentene polymer composition of the present invention has an MFR of 1 to 400 g / 1 as a composition.
When the MFR is less than 1, the spreadability of the composition during lamination molding becomes low, and a lamination paper having a uniform film thickness can be produced. It becomes difficult. On the other hand, MF
When R exceeds 400, the molecular weight of the resin is too small, so that the sway of the ears is increased and the productivity is reduced, and the cracking of the coating film and the peel strength between the resin and the paper are remarkably reduced, so that the resin is practically used as a laminated paper. The tendency for the target value to decrease is large.

To obtain the 4-methyl-1-pentene resin composition of the present invention, the above-mentioned (A) 4-methyl-1-pentene polymer, (B) high-pressure low-density polyethylene,
(C) a graft-modified poly α-olefin and (D) ethylene and at least one monomer selected from the group consisting of (meth) acrylic acid, (meth) acrylic acid ester, and (meth) acrylic acid metal salt; , A predetermined amount of each is dry-blended with various known methods, for example, a V-type blender, a ribbon blender, a Henschel mixer, a tumbler blender, or melt-kneaded with a kneader, a Banbury mixer, etc., and granulated or pulverized. And the like.

In the 4-methyl-1-pentene resin composition of the present invention, a silane coupling agent, a weather stabilizer, a heat stabilizer, a slip agent, a nucleating agent, a pigment, a dye, and the like are usually added to a polyolefin. Various compounding agents may be added as long as the object of the present invention is not impaired.

[Laminate] The 4-methyl-1-pentene resin composition of the present invention is excellent in adhesiveness to a substrate such as paper, metal and plastic, heat resistance and extrusion lamination processability.
Further, since it is excellent in releasing property, it is excellent in performance when laminated with a base material such as paper or metal. Therefore, according to the present invention, secondly, there is provided a laminate in which the 4-methyl-1-pentene resin composition layer of the present invention is laminated on various base material layers such as paper, metal, plastic film, and sheet. Is done.

The substrate used for the laminate of the present invention is not particularly limited, and may be a layered material such as paper, metal, plastic, wood, inorganic material, etc., which can be bonded to 4-methyl-1-pentene resin. Although any material can be used, paper, metal and plastic are particularly preferably used.

In the case of a laminate using paper as a base material, various papers are selected and used as the paper used for the base material layer according to the use and mode of use of the laminate. For example, when the laminated body (laminated paper) is used for synthetic leather manufacturing process paper (release paper) or the like, various process papers are used depending on the type of synthetic leather (leather). , High-quality paper, imitation paper, art paper, and coated paper are used.
/ M ² . For vinyl chloride leather,
Since considerable heat resistance is required, it is preferable to use heat-resistant special paper. In the case of urethane leather or the like that does not require heat resistance as much as vinyl chloride, the above-mentioned high-quality paper may be used.

In order to prepare the laminated paper of the present invention for use as a process paper (release paper) for producing synthetic leather, the 4-methyl-1-pentene resin composition of the present invention is added to the process paper. Stack the layers. The composition layer may be laminated on one side of the paper substrate or on both sides. The thickness of the composition layer is
Usually about 10 to 120 μm, 20 to 40 μm
Is preferable.

As a lamination method, a lamination molding method is typically used. For example, a 4-methyl-1-pentene-based resin composition of the present invention melted on a paper substrate is extruded and coated with a single laminator,
A method such as forming a release layer made of a 4-methyl-1-pentene resin composition on a paper substrate can be used.

As described above, the 4-methyl-1-pentene resin composition of the present invention itself has excellent release properties and heat resistance with respect to the synthetic resin material resin. Of course, it can be used as a release layer as it is, but in some cases, such as when a special resin material is used as a synthetic leather material resin, a release agent such as amino alkyd may be further added to the layer. , Polyvinyl alcohol (PVA), a chromium compound or the like can be applied to further improve the releasability. Generally, process paper is mirror, gloss, semi-gloss, semi-mat,
Although classified into types such as dead mats, the laminate with paper obtained in the present invention can be used for any of the above types of process paper.

Further, the 4-methyl-1-pentene resin composition layer of the present invention is laminated on the above-mentioned paper base material layer, and further a 4-methyl-1-pentene resin layer is laminated thereon. It is also possible to use a process paper or a release paper having a multilayer structure composed of three or more layers coated with the release agent. In the release paper of this embodiment, the resin composition layer of the present invention mainly comprises a base material layer (paper layer) and a polyolefin resin. It functions as an adhesive layer with the 4-methyl-1-pentene layer.

Since the 4-methyl-1-pentene resin composition of the present invention is excellent in heat resistance and surface gloss, a laminate obtained by laminating this with a base material such as carton paper is used for food packaging and containers. It is suitably used for applications of materials. As the base paper, clay coated paper, milk carton paper is used,
The 4-methyl-1-pentene resin composition is coated on the base paper by, for example, extrusion lamination. The laminate of this embodiment can be particularly suitably used for baking carton and the like because the 4-methyl-1-pentene resin composition of the present invention is particularly excellent in heat resistance.

Laminate (Laminated Paper) Based on Paper of the Present Invention
In the production of the laminated paper, in order to further improve the interlayer adhesive strength of the laminated paper, a corona treatment may be performed on the paper base material, or an ozone treatment may be performed on the resin molten film.
Of course, these two processes can be used in combination.

Further, the paper substrate layer may further comprise
A laminate obtained by laminating a pentene-based resin composition layer and further laminating a 4-methyl-1-pentene resin layer thereon is not only more excellent in heat resistance, but also excellent in releasability and surface glossiness, It is particularly suitable as a food packaging material.

Further, a laminate obtained by laminating the resin composition of the present invention on a metal substrate, for example, a sheet, film, foil, etc. of aluminum, steel, tin, zinc, copper, silver, gold, etc. is, for example, a container. It is used for packaging materials, decoration materials, and various other applications. As a base material, these metal foils or films are laminated on films or sheets of paper, plastic, etc., or paper, plastic, etc. Those obtained by depositing these metals on a film or sheet are more commonly used.

Among these base metals, the laminate of the present invention using an aluminum foil as a base is particularly suitable for baking cartons,
It is suitable as a container material for food heating and cooking such as a tray for an oven.

Although the aluminum foil is not particularly limited, a foil having a thickness of usually 5 to 100 μm, preferably 10 to 50 μm is suitably used.

In the case of a metal substrate laminate, a metal surface which has been subjected to a surface treatment such as an anchor coat treatment is used in order to have a sufficient interlayer adhesion strength with the metal layer, and this is laminated with the resin composition of the present invention. The surface treatment of the metal layer and the ozone treatment of the molten resin film may be used in combination.

Further, a laminate obtained by laminating the 4-methyl-1-pentene resin composition of the present invention on a specific plastic film substrate or the like can be used, for example, as a release film for manufacturing a flexible printed board. It can be suitably used. Hereinafter, the present invention will be described in more detail with reference to Examples.

[0045]

EXAMPLES In the following Examples 1 and 2 (paper / laminate composed of the resin composition layer of the present invention) and Comparative Examples 1 to 3, lamination molding conditions of the laminate and an evaluation test of the laminate were carried out. Are each carried out under the following method and conditions.

[Laminating paper forming conditions] Extrusion laminator used: 65 mmφ extrusion laminator manufactured by Sumitomo Heavy Industries Processing conditions: Temperature C1 / C2 / C3 / C4 / XH / FB / D1-D1
5: 300/350/320/320/320/320
/ 320-320 ° C Cooling roll Semi-mat roll Base Clay coated paper Coat width (set value) 500mm Processing speed 50m / min, 100m / min Resin processing thickness Paper / resin composition = paper / 30μm Air gap 130mm Corona treated paper substrate 4KW ozone treatment Performed on resin melt film, treatment amount 35-40
g / m ³ × 2m ³

[Evaluation Items and Methods] Neck-in: After extrusion-coating a resin on a paper substrate with a die width of 500 mm (set value), 1 m in the coating direction
The actual coated width was measured at 20 points at intervals, and the neck-in was determined by the following equation. Wn: Resin coat width (mm) n = 1 to 20 Neck-in = 500− (W1 + W2 +... W20) /
20 ear shaking; visual observation and 2
It was represented by a deviation value σ (mm) of the measured values of zero coat width. Measurement of melt flow rate (MFR) of the resin composition; 4
Of pellets of -methyl-1-pentene resin composition
R was measured according to ASTM D1238 under the conditions of a load of 5 kg and a temperature of 260 ° C. Measurement of Vicat softening point; test specimen (12.5 mm (width) x 1) molded at a cylinder temperature of 300 ° C by injection molding
20 mm (long) x 3 mm (thick)) was used as the measurement sample, and J
The Vicat softening point was measured according to IS 7206. Measurement of the adhesive strength between the resin composition layer and the paper base material layer; a strip-shaped test piece having a width of 15 mm was prepared from the lamination paper obtained by the lamination molding method (processing speed: 50 m / min), and a tensile tester was used. A 180 ° peel test was performed at a test speed of 300 mm / min to measure the interlayer peel strength. Evaluation of heat resistance of laminate: Heat resistance of the laminate was evaluated by the following tests. (1) Oven cake baking test A laminate (laminate paper) is cut out to a predetermined size, and a box (width 7c) is cut out.
m, length 11 cm, height 3 cm, open top)), and in this box, a prescribed amount of the following recipe recipe is placed,
Oven temperature, 180 ° C, 200 ° C, 220 ° C, heating time 20 minutes, baking the cake, butter bleeding into lami paper, delamination phenomenon of lami paper (peeling of paper and resin layer, swelling The phenomenon of occurrence) and the degree of ease of peeling of the cake from the paper were visually observed to evaluate the heat resistance. Microwave oven; National microwave oven NE-A
740 (2) Salad oil heating test Make a similar container with lami paper, add 100g of salad oil, heat in a microwave oven, heat for a predetermined time, seep out oil from the lami paper, delamination of the lami paper, etc. Was visually observed and the heat resistance was evaluated. Microwave oven; Rated power consumption 1.17 kW Rated high-frequency output 600 W (3) Fried chicken heating test Make a container with Rami paper, put one commercially available frozen fried chicken and heat it in a microwave for a predetermined time, and then use the oil from the Rami paper. And the heat resistance was evaluated by visually checking the bleeding of the paper and the delamination phenomenon of the paper.

The graft-modified polyα of the component (C) used in the 4-methyl-1-pentene resin composition of the present invention.
As the olefin resin, a maleic anhydride graft-modified 4-methyl-1-pentene polymer prepared by the following method was used. [Preparation of maleic anhydride graft-modified 4-methyl-1-pentene polymer] 4-methyl-1-pentene homopolymer ([η] = 1.7 dl / g, MFR = 100 g / 1)
(0 min) Using 100 parts by weight, a graft reaction with maleic anhydride was carried out at 145 ° C. in a toluene solvent in the presence of a dicumyl peroxide catalyst. A large amount of acetone was added to the obtained reaction product to precipitate a graft-modified polymer, which was separated by filtration, sufficiently washed with acetone, and grafted with a maleic anhydride-modified 4-methyl-1-pentene polymer (hereinafter referred to as M- PMP). The graft ratio of maleic anhydride units in this M-PMP was 4.0% by weight. The intrinsic viscosity in decalin at 135 ° C. was 0.95 dl / g.

Example 1 4-Methyl-1-pentene
1-decene copolymer (decene content 2.2% by weight, MF
R: 180 g / 10 min) 75 parts by weight of low-density polyethylene (manufactured by Mitsui Chemicals, Inc., trade name: Mirason 11P, MFR: 7.2 g / 10 min, density: 0.917)
g / cm ³ ) 10 parts by weight, maleic anhydride-modified 4-methyl-1-pentene polymer (M-PMP) 5 parts by weight, ethylene / methacrylic acid / isobutyl acrylate terpolymer (content of methacrylic acid component) 10% by weight, content of isobutyl acrylate component 10% by weight, MFR: 10 g / 1
(0 min) 10 parts by weight were supplied to an extruder and melt-blended at 260 ° C. to produce a composition. Next, the MFR and the Vicat softening point of the obtained composition were measured. In addition, lamination moldability (neck-in, ear tremor) of this composition was evaluated, and the adhesive strength of the obtained lami paper was measured. Table 1 shows the results. Further, a box was prepared from wrapping paper, and the heat resistance was evaluated. The results are shown in Table 2.

Example 2 The same 4-methyl- as in Example 1
70 parts by weight of a 1-pentene / 1-decene copolymer, 10 parts by weight of low-density polyethylene, 10 parts by weight of M-PMP, and 10 parts by weight of a terpolymer of ethylene, methacrylic acid and isobutyl acrylate were supplied to an extruder to give 260 parts. The composition was produced by melt blending at a temperature of ° C., and a laminated paper was formed in the same manner as in Example 1. Each evaluation item was evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.

Comparative Example 1 The same 4-methyl-
90 parts by weight of 1-pentene / 1-decene copolymer and 10 parts by weight of low-density polyethylene were supplied to an extruder, and 260 ° C.
Was melt-blended to produce a composition, and the MFR and Vicat softening point were measured. The lamination molding properties of this composition were evaluated, and the adhesive strength of the obtained lami paper was measured. Table 1 shows the results.

[Comparative Example 2] The same 4-methyl-
The MFR and the Vicat softening point of the 1-pentene-1-decene copolymer were measured. The lamination moldability of this copolymer was evaluated, and the adhesive strength of the obtained lami paper was measured. Table 1 shows the results.

[Comparative Example 3] 4-Methyl-same as in Example 1
85 parts by weight of a 1-pentene / 1-decene copolymer, 5 parts by weight of a modified poly (4-methyl-1-pentene) and 10 parts by weight of a high-pressure low-density polyethylene were supplied to an extruder to give 260 parts.
The composition was melt-blended at ℃ to obtain a composition, and the MFR and the Vicat softening point were measured. The lamination molding properties of this composition were evaluated, and the adhesive strength of the obtained lami paper was measured. Table 1 shows the results.

[Comparative Example 4] The same 4-methyl-
85 parts by weight of 1-pentene / 1-decene copolymer, 10 parts by weight of high-pressure low-density polyethylene and 5 parts by weight of terpolymer of ethylene, methacrylic acid and isobutyl acrylate are fed to an extruder and melted at 260 ° C. The composition was obtained by blending, and lamination molding was attempted, but the film could not be formed.

[0055]

[Table 1]

[0056]

[Table 2]

[Examples 3 and 4] 4-Methyl-1
-75 parts by weight of pentene / 1-decene copolymer, 10 parts by weight of low-density polyethylene, 5 parts by weight of M-PMP, ethylene / methacrylic acid / isobutyl acrylate terpolymer 1
A resin composition comprising 0 parts by weight and pellets of a 4-methyl-1-pentene-1-decene copolymer (decene content: 2.2% by weight, MFR: 180 g / 10 min) were prepared and used. Then, under the following lamination processing conditions, a three-layer laminated paper consisting of a copolymer layer / composition layer / paper was produced (Example 3). Separately, 4-methyl-1-
Pentene / 1-decene copolymer 65 parts by weight, low-density polyethylene 10 parts by weight, M-PMP 5 parts by weight, ethylene
Methacrylic acid / isobutyl acrylate terpolymer 20
A resin composition consisting of parts by weight and pellets of 4-methyl-1-pentene-1-decene copolymer were prepared, and a three-layer laminated paper was similarly produced using these pellets (Example 4). ). Table 3 shows the evaluation results of the lamination moldability (neck-in, ear turbulence) during the laminating process. The lamination moldability was evaluated in the same manner as in Example 1.

[Laminating Paper Forming Conditions] Extrusion laminator used: No. Extruder: 65 mmφ extrusion laminator No. manufactured by Sumitomo Heavy Industries, Ltd. 2 Extruder: 65mmφ extrusion laminator made by Sumitomo Heavy Industries Processing condition: Temperature condition No1 extruder C1 / C2 / C3 / C4 / XH / FB
/ D1 to D5: 300/350/320/320/32
0/320 / 320-320 ° C No2 extruder C1 / C2 / C3 / C4 / XH / FB
/ D1 to D5: 300/350/320/320/32
0/320 / 320-320 ° C Cooling roll Semi-mat roll Base Clay coated paper Coat width (set value) 500 mm Processing speed 50 mm / min, 150 m / min Resin processed thickness Paper / composition / copolymer = paper / 15 μm /
15μm Air gap 130mm Corona treatment Applied to paper substrate, treatment amount 4KW ozone treatment Applied to resin melt film, treatment amount 35-40
g / m ³ × 2m ³

[0059]

[Table 3]

Examples 5, 6, 7 and Comparative Example 4 55 parts by weight of a 4-methyl-1-pentene-1-decene copolymer,
10 parts by weight of low density polyethylene, 5 parts by weight of M-PMP,
A resin composition comprising 30 parts by weight of an ethylene / methacrylic acid / isobutyl acrylate terpolymer (Example 5), 45 parts by weight of the copolymer, 10 parts by weight of low-density polyethylene, 5 parts by weight of M-PMP, Resin composition comprising 40 parts by weight of terpolymer (Example 6), 35 parts by weight of copolymer, 10 parts by weight of low-density polyethylene, 5 parts by weight of M-PMP, 50 parts by weight of terpolymer (Example 7) and a resin composition (Comparative Example 4) composed of 25 parts by weight of a copolymer, 10 parts by weight of low-density polyethylene, 5 parts by weight of M-PMP, and 60 parts by weight of a terpolymer. hand,
Each laminate having a two-layer structure composed of a composition layer / aluminum foil layer was produced using an aluminum foil as a base material under the following lamination processing conditions. Table 4 shows the evaluation results of the delamination strength and heat resistance of each of the obtained laminates. In addition, each evaluation method was based on the following method.

[Laminate molding conditions] Extrusion laminator used: Extruder: 65 mmφ extrusion laminator manufactured by Sumitomo Heavy Industries Processing conditions: Temperature conditions C1 / C2 / C3 / C4 / XH / FB / D1 to D5: 3
00/350/320/320/320/320/32
0-320 ° C Cooling roll Semi-mat roll Base material Aluminum foil Coating width (set value) 500mm Processing speed 50m / min Resin processing thickness 30μm Air gap 130mm Anchor coating treatment Anchor coating treatment is performed on aluminum foil, and anchor coating treatment agent is applied. The prescription is as follows. Colonel 1.89 kg Nipporan L 1.0 kg Ethyl acetate 44.7 kg Ozone treatment Performed on resin melt film, treatment amount 35-40
g / m ³ × 2m ³

[Laminate Evaluation Method] Peel Test Apparatus: INTESCO MODEL2005 Model Universal Testing Machine Test Method: Laminate (resin composition / aluminum foil laminate) was cut into a strip having a width of 15 mm in parallel with the processing direction (MD). A sample was cut out, and one side of the sample was manually peeled off to a resin layer and an aluminum foil layer. Then, the part was attached to a testing machine, and peeled at a test speed of 300 mm / min to determine the strength. Heat resistance test The laminate is cut out to a predetermined size and a box (width 7 cm, length 7 c)
m, height 3 cm, open top), and a predetermined amount of the following recipe formula is put therein, and oven temperatures 180 and 20 are prepared.
The cake was baked at 0, 220 ° C. and a heating time of 20 minutes, and heat resistance such as delamination of the laminated portion was evaluated. Microwave oven; National microwave oven N
E-A740

[0063]

[Table 4]

[0064]

Industrial Applicability The 4-methyl-1-pentene resin composition of the present invention has greatly improved neck-in and ear sway during lamination molding, does not cause drawdown surging, and has excellent lamination moldability. In addition, the obtained lamination molded product has excellent adhesive strength to a substrate such as paper. Further, a laminate obtained by laminating the composition of the present invention on a substrate is excellent in release property and heat resistance, for example, baking carton, process paper for synthetic leather, release paper for synthetic adhesive, or heat-resistant copy paper, It can be suitably used for applications such as synthetic paper.

Claims (12)

[Claims] 1. A melt flow rate (temperature: 260 ° C.)
C., a load of 5.0 kg) in the range of 1 to 400 g / 10 min.
5 parts by weight, (B) melt flow rate (temperature 190 ° C., load 2.1
6 kg), 2 to 30 parts by weight of high-pressure low-density polyethylene in the range of 0.1 to 100 g / 10 min, (C) the amount of grafting in the range of 0.01 to 10% by weight by unsaturated carboxylic acid or its derivative. 0.1 to 20 parts by weight of a modified poly α-olefin polymer graft-modified with (D) a melt flow rate (at a temperature of 190 ° C. under a load of 2.1
6 kg) of 1 to 100 g / 10 min with ethylene and at least one monomer selected from the group consisting of (meth) acrylic acid, (meth) acrylic acid ester and (meth) acrylic acid metal salt. A 4-methyl-1-pentene resin composition containing 100 parts by weight of the polymer (A), (B), (C) and (D) in an amount of 2 to 55 parts by weight of the polymer. 2. The (A) 4-methyl-1-pentene polymer comprises 80% by weight or more of a 4-methyl-1-pentene component unit and 20% by weight or less of an α-olefin having 2 to 20 carbon atoms. The 4-methyl-1-pentene resin composition according to claim 1, which is a random copolymer composed of component units. 3. The high-pressure low-density polyethylene (B) has a density of 0.910 to 0.935 g / cm ³ and a melting point of 1
00 to 110 ° C. and a melt flow rate (190
The low-methyl polyethylene according to claim 1, which is a low-density polyethylene of 1.0 to 100 g / 10 min.
1-pentene resin composition. 4. The 4-methyl-1-pentene-based polymer according to claim 1, wherein said (C) modified poly-α-olefin-based polymer is modified with maleic acid, nadic acid or an acid anhydride thereof. Resin composition. 5. The 4-methyl-1-pentene resin composition according to claim 4, wherein (C) the modified poly-α-olefin-based polymer is a grafted acid-modified poly-4-methyl-1-pentene polymer. Stuff. 6. The 4-methyl-1-pentene resin composition according to claim 1, wherein the copolymer (D) is an ethylene / (meth) acrylic acid / (meth) acrylate terpolymer. Stuff. 7. The ethylene / (meth) acrylic acid ·
(Meth) acrylic acid ester terpolymer (D) having a (meth) acrylic acid component unit content of 1 to 25% by weight,
(Meth) acrylate component unit content is 1 to 2
The 4-methyl-1-pentene resin composition according to claim 6, which is 5% by weight. 8. A laminate formed by laminating a layer of the 4-methyl-1-pentene resin composition according to claim 1 on a base material layer. 9. A 4-methyl-1-pentene polymer layer,
The laminate according to claim 8, wherein the 4-methyl-1-pentene resin composition layer according to claim 1 and a base material layer are laminated in this order. 10. The paper according to claim 8, wherein the base material layer is paper.
The laminate according to any one of the above. 11. The laminate according to claim 8, wherein the base material layer is a layer made of a metal. 12. The laminate according to claim 11, wherein the base material layer is a layer made of an aluminum foil or a layer made of an aluminum vapor-deposited film.