JP2016014129A - Resin composition, film, laminate film, laminate, material for easy peeling and cover tape - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition excellent in release-ability without significantly impairing heat sealability and to provide a film comprising the resin composition or the like.SOLUTION: There is provided a resin composition which comprises a 4-methyl-1-pentene copolymer (A) and a thermoplastic resin (B), wherein the content of the 4-methyl-1-pentene copolymer (A) is 0.5 mass% or more and less than 50 mass% based on the total mass of the resin composition, the content of the thermoplastic resin (B) is 50 mass% or more and less than 99.5 mass% based on the total mass of the resin composition and the 4-methyl-1-pentene copolymer (A) satisfies the following requirement [1]: [1] the constitutional unit derived from 4-methyl-1-pentene is 99.5 to 60 mol% and the total of the constitutional unit derived from an α-olefin having 2 to 20 carbon atoms (excluding 4-methyl-1-pentene) is 0.5 to 40 mol%.

Description

  The present invention relates to a resin composition comprising 4-methyl-1-pentene copolymer of 0.5% by mass or more and less than 50% by mass and a thermoplastic resin of 50% by mass or more and less than 99.5% by mass. Moreover, it is related with the cover tape containing the film containing the said resin composition, a laminated film, the laminated body containing the said laminated film, the material for easy peels, and the said material for easy peels.

  For transporting and storing microchips such as semiconductors and electronic parts, such as carrier tapes with interlocked embossed pockets that can be stored in accordance with the shape of electronic parts, cup noodles, jelly, yogurt, etc. Plastic containers having easy-open lids are widely used for various beverages and pharmaceutical containers. Many cover tapes and seal materials that can be extrusion laminated have been proposed and put to practical use for the seal layer of such easy-open lids. Generally, an ethylene / vinyl acetate copolymer, an ethylene / ethyl acrylate copolymer and a tackifier composition, a composition to which polyethylene, an ethylene / α-olefin copolymer, etc. are added. However, it has been proposed as a sealing material having sealing properties and easy opening properties (see, for example, Patent Documents 1 to 5).

  At present, there is an increasing demand for sealing materials that can withstand various requirements, such as the increase in the types of plastic materials used in container bodies and the different heat seal characteristics that are desired depending on the application. For example, the carrier tape described above has been conventionally used as a base material of polystyrene (PS), but in recent years, the tape strength is high from the viewpoint of productivity improvement, and the sealing material used in the conventional cover tape and Tends to use polycarbonate (PC) which is difficult to adhere. Further, in a short time from the viewpoint of processing cost, adhesion in a short time is required, and it has been studied to increase the adhesive strength of a conventional sealing material. For example, Patent Document 5 proposes a sealing material with improved adhesion to a PC.

JP-A-6-309472 Japanese Patent Laid-Open No. 10-337829 JP 2000-062116 A Japanese Patent Laying-Open No. 2005-041890 JP 2012-188509 A

  4-Methyl-1-pentene copolymer is used as a release film and as a material for electronic and information materials as a resin having excellent characteristics such as heat resistance, transparency and releasability compared to polyethylene and polypropylene. Has been. However, when added to the sealing material, the melting point is significantly different from the ethylene copolymer that is the main component of the raw material of the sealing material, so that the molding temperature of the 4-methyl-1-pentene copolymer is 250 ° C. If it is above, unmelted resin is generated and there is a risk of causing molding failure due to gelation or the like.

  Moreover, although the polyethylene-type resin, such as an ethylene-vinyl acetate copolymer and a low density polyethylene, is used for the sealant layer and sealant material of the said patent documents 1-5, a molding temperature is raised to 250 degreeC or more. And may become a molding defect. On the other hand, when molding is performed using a high-melting-point resin for the sealant layer, gelation during molding can be prevented, but unmelted resin is present during molding, which may impair molding defects and appearance.

  Further, the conventional laminated film has a problem that the film cannot be released from the roll at the time of manufacture (also referred to as roll release property), so that the processing speed cannot be increased and the productivity is difficult to improve. Moreover, since the sound is produced when the film is peeled from the roll, there is a problem that the production efficiency of the film is lowered.

  Moreover, since it becomes difficult to peel from the roll of a film winder when shape | molding a sealing material because sealing strength becomes large, there exists a tendency for a production rate to fall. Moreover, there is a concern that the sealing material may be stretched or broken when it is peeled off from the roll.

  An object of the present invention is to provide a resin composition capable of providing a film having excellent releasability without greatly deteriorating adhesiveness and heat sealability, a film containing the resin composition, a laminated film, and the laminated film. It is providing the laminated body containing, the material for easy peel, and the cover tape containing the said material for easy peel.

  Specific means for achieving the above object are as follows.

<1> A resin composition comprising a 4-methyl-1-pentene copolymer (A) and a thermoplastic resin (B), wherein the content of the 4-methyl-1-pentene copolymer (A) However, it is 0.5 mass% or more and less than 50 mass% with respect to the total mass of the said resin composition, and content of the said thermoplastic resin (B) is 50 mass% with respect to the total mass of the said resin composition. Or more and less than 99.5% by mass,
A resin composition in which the 4-methyl-1-pentene copolymer (A) satisfies the following requirement [1].
[1] A structural unit derived from 4-methyl-1-pentene is derived from 99.5 mol% to 60 mol% and an α-olefin having 2 to 20 carbon atoms (excluding 4-methyl-1-pentene). The total of the structural units to be performed is 0.5 mol% to 40 mol%.

<2> The resin composition according to <1>, wherein the 4-methyl-1-pentene copolymer (A) satisfies all the following requirements [2] to [5].
[2] Intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.5 dl / g to 5.0 dl / g [3] Weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) The molecular weight distribution (Mw / Mn), which is the ratio to the number average molecular weight (Mn), is 1.0 to 3.5 [4] The density is 825 kg / m ^{3 to} 860 kg / m ³ [5] Differential scanning calorific value The melting point (Tm) measured with a meter (DSC) is in the range of 100 ° C. to 199 ° C.

<3> The resin composition according to <1> or <2>, wherein the thermoplastic resin (B) is an olefin resin.

<4> The resin composition according to any one of <1> to <3>, wherein the 4-methyl-1-pentene copolymer (A) satisfies the requirement [6] below.
[6] The α-olefin having 2 to 20 carbon atoms is propylene.

<5> A film comprising the resin composition according to any one of <1> to <4>.

<6> A laminated film including at least two layers of a sealant layer including the resin composition according to any one of <1> to <5> and a base material layer.

<7> A laminate comprising the laminated film according to <6>.

<8> Easy peel material including the laminated film according to <6>.

<9> A cover tape containing the easy peel material according to <8>.

  According to the present invention, a resin composition capable of providing a film having excellent releasability without significantly deteriorating adhesiveness and heat sealability, a film containing the resin composition, a laminated film, and the laminated film It is possible to provide a laminate including, an easy peel material, and a cover tape including the easy peel material.

  Hereinafter, specific embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and may be implemented with appropriate modifications within the scope of the object of the present invention. be able to.

In addition, in this specification, the numerical range represented using "to" means the range which includes the numerical value described before and behind "to" as a lower limit and an upper limit.
In addition, in this specification, when referring to the amount of each component in the composition, when there are a plurality of substances corresponding to each component in the composition, the plurality present in the composition unless otherwise specified. Means the total amount of substances.

  Hereinafter, the resin composition containing the 4-methyl-1-pentene copolymer (A) of the present invention will be described in detail.

[Resin composition]
The resin composition of the present invention contains a 4-methyl-1-pentene copolymer (A) and a thermoplastic resin (B), and the content of the 4-methyl-1-pentene copolymer (A) is The thermoplastic resin (B) content is 50% by mass or more based on the total mass of the resin composition, and is 0.5% by mass or more and less than 50% by mass with respect to the total mass of the resin composition. It is less than 99.5 mass%.
By using the resin composition of this invention, the film excellent in mold release property can be provided, without impairing adhesiveness and heat-sealability largely.
Moreover, when manufacturing a laminated | multilayer film using the resin composition of this invention, since the detachability of the film from a roll is excellent, a processing speed can be raised and productivity can be improved. Furthermore, it is possible to suppress the generation of sound when the film is peeled from the roll, and the film production efficiency is excellent.

  When the film wound on the roll is subjected to secondary processing, there is a concern that blocking between the films occurs and the film is difficult to peel off. For this reason, an antiblocking agent may be added to the film to prevent blocking, or a release layer may be provided, but it is still difficult to remove the film, and when the film and the release layer are peeled off, the releasability is not sufficient. There's a problem.

  On the other hand, when secondary processing is performed by using the resin composition of the present invention, blocking between films is suppressed, and a film excellent in releasability is obtained.

[4-Methyl-1-pentene copolymer (A)]
Hereinafter, the 4-methyl-1-pentene copolymer (A) will be described.
The 4-methyl-1-pentene copolymer (A) contains 99.5 mol% to 60 mol% of structural units derived from (derived from) 4-methyl-1-pentene, and has 2 to 20 carbon atoms. The structural unit derived from an α-olefin (excluding 4-methyl-1-pentene) is contained in a proportion of 0.5 mol% to 40 mol%. Note that the α-olefin having 2 to 20 carbon atoms is not limited to one type, and two or more types may be selected. When a plurality of α-olefins are selected, the above range is satisfied as the sum of the structural units. That's fine.

  Here, from the viewpoint of heat resistance, releasability, and moldability, the upper limit of the structural unit derived from 4-methyl-1-pentene is preferably 99.5 mol%, and 97 mol% is included. More preferably, it is more preferably 93 mol%. Further, the lower limit of the structural unit derived from 4-methyl-1-pentene is preferably 60 mol%, more preferably 70 mol%, and 83 mol%. More preferably, it is particularly preferably contained in an amount of 87 mol%.

  On the other hand, it is preferable that 40 mol% is included as the upper limit of the structural unit derived from an α-olefin having 2 to 20 carbon atoms (excluding 4-methyl-1-pentene), and 30 mol% is included. Is more preferable, 17 mol% is further more preferable, and 13 mol% is particularly preferable. Moreover, it is preferable that 0.5 mol% is contained as a minimum of the structural unit derived from a C2-C20 alpha olefin (except 4-methyl-1-pentene), and 3 mol% is contained. It is more preferable that 7 mol% is contained. Here, the total of the structural units of 4-methyl-1-pentene and the α-olefin having 2 to 20 carbon atoms is preferably 100 mol%.

  4 obtained by bringing the proportion of structural units derived from 4-methyl-1-pentene and an α-olefin having 2 to 20 carbon atoms (excluding 4-methyl-1-pentene) within the above range. The melting point of the methyl-1-pentene copolymer (A) satisfies the requirement [5]: the melting point (Tm) measured with a differential scanning calorimeter (DSC) is in the range of 100 ° C. to 199 ° C. Can be adjusted. Therefore, when producing a film comprising a layer containing 4-methyl-1-pentene copolymer (A), a conventionally used 4-methyl-1-pentene polymer, particularly 4-methyl-1- The molding temperature can be lowered as compared with a pentene homopolymer. Furthermore, it becomes possible to maintain the heat resistance of 4-methyl- 1-pentene copolymer (A) at a high level by making the ratio of a structural unit in the said range.

  The 4-methyl-1-pentene copolymer (A) is derived from a 4-methyl-1-pentene structural unit chain and an α-olefin having 2 to 20 carbon atoms (excluding 4-methyl-1-pentene). It may be a block copolymer including a block in which structural units of the same type are continuous. From the viewpoints of transparency and moldability, a random copolymer of 4-methyl-1-pentene and an α-olefin having 2 to 20 carbon atoms is preferable.

  Examples of the α-olefin having 2 to 20 carbon atoms contained in the 4-methyl-1-pentene copolymer (A) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene and 3-methyl-1. Preferred examples include -butene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-eicocene, and the like. .

  In addition, examples of the α-olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-hexene, and 3-methyl-1-butene from the viewpoints of copolymerizability and physical properties of the obtained copolymer. 3-methyl-1-pentene, 1-octene, 1-decene, 1-hexadecene, 1-heptadecene, 1-octadecene, ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene 1-hexadecene, 1-heptadecene and 1-octadecene are more preferable, and ethylene, propylene, 1-butene, 1-octene, 1-decene, 1-hexadecene, 1-heptadecene and 1-octadecene are more preferable. Of these, α-olefins having 2 to 4 carbon atoms are preferable, and specific examples include ethylene, propylene, and 1-butene.

  These α-olefins having 2 to 20 carbon atoms can be used alone or in combination of two or more. Furthermore, propylene is most preferable from the viewpoints of copolymerizability and dispersibility.

  The 4-methyl-1-pentene copolymer (A) is a 4-methyl-1-pentene and an α-olefin having 2 to 20 carbon atoms (4-methyl-), as long as the object of the present invention is not impaired. A structural unit derived from a polymerizable compound other than 1-pentene (hereinafter also referred to as a polymerizable compound) may be included.

  Examples of the polymerizable compound include vinyl compounds having a cyclic structure such as styrene, vinylcyclopentene, vinylcyclohexane, and vinylnorbornane; vinyl esters such as vinyl acetate; unsaturated organic acids such as maleic anhydride or derivatives thereof; butadiene, Conjugated dienes such as isoprene, pentadiene, 2,3-dimethylbutadiene; 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7- Methyl-1,6-octadiene, dicyclopentadiene, cyclohexadiene, dicyclooctadiene, methylene norbornene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2 -Norbornene, 6- Non-conjugated polyenes such as olomethyl-5-isopropylene-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene Etc.

  In the present invention, the 4-methyl-1-pentene copolymer (A) includes all the polymerizable compounds contained in the 4-methyl-1-pentene copolymer (A) as units derived from the polymerizable compound. It may be contained in an amount of 10 mol% or less, or may be contained in an amount of 5 mol% or less and 3 mol% or less with respect to the structural unit derived from.

  In the present invention, the structural unit derived from 4-methyl-1-pentene, which is contained in the 4-methyl-1-pentene copolymer (A), and 2 to 20 carbon atoms other than 4-methyl-1-pentene. The content (mol%) of the structural unit derived from the α-olefin can be measured by the following method.

~Measurement condition~
Measuring apparatus: Nuclear magnetic resonance apparatus (ECP500 type, manufactured by JEOL Ltd.)
Observation nucleus: ¹³ C (125 MHz)
Sequence: Single pulse proton decoupling Pulse width: 4.7 μsec (45 ° pulse)
Repeat time: 5.5 seconds Accumulated number: 10,000 times or more Solvent: Orthodichlorobenzene / deuterated benzene (volume ratio: 80/20) mixed solvent Sample concentration: 55 mg / 0.6 mL
Measurement temperature: 120 ° C
Standard value of chemical shift: 27.50ppm

In the present invention, the intrinsic viscosity [η] of the 4-methyl-1-pentene copolymer (A) measured in 135 ° C. decalin is preferably 0.5 dL / g to 5.0 dL / g.
Here, the intrinsic viscosity [η] is preferably in the range of 1.0 dL / g to 4.0 dL / g, and more preferably in the range of 1.2 dL / g to 3.5 dL / g.
The value of the intrinsic viscosity [η] can be adjusted by the amount of hydrogen added during the polymerization when the 4-methyl-1-pentene copolymer (A) is produced.

  The 4-methyl-1-pentene copolymer (A) having an intrinsic viscosity [η] in the above range exhibits good fluidity during production of the resin composition and various moldings. Further, by using the 4-methyl-1-pentene copolymer (A), the dispersibility in the thermoplastic resin (B) including polyethylene and ethylene / vinyl acetate copolymer is improved, and the appearance is beautiful. Can be obtained.

The intrinsic viscosity [η] of the 4-methyl-1-pentene copolymer (A) is a value measured by the following method using an Ubbelohde viscometer.
About 20 mg of 4-methyl 1-pentene copolymer (A) is dissolved in 25 ml of decalin, and then the specific viscosity ηsp is measured in an oil bath at 135 ° C. using an Ubbelohde viscometer. After 5 ml of decalin is added to the decalin solution for dilution, the specific viscosity ηsp is measured in the same manner as described above. This dilution operation is further repeated twice, and the value of ηsp / C when the concentration (C) is extrapolated to 0 is obtained as the intrinsic viscosity [η] (unit: dl / g) (see the following formula 1).
[Η] = lim (ηsp / C) (C → 0) Equation 1

In the present invention, molecular weight distribution (ratio of weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of 4-methyl-1-pentene copolymer (A) ( Mw / Mn) is preferably 1.0 to 3.5. Here, the molecular weight distribution (Mw / Mn) is preferably in the range of 1.0 to 3.0, and more preferably in the range of 1.5 to 2.5.
The value of the molecular weight distribution (Mw / Mn) can be adjusted according to the type of olefin polymerization catalyst described later.

  The resin composition containing 4-methyl-1-pentene copolymer (A) having a molecular weight distribution (Mw / Mn) value in the above range tends to have a relatively low molecular weight component content. Therefore, when the resin composition containing 4-methyl-1-pentene copolymer (A) is pelletized or film-molded, the blocking property is lowered and the film properties are generally low. In particular, it is preferable from the viewpoint of excellent mechanical strength and beautiful appearance.

In the present invention, the molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), of the 4-methyl-1-pentene copolymer (A) is the following gel permeation chromatography. It is a value calculated by a standard polystyrene conversion method using a graph (GPC).
~Measurement condition~

Measuring device: GPC (ALC / GPC 150-C plus type, suggested refractometer detector integrated type, manufactured by Waters)
Column: 2 GMH6-HT (manufactured by Tosoh Corp.) and 2 GMH6-HTL (manufactured by Tosoh Corp.) connected in series Eluent: o-dichlorobenzene Column temperature: 140 ° C
Flow rate: 1.0 mL / min

The density of the 4-methyl-1-pentene copolymer (A) in the present invention is preferably 825 kg / m ^{3 to} 860 kg / m ³ .

Here, the density ^is preferably in the range of ^{830kg / m 3 ~855kg / m 3} , more preferably in the range of ^{830kg / m 3 ~850kg / m 3} , 830kg / m 3 ~845kg / m 3 More preferably, it is the range.
The density value can be adjusted by selecting the type and blending amount of other α-olefins polymerized with 4-methyl-1-pentene.
The resin composition containing 4-methyl-1-pentene copolymer (A) having a density value in the above range is preferable from the viewpoints of heat resistance and light weight.
The density of the 4-methyl 1-pentene copolymer (A) is a value measured according to JIS K7112 (density gradient tube method).

In the present invention, the melt flow rate (MFR) of the 4-methyl-1-pentene copolymer (A) is 0.01 g / 10 min to 100 g / 10 min from the viewpoint of fluidity during molding. It is preferably 0.5 g / 10 min to 50 g / 10 min, more preferably 0.5 g / 10 min to 30 g / 10 min.
The melt flow rate (MFR) of the 4-methyl-1-pentene copolymer (A) is a value measured at 230 ° C. and a load of 2.16 kg in accordance with ASTM D1238.

In the present invention, the melting point (Tm) measured by DSC of the 4-methyl-1-pentene copolymer (A) preferably has no melting point or is 100 ° C to 199 ° C.
Here, the melting point (Tm) is preferably in the range of 110 ° C. to 190 ° C., more preferably in the range of 125 ° C. to 185 ° C., and further preferably in the range of 125 ° C. to 180 ° C., A range of 140 ° C to 180 ° C is particularly preferable.
The melting point (Tm) value varies depending on the stereoregularity of the polymer and the amount of α-olefin polymerized together, and is controlled and adjusted to a desired value using an olefin polymerization catalyst described later. Is possible.
The resin composition containing the 4-methyl-1-pentene copolymer (A) having a melting point (Tm) in the above-mentioned range is less sticky at room temperature, so that the handleability is good and the moldability is favorable. preferable.

The melting point (Tm) of the 4-methyl-1-pentene copolymer is a value measured by the following method using a differential scanning calorimetry (DSC).
About 5 mg of 4-methyl-1-pentene copolymer (A) was sealed in an aluminum pan for measurement of a differential scanning calorimeter (DSC220C type) manufactured by Seiko Instruments Inc. To 200 ° C. In order to completely melt the 4-methyl-1-pentene copolymer (A), it is held at 200 ° C. for 5 minutes and then cooled to −50 ° C. at 10 ° C./min. After 5 minutes at −50 ° C., the second heating is performed to 200 ° C. at 10 ° C./min, and the peak temperature (° C.) at the second heating is defined as the melting point (Tm) of the copolymer. When a plurality of peaks are detected, the peak detected on the highest temperature side is adopted.

  In the present invention, 4-methyl-1-pentene copolymer (A) comprises 4-methyl-1-pentene and the above-mentioned specific α-olefin in the presence of an olefin polymerization catalyst, and further, if necessary, the polymerization. It can be obtained by polymerizing the active compound.

Among the olefin polymerization catalysts, a metallocene catalyst can be mentioned as a preferred embodiment of the catalyst for producing the 4-methyl-1-pentene copolymer (A).
Preferred metallocene catalysts include those described in WO 01/53369, WO 01/27124, JP-A-3-19396, JP-A-02-41303, or WO 06/025540, The metallocene catalyst described in the international publication 2014/050817 pamphlet is mentioned.

  The content of the 4-methyl-1-pentene copolymer (A) in the resin composition of the present invention is preferably 0.5% by mass or more and less than 50% by mass with respect to the total mass of the resin composition. % To 40% by mass is more preferable, and 3% to 30% by mass is more preferable. If it is within the above range, the affinity for the thermoplastic resin (B) is high, so that the 4-methyl-1-pentene copolymer (A) can be finely dispersed in the system. When a film is produced using a plastic resin composition, the 4-methyl-1-pentene copolymer (A) is less likely to fall off and can improve the roll-off property, and the film is also resistant to blocking over a long period of time. It is possible to maintain sex.

[Thermoplastic resin (B)]
In the present invention, the thermoplastic resin (B) is an olefin polymer; for example, low density, medium density, high density polyethylene, ultrahigh molecular weight polyethylene, high pressure method low density polyethylene, isotactic polypropylene, syndiotactic polypropylene, Atactic polypropylene, poly 1-butene, poly 4-methyl-1-pentene, poly 3-methyl-1-butene, ethylene / α-olefin copolymer, propylene / α-olefin copolymer, 1-butene / α -Olefin copolymer, cyclic olefin copolymer, ethylene / vinyl alcohol copolymer, ethylene / vinyl acetate copolymer, ethylene / unsaturated carboxylic acid copolymer; for example, ethylene / acrylic acid copolymer, ethylene Methacrylic acid copolymer, ethylene / unsaturated carboxylic acid ester copolymer ; Ethylene / (meth) acrylic acid ester copolymer ethylene / crotonic acid ester copolymer, ethylene / (meth) acrylic acid methyl ester, ethylene / (meth) acrylic acid ethyl ester, ethylene / (meth) acrylic acid normal butyl , Ethylene / (meth) acrylate isobutyl, ethylene / (meth) acrylate cyclohexyl copolymer, ethylene / (meth) acrylate glycidyl copolymer, ethylene / unsaturated carboxylic acid / unsaturated carboxylic acid ester copolymer; For example, ethylene / vinyl acetate / (meth) acrylic acid glycidyl copolymer, ethylene / (meth) acrylic acid / (meth) acrylic acid glycidyl copolymer, ionomer, styrenic resin; for example, polystyrene, styrene / ethylene / butylene・ Styrene block copolymer, styrene / ethylene・ Propylene / styrene block copolymer, styrene / butadiene copolymer and hydrogenated product thereof, styrene / isoprene copolymer and hydrogenated product thereof, styrene / isobutylene copolymer, styrene / isobutylene / styrene block copolymer, Styrene / acrylonitrile copolymer, ABS resin, ACS resin, AES resin, ASA resin, fluorine resin, rosin resin, terpene resin and petroleum resin, polyvinyl chloride, chlorinated polyethylene, chlorinated polypropylene, polyacrylonitrile, polyethylene Terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polylactic acid, polycaprolactone, polybutylene succinate, polyamino acid, polydi Tylsiloxane, polytetramethylene glycol, polyhydroxyethyl methacrylate, polyphenylene terephthalamide, polyacrylamide, polyurethane, polyamide, polyoxymethylene, polycarbonate, polyphenylene ether, polyphenylene sulfide, polysulfone, polyether ether ketone, polyether ketone, polyethylene oxide , Polymethyl methacrylate, polyimide, liquid crystal polymer, polyamideimide, polyaminobismaleimide, polyarylate, polyetherimide, polyketone, polybenzimidazole, silicone resin, polybutadiene, cellulose resin, and mixtures of these polymers, among them It is preferable to use an olefin polymer (olefin resin).

  Among olefin polymers, it is particularly preferable to use an ethylene polymer. The ethylene-based polymer is a known polymer mainly composed of ethylene. Examples thereof include ethylene homopolymers, copolymers of ethylene and other α-olefins; for example, ethylene / propylene copolymers, Propylene / 1-butene copolymer, ethylene / 1-hexene copolymer, ethylene / 1-octene copolymer, ethylene and other vinyl monomers; for example, ethylene / vinyl acetate copolymer, ethylene / unsaturated carboxylic acid Copolymer; for example, ethylene / acrylic acid copolymer, ethylene / methacrylic acid copolymer, ethylene / unsaturated carboxylic acid ester copolymer; for example, ethylene / (meth) acrylic acid ester copolymer ethylene / crotonic acid Ester copolymer, ethylene / methyl (meth) acrylate, ethylene / ethyl (meth) acrylate, ethylene / (meth) N-butyl acrylate, isobutyl ethylene / (meth) acrylate, ethylene / (meth) acrylic acid cyclohexyl copolymer, ethylene / (meth) acrylic acid glycidyl copolymer, ethylene / unsaturated carboxylic acid / unsaturated carboxylic acid ester Copolymer; for example, ethylene / vinyl acetate / glycidyl (meth) acrylate copolymer, ethylene / (meth) acrylic acid / glycidyl (meth) acrylate copolymer, ionomer, and mixtures thereof it can. In addition, polyolefin polymers such as polypropylene, poly 1-butene, styrene resin, ethylene / propylene rubber, and ethylene / propylene / diene copolymer rubber can be added to these polymers as necessary. is there.

[Other resins]
The resin composition of the present invention contains other resins other than the above-mentioned 4-methyl-1-pentene copolymer (A) and thermoplastic resin (B) within a range not impairing the object of the present invention. May be.

〔Additive〕
The resin composition of the present invention contains a specific amount of 4-methyl-1-pentene copolymer (A) and a specific amount of thermoplastic resin (B), and further does not impair the object of the present invention. In, for example, weathering stabilizers, heat stabilizers, antioxidants, UV absorbers, antistatic agents, antislip agents, antiblocking agents, antifogging agents, nucleating agents, lubricants, pigments, dyes, antiaging agents, hydrochloric acid Various additives such as an absorbent, an inorganic or organic filler, an organic or inorganic foaming agent, a crosslinking agent, a crosslinking aid, an adhesive, a softening agent, a flame retardant, and a conductive filler may be contained.

In the present invention, the resin composition containing the 4-methyl-1-pentene copolymer (A) (hereinafter referred to as a thermoplastic resin composition) further improves its moldability, that is, the crystallization temperature is increased. In order to increase the crystallization rate, a nucleating agent that is a specific optional component may be blended.
In this case, for example, the nucleating agent is dibenzylidene sorbitol nucleating agent, phosphate ester nucleating agent, rosin nucleating agent, benzoic acid metal salt nucleating agent, fluorinated polyethylene, 2,2-methylenebis (4,6-di- -T-butylphenyl) sodium phosphate, pimelic acid and salts thereof, 2,6-naphthalene dicarboxylic acid dicyclohexylamide, etc., and the amount is not particularly limited, but with respect to 100 parts by mass of the (co) resin composition It is preferable that there is about 0.1 to 1 part by mass. There is no restriction | limiting in particular in a mixing | blending timing, It can add during superposition | polymerization, after superposition | polymerization, or a shaping | molding process.

  In the thermoplastic resin composition, a secondary antioxidant, a heat stabilizer, a weather stabilizer, an antistatic agent, a slip agent, an antifogging agent, if necessary, as long as the object of the present invention is not impaired. Lubricants, dyes, pigments, natural oils, synthetic oils, waxes, fillers, hydrochloric acid absorbents, and other olefinic polymers can be blended. The blending amount is not particularly limited, but is usually 0 to 50 parts by weight, preferably 0 to 30 parts by weight, and preferably 0 to 10 parts by weight with respect to 100 parts by weight of the thermoplastic resin composition. More preferred is 0 to 1 part by mass.

  A known antioxidant can be used as the antioxidant. Specifically, a hindered phenol compound, a sulfur-based antioxidant, a lactone-based antioxidant, an organic phosphite compound, an organic phosphonite compound, or a combination of these can be used.

  Examples of the lubricant include sodium, calcium and magnesium salts of saturated or unsaturated fatty acids such as lauric acid, palmitic acid, oleic acid and stearic acid, and these may be used alone or in combination of two or more. it can. Moreover, 0.1 mass part-3 mass parts are preferable normally with respect to 100 mass parts of this thermoplastic resin composition, and, as for the compounding quantity of this lubricant, 0.1-2 mass parts is more preferable.

  As the slip agent, it is preferable to use amides of saturated or unsaturated fatty acids such as lauric acid, palmitic acid, oleic acid, stearic acid, erucic acid and hebenic acid, or bisamides of these saturated or unsaturated fatty acids. Of these, erucic acid amide and ethylene bisstearamide are particularly preferred. These fatty acid amides are preferably blended in the range of usually 0.01 to 5 parts by mass with respect to 100 parts by mass of the thermoplastic resin composition of the present invention.

〔Production method〕
About the mixing method of each component, various well-known methods, for example, a multistage polymerization method, a plastmill, a Henschel mixer, a V-blender, a ribbon blender, a tumbler, a blender, a kneader ruder or the like, or after mixing, a single screw extruder A method of granulating or pulverizing after melt-kneading with a twin screw extruder, kneader, Banbury mixer or the like can be employed. By this method, it is possible to obtain a high-quality thermoplastic resin composition in which each component and additive are uniformly dispersed and mixed.

  In the present invention, in particular, a master batch containing 1 to 90 parts by mass of the 4-methyl-1-pentene copolymer (A) in the thermoplastic resin (B) (100 parts by mass of the entire resin composition). Can be prepared in advance and used as a concentration of the predetermined 4-methyl-1-pentene copolymer (A) by appropriately blending them.

  The molding processing temperature of the film of the present invention is preferably 140 ° C to 250 ° C, more preferably 180 ° C to 230 ° C, and further preferably in the range of 190 ° C to 220 ° C.

  The higher one of the glass transition temperature (Tg) or the melting point (Tm) of the thermoplastic resin composition of the present invention is preferably a thermoplastic resin of 100 ° C. or higher. The Tg or Tm of the thermoplastic resin composition is more preferably 110 ° C. or higher, and further preferably 120 ° C. or higher. Further, Tg or Tm is suitably 250 ° C. or lower, and preferably 200 ° C. or lower. When Tg or Tm satisfies the above range, the thermoplastic resin composition does not require a high molding temperature, and therefore it is possible to suppress deterioration of the material during molding. In the present invention, the glass transition temperature (Tg) and the melting point (Tm) are measured by the methods defined in JIS K7121.

  The film of the present invention can be obtained by melt-extruding the above-described thermoplastic resin composition at a cylinder temperature of usually 180 ° C to 300 ° C.

  The film of the present invention is, for example, a sheet-like film obtained by kneading and melt-extruding the above-described thermoplastic resin composition using an extruder, and the sheet-like film is guided to the first roll. It can be manufactured by being cooled by the first roll before it is released from and then guided to the second roll. Furthermore, it can be cooled and solidified by the second roll to produce a sheet-like film, and finally wound up to produce a sheet-like laminate. Although there is no restriction | limiting in particular regarding the temperature of a 1st roll and a 2nd roll, In order to improve cooling efficiency and improve productivity, the range of 15 degreeC-150 degreeC is preferable. In order to improve the production efficiency of the sheet-like film, it is desirable to maintain it at 100 ° C. or lower, and 80 ° C. or lower is more preferable. The surface shape of the cooling roll may be a mirror-polished polish roll or an embossed roll that has been embossed. Moreover, you may have a some roll in the post process after a 2nd roll.

  Since the 4-methyl-1-pentene copolymer (A) is present in the film of the present invention with high affinity to the thermoplastic resin (B), the 4-methyl-1-pentene copolymer (A) Is less likely to fall off and has excellent blocking resistance over a long period of time.

  In the present invention, “film” is a convenient name for indicating the appearance structure of the thermoplastic resin composition, and “film” is a general term for a molded product on a plane, and this includes the film. Other concepts include sheets, membranes (membranes), tapes, and the like.

  The thermoplastic resin composition of the present invention can be formed into a film or a sheet by a known method. As a specific molding method, melt extrusion molding, press molding, injection molding, calendar molding, or a molding method using a casting method is used. Further, it is also preferable that a molded product obtained by molding into a film or a sheet by a T-die extrusion molding method or the like is further obtained by uniaxial stretching or biaxial stretching.

[Laminated film]
Moreover, the laminated film of the present invention is a laminated film having a base material layer in any one layer in addition to the single-layer film obtained from the resin composition containing the above-described 4-methyl-1-pentene copolymer (A). Including. Moreover, what wound up the multilayer body of two or more layers and the said laminated | multilayer film, and was made into roll shape is also called a laminated body. The method for obtaining such a laminated film is not particularly limited, but a method of laminating by a known laminating method such as extrusion lamination or extrusion coating on a surface layer film obtained in advance by T-die molding or inflation molding. Or a method of laminating each film by dry lamination after independently molding a plurality of films, etc. From the viewpoint of productivity, coextrusion in which a plurality of components are subjected to a multilayer extruder for molding. Molding is preferred.

  Although the thickness of the film obtained from the resin composition containing 4-methyl-1-pentene copolymer (A) is not particularly limited, it is usually 500 μm or less, preferably 1 μm to 250 μm, more preferably 2 μm to 100 μm. is there.

[Sealant layer]
In the present invention, the sealant layer can be used alone. The sealant layer includes a 4-methyl-1-pentene copolymer (A) and a thermoplastic resin (B), and the content of the 4-methyl-1-pentene copolymer (A) is based on the total mass. 1 mass% or more and less than 50 mass%, the content of the thermoplastic resin (B) is 50 mass% or more and less than 99 mass% with respect to the total mass, and the 4-methyl-1-pentene copolymer The coalescence (A) satisfies all the following requirements [1] to [5].
[1] A structural unit derived from 4-methyl-1-pentene is derived from 99.5 mol% to 60 mol% and an α-olefin having 2 to 20 carbon atoms (excluding 4-methyl-1-pentene). The total of the structural units to be performed is 0.5 mol% to 40 mol%.
[2] The intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.5 dl / g to 5.0 dl / g.
[3] The molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC), is 1.0 to 3.5.
[4] The density is 825 kg / m ^{3 to} 860 kg / m ³ .
[5] The melting point (Tm) measured with a differential scanning calorimeter (DSC) is in the range of 100 ° C to 199 ° C.

  The sealant layer is a resin composition containing a 4-methyl-1-pentene copolymer (A) and a thermoplastic resin (B), and each composition is 4-methyl-1 described in the section of the resin composition. -Since it is synonymous with the composition of a pentene copolymer (A) and the composition of a thermoplastic resin (B), and a preferable aspect is also the same, description is abbreviate | omitted here.

[Base material layer]
The material for the base material layer is not particularly limited, but polyethylene (low density, high density), ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, Polyolefin resins such as polypropylene, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ionomer resin, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, nylon-6, nylon-6, 6. Metaxylenediamine-adipic acid condensation polymer, amide resin such as polymethylmethacrylamide, acrylic resin such as polymethylmethacrylate, polystyrene, styrene-acrylonitrile copolymer, styrene-acrylonitrile- Tadiene copolymers, styrene-acrylonitrile resins such as polyacrylonitrile, hydrophobic cellulose resins such as cellulose triacetate and cellulose diacetate, halogens such as polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, and Teflon (registered trademark) -Containing resin, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, high hydrogen bonding resin such as cellulose derivative, polycarbonate resin, polysulfone resin, polyethersulfone resin, polyetheretherketone resin, polyphenylene oxide resin, polymethylene oxide resin And engineering plastic resins such as liquid crystal resins.

Among these, biaxially stretched polypropylene, polyethylene terephthalate, nylon, and biaxially stretched polypropylene coated with polyvinylidene chloride called K coat, polyethylene terephthalate, nylon, and silica, alumina, and aluminum were deposited. Polyethylene terephthalate, polypropylene, nylon, polycarbonate, polystyrene, strong antistatic use OPP (AS-OP) and the like are preferably used.
The material for the base material layer is preferably a resin composed only of carbon and hydrogen, or a resin composed only of carbon, hydrogen, and oxygen in consideration of environmental protection at the time of disposal or recycling.

In the laminated film of the present invention, it is preferable that at least a part of the base material layer is in contact with a layer (for example, a sealant layer) containing 4-methyl-1-pentene copolymer (A). Here, “at least a part is in contact with the layer containing 4-methyl-1-pentene copolymer (A)” means that the base material layer is 4-methyl-1-pentene copolymer (A). Means that the base material layer is in contact with the entire layer containing the thermoplastic resin composition, and the 4-methyl-1-pentene copolymer (A) It is preferable that the contact ratio of the layer containing the substrate and the base material layer is 30% to 100% with respect to the total area of the layer containing the 4-methyl-1-pentene copolymer (A), and 50% to More preferably, it is 100%.
As the preferred form, it can be suitably used for a multilayer type release film containing the film of the present invention in the film surface layer.

[Use]
Resin composition and film containing 4-methyl-1-pentene copolymer (A), laminated film, laminated body, easy peel material containing laminated film, and cover tape containing easy peel material are various packaging materials Can be used as As specific applications, for example, the following can be used for easy-opening sealing materials, particularly easy-opening sealing materials for packaging materials, carrier tapes (packaging for transportation), cover tapes for carrier tapes, and the like. .

  For example, it can be used as a sheet for paper (cellulose), polypropylene, polystyrene, polyester, polyethylene terephthalate, polycarbonate, polyvinyl chloride, and a container lid. Such sheets and containers include, for example, foods and drinks such as jelly, pudding, yogurt, lactic acid beverages, Japanese confectionery, processed meat, microchips, IC chips and capacitors, electrostatic sensitive devices, electronic components such as toners, chemicals, infusions It can be used for various packaging of medical devices such as medical instruments and packaging for transportation.

[Cover tape]
The cover tape is used as a cover material for a carrier tape that is a storage container for electronic components. The carrier tape is a belt-like object having a width of about 8 mm to 100 mm having a recess for accommodating electronic components. When heat-sealing using a cover tape as a lid material, the carrier tape material is not particularly limited, and commercially available materials can be used, for example, polystyrene, polyester, polycarbonate, polyvinyl chloride, and the like. Carrier tapes are those in which conductivity is imparted by kneading carbon nanotubes into the resin, those in which an antistatic agent or conductive filler is kneaded, or surfactant type antistatic agents or polypyrrole on the surface, An antistatic property can also be used by applying a coating liquid in which a conductive material such as polythiophene is dispersed in an organic binder such as acrylic.

  For example, after packaging electronic components in the electronic component storage portion of the carrier tape, the electronic component packaging body uses the cover tape as a lid, and continuously seals and wraps both edges in the longitudinal direction of the cover tape. It is obtained by winding it on Electronic parts and the like are stored and transported by packaging in this form. An electronic component package containing electronic components, etc. is intermittently peeled off the cover tape while being conveyed by a feed hole provided at the longitudinal edge of the carrier tape, and the presence of the electronic components etc. by the pickup device, It can be taken out while checking the direction and position.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. In the examples, each physical property was measured as follows.

〔composition〕
The content (mol%) of 4-methyl-1-pentene and propylene (α-olefin having 3 carbon atoms) in the copolymer was measured by ¹³ C-NMR. The measurement conditions are as follows.

~Measurement condition~
Measuring apparatus: Nuclear magnetic resonance apparatus (ECP500 type, manufactured by JEOL Ltd.)
Observation nucleus: ¹³ C (125 MHz)
Sequence: Single pulse proton decoupling Pulse width: 4.7 μsec (45 ° pulse)
Repeat time: 5.5 seconds Accumulated number: 10,000 times or more Solvent: Orthodichlorobenzene / deuterated benzene (volume ratio: 80/20) mixed solvent Sample concentration: 55 mg / 0.6 mL
Measurement temperature: 120 ° C
Standard value of chemical shift: 27.50ppm

[Intrinsic viscosity [η]]
The intrinsic viscosity [η] of the copolymer was measured at 135 ° C. in a decalin solvent using an Ubbelohde viscometer as a measuring device.
Specifically, about 20 mg of the powdery copolymer was dissolved in 25 ml of decalin, and then the specific viscosity ηsp was measured in an oil bath at 135 ° C. using an Ubbelohde viscometer. After 5 ml of decalin was added to the decalin solution for dilution, the specific viscosity ηsp was measured in the same manner as described above.
This dilution operation was further repeated twice, and the value of ηsp / C when the concentration (C) was extrapolated to 0 was determined as the intrinsic viscosity [η] (unit: dl / g) (see the following formula 1).
[Η] = lim (ηsp / C) (C → 0) Equation 1

[Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)]
The weight average molecular weight (Mw) of the copolymer and the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) are determined by gel permeation chromatography (GPC: Gel). It calculated by the standard polystyrene conversion method using Permeation Chromatography). The measurement conditions are as follows.
~Measurement condition~
Measuring device: GPC (ALC / GPC 150-C plus type, suggested refractometer detector integrated type, manufactured by Waters)
Column: 2 GMH6-HT (manufactured by Tosoh Corp.) and 2 GMH6-HTL (manufactured by Tosoh Corp.) connected in series Eluent: o-dichlorobenzene Column temperature: 140 ° C
Flow rate: 1.0 mL / min

[Melt flow rate (MFR)]
The melt flow rate (MFR) of the copolymer was measured at 230 ° C. and a load of 2.16 kg in accordance with ASTM D1238. The unit is g / 10 min).

〔density〕
The density of the copolymer was measured according to JIS K7112 (density gradient tube method). This density (kg / m ³ ) was used as an indicator of lightness.

[Melting point (Tm) and glass transition temperature (Tg)]
The melting point (Tm) of the copolymer was measured as follows using a differential scanning calorimeter (DSC220C type, manufactured by Seiko Instruments Inc.) as a measuring device.
About 5 mg of the copolymer was sealed in a measurement aluminum pan and heated from room temperature to 200 ° C. at 10 ° C./min. In order to completely melt the copolymer, it was kept at 200 ° C. for 5 minutes and then cooled to −50 ° C. at 10 ° C./min. After 5 minutes at −50 ° C., the second heating was performed to 200 ° C. at 10 ° C./min. The peak temperature (° C.) at the second heating was defined as the melting point (Tm) of the copolymer, and the displacement point corresponding to the glass transition was defined as the glass transition temperature (Tg). The higher one of the melting point (Tm) and the glass transition temperature (Tg) of this copolymer was used as an index of heat resistance.

[Synthesis Example 1] Production of 4-methyl-1-pentene copolymer (A-1)
750 ml of 4-methyl-1-pentene was charged at 23 ° C. into a SUS autoclave with a stirring blade having a capacity of 1.5 liters sufficiently purged with nitrogen. The autoclave was charged with 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL), and stirring was started.

  Next, the autoclave was heated to an internal temperature of 60 ° C. and pressurized with propylene so that the total pressure was 0.17 MPa (gauge pressure). Subsequently, 1 mmol of methylaluminoxane prepared in advance, diphenylmethylene (1-ethyl-3-tert-butyl-cyclopentadienyl) (2,7-di-tert-butyl-fluorenyl) zirconium in terms of Al Polymerization was initiated by injecting 0.34 ml of a toluene solution containing 0.005 mmol of dichloride into an autoclave with nitrogen. During the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave was 60 ° C. Sixty minutes after the start of polymerization, 5 ml of methanol was injected into the autoclave with nitrogen to stop the polymerization, and the autoclave was depressurized to atmospheric pressure. Acetone was poured into the reaction solution with stirring.

The obtained powdery polymer containing the solvent was dried at 130 ° C. under reduced pressure for 12 hours. The mass of the obtained copolymer was 35.2 g, the 4-methyl-1-pentene content in the copolymer was 93.0 mol%, and the propylene content was 7.0 mol%. The Tm of the polymer was 180.2 ° C., the intrinsic viscosity [η] was 1.66 dl / g, and the density was 832 kg / m ³ .

[Synthesis Example 2] Production of 4-methyl-1-pentene copolymer (A-2)
A SUS autoclave with a stirring blade having a capacity of 1.5 liters sufficiently purged with nitrogen was charged with 300 ml of normal hexane at 23 ° C. (dried in a dry nitrogen atmosphere and activated alumina) and 450 ml of 4-methyl-1-pentene. . The autoclave was charged with 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL), and the stirrer was rotated. Next, the autoclave was heated to an internal temperature of 60 ° C. and pressurized with propylene so that the total pressure was 0.19 MPa (gauge pressure). Subsequently, 1 mmol of methylaluminoxane prepared in advance and diphenylmethylene (1-ethyl-3-t-butyl-cyclopentadienyl) (2,7-di-t-butyl-fluorenyl) zirconium in terms of Al were prepared. Polymerization was initiated by injecting 0.34 ml of a toluene solution containing 0.01 mmol of dichloride with nitrogen into an autoclave. During the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave was 60 ° C. Sixty minutes after the start of polymerization, 5 ml of methanol was injected into the autoclave with nitrogen to stop the polymerization, and the autoclave was depressurized to atmospheric pressure. Acetone was poured into the reaction solution with stirring.

  The obtained powdery polymer containing the solvent was dried at 100 ° C. under reduced pressure for 12 hours. The mass of the obtained copolymer was 44.0 g, and the 4-methyl-1-pentene content in the copolymer was 84 mol% and the propylene content was 16 mol%. The copolymer had a melting point (Tm) of 132 ° C. and an intrinsic viscosity [η] of 1.5 dl / g. Table 1 shows the measurement results of various physical properties.

[Synthesis Example 3] Production of 4-methyl-1-pentene copolymer (A-3)
When the autoclave is heated to an internal temperature of 60 ° C. and pressurized with propylene, the same as (A-1) above, except that the total pressure is changed from 0.17 MPa (gauge pressure) to 0.20 MPa (gauge pressure). Then, a copolymer was obtained.
The mass of the obtained copolymer was 40.3 g, the 4-methyl-1-pentene content in the copolymer was 90.1 mol%, and the propylene content was 9.9 mol%. The polymer had a Tm of 162.1 ° C., an intrinsic viscosity [η] of 1.65 dl / g, and a density of 833 kg / m ³ . Table 1 shows the measurement results of various physical properties.

[Example 1]
3 parts by mass of 4-methyl-1-pentene copolymer A-1 and 97 parts by mass of an ethylene-based polymer (CMPS brand: V-70 manufactured by Mitsui DuPont Polychemical Co., Ltd.) were mixed (dry blended). Next, the obtained mixture was put into a hopper of a 20 mmφ single screw extruder (single screw sheet forming machine, manufactured by Tanaka Iron Works Co., Ltd.) equipped with a T die having a lip width of 240 mm. And the cylinder temperature was set to 230 degreeC, the die temperature was set to 230 degreeC, the sheet-like film of Example 1 was obtained by extruding the melt-kneaded material from a T-die by 50 micrometers in thickness, and cast-molding. For heat seal strength measurement, a 20 mmφ single screw extruder (2 type 3 layer sheet molding machine, Technobel Co., Ltd.) equipped with a T-die for forming 2 types 3 layers film with 200 mm lip width was used. (Base material layer) Ethylene polymer (Prime Polymer Evolue brand: SP2540), surface layer (sealant layer) mixture obtained above, cylinder temperature is set to 230 ° C, die temperature is set to 230 ° C The sheet-like laminated film of Example 1 was obtained by extruding the melt-kneaded material from a T die with a thickness of 70 μm (20 μm / 30 μm / 20 μm) and cast molding.

[Example 2]
5 parts by mass of 4-methyl-1-pentene copolymer A-1 and 95 parts by mass of an ethylene-based polymer (CMPS brand: V-70 manufactured by Mitsui DuPont Polychemical Co., Ltd.) were mixed (dry blended). Next, the obtained mixture was put into a hopper of a 20 mmφ single screw extruder (single screw sheet forming machine, manufactured by Tanaka Iron Works Co., Ltd.) equipped with a T die having a lip width of 240 mm. Then, the cylinder temperature was set to 230 ° C., the die temperature was set to 230 ° C., the melt-kneaded product was extruded from the T die with a thickness of 50 μm, and cast-molded to obtain a sheet-like laminated film of Example 2.

Example 3
Except for mixing (dry blending) 10 parts by mass of 4-methyl-1-pentene copolymer A-1 and 90 parts by mass of an ethylene-based polymer (CMPS brand: V-70 manufactured by Mitsui DuPont Polychemical Co., Ltd.). Obtained a sheet-like laminated film by the same method as in Example 1.

Example 4
Other than mixing (dry blending) 5 parts by mass of 4-methyl-1-pentene copolymer A-2 and 95 parts by mass of an ethylene-based polymer (CMPS brand: V-70 manufactured by Mitsui DuPont Polychemical Co., Ltd.) Obtained a sheet-like laminated film by the same method as in Example 1.

[Comparative Example 1]
Except that the 4-methyl-1-pentene copolymer (A) was not added and the film was formed only with an ethylene polymer (CMPS brand manufactured by Mitsui DuPont Polychemical Co., Ltd .: V-70), the same as in Example 1 By the method, a sheet-like laminated film was obtained.

[Evaluation]
The films of Examples 1 to 4 and Comparative Example 1 were evaluated as follows. The evaluation results are shown in Table 2 and Table 3 below.

[Removal / sound from roll]
A film of a resin composition containing 4-methyl-1-pentene copolymer (A) is molded in an environment where the sound background level is 70 dB or less. At that time, the sheet-like molten resin coming out of the die is transferred at a constant speed (1.5 to 4 m / min) by a take-up roll machine. First, it was visually confirmed whether or not the sheet-like film was peeled off from the first roll (first roll; temperature 20 ° C., surface mirror finish).
○ when it peels off from the roll (first roll; temperature 20 ° C, surface mirror finish) and can move to the next roll (second roll; surface mirror finish) without any problems. ○, sticks to the roll and moves to the next roll When it was difficult to do, it was set as x. ○ has practical performance.
Further, the case where an abnormal noise was generated when the sheet-like film was peeled from the roll was set to be loud, and the case where the abnormal sound was not generated was set to be low. Small has practical performance.

[Sound when feeding out from a roll-shaped laminate]
A roll film was produced by winding up a 100 m laminated film. When a laminated film containing the 4-methyl-1-pentene copolymer (A) is fed out from this roll-shaped laminate, the noise is increased when the noise is generated, and the sound is decreased when the noise is not generated. Small has practical performance.

  When Example 1 is compared with Comparative Example 1 that does not contain 4-methyl-1-pentene copolymer, it is possible to use (A-1) or (A-2) to remove the body from the roll. It can be seen that the separation is excellent and there is no sound when peeled off from the roll, and the roll-off property is good. Moreover, when the case where the comparative example 1 which does not contain a 4-methyl-1-pentene copolymer is used with respect to Example 1, it turns out that a noise does not generate | occur | produce when paying out a laminated | multilayer film.

[Heat seal strength]
Using the above Examples 1 to 4 and Comparative Example 1, the heat seal strength was measured. Sealing conditions were performed under the following two conditions.
Condition 1 (sealant layers); seal temperature = 120, 140, 160 ° C., seal condition = 0.3 MPa, 0.5 second condition 2 (CPP); seal temperature = 120, 140, 160 ° C., seal condition = 0. 3 MPa, 1.0 second Under condition 2, homopolypropylene (Prime Polypro (registered trademark) brand: F107BV manufactured by Prime Polymer Co., Ltd.) was used as CPP. In the same manner as in Examples 1 to 4 and Comparative Example 1, CPP was formed using a single screw extruder (single screw sheet forming machine, manufactured by Tanaka Iron Works Co., Ltd.), and a cast film having a thickness of 100 μm was attached. The body.

  Moreover, the peeling test recorded the seal strength when peeling at a tensile speed of 300 mm / min with respect to a sealant portion having a width of 15 mm under any conditions.

Example 5
3 parts by mass of 4-methyl-1-pentene copolymer (A-3) and 97 parts by mass of an ethylene polymer (B-3 (Evaflex brand: EV-550 manufactured by Mitsui DuPont Polychemical Co., Ltd.)) Next, the obtained mixture was put into a hopper of a 20 mmφ single screw extruder (single screw sheet forming machine, manufactured by Tanaka Iron Works Co., Ltd.) equipped with a T die having a lip width of 240 mm. Then, the cylinder temperature is set to 210 ° C., the die temperature is set to 210 ° C., the melt-kneaded material is extruded from the T die with a thickness of 50 μm, and laminated with a 50 μm PET film (Lumirror film manufactured by Toray Industries, Inc.) and cast-molded. Thus, a sheet-like laminated film (PET film layer / thermoplastic resin layer) of Example 5 was obtained.

Example 6
10 parts by mass of 4-methyl-1-pentene copolymer (A-3) and 90 parts by mass of ethylene polymer (B-3) (Evaflex brand: EV-550 manufactured by Mitsui DuPont Polychemical Co., Ltd.) A sheet-like laminated film was obtained by the same method as in Example 5 except that mixing (dry blending) was performed.

Example 7
10 parts by mass of 4-methyl-1-pentene copolymer (A-3) and 90 parts by mass of ethylene polymer (B-2) (Evaflex brand: EV-250 manufactured by Mitsui DuPont Polychemical Co., Ltd.) A sheet-like laminated film was obtained by the same method as in Example 5 except that mixing (dry blending) was performed.

[Comparative Example 2]
Except that the 4-methyl-1-pentene copolymer (A) was not used and the film was formed only with an ethylene polymer (B-2) (Evaflex brand: EV-250 manufactured by Mitsui DuPont Polychemical Co., Ltd.) A sheet-like laminated film was obtained in the same manner as in Example 5.

[Comparative Example 3]
Except that the 4-methyl-1-pentene copolymer (A) was not used and the ethylene polymer (B-3) (Evaflex brand manufactured by Mitsui DuPont Polychemical Co., Ltd .: EV-550) alone was used to form a film. A sheet-like laminated film was obtained in the same manner as in Example 5.

Ethylene polymer (B-2) (Evaflex brand: EV-250 manufactured by Mitsui DuPont Polychemical Co., Ltd.) and ethylene polymer (B-3) (Mitsui) used in Examples 5 to 7 and Comparative Examples 2 and 3 The melt flow rate (MFR), density, vinyl acetate content (VA%), and melting point (Tm) of Evaflex brand (EV-550 manufactured by DuPont Polychemical Co., Ltd.) were measured. Melt flow rate (MFR), density, and melting point (Tm) were measured by the same method as the above-mentioned copolymer, and vinyl acetate content (VA%) was measured according to JIS K7192. The results are as follows.
B-2: MFR 15 g / 10 min, density 950 kg / m ³ , VA% 28 mass%, Tm 72 ° C.
B-3: MFR 15 g / 10 min, density 930 kg / m ³ , VA% 14 mass%, Tm 89 ° C.

[Peel strength evaluation]
The peel strength was measured according to the pressure-sensitive adhesive sheet test method (JIS Z0237-2000). Specifically, after the sheet-like laminated films obtained in Examples 5 to 7 and Comparative Examples 2 and 3 were placed in a constant environment at a temperature of 23 ° C. and a relative humidity of 50% for 3 days, the temperature was 23 ° C. relative humidity. The peel strength when the PET film layer and the thermoplastic resin layer were peeled off at a speed of 300 mm / min in a 180 ° direction in a 50% environment was determined as the peel strength at 23 ° C. In addition, after placing the sheet-like laminated film in an oven at a temperature of 50 ° C. for 3 days, a PET film layer and a thermoplastic resin layer at a speed of 300 mm / min in a 180 ° direction in an environment of a temperature of 23 ° C. and a relative humidity of 50% The peel strength when the film was peeled was measured and determined as the peel strength at 50 ° C.

As shown in Table 2 and Table 3, it can be seen that the films obtained in Examples 1 to 4 are excellent in releasability without greatly impairing the tackiness and heat sealability. As shown in Table 4, the films obtained in Examples 5 to 7 were obtained in Comparative Example 2 and Comparative Example 3 in which the thermoplastic resin layer did not contain 4-methyl-1-pentene copolymer. When compared with the film, it was found that the peel strength at 23 ° C. from the PET film was small, and the film was excellent in releasability and blocking resistance.
Moreover, when the film obtained in Example 5-Example 7 was compared with the film obtained in the comparative example 2 and the comparative example 3 whose thermoplastic resin layer does not contain a 4-methyl-1-pentene copolymer. It can be seen that the peel strength from the PET film after heating at 50 ° C. is small, and the film is excellent in releasability and blocking resistance.

The film according to the present invention has sufficient heat-sealing properties, is excellent in roll release properties during molding, and can be obtained by low-temperature molding.
Thereby, it can use suitably as sealant films, such as a packaging material, the material for easy peels, and a cover tape.

Claims (9)

A resin composition comprising a 4-methyl-1-pentene copolymer (A) and a thermoplastic resin (B), wherein the content of the 4-methyl-1-pentene copolymer (A) is It is 0.5 mass% or more and less than 50 mass% with respect to the total mass of a resin composition, and content of the said thermoplastic resin (B) is 50 mass% or more and 99.99 with respect to the total mass of the said resin composition. The resin composition which is less than 5 mass%, and the said 4-methyl-1- pentene copolymer (A) satisfy | fills the requirements of following [1].
[1] A structural unit derived from 4-methyl-1-pentene is derived from 99.5 mol% to 60 mol% and an α-olefin having 2 to 20 carbon atoms (excluding 4-methyl-1-pentene). The total of the structural units to be performed is 0.5 mol% to 40 mol% The resin composition according to claim 1, wherein the 4-methyl-1-pentene copolymer (A) satisfies all the following requirements [2] to [5].
[2] Intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.5 dl / g to 5.0 dl / g [3] Weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) The molecular weight distribution (Mw / Mn), which is the ratio to the number average molecular weight (Mn), is 1.0 to 3.5 [4] The density is 825 kg / m ^{3 to} 860 kg / m ³ [5] Differential scanning calorific value The melting point (Tm) measured with a meter (DSC) is in the range of 100 ° C. to 199 ° C.   The resin composition according to claim 1 or 2, wherein the thermoplastic resin (B) is an olefin resin. The resin composition according to any one of claims 1 to 3, wherein the 4-methyl-1-pentene copolymer (A) satisfies the requirement [6] below.
[6] The α-olefin having 2 to 20 carbon atoms is propylene.   The film containing the resin composition of any one of Claims 1-4.   A laminated film comprising at least two layers of a sealant layer containing the resin composition according to any one of claims 1 to 5 and a base material layer.   A laminate comprising the laminated film according to claim 6.   An easy peel material comprising the laminated film according to claim 6.   A cover tape comprising the easy peel material according to claim 8.