JP5127158B2 - Methylpentene polymer resin composition for release layer of release paper, film or sheet thereof, and laminate containing the resin composition layer - Google Patents

Description

The present invention relates to a methylpentene polymer resin composition for a release layer of a release paper, a film or sheet comprising the resin composition, and a laminate including the resin composition layer.

4-methyl-1-pentene polymer, 3-methyl-1-pentene polymer or a methylpentene polymer resin composed of a resin composition mainly composed thereof, so-called TPX, is transparent, flexible, heat resistant, Excellent in steam resistance, chemical resistance, oxygen permeability, etc., and lightweight, for example, industrial material fields such as sheaths and mandrels for manufacturing high-pressure rubber hoses and LED moldings, heat-resistant wrap films, and fruits and vegetables Widely used in food packaging fields such as freshness-keeping bags, physics and chemistry laboratory instruments, microwave oven dishes, and other fields.
For example, Patent Document 1 proposes a freshness-keeping packaging film made of a resin composition containing a 4-methyl-1-pentene polymer as a main component.

Further, TPX has a surface tension of 24 dyne / cm, which is the second smallest after fluororesin, and is excellent in releasability and releasability.
For this reason, it is widely used for release films and release papers such as adhesive labels, release papers such as sheets, process release papers from other materials such as urethane and epoxy, and release films for printed boards.
For example, Patent Document 2 discloses an invention of a release film used in a production process of a flexible printed wiring board using a release layer of polymethylpentene or a copolymer of polymethylpentene and α-olefin.
Japanese Patent Laid-Open No. 10-279703 JP 2003-276139 A

However, the methylpentene polymer resin is generally highly crystalline, has a melting point of 220 to 240 ° C., which is higher than that of polyethylene and the like, and has a melt viscosity of 10 ² to 10 ³ poise, which is a low level compared to other polyolefins. However, the moldability, particularly the processability in extrusion coating, is insufficient because the temperature dependence of the melt viscosity tends to be large. For example, proper settings such as kneading conditions and extrusion conditions for film and sheet forming by T-die extrusion, inflation, extrusion lamination, etc. are quite difficult. Changes are likely to occur, and inconveniences such as film drawdown and neck-in are likely to occur, and as a result, the high-speed take-up property at the time of film molding etc. is considerably inferior to general-purpose polyolefin resins such as polyethylene and polypropylene. is there. Further, the methylpentene polymer resin usually has poor adhesion to a substrate such as paper.

This means that the productivity of the film is impaired as compared with other olefin resins.
In particular, the above-mentioned problem appears remarkably in the form of high cost in film formation by inflation or laminate formation by extrusion lamination.

  Accordingly, an object of the present invention is to provide molding processability, particularly processing in extrusion coating, without impairing attributes that TPX originally retains, for example, excellent attributes such as suitable releasability and release properties for adhesive resins and adhesives. The object of the present invention is to provide a methylpentene polymer resin composition with significantly improved properties.

Another object of the present invention is to provide a film or sheet comprising the methylpentene polymer resin composition of the present invention.
Furthermore, another object of the present invention is to provide a laminate comprising the resin composition layer, and a release paper obtained by laminating the resin composition layer on a paper substrate as a releasable layer.

According to the present invention, 50 to 79 parts by mass of methylpentene polymer resin (A), at least one ethylene-based copolymer selected from ethylene / (meth) acrylic acid copolymer resin (a) and ionomer (b) thereof. There is provided a methylpentene polymer resin composition for a release layer of release paper comprising 21 to 50 parts by mass of polymer resin (B) (however, the sum of (A) and (B) is 100 parts by mass). .

The resin composition of the present invention is mainly composed of methylpentene polymer resin, which in ethylene (meth) specific amount of at least one acrylic acid copolymer resin and / or ethylene copolymer resins of the ionomer over The point which mix | blended with ratio is the characteristic on a structure.

The above composition has extremely good molding processability in T-die extrusion, inflation, extrusion lamination, etc. compared to the methylpentene polymer resin alone, and it was extruded and laminated not only on single-piece films and sheets, but also on substrates. In this case, the take-up speed in forming the lamination film and sheet can be remarkably improved.
However, the resin composition layer of the present invention formed as a release agent layer on a substrate such as paper or other plastic has a moderate delamination strength between the adhesive surface and the adhesive surface or adhesive surface. Excellent releasability and releasability.
In addition, since no solvent or the like is used for molding and lamination, problems such as safety, occupational health and the environment are not caused.

In the resin composition of the present invention, the methylpentene polymer resin (A) is preferably a resin composed of a 4-methyl-1-pentene polymer.
The ethylene-based copolymer resin (B) is preferably an ethylene / (meth) acrylic acid copolymer resin (a), and in particular, an ethylene / (meth) acrylic acid binary copolymer resin or ethylene / (meta ) Acrylic acid / (meth) acrylic acid ester terpolymer resin is preferred.

  According to the present invention, a film or sheet made of the resin composition of the present invention, a laminate including the resin composition layer, and a layer of the resin composition are laminated on a paper substrate as a release layer. Each release paper is provided.

Methylpentene polymer resin composition of the present invention, ethylene (meth) acrylic acid copolymer methylpentene polymer, than that specified amount of a specific polar group-containing copolymer of the ionomer over, methylpentene Compared to homopolymers and conventional polymethylpentene resin compositions, the molding processability, particularly the processability in extrusion coating, is significantly improved.

For example, workability such as high-speed take-up speed at the time of T-die extrusion molding and inflation molding of films and sheets, or high-speed take-up performance when laminated on paper, plastic, etc., is remarkable compared to conventional products. Can be improved.
For this reason, by using the said resin composition concerning this invention as a raw material, productivity of molded articles, such as a film, a sheet | seat, a laminated body, a process release paper, can be raised remarkably, and manufacturing cost can be reduced.
The resin composition of the present invention exhibits good adhesion to paper when it is laminated on paper by, for example, extrusion coating.

Hereinafter, preferred embodiments according to the present invention will be described in detail and specifically.
The methylpentene polymer resin composition of the present invention is characterized in that it is a resin composition obtained by blending a specific ethylene copolymer resin in a specific amount ratio with a methylpentene polymer resin.

  In the resin composition of the present invention, the methylpentene polymer resin (A) as the main resin component includes 3-methyl-1-pentene polymer resin, 4-methyl-1-pentene polymer resin, and the like. It can be illustrated.

The methylpentene polymer resin used in the present invention is a polymer obtained by polymerizing methylpentene such as 3-methyl-1-pentene or 4-methyl-1-pentene or a monomer containing methylpentene as a main component. Examples thereof include a homopolymer of methylpentene or a copolymer of methylpentene and another compound copolymerizable with the methylpentene. Examples of these methylpentene polymer resins include so-called polymer resins called TPX.
In the present invention, among methylpentene polymer resins, 4-methyl-1-pentene homopolymer resin or 4-methyl-1-pentene copolymer resin is particularly preferable.

Examples of other compounds copolymerizable with methylpentene include 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-tetradecene and 1-octadecene. Α-olefins and the like.
One or more of these may be contained in the methylpentene polymer.
The content of methylpentene in the methylpentene polymer is usually 85 mol% or more, preferably 90 mol% or more.

  The melt flow rate (MFR) of this methylpentene polymer is usually 0.05 to 500 g / 10 min (ASTM D1238, load: 5 Kg, temperature: measured at 260 ° C.), preferably 0.1 to 300 g / 10. Minutes.

In the resin composition of the present invention, which is another resin component ethylene copolymer resin (B), ethylene (meth) acrylic acid copolymer resin (a) and its ionomers (b) or al It consists of at least one selected.

Among these, the ethylene / (meth) acrylic acid copolymer resin (a) is a copolymer of ethylene and acrylic acid and / or methacrylic acid, or the ethylene and (meth) acrylic acid. A saturated monomer component is copolymerized.
Examples of the other unsaturated monomer component include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, and (meth) acrylic acid n. -Butyl, s-butyl (meth) acrylate, i-butyl (meth) acrylate, n-hexyl (meth) acrylate, i-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth ) (Meth) acrylic acid alkyl ester components such as isooctyl acrylate, vinyl ester components such as vinyl acetate and vinyl propionate, monomers such as olefins other than ethylene, carbon monoxide, and sulfur dioxide.

  Among these, ethylene / (meth) acrylic acid binary copolymer resin or ethylene / (meth) acrylic acid / (meth) acrylic acid ester terpolymer resin is preferable, and among them, ethylene / (meth) Acrylic acid / (meth) acrylic acid ester terpolymer resins are particularly preferred because the physical properties of the resulting resin composition such as extrusion coating processability, heat resistance and peelability are not impaired at all.

In the present invention, since the resin composition obtained is formed into a film, sheet or laminate, the melt flow rate (MFR) of the ethylene-based copolymer resin (B) is 1 to 500 g / 10 min (JIS K7210 ( 1999), load: 2.16 Kg, temperature: measured at 190 ° C.), more preferably 1 to 100 g / 10 min.
Moreover, in the said resin (a), the content rate of a (meth) acrylic acid component is 1-20 mass%, Especially the thing of 5-15 mass% is preferable.

Next, as the ionomer (b), any ionomer composed of a metal ion salt of the ethylene / (meth) acrylic acid copolymer resin (a) can be used without any particular limitation. Examples include alkali metal ion ionomers such as Li, Na and K, alkaline earth metal ion ionomers such as Be, Mg, Ca, Sr and Ba, and other Zn ion ionomers.
Of these, Na and Zn ionomers are preferred.
The neutralization degree of the ionomer is preferably 1 mol% or more, particularly preferably 10 to 70 mol%.

In the resin composition of the present invention, the methylpentene amount of polymer resin (A) and the ethylene-based copolymer resin (B) resin (A) is 50 to 79 parts by weight, dendritic fat (B) is 21 to 50 parts by mass ( however, the total amount of (A) and (B) is 100 parts by mass).
When the blending amount of the resin (B) is less than 21 % by mass, it is not possible to sufficiently improve the take-up performance at the time of T-die extrusion molding, inflation molding, extrusion lamination molding and the like as the object of the present invention.

  On the other hand, when the compounding quantity of resin (B) exceeds 50 mass%, the outstanding characteristics which methylpentene resin originally has, for example, various characteristics, such as a heat resistance characteristic, steam resistance, and peelability, will fall.

In order to prepare the resin composition of the present invention, the resin (A) and the resin (B) can be respectively measured according to the formulation, mixed and melt-kneaded using an extruder, a kneader or the like.
The resin composition obtained by the above melt-kneading or the like may be used immediately for laminate molding, or may be once pelletized and then used for laminate molding.

  In the resin composition preparation method of the present invention, as a particularly suitable preparation method, for example, a masterbatch in which a predetermined amount of (B) resin is previously mixed with a small amount of (A) resin is prepared, (A) The method of melt-kneading a component by a conventional method can be mentioned.

  The resin composition prepared by the above method has a homogeneous composition, and the reason is not completely understood yet, but other attributes such as extrusion coating processability are also improved.

The above-mentioned resin composition of the present invention can be formed into a molded body such as a film or sheet by a molding method such as T-die extrusion or inflation while being melted.
Furthermore, it can also be made into a laminate by lamination on a substrate such as paper, other resin film, sheet, or the like, or by coextrusion with a methylpen-extended polymer resin alone or with another resin.
The resin composition of the present invention and the film or sheet comprising the resin composition are release labels such as adhesive labels, release paper such as sheets, process paper and release paper from other materials such as urethane and epoxy, release films for printed boards, etc. It is preferably used in a film (as a release layer). Moreover, the laminated body which laminated | stacked the layer which consists of the resin composition of this invention on a paper base material is preferably used as process paper from release paper, such as an adhesive label and a sheet | seat, urethane, an epoxy, etc. other materials.

  Examples of the base material include craft paper, glassine paper, supercalendered paper, parchment paper, paper such as synthetic paper made of polystyrene and polyethylene, surface-treated paper such as clay coated paper and polyethylene laminated paper, polyester, and the like. Examples thereof include plastic films such as (PET), polypropylene (OPP), and polyethylene (PE).

The resin composition can be laminated on one side or both sides of a substrate.
The thickness of the resin composition layer to be laminated varies depending on its use, shape, substrate thickness, etc., and is set appropriately. For example, the resin composition of the present invention is extrusion laminated to a paper substrate such as kraft paper. And when manufacturing a laminated body, it is 5-50 micrometers normally, Preferably it is about 10-30 micrometers.

The laminate of the present invention can be produced by a method such as coating using a solvent, but it is particularly preferred to laminate by extrusion lamination.
For example, it is equipped with an extruder with a die and both cooling and nip rolls, and an extrusion laminator generally used for laminating a resin on a base material such as paper or PET, and a base material such as paper or PET is a nip roll. It is fed into the gap with the cooling roll and taken along the cooling roll.

Then, the melt-kneaded composition of the present invention is pressed down from the inside of the T die, spreads to the full width of the die with a manifold, and then extruded out of the T die as a molten web.
After the molten web layer extruded out of the T-die is pressure-bonded to the surface of the base material, it is cooled to complete the lamination, and the laminated sheet is obtained by taking it out.
The laminated sheet thus obtained is cut into a predetermined shape as release paper.

The present invention will be specifically described by the following examples, but the present invention is not limited to these examples.
The compositions of the methylpentene polymer resin (A) and the ethylene copolymer resin (B) used in the following examples, comparative examples, and reference examples are as follows.

1. Methylpentene polymer resin (A): Sample (I) TPX (DX820) manufactured by Mitsui Chemicals, Inc., MFR 180 g / min ((ASTM D1238, load: 5 Kg, temperature: 260 ° C.), density 833 kg / m ³ , melting point 238 ° C
2. Ethylene-based copolymer resin (B): Sample (b) Ethylene (E) / methacrylic acid (MAA) / isobutyl acrylate (IBA) terpolymer resin, MFR 10 g / min (JIS K7210 (1999), load: 2.16 kg, temperature: 190 ° C.), MAA content 11 mass%, IBA content 8 mass%
Sample (C) Ethylene / methacrylic acid binary copolymer resin, MFR 8 g / min (JIS K7210 (1999), load: 2.16 Kg, temperature: 190 ° C.), MAA content 9% by mass
Sample (d) Zinc ionomer of ethylene / methacrylic acid binary copolymer (MAA content 9 mass%) MFR 5.5 g / min (JIS K7210 (1999), load: 2.16 Kg, temperature: 190 ° C.), metal ion species : Zn Neutralization degree: 17 mol%
Sample masterbatch (MB) TPX (A) 40% by mass + ethylene copolymer (B) 60% by mass (sample (b) (c) (d) and sample (a) at a mass ratio of 60:40 (Mixed, melt kneaded into a master batch)

Reference example
80 parts by mass of sample (ii ) as TPX (A) and 20 parts by mass of sample (ii) as ethylene copolymer resin are blended, and a screw rotation speed of 200 min ⁻¹ (set temperature (° C.) using a 30 mmΦ twin screw extruder. ): C1 / C2-C9 / A · D = 200/260/250) to obtain a resin composition sample (1).

Next, the above resin composition (1) was applied to a kraft paper (50 g / m ² ) substrate surface using an extrusion laminator (caliber 40 mmφ, die: 450 mm width, cooling roll 35 mmφ, nip roll 200 mmφ) at 20 m at 45 m / min. The take-off speed (m / min) just before the extrusion amount and the processing instability ^* occurred was taken as the evaluation value of workability.
Next, the surface of the resin composition sample (1) layer laminated on the surface of the kraft paper to a thickness of about 20 μm is subjected to corona treatment, and then a cello tape (manufactured by Nichiban Co., Ltd.) is applied, and the load is peeled off after standing for 1 kg × 5 minutes. The strength (N / 18 mm) was measured and the performance as a release paper layer was evaluated.
The results are shown in Table 1.
Peel strength measurement conditions: Peel strength measurement test using a tensile tester; Test width: 18 mm (cello tape width), peel strength measurement distance: 30 mm, peel angle: 180 ° peel tensile speed: 300 mm / min

"Example 1 "
A resin composition sample (2) was prepared in the same manner as in the Reference Example except that 65 parts by mass of sample (b) was blended with 35 parts by mass of sample (b) 60% by mass + sample (b) 40% by mass (preparation) Post-component composition (A) 79% by mass, (B) 21% by mass), using the same as in the reference example , processability during extrusion lamination to a kraft paper substrate, and resin composition sample of laminate (2) The cellotape peel strength of the layer was measured.
The results are shown in Table 1.

"Example 2 "
A resin composition sample (3) was prepared in the same manner as in Reference Example except that 65 parts by mass of sample (I) was blended with 35 parts by mass of MB of 60% by mass of sample (C) + 40% by mass of sample (I) (preparation) Post-component composition (A) 79% by mass, (C) 21% by mass), using the same as in the reference example , processability during extrusion lamination to a kraft paper base material, and resin composition sample of laminate (3) The cellotape peel strength of the layer was measured.
The results are shown in Table 1.

"Example 3 "
A resin composition sample (4) was prepared in the same manner as in the Reference Example except that 65 parts by mass of sample (b) was blended with 35 parts by mass of sample (d) 60% by mass + sample (b) 40% by mass (preparation) rear component composition (i) 79 wt%, (d) 21 wt%), similar to the reference example by using the workability in extrusion lamination to kraft paper substrate, and a resin composition sample of laminate (4) The cellotape peel strength of the layer was measured.
The results are shown in Table 1.
In addition, as a result of peeling between the kraft paper / resin composition sample of the laminate of the kraft paper and the resin composition sample of Reference Example and Examples 1 to 3 , the paper base material was destroyed in both cases, and the paper and the resin composition were good. Showed good adhesion.

“Comparative Example 1”
Similar to Reference Example using as the TPX sample (a), processability in extrusion lamination to kraft paper substrate and was measured cellophane tape peel strength of the resin composition sample (4) layers of the laminate.
The results are shown in Table 1.

  From the results of Table 1, the resin composition of the present invention is remarkably superior in workability at the time of molding as compared with the conventional product TPX, but it has an appropriate peel strength (releasability) with respect to an adhesive surface such as “cello tape”. It can be seen that it is extremely suitable as a release layer for release paper.

Claims (6)

Methylpentene polymer resin (A) 50 to 79 parts by weight and the ethylene (meth) acrylic acid copolymer resin (a) and at least one ethylene copolymer resin thereof selected from ionomer (b) (B) A methylpentene-based polymer resin composition for a release layer of a release paper comprising 21 to 50 parts by mass (however, the sum of (A) and (B) is 100 parts by mass).   The resin composition according to claim 1, wherein the methylpentene polymer resin (A) is a resin comprising a 4-methyl-1-pentene polymer.   The resin composition according to claim 1 or 2, wherein the ethylene copolymer resin (B) is an ethylene / (meth) acrylic acid copolymer resin (a).   The ethylene / (meth) acrylic acid copolymer resin (a) is an ethylene / (meth) acrylic acid binary copolymer resin or an ethylene / (meth) acrylic acid / (meth) acrylic ester terpolymer resin. The resin composition according to claim 3.   A film or sheet comprising the resin composition according to claim 1.   The laminated body containing the layer of the resin composition in any one of Claims 1 thru | or 4.