JP2006130851A - Multi-layer polyolefin film or sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To make a resin material which has good high frequency welder properties, is excellent in transparency, flexibility, heat resistance, etc., and can replace a flexible vinyl chloride resin fit for practical use. <P>SOLUTION: In a multi-layer film or sheet, on a polar group-containing ethylene resin substrate layer, a propylene-ethylene random block copolymer meeting the following conditions (i)-(iv) is laminated: (i) in a TREF elution curve, a peak T (A1) observed on the side of high temperatures is 65-90°C, and a peak T (A2) observed on the lower temperature side is 50°C or below; (ii) in the TREF elution curve, a temperature where 99 wt.% of the total is eluted is 92°C or below; (iii) in the TREF elution curve, the cumulative amount (A2) of components eluted at temperatures not exceeding the temperature of an intermediate point is 30-70 wt.%, and the cumulative amount (A1) of components eluted at temperatures above the temperature of the intermediate point is 70-30 wt.%; and (iv) a tan δ curve in solid viscoelasticity measurement has a single peak at 0°C or below. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a polyolefin-based multilayer film or multilayer sheet. Specifically, a specific propylene-ethylene random block copolymer is laminated as a surface layer on a substrate layer made of a polar group-containing ethylene-based resin, and has transparency. A new polyolefin-based multilayer film or sheet having excellent glossiness and flexibility, improved heat resistance and cold resistance, no stickiness of the product, bleed-out is suppressed, and particularly good high-frequency sealability, and It relates to a molded product formed by molding them.

Soft vinyl chloride resin (PVC) is inexpensive, excellent in transparency, gloss and flexibility, and has high secondary workability such as high-frequency sealing, so it can be used for stationery such as card folders and desk mats, Widely used as vehicle interior leather and packaging materials.
However, soft vinyl chloride resin contains a plasticizer as a necessary component, and bleeding out of plasticizers and monomers causes blocking, stickiness, contamination of stored contents such as cards, and whitening over time. have. In addition, when burning during disposal, etc., toxic hydrogen chloride gas and dioxin may be generated, or substances that cause acid rain that may cause environmental pollution may be generated. In addition, there is a strong demand for an alternative to a resin material having a higher environmental suitability than a soft vinyl chloride resin.

In order to meet this social demand, as seen in Patent Document 1, many proposals have been made so far to replace a soft vinyl chloride resin with a polyolefin resin. High sealing performance by high frequency welder, which is excellent for secondary processing, whereas polyolefin resin does not have a polar group. Despite its excellent physical properties, it could not be used as a substitute for a soft vinyl chloride resin that requires processing by a high-frequency welder.
Meanwhile, ethylene-vinyl acetate copolymer (EVA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA), etc. It is well known that polar group-containing ethylene-based resins have excellent high-frequency welder suitability, but they are inferior in gloss and surface scratch resistance, and also have low heat resistance, so they deform even at moderately high temperatures (about 80 ° C). Has the disadvantage of producing.

  Therefore, a combination of the advantages of both polyolefin resin with excellent transparency and heat resistance and polar group-containing ethylene resin with good high-frequency welder suitability can be used as a composite material to replace soft vinyl chloride resin. For this purpose, a method of making each resin composition (blend) or laminate (multi-layer sheet) can be adopted, but many improvement proposals by such methods have been made so far. ing.

As a method of blending each resin into a composition, for example, a composition comprising 65 to 97 wt% of an ethylene copolymer having a polar group and 3 to 35 wt% of a polypropylene resin having an MFR of 3 or less. Propylene-based resin and ethylene-based resin are incompatible with each other, but are inferior in transparency and glossiness. Propylene-based resin can only give high-frequency welder suitability within a range of 35 wt% or less. The heat resistance is not sufficient (see Patent Document 2).
Also proposed is a film comprising a composition comprising an ethylene-vinyl acetate copolymer and an isotactic propylene polymer component, the ratio of which is 95: 5 to 40:60 and the difference in refractive index is 0.005 or less. However, although the deterioration of transparency is suppressed by adjusting the refractive index, a normal propylene-ethylene random copolymer is used, and sufficient high-frequency welder suitability cannot be imparted. It is also inferior to bleed-out (see Patent Document 3).
Similarly, a composition comprising 60 to 95 wt% of an ethylene copolymer having a polar group, 40 to 5 wt% of a polypropylene resin specified by so-called cross fractionation and spherical resin fine particles has been proposed. Has a high crystallinity component that elutes at 95 to 125 ° C. in cross fractionation, so that propylene-based resin can impart high-frequency welder suitability only within a small range of 40 wt% or less, and it cannot be compatible with heat resistance. However, the stickiness and bleed-out are not sufficiently improved (see Patent Document 4).
Further, 100 parts by weight of a polyolefin-based resin composition composed of amorphous polyolefin 20 to 100 wt%, crystalline polypropylene 80 to 0 wt%, block copolymer 30 to 100 composed of an aromatic vinyl compound polymer and a conjugated diene copolymer. A resin composition comprising three parts by weight and 10 to 40 parts by weight of a polar group-containing ethylene copolymer has also been proposed, but a polyolefin resin and a polar group-containing ethylene copolymer alone are sufficiently transparent. The block copolymer consisting of an aromatic vinyl compound polymer and a conjugated diene copolymer is indispensable, and is expensive, and as a crystalline component in a polyolefin resin composition, Polypropylene is used, and this polypropylene component contains high crystallinity components so -Copolymer of α-olefin and cyclic olefin, cyclic olefin ring-opening polymer or hydride thereof, which is considered to be insufficient in suitability (see Patent Document 5) and has specified heat of fusion, dielectric loss tangent, etc. Alternatively, a resin composition comprising either a copolymer of ethylene and styrene has been proposed, but even if high frequency suitability is imparted, these components are expensive and have a high glass transition temperature and cold resistance. (Patent document 6).

As a method for forming a laminate using each resin as a layer material, for example, a proposal has been made to laminate a relatively low melting point random polypropylene on a surface layer for an intermediate layer made of a polar group-containing ethylene resin. Since a random polypropylene with relatively high rigidity is laminated on the surface layer, the flexural modulus of the laminated sheet is increased and the flexibility is impaired, and the propylene-ethylene random copolymer is based on a Ziegler-Natta catalyst. It has an inferior problem (see Patent Document 7).
In addition, it has also been proposed to use a propylene-ethylene random copolymer produced by a metallocene-based catalyst that has been conventionally used as a random polypropylene for the intermediate layer made of a polar group-containing ethylene-based resin for the surface layer. However, since the propylene-ethylene random copolymer produced using the metallocene catalyst has high crystallinity with respect to the melting point, the surface layer has higher rigidity and flexibility than the copolymer based on the Ziegler-Natta catalyst. In addition to being damaged, the amount of heat necessary for melting for heat sealing is large, so that the time required for high-frequency welder fusion becomes long and the seal workability is poor (see Patent Document 8). Here, when the melting point of the surface layer resin is lowered in order to improve the suitability and flexibility of the high frequency welder, the heat resistance is remarkably deteriorated, and the stickiness is increased. It is difficult to achieve both.

  In addition, the resin layer and molecular weight distribution ratio of ethylene-vinyl acetate copolymer were specified as a polyolefin-based resin laminate material that can be used as a substitute material for a soft vinyl chloride resin that has both high-frequency welder processability and flexibility and transparency. A laminate for a specific application comprising a polyolefin resin surface layer (see Patent Document 9), a resin layer having high-frequency exothermic properties such as a polar group-containing ethylene resin or polyamide resin, and a tackifying resin-containing polyolefin resin surface layer A multilayer resin film having improved high-frequency welder properties (see Patent Document 10), and a polypropylene containing no functional group component on both sides of a resin layer made of a polypropylene-based resin and an amorphous polyolefin having a functional group component Many proposals for improvement have been disclosed, such as a laminate in which a resin layer is disposed (see Patent Document 11). That is, not always to be improved well enough balanced simultaneously many other properties such as transparency and gloss and flexibility or heat resistance together with high-frequency welder processability.

Japanese Patent Laid-Open No. 6-218892 (summary) JP 2001-146524 A (summary) JP 2003-41070 A (summary) JP 2001-288312 (Abstract, Claim 1) JP 10-45963 A (summary) JP 2001-226533 A (Abstract, Claim 2) Japanese Patent Laid-Open No. 11-235795 (summary) JP 2003-266618 A (summary) Japanese Patent Laid-Open No. 10-250008 (Abstract) JP 2002-46236 A (summary, paragraph 0009) JP 2002-361810 A (Abstract, Claim 1, Claim 0019)

  As outlined in paragraphs 0002 to 0007, there is a strong demand for an alternative material for soft vinyl chloride resin due to the disadvantages of bleed-out such as plasticizers and environmental problems during disposal and combustion. Many composite materials have been disclosed as compositions or laminated materials in combination with polyolefin-based resins and polar group-containing resins, etc., but with high frequency welder workability equivalent to that of soft vinyl chloride resin. In the situation where a material that is inexpensive and has a sufficient balance of other physical properties such as transparency, gloss, flexibility, and heat resistance at the same time has not yet been realized, the present invention provides such an alternative material. The practical application is a problem to be solved by the invention.

  In order to solve the above-mentioned problems, the present inventors have examined in detail the blending of various resins in a composite material as a resin composition or a laminate, the combination of each layer material, etc., and conducted an experimental evaluation, and In order to provide high-frequency welder performance equivalent to that of vinyl chloride resin, an ethylene-based resin containing a polar group typified by an ethylene-vinyl acetate copolymer is useful as a component of a composite material. Based on the recognition that a unique olefinic resin is necessary as a component of the composite material in order to bring many other excellent physical properties such as heat resistance, a multifaceted study was advanced. The present inventors have long been a propylene-ethylene which improves the properties of polyolefin elastomers in a well-balanced manner such as transparency, flexibility, heat resistance, and cold resistance. A series of research and development of random block copolymers has been made and filed as an earlier invention (Japanese Patent Application No. 2003-371458 and others), and such propylene-ethylene random block copolymers have a unique property in the above composite materials. When used as a component of an olefin resin and combined with a polar group-containing ethylene resin component to form a resin composition, it has high-frequency welder properties equivalent to those of a soft vinyl chloride resin. New polyolefin system that can be found to be able to obtain composite materials exhibiting many other outstanding physical properties such as transparency, flexibility or heat resistance that could not be realized in the past, and can be substituted for soft vinyl chloride resin The application was previously filed as a resin composition (Japanese Patent Application No. 2004-232858).

Then, the inventors of the present invention materialize such knowledge also in a laminate (a multilayer film or a multilayer material as a multilayer sheet) as a composite material, and form a new related invention, which is the present invention.
Specifically, as a specific polyolefin-based resin, a propylene-ethylene random block copolymer that has been devised in a novel and specific manner described in detail below is adopted, and used as a surface layer constituting resin of a laminated material. By using a polar group-containing ethylene-based resin, particularly a specific ethylene-vinyl acetate copolymer (EVA) as a base material constituent resin of a laminated material in relation to such a random block copolymer, An unprecedented multilayer material that can be used as a substitute for soft vinyl chloride resin, which has excellent fusion processability, excellent transparency, gloss and flexibility, and also has heat resistance and cold resistance. It was discovered and led to the creation of the present invention.

  In order to improve transparency, gloss, flexibility, heat resistance, etc., the specific propylene-ethylene random block copolymer resin material is mainly soluble in temperature by temperature-temperature elution fractionation (TREF), and A unique copolymer characterized by a temperature-loss tangent (tan δ) curve obtained by solid viscoelasticity measurement (DMA) is adopted, and a polar group-containing ethylene-based resin material is a material for expressing high-frequency welder processability It is a material having good laminate bonding property in relation to the propylene-ethylene random block copolymer component.

  More specifically, the propylene-ethylene random block copolymer is a so-called random block copolymer obtained by sequentially polymerizing the component (A1) and the component (A2) having different crystallinity, and the block copolymer. Stipulated by a TREF elution curve obtained as a plot of elution amount (dwt% / dT) against temperature by a temperature rising elution fractionation method (TREF) in a temperature range of −15 ° C. to 140 ° C. using an o-dichlorobenzene solvent In the temperature-loss tangent (tan δ) curve obtained by solid-state viscoelasticity measurement (DMA), the tan δ curve has a single peak below 0 ° C. It has the single phase prescribed | regulated by these, It is characterized by the above-mentioned.

  The propylene-ethylene random block copolymer is preferably produced by sequential multi-stage polymerization using a metallocene catalyst as an additional condition, and the ethylene content, molecular weight or intrinsic viscosity of each component is specified, and a polar group-containing ethylene resin As a material, in order to express a high frequency welder characteristic, it contains a polar group, and preferably additionally, the type, content or MFR of the polar group is also defined.

In the present invention, a specific propylene-ethylene random block copolymer that is novel and unique in a composite material is employed, and a laminated material (multilayer film) in combination with a polar group-containing ethylene resin in relation to the random block copolymer. Or a multilayer material as a multilayer sheet), it has high frequency welder properties equivalent to those of soft vinyl chloride resin, and also has many other excellent physical properties such as transparency, flexibility and heat resistance. The composite material is obtained, and is clearly superior to each of the conventional technologies described above as the background art, and sufficiently replaces the soft vinyl chloride resin material inherent in the various problems described above. It can be said that it is a remarkable improvement technique that can put a resin material having excellent properties into practical use.
Then, the above-described prior art (paragraphs 0002 to 0007) is looked down on, and even if any prior literature is scrutinized, the above-described specific propylene-ethylene random block copolymer of the present invention is adopted, and the random A laminated material combined with a polar group-containing ethylene-based resin in the context of a block copolymer has not been found at all, and no suggestion of the structure of such a laminated material has been made.

  In the above, since the main part of the present invention and the background of the creation have been described generally, when the entire structure of the present invention is clearly described here, the present invention comprises the following invention unit groups, 1] is a basic invention, and [2] the following invention is to add basic requirements to the basic invention or to make it an embodiment. (The invention group as a whole is collectively referred to as “the present invention”.)

[1] A propylene-ethylene random block comprising components (A1) and (A2) satisfying the following conditions (Ai) to (A-iv) on a base material layer comprising a polar group-containing ethylene-based resin (B) A polyolefin-based multilayer film or a polyolefin-based multilayer sheet, comprising a laminate of the copolymer (A).
(Ai) TREF obtained as a plot of the elution amount (dwt% / dT) against temperature by the temperature rising elution fractionation method (TREF) in the temperature range of −15 ° C. to 140 ° C. using an o-dichlorobenzene solvent In the elution curve, the peak T (A1) observed on the high temperature side is in the range of 65 ° C. to 90 ° C., and the peak T (A2) observed on the low temperature side is below 50 ° C., or the peak T (A2) (If no peak is observed, the component (A2) is eluted into the solvent and the concentration is observed at −15 ° C., the lower limit of the measurement temperature.) (A-ii) In the TREF elution curve, the component (A ) The temperature T (A4) at which 99 wt% of the whole elutes is 92 ° C. or less (A-iii) In the TREF elution curve, peaks T (A1) and T (A2) (component (A2) is the peak If not shown, T (A2) is −15 ° C., which is the lower limit of the measurement temperature.) The accumulated amount W (A2) of the component eluted until the temperature T (A3) at the midpoint of both peaks is 30 to 30. 70% by weight, and the integrated amount W (A1) of the component eluted at T (A3) or higher is 70 to 30% by weight (A-iv) Temperature-loss tangent (tan δ) obtained by solid viscoelasticity measurement (DMA) ) In the curve, the tan δ curve has a single peak at 0 ° C. or lower. [2] The propylene-ethylene random block copolymer (A) is coated on the outer surface of the intermediate layer made of the polar group-containing ethylene resin (B). The polyolefin-based multilayer film or polyolefin-based multilayer sheet according to [1], which is laminated on the layer and the inner surface layer.
[3] Propylene-ethylene random block copolymer (A) is a metallocene-based catalyst, 30 to 70 wt% of a propylene-ethylene random copolymer containing 1 to 7 wt% of ethylene in the first step, the second step The propylene-ethylene random block copolymer is obtained by sequentially polymerizing 70-30 wt% of a propylene-ethylene random copolymer containing 6-12 wt% more ethylene than in the first step. The polyolefin-based multilayer film or polyolefin-based multilayer sheet according to [1] or [2].
[4] The polar group-containing ethylene-based resin (B) is an ethylene-vinyl acetate copolymer, the vinyl acetate content is 15 wt% or more, and the melt flow rate (MFR: 190 ° C. 2.16 kg load) is 0.1 to 0.1%. The polyolefin-based multilayer film or polyolefin-based multilayer sheet according to any one of [1] to [3], which is 100 g / 10 minutes.
[5] The polyolefin-based multilayer film or polyolefin-based multilayer according to any one of [1] to [4], wherein the propylene-ethylene random block copolymer (A) satisfies the following conditions (A-v): Sheet.
(Av) The weight average molecular weight Mw of the block copolymer (A) obtained by gel permeation chromatography (GPC) measurement is in the range of 100,000 to 400,000, and the weight average molecular weight is 5,000. The following component amount W (Mw ≦ 5,000) is 0.8 wt% or less in the block copolymer (A). [6] The propylene-ethylene random block copolymer (A) satisfies the following conditions (A The polyolefin multilayer film or polyolefin multilayer sheet according to any one of [1] to [5], which satisfies -vi).
(A-vi) The intrinsic viscosity [η] cxs measured in a decalin at 135 ° C. of the 23 ° C. xylene soluble component is in the range of 1 to 2 (dl / g) [7] propylene-ethylene random block It is composed of a surface layer made of a polymer (A) and a base material layer made of a polar group-containing ethylene-based resin (B), and the thickness of the surface layer is 20% or less or 70 μm or less with respect to the total thickness of the multilayer sheet. The polyolefin-based multilayer film or polyolefin-based multilayer sheet according to any one of [1] to [6].
[8] A molded product obtained by molding the polyolefin multilayer film or polyolefin multilayer sheet according to any one of [1] to [7] by high frequency welding.

In the polyolefin-based multilayer film or multilayer sheet using the propylene-ethylene random block copolymer in the present invention as a surface layer and laminated on a base layer composed of a polar group-containing ethylene-based resin, transparency, gloss and flexibility Excellent heat resistance and heat resistance, especially high sealability with high frequency welders, and no stickiness of the product, and bleed-out is suppressed.
Therefore, the polyolefin-based multilayer film or multilayer sheet in the present invention can be widely used as an alternative material in the industrial field where a soft vinyl chloride resin has been conventionally used.

  In the following, in order to describe the present invention in detail, the embodiments of the present invention are divided into propylene-ethylene random block copolymers (A) and polar group-containing ethylene resins (B) constituting each layer of the laminated material. Specific details will be described, focusing on each component.

1. As described above (paragraph 0011), the main component of the present invention is a laminate as a composite material (multilayer film or multilayer material as a multilayer sheet).
The present invention is a polyolefin-based multilayer film or multilayer sheet obtained by laminating a propylene-ethylene random block copolymer (A) as a surface layer and laminating it on a base material layer composed of a polar group-containing ethylene-based resin (B). is there. Moreover, various lamination | stacking aspects, such as laminating | stacking the inner surface layer and outer surface layer of a copolymer (A) on both surfaces by making a base material layer into an intermediate | middle layer, can be taken. Usually, the inner surface layer is a surface on which high-frequency welder sealing is performed.

Here, since the propylene-ethylene random block copolymer (A) is used as a surface layer, there is no stickiness or bleed out, excellent transparency, gloss and flexibility, and appropriate heat resistance, It is required to be easily fused by a high frequency welder. This requirement is achieved by various regulations regarding the copolymer (A) described in detail below.
The high-frequency welder processability is imparted by heat generated by the polar groups of the polar group-containing ethylene resin (B), and the surface layer copolymer (A) is heated and welded by the heat generated. The polar group-containing ethylene-based resin (B) has a polar group that can be fused by a high-frequency welder, and does not peel at the interface when a laminate with the propylene-ethylene random block copolymer (A) is formed. It is necessary. Although it has good bondability due to the polar group, a normal bonding improvement method such as corona treatment may be added.

2. Component of propylene-ethylene random block copolymer component (A) (2-1) Basic definition of propylene-ethylene random block copolymer (A) Propylene-ethylene random block copolymer component (A) itself Even though it does not have high-frequency welder heat generation properties, it requires high-frequency welder suitability such as easy heating and easy melting at the welding temperature, and TREF elution is required to enhance various physical properties such as flexibility and heat resistance. It has a specific crystallinity distribution and composition distribution defined by a curve, and has a single phase defined by solid viscoelasticity measurement in order to obtain high transparency.
By the way, the propylene-ethylene random block copolymer (A) used for the surface layer is excellent in transparency, gloss and flexibility, has high heat resistance, and does not easily cause delamination between layers. Although it is necessary to be able to demonstrate suitability, conventional polyolefin resins cannot satisfy all of these simultaneously in a well-balanced manner, and according to a new recognition based on the detailed consideration and experimental evaluation by the present inventors. In order to satisfactorily satisfy all of these simultaneously, it is necessary to have a specific controlled crystallinity distribution, composition distribution, and compatibility characteristics. It is necessary to use a specific block copolymer composed of components (A1) and (A2).

(2-2) Regulation relating to crystallinity distribution by TREF elution curve The crystallinity distribution and composition distribution of the propylene-ethylene random copolymer in the present invention are defined by the temperature rising elution fractionation method (TREF). The technique for evaluating the crystallinity distribution by the method is well known to those skilled in the art. For example, the following literatures show detailed measurement methods.
G. Glockner, J. et al. Appl. Polym. Sci. : Appl. Po
lym. Symp. 45, 1-24 (1990)
L. Wild, Adv. Polym. Sci. 98, 1-47 (1990)
J. et al. B. P. Soares, A .; E. Hamielec, Polymer; 36,
8, 1639-1654 (1995)
In TREF measurement, the lower the crystallinity, the lower the elution, and the higher the crystallinity, the higher the elution, so it is possible to accurately grasp the distribution of the crystallinity of the polypropylene resin. .

(A) Regulation by Elution Peak Temperature The propylene-ethylene random block copolymer (A) in the present invention comprises a sequential polymerization comprising a crystalline component (A1) and a low crystalline or amorphous component (A2). Is a block copolymer produced by
Here, the component (A1) exhibits a high temperature elution peak temperature T (A1) in the range of 65 to 90 ° C. in the TREF elution curve, and the low crystalline or amorphous component (A2) peaks at 50 ° C. or less. Shows temperature T (A2) or shows no peak in the measurement temperature range (in this case, the amount of elution component is observed at the measurement temperature lower limit of −15 ° C. T (A2) is the lower limit temperature −15 A copolymer is used.
That is, the component (A1) that causes the peak T (A1) on the high temperature side is a component that imparts heat resistance to the surface layer of the laminate and suppresses the occurrence of stickiness, blocking, scratches, etc. T (A1) If the temperature is too low, sufficient heat resistance cannot be exhibited, and stickiness and bleed-out are deteriorated. On the other hand, if T (A1) is too high, the suitability of the surface layer for high-frequency welder deteriorates, so it should be 90 ° C. or lower. Note that, as will be apparent from a comparison between examples and comparative examples, which will be described later, such numerical values are based on experimental data examination, and the same applies to the other numerical values described below.

By the way, when the copolymer (A) used for the surface layer is a conventional ordinary propylene-ethylene random copolymer composed only of the component (A1), fusion with a high frequency welder is possible. However, its moldability is unsatisfactory. In the single component (A1), the crystallinity is not sufficiently lowered, and a large amount of heat is generated by the high-frequency welder, so that a long time is required for molding and the productivity is deteriorated. On the other hand, if the crystallinity of the component (A1) is reduced in order to improve the suitability of the high frequency welder, various problems such as a reduction in heat resistance will occur.
Therefore, in the present invention, by making a block copolymer obtained by adding a lower crystalline or amorphous component (A2) to the component (A1), T (A1) can exhibit heat resistance. The crystallinity of the component (A) was reduced while maintaining the same, and the suitability for high-frequency welder and heat resistance were improved by improving the suitability for high-frequency welder. This is one of the remarkable features.
However, even if the crystallinity of the entire block copolymer is reduced by adding the component (A2), if the crystallinity of the component (A1) is too high, fusion with a high-frequency welder becomes difficult. The upper limit of the peak T (A1) is 90 ° C, preferably 85 ° C or lower, more preferably 80 ° C or lower.

  Since the component (A2) is a component necessary for reducing the crystallinity of the block copolymer component (A) and improving the suitability for high frequency welder, the component (A2) has a lower crystallinity or non-crystallinity than the component (A1). It must be a component and shows a peak at 50 ° C. or lower in the TREF elution curve or does not show a peak within the measurement temperature range but elutes into the o-dichlorobenzene solvent at the measurement temperature lower limit of −15 ° C. The cage concentration is specified as an observed component.

(B) Regulation concerning the elution end temperature T (A4) Even if the average crystallinity of the component (A1) is lowered, this component has high-frequency welder suitability if it contains a highly crystalline component. In order to inhibit, it is important that the component (A1) does not contain a highly crystalline component. The spread of crystallinity toward the high crystal side can be evaluated by TREF measurement, and the elution end temperature T (A4) of the entire component (A) with respect to the peak temperature T (A1) (however, an error in TREF measurement is considered). Therefore, in the present invention, the temperature at which 99 wt% of the whole is eluted is defined as the elution end temperature T (A4)) needs to be 92 ° C. or less.
Furthermore, the temperature difference ΔT (T (A4) −T (A1)) from the elution peak temperature T (A1) to the end temperature T (A4) is 5 ° C. or less, more preferably 4 ° C. or less, and further preferably 3 ° C. or less. It should be in the range of.

(C) Specification relating to the quantitative ratio of components (A1) and (A2) Regarding the amount of each component (A1) and (A2), the amount of component (A1) is too large, that is, the amount of component (A2) is too small. In the case where the crystallinity of the block copolymer (A) is not sufficiently lowered and high-frequency welder suitability cannot be exhibited, while the component (A1) is too small, that is, the component (A2) is too large. Since the heat resistance is significantly reduced, it is necessary to specify them.
At this time, since the component (A1) and the component (A2) have a large difference in crystallinity, both can be roughly divided by TREF.
That is, in the TREF elution curve, components (A1) and (A2) show their elution peaks at T (A1) and T (A2), respectively, due to the difference in crystallinity. The amount of the component eluted before the temperature T (A3) (= {T (A1) + T (A2)} / 2) and the amount eluted at a temperature equal to or higher than T (A3) are roughly the components (A2) and ( This corresponds to the amount of A1).
Therefore, if the integrated amount of the component eluted before T (A3) is defined as W (A2) wt%, and the integrated amount of the component eluted at T (A3) or higher is defined as W (A1) wt%, it exhibits heat resistance. In order to reduce the crystallinity of the block copolymer component (A), W (A1) needs to be at least 30 wt%, preferably 35 wt%, more preferably 40 wt%. W (A2) needs to be at least 30 wt%, preferably 35 wt%, more preferably 40 wt% or more.
In summary, W (A1) needs to be 30 to 70 wt%, preferably 35 to 65 wt%, and more preferably 40 to 60 wt%.
Similarly, W (A2) needs to be 30 to 70 wt%, preferably 35 to 65 wt%, more preferably 40 to 60 wt%.

(D) TREF measurement method In the present invention, specifically, measurement is performed as follows. A sample is dissolved in o-dichlorobenzene (containing 0.5 mg / mL BHT) at 140 ° C. to prepare a solution. This is introduced into a 140 ° C. TREF column, cooled to 100 ° C. at a rate of 8 ° C./min, subsequently cooled to −15 ° C. at a rate of 4 ° C./min, and held for 60 minutes. Then, -15 ° C o-dichlorobenzene (containing 0.5 mg / mL BHT) as a solvent is passed through the column at a flow rate of 1 mL / min, and dissolved in -15 ° C o-dichlorobenzene in the TREF column. The components are eluted for 10 minutes, and then the column is linearly heated to 140 ° C. at a heating rate of 100 ° C./hour to obtain an elution curve. In addition, the example of a TREF elution curve is illustrated in FIG. 1 as an example in manufacture example PP-1 (Example 1) in the Example mentioned later.

(E) Measurement of ethylene content Ethylene content E (A1) and E (A2) in components (A1) and (A2) use various measurement methods known as ethylene content measurement methods for propylene-ethylene random copolymers. However, in the present invention, since the components (A1) and (A2) can be clearly distinguished by TREF, each component is fractionated by a temperature rising column fractionation method, and the ethylene content in each component is determined by NMR analysis. It measured using.

i) Separation of components (A1) and (A2) Based on T (A3) obtained by the previous TREF measurement, the soluble components in T (A3) were analyzed by a temperature rising column fractionation method using a preparative fractionator. The component (A2) and the insoluble component (A1) in T (A3) are fractionated, and the ethylene content of each component is determined by NMR.
The temperature rising column fractionation method is a measurement method as disclosed in, for example, Macromolecules 21 314-319 (1988). Specifically, the following method was used in the present invention.

ii) Fractionation conditions A cylindrical column having a diameter of 50 mm and a height of 500 mm is filled with a glass bead carrier (80 to 100 mesh) and maintained at 140 ° C. Next, 200 mL of an o-dichlorobenzene solution (10 mg / mL) of the sample dissolved at 140 ° C. is introduced into the column. Thereafter, the temperature of the column is cooled to 0 ° C. at a temperature decreasing rate of 10 ° C./hour. After holding at 0 ° C. for 1 hour, the column temperature is heated to T (A3) at a heating rate of 10 ° C./hour and held for 1 hour. Note that the temperature control accuracy of the column through a series of operations is ± 1 ° C.
Next, while maintaining the column temperature at T (A3), 800 mL of o-dichlorobenzene of T (A3) is allowed to flow at a flow rate of 20 mL / min, so that components soluble in T (A3) existing in the column can be obtained. Elute and collect.
Next, the column temperature was increased to 140 ° C. at a rate of temperature increase of 10 ° C./min, left at 140 ° C. for 1 hour, and then 800 mL of 140 ° C. solvent o-dichlorobenzene was allowed to flow at a flow rate of 20 mL / min. Insoluble components are eluted with T (A3) and collected.
The solution containing the polymer obtained by fractionation is concentrated to 20 mL using an evaporator and then precipitated in 5 times the amount of methanol. The precipitated polymer is recovered by filtration and then dried overnight in a vacuum dryer.

iii) Measurement of ethylene content by ¹³ C-NMR The ethylene content of each of the components (A1) and (A2) obtained by the above fractionation was measured by the proton complete decoupling method according to the following conditions: ¹³ C-NMR Obtained by analyzing the spectrum.
Model: GSX-400 manufactured by JEOL Ltd. or equivalent device (carbon nuclear resonance frequency of 100 MHz or more)
Solvent: o-dichlorobenzene / heavy benzene = 4/1 (volume ratio)
Concentration: 100 mg / mL
Temperature: 130 ° C
Pulse angle: 90 °
Pulse interval: 15 seconds Integration number: 5,000 times or more The attribution of the spectrum may be performed with reference to, for example, Macromolecules 17 1950 (1984). The attribution of spectra measured under the above conditions is as shown in the table below. Symbols such as S _{αα in the} table follow the notation of Carman et al. (Macromolecules 10 536 (1977)), P represents a methyl carbon, S represents a methylene carbon, and T represents a methine carbon.

Hereinafter, when “P” is a propylene unit in a copolymer chain and “E” is an ethylene unit, six types of triads of PPP, PPE, EPE, PEP, PEE and EEE may exist in the chain. As described in Macromolecules 15 1150 (1982) and the like, the concentration of these triads and the peak intensity of the spectrum are linked by the following relational expressions (1) to (6).
[PPP] = k × I (T _ββ ) (1)
[PPE] = k × I (T _βδ ) (2)
[EPE] = k × I (T _δδ ) (3)
[PEP] = k × I (S _ββ ) (4)
[PEE] = k × I (S _βδ ) (5)
[EEE] = k × {I (S _δδ ) / 2 + I (S _γδ ) / 4} (6)
Here, [] indicates the fraction of triads, for example, [PPP] is the fraction of PPP triads in all triads.
Therefore,
[PPP] + [PPE] + [EPE] + [PEP] + [PEE] + [EEE] = 1 (7)
It is. Further, k is a constant, I indicates the spectral intensity, and for example, I (T _ββ ) means the intensity of the peak at 28.7 ppm attributed to T _ββ .
By using the relational expressions (1) to (7) above, the fraction of each triad is obtained, and the ethylene content is obtained from the following expression.
Ethylene content (mol%) = ([PEP] + [PEE] + [EEE]) × 100
In addition, the propylene random copolymer of the present invention contains a small amount of a propylene hetero bond (2,1-bond and / or 1,3-bond), thereby producing the following minute peak.

In order to obtain an accurate ethylene content, it is necessary to include these peaks derived from heterogeneous bonds in the calculation, but it is difficult to completely separate and identify the peaks derived from heterogeneous bonds, and the amount of heterogeneous bonds is small. Therefore, the ethylene content of the present invention is obtained by using the relational expressions (1) to (7) as in the analysis of the copolymer produced with a Ziegler-Natta catalyst that does not substantially contain a heterogeneous bond. I will do it.
Conversion from mol% to wt% of ethylene content is performed using the following formula.
Ethylene content (% by weight) = (28 × X / 100) / {28 × X / 100 + 42 × (1-x / 100)} × 100 where X is the ethylene content in mol%.
Further, the ethylene content E (W) of the entire block copolymer is calculated from the ethylene contents E (A1), E (A2) and TREF of the components (A1) and (A2) measured above. The weight ratio W (A1) and W (A2) wt% is calculated by the following formula.
E (W) = {E (A1) × W (A1) + E (A2) × W (A2)} / 100 (wt%)

(2-3) Specification by Solid Viscoelasticity Measurement (DMA) The block copolymer (A) in the present invention is composed of two components (A1) and (A2) having different crystallinity clarified by the TREF specification. The
At this time, a general block copolymer has a phase separation structure in which both components are divided into a matrix and a domain, and a large difference in refractive index between the matrix and the domain causes a remarkable deterioration in transparency and gloss.
Therefore, as the block copolymer component used in the present invention, it is necessary to control the composition of the components (A1) and (A2) within a range in which the transparency does not deteriorate, in order to avoid a decrease in transparency. It should be a block copolymer with a single phase that does not take a phase separation structure, which can be specified by solid viscoelasticity measurements.

(A) Definition by peak of tan δ curve In the present invention, in the temperature-loss tangent (tan δ) curve obtained by solid viscoelasticity measurement (DMA) in order to obtain excellent transparency in the surface layer of the laminated structure, tan δ It is necessary for the curve to have a single peak below 0 ° C.
When the component (A) has a phase separation structure, the glass transition temperature of the amorphous part contained in the component (A1) and the glass transition temperature of the amorphous part contained in the component (A2) are different from each other. Multiple. In this case, there arises a problem that transparency and gloss are remarkably deteriorated, and when a propylene-ethylene random copolymer having a plurality of peaks of tan δ by using a phase separation structure is used, Even when a laminate with the ethylene-containing resin (B) is used, remarkable transparency and glossiness are deteriorated, and high transparency and glossiness which are one object of the present invention cannot be exhibited.
Whether or not the phase separation structure is taken can be determined in the tan δ curve in the measurement of solid viscoelasticity, and the avoidance of the phase separation structure that affects the transparency of the molded product has a single peak in the tan δ curve below 0 ° C. Is brought about by having.
Therefore, since the propylene-ethylene random block copolymer (A) used for the polyolefin-based multilayer film or multilayer sheet of the present invention exhibits high transparency and gloss, it has a single tan δ curve in solid viscoelasticity measurement. It is necessary to have a peak.
An example of the peak of the tan δ curve is shown in FIGS. 2 and 3 as an example in Production Examples PP-1 (Example 1) and PP-4 (Comparative Example 3) in Examples described later.

(B) Measurement method The solid viscoelasticity measurement is specifically performed by applying a sinusoidal strain of a specific frequency to a strip-shaped sample piece and detecting the generated stress. Here, the frequency is 1 Hz and the measurement temperature is raised stepwise from −60 ° C. until the sample is melted and cannot be measured. Further, it is recommended that the magnitude of distortion is about 0.1 to 0.5%. From the obtained stress, the storage elastic modulus and the loss elastic modulus are obtained by a known method, and the loss tangent (= loss elastic modulus G ″ / storage elastic modulus G ′) defined by the ratio is plotted against the temperature. Then, a sharp peak is shown in a temperature range of 0 ° C. or lower. In general, the peak of the tan δ curve at 0 ° C. or lower observes the glass transition of the amorphous part, and this peak temperature is defined as the glass transition temperature Tg (° C.).

(2-4) Additional regulations concerning the molecular weight of the propylene-ethylene random block copolymer (A) (a) Regulation of the molecular weight The block copolymer component (A) in the present invention additionally has a low molecular weight component. Features.
It is considered that a low molecular weight component, particularly a component whose molecular weight is less than the molecular weight between the entanglement points, bleeds out to the surface of the molded article, and deteriorates stickiness and transparency. In addition, this component is also considered to reduce the strength of the interface at the time of lamination and to easily cause peeling.
The molecular weight between the entanglement points of polypropylene is about 5,000 as described in Journal of Polymer Science: Part B: Polymer Physics; 37 1023-1103 (1999).
Therefore, the block copolymer in the present invention has a low low molecular weight component, and the amount of the component having a weight average molecular weight of 5,000 or less is 0.8 wt% or less, preferably 0.5 wt% or less. Features.
The lower limit of the weight average molecular weight is in the range where the component of Mw ≦ 5,000 does not exceed 0.8 wt%. If the molecular weight is too low, a problem of moldability and a decrease in strength occur. It is preferable to be in the range. The upper limit is 400,000, and if this is exceeded, the moldability and the like are reduced.

(B) Molecular weight measurement In this invention, a weight average molecular weight (Mw) and a number average molecular weight (Mn) say what was measured by the gel permeation chromatography (GPC) method.
Conversion from the retention volume to the molecular weight is performed using a calibration curve prepared in advance with standard polystyrene.
Standard polystyrenes used are the following brands manufactured by Tosoh Corporation.
F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000
A calibration curve is created by injecting 0.2 mL of a solution dissolved in o-dichlorobenzene (containing 0.5 mg / mL BHT) so that each is 0.5 mg / mL.
The calibration curve uses a cubic equation obtained by approximation by the least square method. The following numerical values are used in the viscosity equation [η] = K × M ^α used for conversion to molecular weight.
PS: K = 1.38 × 10 ⁻⁴ α = 0.7
PP: K = 1.03 × 10 ⁻⁴ α = 0.78
The measurement conditions for GPC are as follows.
Equipment: GPC (ALC / GPC 150C) manufactured by WATERS
Detector: MIRAN 1A IR detector manufactured by FOXBORO (measurement wavelength: 3.4)
2μm)
Column: AD806M / S (3 pieces) manufactured by Showa Denko KK
Mobile phase solvent: o-dichlorobenzene Measurement temperature: 140 ° C.
Flow rate: 1.0 ml / min Injection volume: 0.2 ml
Sample Preparation Prepare a 1 mg / mL solution using o-dichlorobenzene (containing 0.5 mg / mL BHT) and dissolve it at 140 ° C. for about 1 hour.
The amount of the component having a molecular weight of 5,000 or less can also be determined from a plot of the elution ratio with respect to the molecular weight obtained by GPC measurement.

(2-5) Additional regulations on intrinsic viscosity [η] cxs of 23 ° C. xylene solubles In block copolymer (A), stickiness and bleed-out are particularly problematic because it is soluble in xylene at room temperature. Therefore, the intrinsic viscosity [η] (dl / g) is preferably measured for the CXS component.
Here, the CXS component is prepared by dissolving the block copolymer in p-xylene at 130 ° C. to form a solution, and then leaving it at 25 ° C. for 12 hours, filtering the precipitated polymer, and evaporating p-xylene from the filtrate. The intrinsic viscosity [η] cxs of the obtained CXS component can be measured using Decalin as a solvent at a temperature of 135 ° C. using an Ubbelohde viscometer.
At this time, since the block copolymer (A) in the present invention does not increase the generation of a component having a molecular weight of 5,000 or less that tends to bleed out, the conventional Ziegler-Natta catalyst has problems in production. Even if the intrinsic viscosity [η] cxs of the CXS component, which has a practical problem due to deterioration such as blocking, is in the region of 2 or less, it can be produced and used without causing any particular deterioration in physical properties.
Such a block copolymer that does not increase the component having a molecular weight of 5,000 or less while reducing the intrinsic viscosity of the CXS component has characteristics in terms of physical properties such as high tensile elongation at break and high tensile strength at break. And the appearance of a molded product called fisheye is less likely to be defective.

3. Propylene-Ethylene Random Block Polymer Component (A) Production Method The propylene-ethylene random block copolymer (A) used in the present invention is composed of two types of components having large crystallinity as clearly shown in the TREF elution curve. Although any production method may be used as long as it comprises (A1) and component (A2) and satisfies the above-mentioned regulations, it is preferable to sequentially polymerize each component during the production.

(3-1) Polymerization Catalyst Regarding the production of the propylene-ethylene random block copolymer (A) used in the present invention, the polymerization method using a Ziegler-Natta catalyst widely used in the past has a wide crystallinity distribution, As a catalyst, it is difficult to produce a propylene-ethylene random copolymer that does not contain a highly crystalline component, and even if it can be produced, the formation of a low crystalline low molecular weight component leads to deterioration of stickiness and bleedout. It is preferable to use a metallocene catalyst.

Laminate materials using a propylene-ethylene random copolymer produced using a metallocene-based catalyst for the surface layer are known in the past, but propylene-ethylene produced using a conventional ordinary metallocene-based catalyst. Since the random copolymer has a narrow crystallinity distribution, the entire crystallinity must be increased to some extent in order to maintain heat resistance and not deteriorate the blocking. As a result, in the fusion process using a high frequency welder, a larger amount of heat is required, so that a longer time is required for molding, resulting in poor productivity.
On the other hand, the propylene-ethylene random block copolymer (A) used in the present invention is a component in which a TREF elution peak T (A2) is observed at 50 ° C. or lower, as is clear from the definition by the TREF elution curve, or The block T (A2) is not observed (if the peak is not observed, the component (A2) is eluted in the solvent and the concentration is observed at −15 ° C., which is the lower limit of the measurement temperature). (A) The crystallinity of the whole is lowered, and the suitability of the high frequency welder is remarkably improved while maintaining the heat resistance, so that the fusion can be performed with a smaller amount of heat in a short time.

In order to produce two kinds of components having different crystallinity defined by the TREF elution behavior, specifically, propylene-ethylene random copolymer containing about 1 to 7 wt% of ethylene in the first step. It is preferable to carry out sequential multi-stage polymerization of 30 to 70 wt% of the combined polymer and 70 to 30 wt% of propylene-ethylene random copolymer containing about 6 to 12 wt% more ethylene than the first process in the second step.
That is, the heat resistance is maintained by the component having a relatively small ethylene content produced in the first step, and the stickiness is also suppressed, but the component containing a relatively large amount of ethylene produced in the second step is By reducing the overall crystallinity with a low crystalline or amorphous component, suitability for high frequency welder can be improved.
Here, it is important that the block copolymer (A) does not contain a highly crystalline component, and the components (A1) and (A2) are specific crystalline or amorphous and each component is a phase. In order to control as much as possible within the melting range, it is required that the obtained polymer has a narrow crystallinity distribution and less stickiness and bleedout deterioration even in a low crystallinity region. 30 to 70 wt% of propylene-ethylene random copolymer containing 1 to 7 wt% ethylene as component (A1) in the first step, and propylene containing 6 to 12 wt% more ethylene than the first step in the second step Most preferably, 70-30 wt% of the ethylene random copolymer is sequentially polymerized.

(3-2) Comonomer In order to reduce the crystallinity of the polypropylene-based resin, techniques such as lowering regularity, increasing heterogeneous insertion, and copolymerizing various copolymers are used. Copolymerizing the copolymer is most easily controlled and is most preferred when it is necessary to have a specified crystalline distribution as in the present invention.
As the type of copolymer, various α-olefins are widely used, but it is optimal to use ethylene which is inexpensive and particularly capable of producing a copolymer having excellent cold resistance and flexibility. At this time, the amount of ethylene to be copolymerized is preferably 1 to 7 wt% so that the component (A1) exhibits a predetermined TREF elution behavior, and the component (A2) exhibits a predetermined TREF behavior. And in order to make the range compatible with a component (A1), it is preferable to contain 6-12 wt% ethylene much with respect to a component (A1).

(3-3) Metallocene catalyst
In producing the propylene-ethylene random block copolymer (A) of the present invention, a metallocene catalyst is preferably used as described above.
Although it is well known to those skilled in the art that the propylene-ethylene random block copolymer has a wide molecular weight and crystallinity distribution, the stickiness and bleedout are deteriorated. However, in the block copolymer (A) used in the present invention, However, in order to suppress stickiness and bleed out, it is necessary to polymerize using a metallocene catalyst capable of narrowing the molecular weight and crystallinity distribution. In the Ziegler-Natta catalyst, the excellent propylene-ethylene of the present invention is used. It is very difficult to obtain a random block copolymer (A).

The type of the metallocene-based catalyst is not particularly limited as long as the copolymer having the performance of the present invention can be produced. However, in order to satisfy the requirements of the present invention, for example, the following components ( It is preferable to use a metallocene catalyst comprising a) and (b) and, if necessary, the component (c) used.
Component (a): At least one metallocene transition metal compound selected from transition metal compounds represented by formula (1) Component (b): At least one selected from the following (b-1) to (b-4) Solid component of seed (b-1) Fine particle carrier on which organoaluminum compound is supported (b-2) An ionic compound capable of reacting with component (A) to convert component (A) into a cation or Fine carrier on which Lewis acid is supported (b-3) Solid acid fine particle (b-4) Ion exchange layered silicate Component (c): Organoaluminum compound

(I) Component (a)
As the component (a), at least one metallocene transition metal compound selected from transition metal compounds represented by the following general formula (1) can be used.
^{_{Q (C 5 H 4-a}} -aR 1) (C 5 H 4-b -bR 2) MeXY (1)
[Wherein Q represents a divalent linking group that bridges two conjugated five-membered ring ligands, Me represents a metal atom selected from titanium, zirconium, and hafnium, and X and Y represent hydrogen atoms. Atom, halogen atom, hydrocarbon group, alkoxy group, amino group, nitrogen-containing hydrocarbon group, phosphorus-containing hydrocarbon group or silicon-containing hydrocarbon group, X and Y are each independently, ie, the same or different. Also good. R ¹ and R ^{2 each} represent hydrogen, a hydrocarbon group, a halogenated hydrocarbon group, a silicon-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, an oxygen-containing hydrocarbon group, a boron-containing hydrocarbon group, or a phosphorus-containing hydrocarbon group. . a and b are the number of substituents. ]

Specifically, Q represents a divalent linking group that bridges two conjugated five-membered ring ligands. For example, a divalent hydrocarbon group, a silylene group, an oligosilylene group, or a hydrocarbon group as a substituent. Examples thereof include a silylene group or an oligosilylene group, or a germylene group having a hydrocarbon group as a substituent. Among these, preferred is a silylene group having a divalent hydrocarbon group and a hydrocarbon group as a substituent.
X and Y represent a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, an amino group, a nitrogen-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, or a silicon-containing hydrocarbon group. Among these, hydrogen is preferable , Chlorine, methyl, isobutyl, phenyl, dimethylamide, diethylamide and the like.
R ¹ and R ² represent hydrogen, a hydrocarbon group, a halogenated hydrocarbon group, a silicon-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, an oxygen-containing hydrocarbon group, a boron-containing hydrocarbon group, or a phosphorus-containing hydrocarbon group. . Specific examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a phenyl group, a naphthyl group, a butenyl group, and a butadienyl group. In addition, halogenated hydrocarbon group, silicon-containing hydrocarbon group, nitrogen-containing hydrocarbon group, oxygen-containing hydrocarbon group, boron-containing hydrocarbon group or phosphorus-containing hydrocarbon group include methoxy group, ethoxy group, phenoxy group, trimethylsilyl group. Typical examples include a group, a diethylamino group, a diphenylamino group, a pyrazolyl group, an indolyl group, a dimethylphosphino group, a diphenylphosphino group, a diphenylboron group, and a dimethoxyboron group. Among these, a hydrocarbon group having 1 to 20 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, and a butyl group are particularly preferable. By the way, adjacent R ¹ and R ² may combine to form a ring, on which a hydrocarbon group, halogenated hydrocarbon group, silicon-containing hydrocarbon group, nitrogen-containing hydrocarbon group, oxygen-containing You may have a substituent which consists of a hydrocarbon group, a boron containing hydrocarbon group, or a phosphorus containing hydrocarbon group.
Me is a metal atom selected from titanium, zirconium and hafnium, preferably zirconium and hafnium.

  Among the components (a) described above, preferred for the production of the propylene polymer of the present invention is a substituted cyclopentadienyl group crosslinked with a silylene group, a germylene group or an alkylene group having a hydrocarbon substituent. A transition metal compound comprising a ligand having a substituted indenyl group, a substituted fluorenyl group or a substituted azulenyl group, particularly preferably a 2,4-position crosslinked with a silylene group having a hydrocarbon substituent or a germylene group It is a transition metal compound comprising a ligand having a substituted indenyl group and a 2,4-position substituted azulenyl group.

Non-limiting specific examples include dimethylsilylene bis (2-methyl-4-phenylindenyl) zirconium dichloride, diphenylsilylene bis (2-methyl-4-phenylindenyl) zirconium dichloride, dimethylsilylene bis (2-methyl). Benzoindenyl) zirconium dichloride, dimethylsilylenebis {2-isopropyl-4- (3,5-diisopropylphenyl) indenyl} zirconium dichloride, dimethylsilylenebis (2-propyl-4-phenanthrylindenyl) zirconium dichloride, dimethyl Silylenebis (2-methyl-4-phenylazurenyl) zirconium dichloride, dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) azurenyl} zirconium dichloride, dimethylsilylenebi (2-Ethyl-4-phenylazurenyl) zirconium dichloride, dimethylsilylenebis (2-isopropyl-4-phenylazurenyl) zirconium dichloride, dimethylsilylenebis {2-ethyl-4- (2-fluorobiphenyl) azurenyl} zirconium Examples thereof include dichloride, dimethylsilylene bis {2-ethyl-4- (4-t-butyl-3-chlorophenyl) azurenyl} zirconium dichloride, and the like.
A compound in which the silylene group of the compound of these specific examples is replaced with a germylene group and zirconium is replaced with hafnium is also exemplified as a suitable compound. In addition, since the catalyst component is not an important element of the present invention, it avoids complicated listing and is limited to representative examples, but it is obvious that the effective range of the present invention is not limited thereby. That is.

(B) Component (b)
As the component (b), at least one solid component selected from the components (b-1) to (b-4) described above is used. Each of these components is known and can be used by appropriately selecting from known techniques. Specific examples and manufacturing methods thereof are described in detail in JP-A No. 2002-284808, JP-A No. 2002-53609, JP-A No. 2002-69116, JP-A No. 2003-105015, and the like.
Here, as the particulate carrier used for the component (b-1) and the component (b-2), inorganic oxides such as silica, alumina, magnesia, silica alumina, silica magnesia, magnesium chloride, magnesium oxychloride, chloride Examples thereof include inorganic halides such as aluminum and lanthanum chloride, and porous organic carriers such as polypropylene, polyethylene, polystyrene, styrene divinyl benzene copolymer, and acrylic acid copolymer.

As a non-limiting specific example of the component (b), as the component (b-1), a fine particle carrier on which methylalumoxane, isobutylalumoxane, methylisobutylalumoxane, aluminum butylboronate tetraisobutyl or the like is supported, As component (b-2), triphenylborane, tris (3,5-difluorophenyl) borane, tris (pentafluorophenyl) borane, triphenylcarbonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium Particulate carrier carrying tetrakis (pentafluorophenyl) borate, etc. as component (b-3), alumina, silica alumina, magnesium chloride, etc. as component (b-4), montmorillonite, zakonite, beidellite, non Tronite, Sa Knight, hectorite, stevensite, bentonite, smectite group such as taeniolite, vermiculite, and the like mica group. These may form a mixed layer.
Particularly preferred among the above components (b) is the ion-exchange layered silicate of component (b-4), and more preferred are chemical treatments such as acid treatment, alkali treatment, salt treatment, and organic matter treatment. It is an ion exchange layered silicate applied.

(C) Component (c)
Examples of organoaluminum compounds used as component (c) as needed are:
General formula AlR _a X _3-a
(Wherein R is a hydrocarbon group having 1 to 20 carbon atoms, X is hydrogen, halogen, alkoxy group, a is a number of 0 <a ≦ 3), trimethylaluminum, triethylaluminum, tripropylaluminum, Trialkylaluminum such as triisobutylaluminum or halogen- or alkoxy-containing alkylaluminum such as diethylaluminum monochloride, diethylaluminum monomethoxide. In addition, aluminoxanes such as methylaluminoxane can also be used. Of these, trialkylaluminum is particularly preferred.

(D) Formation of catalyst Component (a), component (b) and, if necessary, component (c) are brought into contact to form a catalyst. The contact method is not particularly limited, but the contact can be made in the following order. Moreover, this contact may be performed not only at the time of catalyst preparation but also at the time of prepolymerization with olefin or at the time of polymerization of olefin.
1) Contact component (a) and component (b) 2) Add component (c) after contacting component (a) and component (b) 3) Contact component (a) and component (c) 4) Add component (b) after contact 4) Contact component (b) and component (c), then add component (a) 5) Contact three components simultaneously.

The amount of components (a), (b) and (c) used in the present invention is arbitrary. For example, the amount of component (a) used relative to component (b) is preferably in the range of 0.1 μmol to 1,000 μmol, particularly preferably 0.5 μmol to 500 μmol, relative to 1 g of component (b). The amount of component (c) used relative to component (b) is preferably such that the amount of aluminum metal is 0.001 to 100 mmol, particularly preferably 0.005 to 50 mmol, relative to 1 g of component (b). Therefore, the amount of component (c) to component (a) is preferably in the range of 10 ⁻³ to 10 ⁶ , particularly preferably 10 ⁻² to 10 ⁵ , in terms of the molar ratio of the metal.

It is preferable that the catalyst of the present invention is subjected to a prepolymerization treatment comprising a small amount of polymerization by contacting an olefin in advance. The olefin to be used is not particularly limited, but ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, styrene and the like can be used. It is possible to use, and it is particularly preferable to use propylene. The olefin can be supplied by any method such as a supply method for maintaining the olefin at a constant speed or in a constant pressure state, a combination thereof, or a stepwise change. The prepolymerization temperature and time are not particularly limited, but are preferably in the range of −20 ° C. to 100 ° C. and 5 minutes to 24 hours, respectively. The amount of prepolymerization is preferably 0.01 to 100, more preferably 0.1 to 50 with respect to the component (b). After completion of the prepolymerization, the catalyst can be used as it is depending on the usage form of the catalyst, but may be dried if necessary.
Furthermore, a polymer such as polyethylene, polypropylene, or polystyrene, or an inorganic oxide solid such as silica or titania can be allowed to coexist during or after the contact of the above components.

(3-4) Polymerization Method (a) Sequential Polymerization When the block copolymer (A) of the present invention is produced, the crystalline propylene-ethylene random copolymer component (A1) and a low crystalline or amorphous property are used. It is necessary to sequentially polymerize (multistage polymerization) the propylene-ethylene random copolymer component (A2).
When the resin used for the surface layer is a random copolymer obtained by simply copolymerizing ethylene with propylene, if the ethylene content is low, flexibility and transparency are not sufficient, and furthermore, high frequency welder suitability is poor, Increasing the ethylene content to improve transparency deteriorates the heat resistance, and it is difficult to satisfy all of these simultaneously.
Therefore, in the present invention, the block copolymer (A) is a block copolymer obtained by sequentially polymerizing components having different ethylene contents in the first step and the second step. Required to balance all of the welder suitability.
Further, in the present invention, a copolymer having a low molecular weight and being easily sticky by itself may be used as the component (A2). Therefore, in order to prevent problems such as adhesion to the reactor, the component (A1) is polymerized. It is necessary to use a method of polymerizing component (A2).
When performing sequential polymerization, either a batch method or a continuous method can be used, but it is generally desirable to use a continuous method from the viewpoint of productivity.
In the case of a batch method, it is possible to polymerize component (A1) and component (A2) separately using a single reactor by changing the polymerization conditions with time. As long as the effects of the present invention are not impaired, a plurality of reactors may be connected in parallel.
In the case of the continuous method, it is necessary to use a production facility in which two or more reactors are connected in series because it is necessary to individually polymerize the component (A1) and the component (A2), but as long as the effect of the present invention is not impaired. A plurality of reactors may be connected in series and / or in parallel for each of component (A1) and component (A2).

(B) Polymerization process As the polymerization process (polymerization method), any polymerization method such as a slurry method, a bulk method, or a gas phase method can be used. Although it is possible to use supercritical conditions as intermediate conditions between the bulk method and the gas phase method, they are substantially the same as the gas phase method, and are therefore included in the gas phase method without any particular distinction.
Since the low crystalline or amorphous propylene-ethylene random copolymer component (A2) is easily soluble in organic solvents such as hydrocarbons and liquefied propylene, it is desirable to use a gas phase method for the production of the component (A2).
There is no particular problem in using any process for the production of the crystalline copolymer component (A1). It is desirable to use a gas phase method to avoid it.
Therefore, using a continuous method, the crystalline propylene-ethylene random copolymer component (A1) is first polymerized by the bulk method or the gas phase method, and then the low crystalline or amorphous propylene-ethylene random copolymer component. It is most desirable to polymerize (A2) by a gas phase method.

(C) Other polymerization conditions The polymerization temperature can be used without any particular problem as long as it is within a commonly used temperature range. Specifically, a range of 0 ° C. to 200 ° C., more preferably 40 ° C. to 100 ° C. can be used.
Although the polymerization pressure varies depending on the process to be selected, it can be used without any problem as long as it is in a pressure range usually used. Specifically, a range of greater than 0 to 200 MPa, more preferably 0.1 MPa to 50 MPa can be used. At this time, an inert gas such as nitrogen can be coexisted.
When the sequential polymerization of the component (A1) in the first step and the component (A2) in the second step is performed, it is desirable to add a polymerization inhibitor into the system in the second step. In the case of producing a propylene-ethylene block copolymer, if a polymerization inhibitor is added to a reactor that performs ethylene-propylene random copolymerization in the second step, the particle properties (fluidity, etc.) of the resulting powder, gel, etc. Product quality can be improved. Various technical studies have been made on this technique, and examples thereof include Japanese Patent Publication Nos. 63-54296, 7-25960, and 2003-2939. It is desirable to apply the method to the present invention.

4). Method for controlling component of component (A) Each component of propylene-ethylene block copolymer (A) used in the polyolefin-based multilayer film or multilayer sheet of the present invention is controlled as follows, and the block copolymer of the present invention It can manufacture so that the structural requirements required for unification | combination (A) may be satisfied.
(4-1) Component (A1) For the crystalline propylene-ethylene random copolymer component (A1), it is necessary to control the ethylene content E (A1) and the peak temperature T (A1).
In the present invention, T (A1) is preferably controlled by the ethylene content E (A1) contained in component (A1). Here, in order to control E (A1) within a predetermined range, the amount ratio of propylene and ethylene supplied to the polymerization tank in the first step may be appropriately adjusted. Although the relationship between the supply ratio and the ethylene content in the resulting propylene-ethylene random copolymer varies depending on the type of metallocene catalyst used, the component (A1) having E (A1) required by adjusting the supply ratio is produced. can do. At this time, the ethylene content E (A1) in the component (A1) is preferably such that E (A1) is in the range of 1 to 7 wt%, and in this case, the supply weight ratio of ethylene to propylene is in the range of 0 to 0.3, A range of 0.01 to 0.2 is preferable.
At this time, the component (A1) has a narrow crystallinity distribution, and T (A1) decreases as E (A1) increases. Therefore, in order for T (A1) to satisfy the scope of the present invention, E (A1) and the relationship between these are grasped and adjusted so as to have a target range.

(4-2) Component (A2) For the low crystalline or amorphous propylene-ethylene random copolymer component (A2), it is necessary to control E (A2) and T (A2), and T (A2 ) Must be controlled within the range compatible with component (A1) while lowering to 50 ° C. or lower, and it is desirable to additionally control [η] cxs. (Note that [η] cxs control is described in paragraph 0073.)
In the present invention, the component (A2) is preferably a propylene-ethylene random copolymer containing about 6 to 12 wt% ethylene more than the ethylene content in the component (A1), and the ethylene content in the component (A2) In order to control E (A2) within a predetermined range, the ratio of ethylene supply to propylene in the second process may be controlled in the same manner as in the first process. May be in the range of -5, preferably in the range of 0.05-2.
At this time, although the crystallinity distribution of the component (A2) is slightly increased with the increase of the ethylene content, T (A2) is decreased with the increase of E (A2) like the component (A1). Therefore, in order to satisfy T (A2) within the scope of the present invention, the relationship between E (A2) and T (A2) is grasped, and E (A2) is controlled to be within a predetermined range. That's fine.

(4-3) About W (A1) and W (A2) The amount W (A1) of the component (A1) and the amount W (A2) of the component (A2) are produced in the first step of producing the component (A1). It can be controlled by changing the ratio between the amount and the production amount of component (A2). For example, in order to increase W (A1) and decrease W (A2), the production amount of the second step may be reduced while maintaining the production amount of the first step, which shortens the residence time of the second step. It can be easily controlled by lowering the polymerization temperature or increasing the amount of the polymerization inhibitor. The reverse is also true.
When actually setting the conditions, it is necessary to consider the activity decay. That is, in the range of the ethylene content E (A1) and E (A2) carried out in the present invention, generally, the polymerization activity increases when the ratio of ethylene supply to propylene is increased in order to increase the ethylene content. The activity decay tends to increase. Therefore, in order to maintain the activity of the second step, it is necessary to suppress the polymerization activity of the first step. Specifically, in the first step, the ethylene content E (A1) is lowered and the production amount W (A1) is reduced. ), And if necessary, lower the polymerization temperature and / or shorten the polymerization time (residence time), or increase the ethylene content E (A2) in the second step and increase the production W (A2). If necessary, the conditions may be set by a method that raises the polymerization temperature and / or lengthens the polymerization time (residence time).

(4-4) Glass Transition Temperature Tg In the propylene-ethylene random block copolymer (A) of the present invention, the glass transition temperature Tg described in paragraph 0040 needs to have a single peak. In the propylene-ethylene random copolymer recommended for the components (A1) and (A2) of the present invention, the compatibility decreases when the difference in ethylene content between the two increases, so that Tg has a single peak. [E] gap (= E (A2) −E (A1)) of 12 wt. Of the difference between the ethylene content E (A1) in the component (A1) and the ethylene content E (A2) in the component (A2) %, And E (gap) may be reduced to a range where Tg becomes a single peak in actual measurement.
Depending on the ethylene content E (A1) of the crystalline copolymer component (A1), the ethylene content E (A2) of the low crystalline or non-crystalline copolymer component (A2) is within an appropriate range. By setting the supply weight ratio of ethylene to propylene during the polymerization of component (A2), it is possible to obtain a polymer having a predetermined [E] gap.

The Tg of the block copolymer that does not take a phase separation structure as in the present invention is the ethylene content E (A1) in the component (A1), the ethylene content E (A2) in the component (A2), and It is affected by the ratio of both components. In the present invention, the amount of the component (A2) is 30 to 70 wt%, but in this range, Tg is more strongly affected by the ethylene content E (A2) in the component (A2).
That is, Tg reflects the glass transition of the amorphous part, whereas in the block copolymer component (A) of the present invention, the component (A1) has crystallinity and relatively few amorphous parts. This is because the component (A2) is low crystalline or amorphous and most of it is an amorphous part.
Therefore, the value of Tg is controlled approximately by E (A2), and the control method for E (A2) is as described above in paragraph 0065.

(4-5) Molecular weight Mw In the propylene-ethylene random block copolymer (A) of the present invention, in order to maintain transparency, the crystalline copolymer component (A1) and a low crystalline or amorphous material are used. Since the compatibility of the copolymer elastomer component (A2) is increased to some extent, the viscosity [η] A1 of the component (A1), the viscosity [η] A2 of the component (A2), a propylene-ethylene random block copolymer (A) The apparent viscosity mixing rule generally holds between the overall viscosity [η] W. That is,
Log [η] W = {W (A1) × Log [η] A1 + W (A2) × Log [η] A2} / 100
Is generally established. In general, there is a certain correlation between Mw and [η], so from the viewpoint of flexibility and heat resistance, [η] A2, W (A1), and W (A2) are set first. Mw can be controlled freely by changing [η] A1 according to the above equation.

(4-6) Temperature T (A4) T (A4) is an index of crystallinity distribution indicating how far the crystallinity of component (A1) extends to the high crystal side. The narrower the crystalline distribution of the component (A1), the closer (lower) T (A4) is to T (A1). Therefore, T (A4) can be controlled within the scope of the present invention by controlling T (A1) by ethylene content E (A1) to narrow the crystallinity distribution of component (A1).

In general, a polymer having a narrower crystallinity distribution can be obtained by using a metallocene catalyst than by using a Ziegler-Natta catalyst. In order to obtain a propylene-ethylene random copolymer, it is necessary that the ratio of ethylene and propylene does not change during production and is uniform in the polymerization system.
In order to adjust the final propylene-ethylene random block copolymer (A) to those having desirable physical properties, the component (A1) and the component (A2) need to have different specific polymer compositions. . That is, in the first step and the second step, it is necessary to keep the polymerization conditions corresponding to the respective polymer compositions, particularly the monomer gas composition, at different specific values. Therefore, when the crystallinity distribution of the component (A2) is wide in the adopted process, the transfer step is adjusted so that the specific monomer gas mixture corresponding to the first step is not brought into the second step from the first step. It is necessary to devise such as. Specifically, the crystallinity distribution of the component (A2) can be narrowed by increasing the purge amount in the transfer step, or by diluting or substituting with an inert gas such as nitrogen.

(4-7) About W (Mw ≦ 5,000) A method for controlling W (Mw ≦ 5,000) to be small is also possible by using the same method as described above for narrowing the crystallinity distribution.
In general, by using a metallocene catalyst, a polymer having a narrower molecular weight distribution than that of a Ziegler-Natta catalyst can be obtained. However, in a system that performs sequential polymerization as in the present invention, it is not always sufficient to use a metallocene catalyst in order to narrow the molecular weight distribution. In particular, in order to prevent the formation of low molecular weight components, the time for transferring from the first step to the second step can be shortened, or the monomer gas mixture corresponding to the first step can be replaced with an inert gas such as nitrogen in the transfer step. By completely replacing it, W (Mw ≦ 5,000) can be controlled to be small independently of the polymerization conditions.

(4-8) Intrinsic Viscosity For [η] cxs, since the block copolymer (A) of the present invention uses a metallocene catalyst and the component (A1) contains almost no CXS component, the component (A2 ) Can be controlled by changing the molecular weight.
In order to control [η] cxs, the ratio of hydrogen supply to the monomer in the second step may be controlled as usual. In general, a metallocene catalyst tends to have a lower molecular weight of the polymer as the polymerization temperature is higher. Therefore, [η] cxs can be controlled by changing the polymerization temperature. [Η] cxs can also be controlled by combining both the hydrogen supply ratio and the polymerization temperature.

5. Polar group-containing ethylene resin (B)
The polar group-containing ethylene-based resin (B) that forms the base material layer of the laminated material in the present invention is a component for imparting high-frequency welder suitability to the polyolefin-based multilayer film or multilayer sheet of the present invention. Must be contained, and the bondability with the copolymer (A) layer should also be high.
When laminated with the propylene-ethylene random block copolymer (A), high-frequency welder processability is high, and peeling does not occur at the interface of each layer. Therefore, an ethylene-vinyl acetate copolymer having a vinyl acetate content of 15 wt% or more is used. The coalescence is preferable, and at this time, an additional effect of improving cold resistance, tearing property, heat retention and the like is also brought about.

Typical resins containing polar groups include ethylene-vinyl acetate copolymer (EVA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-methyl acrylate copolymer (EMA), and ethylene-acrylic. Examples include polar group-containing ethylene resins such as acid ethyl copolymer (EEA).
Among such polar group-containing ethylene-based resins, ethylene-vinyl acetate copolymer (EVA), which is the most widely used, inexpensive, easily available, and capable of various selection, has transparency and flexibility. It is most preferable because it is high and has excellent adhesion to the propylene-ethylene random block copolymer (A).

(5-1) Regulation concerning the content of polar groups If the amount of polar groups contained in the polar group-containing ethylene-based resin (B) is too small, sufficient heat generation cannot be obtained in the high-frequency welder and fusion cannot be performed. In order to fully exhibit the suitability, it is desirable to select a polar group content of 10 wt% or more. If the content of the polar group is excessively large, the secondary processability is deteriorated and the generation of bad odor becomes remarkable, so the most preferable is 15 to 30 wt%.

(5-2) Melt Flow Rate MFR A known multilayer molding technique can be widely used for molding a laminated sheet. At this time, the viscosity of the polar group-containing ethylene resin (B) is propylene-ethylene random block copolymer. If the viscosity of the coalescence (A) is greatly different, the thickness of each layer is not uniform due to the difference in fluidity, resulting in problems such as roughening at the interface and poor appearance, and unstable molding. The melt flow rate which is an index of the property is preferably in the range of 0.1 to 100 g / 10 min (190 ° C. 2.16 kg load), and most preferably in the range of 1 to 20 g / 10 min.
The ethylene-vinyl acetate copolymer (B) satisfying such requirements can be appropriately selected from commercially available ones. As a commercial item, Nippon Polyethylene Co., Ltd. Novatec EVA etc. are mentioned.

6). Layer structure of multilayer film or multilayer sheet The polyolefin-based multilayer film or multilayer sheet of the present invention comprises a surface layer (or both surface layers) made of a propylene-ethylene random block copolymer (A) and a polar group-containing ethylene resin ( It is comprised from the base material layer (or intermediate | middle layer etc.) which consists of B).
It is preferable that the thickness of the surface layer subjected to high-frequency welding is 20% or less or 70 μm or less with respect to the thickness of the entire multilayer sheet. High frequency welder suitability is imparted by heat generation by polar groups of the polar group-containing ethylene-based resin (B). At this time, if the ratio of the base material layer or the intermediate layer in the total thickness is small, the calorific value generated in the polar group-containing ethylene resin (B) is the melting of the propylene-ethylene random block copolymer (A) in the surface layer. Therefore, it is preferable that the ratio of the surface layer to be welded is 20% or less because the productivity of the high-frequency fusion processing and molding becomes too small compared with the amount of heat required for the heat treatment. On the other hand, when the entire thickness is thick, even if the proportion of the surface layer is 20% or less, it takes a long time for heat generation from the intermediate layer to be transmitted to the surface due to the increase in the surface layer thickness. Since the productivity at the time of fusion decreases, the thickness of the surface layer is preferably 70 μm or less, and more preferably 50 μm or less.

7). Additional ingredients (additives)
In the propylene-ethylene block copolymer (A) and the polar group-containing ethylene-based resin (B) of the present invention, in order to enhance properties such as transparency or add other properties such as oxidation resistance. Each of the additional components may be added as an optional component within a range that does not significantly impair the effects of the present invention.
As this additional component, a nucleating agent, an antioxidant, a neutralizing agent, a light stabilizer, an ultraviolet absorber, a lubricant, an antistatic agent, a metal deactivator, a surfactant, which are conventionally used as polyolefin resin compounding agents are used. Various additives such as oxides, fillers, antibacterial and antifungal agents, and fluorescent brighteners can be used.
The amount of these additives is generally 0.0001 to 3% by weight, preferably 0.001 to 1% by weight.

(7-1) Specific examples of additives Specific examples of the nucleating agent include sodium 2,2-methylene-bis (4,6-di-t-butylphenyl) phosphate, talc, 1,3,2,4- Sorbitol compounds such as di (p-methylbenzylidene) sorbitol, aluminum hydroxy-di (t-butyl) benzoate, 2,2-methylene-bis (4,6-di-t-butylphenyl) phosphoric acid and 8 carbon atoms To 20 aliphatic monocarboxylic acid lithium salt mixtures (trade name NA21 manufactured by Asahi Denka Co., Ltd.).

Examples of the antioxidant include tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 1,1,3-tris (2-methyl-), as specific examples of phenolic antioxidants. 4-hydroxy-5-t-butylphenyl) butane, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, pentaerythrityl-tetrakis {3- (3,5-di- t-butyl-4-hydroxyphenyl) propionate}, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspir [5,5] undecane, etc. 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid.
Specific examples of phosphoric antioxidants include tris (mixed, mono and dinonylphenyl phosphite), tris (2,4-di-t-butylphenyl) phosphite, 4,4′-butylidenebis (3-methyl). -6-tert-butylphenyl-di-tridecyl) phosphite, 1,1,3-tris (2-methyl-4-di-tridecylphosphite-5-tert-butylphenyl) butane, bis (2,4 -Di-t-butylphenyl) pentaerythritol-di-phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-t- Butyl-5-methylphenyl) -4,4'-biphenylenediphosphonite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phos Or the like can be mentioned a fight.
Specific examples of the sulfur-based antioxidant include di-stearyl-thio-di-propionate, di-myristyl-thio-di-propionate, pentaerythritol-tetrakis- (3-lauryl-thio-propionate), and the like. .

Furthermore, specific examples of the neutralizing agent include calcium stearate, zinc stearate, hydrotalcite, and Mizukarak (manufactured by Mizusawa Chemical Co., Ltd.).
Specific examples of hindered amine stabilizers include polycondensates of dimethyl oxalate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine, tetrakis (1,2 , 2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, N, N- Bis (3-aminopropyl) ethylenediamine · 2,4-bis {N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino} -6-chloro-1,3,5 -Triazine condensate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5- Triazine , 4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {2,2,6,6-tetramethyl-4-piperidyl} imino], poly [(6- Morpholino-s-triazine-2,4-diyl) {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) Imino}] and the like.
Specific examples of the lubricant include oleic acid amide, stearic acid amide, behenic acid amide, higher fatty acid amides such as ethylene bis stearoid, silicone oil, higher fatty acid esters and the like.
Examples of the antistatic agent include higher fatty acid glycerin ester, alkyl diethanolamine, alkyl diethanolamide, alkyl diethanolamide fatty acid monoester and the like.

(7-2) Addition method These additional components can be directly added to each component of the present invention obtained by polymerization and used after melt-kneading or can be added during melt-kneading. Good. Furthermore, it can be added directly after melt-kneading, or can be added as a master batch within a range that does not significantly impair the effects of the present invention. Moreover, you may add by these composite methods.
In general, additives such as an antioxidant and a neutralizing agent are blended, mixed, melted and kneaded, and then molded into a product for use. It is also possible to add and use other resins or other additional components (including a masterbatch) as long as the effects of the present invention are not significantly impaired during molding.
For mixing, melting, and kneading, any conventionally known method can be used. Usually, a Henschel mixer, a super mixer, a V blender, a tumbler mixer, a ribbon blender, a Banbury mixer, a kneader blender, a single or twin screw kneading extruder. Can be implemented. Among these, it is preferable to perform mixing or melt-kneading with a uniaxial or biaxial kneading extruder.

8). Forming Method and Use of the Present Invention (8-1) Forming Method As the forming method of the multilayer film or multilayer sheet of the present invention, a known forming method capable of producing a laminated sheet can be used without limitation.
Specific examples include air-cooled inflation molding using a multilayer die, water-cooled inflation molding, sheet molding using a T-die, non-stretch molding, uniaxial stretching molding, biaxial stretching molding, and calendar molding.
Here, the co-extrusion lamination method is suitable, and it is also possible to form only the intermediate layer in advance and laminate the surface layer by heating lamination or extrusion lamination.

(8-2) Applications The polyolefin-based multilayer film or multilayer sheet of the present invention is excellent in flexibility and transparency, and can be used at a wide range of temperatures because the product has heat resistance and cold resistance. Can be processed at a relatively low temperature, and has low stickiness and bleeding, and has particularly improved high-frequency welder suitability. Conventionally, a soft vinyl chloride resin film or sheet has been used. Can be used in a wide range of applications, such as card cases, clear files, pen cases, stationery such as CDs, DVDs, cosmetics, shampoos, rinses, containers, handbags, swimming bags, umbrellas and rain It can be suitably used for a coat or the like.
Furthermore, when it is used as various packaging materials and containers, it can withstand sterilization in a boiled state from storage in a frozen state, and further, content contamination by bleed is small, which is suitable for food, medical and industrial fields. is there.

In order to describe the present invention more specifically, examples and comparative examples will be described below. In order to clarify the present invention, preferred examples and the like will be described. The present invention demonstrates the significance and rationality of the configuration by comparing these examples and comparative examples. ing.
The measuring methods of various physical properties of the propylene-ethylene random block copolymer (A) and the polar group-containing ethylene resin (B) obtained in the following production examples are as follows.

[Methods for measuring physical properties of propylene-ethylene random block copolymer (A)]
1) Melt flow rate (MFR)
According to JIS K7210 A method condition M, it measured on condition of the following.
Test temperature: 230 ° C
Nominal weight: 2.16kg
Die shape: Diameter 2.095mm Length 8.00mm

2) TREF (outlined in paragraph 0029)
A sample is dissolved in o-dichlorobenzene (containing 0.5 mg / mL BHT) at 140 ° C. to prepare a solution. This is introduced into a 140 ° C. TREF column, cooled to 100 ° C. at a rate of 8 ° C./min, subsequently cooled to −15 ° C. at a rate of 4 ° C./min, and held for 60 minutes. Thereafter, o-dichlorobenzene as a solvent (containing 0.5 mg / mL BHT) is allowed to flow through the column at a flow rate of 1 mL / min, and components dissolved in o-dichlorobenzene at −15 ° C. in the TREF column. Elution is performed for 10 minutes, and then the column is linearly heated to 140 ° C. at a heating rate of 100 ° C./hour to obtain an elution curve.
〔apparatus〕
(TREF part)
TREF column: 4.3 mmφ × 150 mm stainless steel column Column packing material: 100 μm Surface inactive glass beads Heating method: Aluminum heat block Cooling method: Peltier device (Peltier device is cooled by water)
Temperature distribution: ± 0.5 ° C
Temperature controller: Chino Corporation Digital Program Controller KP1000 (Valve Oven)
Heating method: Air bath oven Measurement temperature: 140 ° C
Temperature distribution: ± 1 ° C
Valve: 6-way valve 4-way valve (Sample injection part)
Injection method: Loop injection method Injection volume: Loop size 0.1ml
Inlet heating method: Aluminum heat block measurement temperature: 140 ° C
(Detection unit)
Detector: Fixed wavelength infrared detector FOXBORO MIRAN 1A
Detection wavelength: 3.42 μm
High-temperature flow cell: Micro flow cell for LC-IR Optical path length: 1.5 mm Window shape: 2φ x 4 mm long circle Synthetic sapphire window measurement temperature: 140 ° C
(Pump part)
Liquid feed pump: SSC-3461 pump manufactured by Senshu Kagaku Co. [Measurement conditions]
Solvent: o-dichlorobenzene (containing 0.5 mg / mL BHT)
Sample concentration: 5 mg / mL
Sample injection volume: 0.1 mL
Solvent flow rate: 1 mL / min

3) Measurement of solid viscoelasticity A sample cut into a strip of 10 mm width × 18 mm length × 2 mm thickness from a 2 mm thick sheet injection molded under the following conditions was used. The apparatus used was ARES manufactured by Rheometric Scientific. The frequency is 1 Hz. The measurement temperature was raised stepwise from −60 ° C., and the measurement was performed until the sample melted and became impossible to measure. The strain was performed in the range of 0.1 to 0.5%.
[Creation of specimen]
Standard number: JIS-7152 (ISO294-1)
Molding machine: TU-15 injection molding machine manufactured by Toyo Machine Metal Co., Ltd. Molding machine set temperature: 80, 80, 160, 200, 200, 200 ° C. from below the hopper
Mold temperature: 40 ℃
Injection speed: 200 mm / sec (speed in the mold cavity)
Injection pressure: 800 kgf / cm ²
Holding pressure: 800 kgf / cm ²
Holding time: 40 seconds
Mold shape: Flat plate (2mm thickness, 30mm width, 90mm length)

4) DSC
Using a Seiko DSC, take 5.0 mg of sample, hold at 200 ° C. for 5 minutes, crystallize to 40 ° C. at a rate of temperature decrease of 10 ° C./minute, and further melt at a temperature increase rate of 10 ° C./minute. The melting peak temperature was Tm (unit: ° C.). DHm was determined from the area of the endothermic curve at the time of temperature increase.

5) GPC
The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by gel permeation chromatography (GPC).
Conversion from the retention volume to the molecular weight is performed using a calibration curve prepared in advance with standard polystyrene. The measurement method is the method detailed in paragraph 0042.

6) Room temperature xylene soluble component (CXS)
A 2 g sample is dissolved in 300 ml of p-xylene (containing 0.5 mg / ml BHT) at 130 ° C. to make a solution, and then left at 23 ° C. for 12 hours. Thereafter, the precipitated polymer is filtered off, p-xylene is evaporated from the filtrate, and further dried under reduced pressure at 100 ° C. for 12 hours, and CXS is collected and weighed.

7) Intrinsic viscosity (synonymous with intrinsic viscosity)
Using an Ubbelohde viscometer, decalin was used as a solvent and the temperature was measured at 135 ° C.

8) Calculation of ethylene content Since components (A1) and (A2) can be clearly distinguished by TREF, each component is fractionated by the temperature rising column fractionation method, and the ethylene content in each component is measured using NMR. did. The measurement method is described in detail in paragraphs 0030-0037.

[Method for measuring physical properties of polar group-containing ethylene-based resin (B)]
1) Melt flow rate (MFR)
According to JIS K7210 A method condition D, it measured on condition of the following.
Test temperature: 190 ° C
Nominal weight: 2.16kg
Die shape: Diameter 2.095mm Length 8.00mm

2) Vinyl acetate content Measured according to JIS K6730 A method.

[Production Example of Propylene-Ethylene Random Block Copolymer (A)]
[Production Example PP-1]
Polymerization production example A-1
Preparation of prepolymerization catalyst (chemical treatment of silicate) To a glass separable flask equipped with a 10 L stirring blade, 3.75 L of distilled water was added slowly, followed by 2.5 kg of concentrated sulfuric acid (96%). At 50 ° C., 1 kg of montmorillonite (Menzawa Chemical Co., Ltd. Benclay SL; average particle size = 25 μm, particle size distribution = 10-60 μm) was dispersed, heated to 90 ° C., and maintained at that temperature for 6.5 hours. After cooling to 50 ° C., the slurry was filtered under reduced pressure to recover the cake. 7 L of distilled water was added to the cake and reslurried, followed by filtration. This washing operation was performed until the pH of the washing liquid (filtrate) exceeded 3.5. The collected cake was dried at 110 ° C. overnight under a nitrogen atmosphere. The weight after drying was 707 g.
(Drying of silicate) The silicate previously chemically treated was dried by a kiln dryer. Specifications and drying conditions are as follows.
Rotating cylinder: Cylindrical inner diameter 50 mm Heating zone 550 mm (electric furnace) Revolving speed with lifting blade: 2 rpm Tilt angle: 20/520 Silicate feed rate: 2.5 g / min Gas flow rate: Nitrogen 96 L / hour Countercurrent drying temperature : 200 ° C (powder temperature)
(Preparation of catalyst) 20 g of dry silicate was introduced into a glass reactor equipped with a stirring blade having an internal volume of 1 L, 116 ml of mixed heptane and 84 ml of a heptane solution of triethylaluminum (0.60 M) were added, and the mixture was stirred at room temperature. . After 1 hour, the mixture was washed with mixed heptane to prepare a silicate slurry to 200 ml. Next, 0.96 ml of a heptane solution of triisobutylaluminum (0.71 M / L) was added to the prepared silicate slurry and reacted at 25 ° C. for 1 hour. In parallel, 218 mg (0.3 mM) of (r) -dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azulenyl}] zirconium and 87 ml of mixed heptanes were added to A mixture obtained by adding 3.31 ml of a heptane solution of isobutylaluminum (0.71 M) and reacting at room temperature for 1 hour was added to the silicate slurry, and after stirring for 1 hour, mixed heptane was added to prepare 500 ml.
(Preliminary polymerization / washing) Subsequently, the previously prepared silicate / metallocene complex slurry was introduced into a stirring autoclave having an internal volume of 1.0 L which had been sufficiently substituted with nitrogen. When the temperature was stabilized at 40 ° C., propylene was supplied at a rate of 10 g / hour to maintain the temperature. After 4 hours, the supply of propylene was stopped and maintained for another 2 hours.
After completion of the prepolymerization, the remaining monomer was purged, stirring was stopped, and the mixture was allowed to stand for about 10 minutes, and then the supernatant was decanted. Subsequently, 0.95 ml of a heptane solution of triisobutylaluminum (0.71 M / L) and 560 ml of mixed heptane were further added, stirred for 30 minutes at 40 ° C., allowed to stand for 10 minutes, and then 560 ml of the supernatant was removed. This operation was further repeated 3 times. When the component analysis of the final supernatant was conducted, the concentration of the organoaluminum component was 1.23 mmol / L and the Zr concentration was 8.6 × 10 ⁻⁶ g / L, and the abundance in the supernatant with respect to the amount charged. Was 0.016%. Subsequently, 17.0 ml of a heptane solution of triisobutylaluminum (0.71 M / L) was added, followed by drying at 45 ° C. under reduced pressure. A prepolymerized catalyst containing 2.0 g of polypropylene per 1 g of catalyst was obtained.
Using this prepolymerized catalyst, a propylene-ethylene random block copolymer (A) was produced according to the following procedure.

First step: Propylene-ethylene random copolymerization was carried out using a liquid phase polymerization tank equipped with a stirrer having an internal volume of 0.4 m ³ . Liquefied propylene, liquefied ethylene, and triisobutylaluminum were continuously fed at 90 kg / hour, 4.6 kg / hour, and 21.2 g / hour, respectively. Hydrogen was continuously supplied so that the concentration in the gas phase was 270 volppm. Further, the above prepolymerized catalyst was supplied as a catalyst (excluding the weight of the prepolymerized polymer) so as to be 6.3 g / hour. The polymerization tank was cooled so that the polymerization temperature was 45 ° C.
When the propylene-ethylene random copolymer obtained in the first step was analyzed, BD (bulk density) was 0.47 g / cc, MFR was 16.3 g / 10 min, and ethylene content was 3.7 wt%. .

Second step: In the second step, propylene-ethylene random copolymerization was carried out using a stirred gas phase polymerization tank having an internal volume of 0.5 m ³ . The slurry containing polymer particles was continuously withdrawn from the liquid phase polymerization tank in the first step, flushed with liquefied propylene, and then pressurized with nitrogen and continuously supplied to the gas phase polymerization tank. The polymerization tank was controlled so that the temperature was 80 ° C. and the total partial pressure of propylene, ethylene, and hydrogen was 1.5 MPa. At that time, the concentration of propylene, ethylene and hydrogen in the total partial pressure of propylene, ethylene and hydrogen was controlled to 66.94 vol%, 32.97 vol% and 900 volppm, respectively. Furthermore, ethanol was supplied to the gas phase polymerization tank as an activity inhibitor. The supply amount of ethanol was set to 0.5 mol / mol with respect to aluminum in TIBA supplied along with the polymer particles supplied to the gas phase polymerization tank.
When the propylene-ethylene random block copolymer thus obtained was analyzed, the activity was 9.5 kg / g-catalyst, BD was 0.40 g / cc, MFR was 16.9 g / 10 min, and the ethylene content was 8. It was 7 wt%.

(Additive additive)
The following antioxidant and neutralizing agent were added to the block copolymer powder obtained in Polymerization Production Example A-1, and the mixture was sufficiently stirred and mixed.
Antioxidant: Tetrakis {methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate} methane 500 ppm, Tris (2,4-di-t-butylphenyl) phosphite 500 ppm
Neutralizer: Calcium stearate 500ppm

(Granulation)
The copolymer powder to which the additive has been added is melt-kneaded under the following conditions, and the molten resin extruded from the strand die is taken out while being cooled and solidified in a cooling water tank, and the strand is about 2 mm in diameter and long using a strand cutter. The raw material pellet (PP-1) of the component (A) was obtained by cutting to about 3 mm.
Extruder: Technobel KZW-15-45-MG twin screw extruder
Screw: 15mm caliber L / D45
Extruder set temperature: 40, 80, 160, 200, 220, 220 (die) ° C. from below the hopper
Screw rotation speed: 400rpm
Discharge amount: Adjusted to 1.5 kg / hr with screw feeder Die: 3 mm diameter strand die Number of holes 2

(analysis)
Using the obtained PP-1 pellets, [η] of TREF, NMR (ethylene content), DMA, DSC, GPC, CXS, and CXS was measured. Table 4 shows each data obtained by the measurement. From the measurement results obtained, it can be said that PP-1 satisfies all the requirements as component (A).
Here, in order to show the positioning of each data regarding the TREF measurement result, an elution curve is illustrated in FIG. Further, in order to show the positioning of each data with respect to the solid viscoelasticity measurement results, FIG. 2 illustrates changes in storage elastic modulus G ′, loss elastic modulus G ″ and loss tangent tan δ with respect to temperature.

[Production Examples PP-2 to 6]
Polymerization production examples A-2 to 6
In the same manner as in Polymerization Production Example A-1, the polymerization conditions were changed to produce a propylene-ethylene random block copolymer. The polymerization conditions and polymerization results are shown in Table 3. PP-6 is a normal random copolymer that does not undergo the second stage polymerization.
PP-2 ~ 6
From the obtained polymer powder, PP-2 to 6 raw material pellets were obtained by the same additive formulation and granulation conditions as in Production Example PP-1. Various analysis results are shown in Table 4. FIG. 3 illustrates changes in storage elastic modulus G ′, loss elastic modulus G ″, and loss tangent tan δ with respect to temperature in PP-5.

[Production Example PP-7]
Polymerization production example A-7
2,000 mL of dehydrated and deoxygenated n-heptane was introduced into a flask sufficiently purged with nitrogen, and then 2.6 mol of MgCl ₂ and 5.2 mol of Ti (On-C ₄ H ₉ ) ₄ were introduced. And reacted at 95 ° C. for 2 hours. After completion of the reaction, the temperature was lowered to 40 ° C., and then 320 ml of methylhydropolysiloxane (20 centistokes) was introduced and reacted for 3 hours. The resulting solid component was washed with n-heptane.
Next, 4,000 ml of n-heptane purified in the same manner as described above was introduced into a sufficiently nitrogen-substituted flask, and 1.46 mol of the solid component synthesized above was introduced in terms of Mg atoms. SiCl _{4 in} 25 ml of n-heptane 62 moles were mixed, introduced into the flask at 30 ° C. for 30 minutes, and reacted at 70 ° C. for 3 hours. After completion of the reaction, washing with n-heptane was performed. Next, 0.15 mol of phthalic acid chloride was mixed with 25 ml of n-heptane, introduced into the flask at 70 ° C. for 30 minutes, and reacted at 90 ° C. for 1 hour. After completion of the reaction, it was washed with n-heptane. Next, 11.4 mol of TiCl ₄ was introduced and reacted at 110 ° C. for 3 hours. After completion of the reaction, the solid component (A1) was obtained by washing with n-heptane. The titanium content of this solid component was 2.0 wt%.
Next, 200 ml of n-heptane purified in the same manner as described above was introduced into a sufficiently nitrogen-substituted flask, 4 g of the solid component (A1) synthesized above was introduced, 0.035 mol of SiCl ₄ was introduced, and 90 ° C. The reaction was performed for 2 hours. After completion of the reaction, further (CH ₂ ═CH) Si (CH ₃ ) ₃ 0.006 mol, (t-C ₄ H ₉ ) (CH ₃ ) Si (OCH ₃ ) ₂ 0.003 mol and Al (C ₂ H ₅ ) ₃ 0.016 mol was sequentially introduced and contacted at 30 ° C. for 2 hours. After completion of the contact, the solid catalyst component (A) mainly composed of magnesium chloride was obtained by thoroughly washing with n-heptane. The titanium content of this product was 1.8 wt%.
A propylene-ethylene random block copolymer was produced in the same manner as in Polymerization Production Example A-1, except that the solid catalyst component (A) was used and triethylaluminum was used instead of triisobutylaluminum. The polymerization conditions and polymerization results are shown in Table 3.
PP-7 raw material pellets were obtained from the obtained polymer powder under the same additive formulation and granulation conditions as in Production Example PP-1. Various analysis results are shown in Table 4.

[Polar group-containing ethylene resin (B)]
As the polar group-containing ethylene resin (B), Novatec EVA LV540 commercially available from Nippon Polyethylene Co., Ltd. was selected as the ethylene-vinyl acetate copolymer. The analytical values were MFR 2.5 g / 10 min and vinyl acetate content 20 wt%.

[Example-1]
[Molding]
The obtained composition pellets were laminated by a feed block method using two extruders and formed into a sheet under the following conditions to obtain a multilayer sheet having a thickness of 200 μm.
Extruder 1 (both surface layers): IKG PMS30-32 single screw extruder Extruder 2 (intermediate layer): IKG PMS30-36 single screw extruder die: width 150 mm Lip thickness 0.6 mm Coat hanger die molding Machine set temperature: 80, 80, 160, 200, 200, 200 ° C from below the hopper
Cooling roll temperature: 20 ° C
(Cooling by blowing air from an air knife until the sheet is in close contact with the cooling roll and does not touch the film)
Molding speed: 1.2 m / min Layer structure: PP-1 / LV540 / PP-1 = 50/100/50 [μm]
(The discharge rate is adjusted by the screw rotation speed of the extruder so that the molding speed and thickness are the above values, and about 1 kg / hour for each extruder)

〔Evaluation of the physical properties〕
(transparency)
The transparency of the test piece was evaluated under the following conditions.
Standard number: JIS K-7136 (ISO 14782) JIS K-7361-1 compliant measuring machine: Haze meter NDH2000 (manufactured by Nippon Denshoku Industries Co., Ltd.)
Test piece thickness: 200 μm
Test piece preparation method: Sheet cut into 50 × 50 mm Adjustment of state: Number of test pieces left for 24 hours in a constant temperature room adjusted to room temperature 23 ° C. and humidity 50% after molding: 3
Evaluation item: Haze

(Glossiness)
The transparency of the test piece was evaluated under the following conditions.
Standard number: JIS K7105
Measuring machine: Digital variable angle gloss meter UGV-5K manufactured by Suga Test Instruments
Test piece thickness: 200 μm
Test piece preparation method: Sheet cut into 50 × 50 mm Adjustment of state: Number of test pieces left for 24 hours in a constant temperature room adjusted to room temperature 23 ° C. and humidity 50% after molding: 3
Evaluation item: 20 degree specular glossiness

(Tensile test)
The tensile properties of the obtained multilayer sheet were evaluated under the following conditions.
Standard number: JIS K-7162 (ISO527-1) compliant tester: Precision universal tester Autograph AG-5kNG-with micro extensometer (manufactured by Shimadzu Corporation)
Specimen sampling direction: Flow direction Specimen shape: JIS K7162-5A type Specimen preparation method: Sheet punched out into the above shape: Conditioned at room temperature 23 ° C., humidity controlled at 50% for 24 hours Test room: Number of temperature-controlled specimens adjusted to room temperature 23 ° C. and humidity 50%: 5
Test speed: 1.0 mm / min (elongation up to 5 mm), 25.0 mm / min (elongation over 5 mm)
Evaluation item: Tensile modulus

(Tensile impact test)
The resulting multilayer sheet was evaluated for impact resistance under the following conditions.
Standard number: JIS K-7160 B method reference specimen collection direction: flow (MD) direction, width (TD) direction Specimen shape: JIS K7160-4 type Specimen creation method: sheet punched into the above shape Control: Number of test pieces left for 24 hours or more in a temperature-controlled room adjusted to room temperature 23 ° C. and humidity 50%: 5
Potential energy before swinging down: 20kgcm
Impact speed: 3.4 m / sec Crosshead mass: 65 g
Measurement temperature: 23 ° C
Evaluation item: Tensile impact strength (T)
Formula T = (E1−E) / (a × b)
T: Tensile impact strength (kgcm / cm ² )
E1: Tensile impact energy (kgcm)
E: Friction loss energy (kgcm)
a: Thickness (cm) of the narrow portion of the test piece
b: Minimum width (cm) of the parallel part of the test piece

(Heat-resistant)
The obtained sheet was immersed in boiling water at 100 ° C., boiled for 2 minutes, and then taken out. The heat resistance was evaluated according to the state of the removed sheet. The symbols in the table indicate the following states.
○: The sheet is not deformed and has sufficient heat resistance. Δ: The sheet is deformed but does not melt. ×: The sheet is melted and significantly deformed.

(Bending whitening)
The obtained sheet was bent 180 ° and then bent 180 ° in the opposite direction 10 times, and bending whitening was evaluated. The symbols in the table indicate the following states.
○: The sheet is not whitened and is excellent in bending whitening. Δ: The sheet is slightly whitened but does not peel off and is not noticeable. ×: The sheet is markedly whitened and peeled off.

(Evaluation of stickiness)
The stickiness of the test piece was evaluated by the following method.
In a temperature-controlled room adjusted to room temperature 23 ° C and humidity 50%, two sheets are stacked and sandwiched between iron plates, 1 kg is applied to the iron plate and left for 10 minutes, then taken out from between the iron plates and tested at that time The stickiness was evaluated based on how the pieces were attached. The symbols in the table indicate the following states.
○: The sample did not stick, but was peeled off immediately after removal. Δ: The sample was stuck, but it was easily peeled off when peeled by hand. ×: The sample was in close contact and required considerable force to peel off.

(Bleedout evaluation)
The bleed out of the test piece was evaluated by the following method.
The surface of the obtained sheet was wiped off with a cloth once within 24 hours after molding, and then left in a constant temperature bath at 40 ° C. for 24 hours. The symbols in the table indicate the following states.
○: There was no bleed out in the sample, and there was no change in the state before being left. △: Some bleed out was observed in the sample, but it was not noticeable. Expected x: The sample had many bleedouts and marked whitening on the surface

(Evaluation of suitability for high frequency welder)
Two sheets of 200 μm thickness obtained were overlapped, and the welding time was changed under the following conditions to perform high-frequency welder sealing, and the resulting sample was cut into a 15 mm width and evaluated for sealing strength at 180 °.
High frequency welder: YC-7000F manufactured by Yamamoto Vinita Co., Ltd.
Anode current: 0.4 amp tuning speed: 10
Tuning position: 70
Welding time: 0.5, 1, 2, 3, 4 seconds Platen temperature: 20 ° C
Cooling time: 2 seconds Table 5 shows the evaluation results of the above physical properties.

[Example-2]
As shown in Table 4, it was similarly molded and evaluated for Example-1 except that the propylene-ethylene random block copolymer (A) was changed to PP-2. The evaluation results are shown in Table 5.

[Comparative Examples-1 to 5]
As shown in Table 4, it was similarly molded and evaluated for Example-1 except that the propylene-ethylene random block copolymer (A) was changed to PP-3-7. The evaluation results are shown in Table 5.

[Consideration by contrast between Example and Comparative Example]
Considering each of the above Examples and Comparative Examples in contrast, in the novel polyolefin-based multilayer films or multilayer sheets of Examples-1 and 2 that satisfy the respective regulations in the configuration of the present invention, transparency and Excellent gloss, flexibility, heat resistance and whitening properties expressed in tensile modulus, impact resistance in strength test, no stickiness of product, bleed out is suppressed It is clear that it is also excellent in high-frequency welder suitability.
Therefore, in the configuration of the present invention, the provisions of the constituent requirements for the propylene-ethylene random block copolymer (A) and the polar group-containing ethylene-based resin (B) are reasonable and proved by experimental data. Understand clearly.
In Comparative Example-1, the crystallinity of the component (A1) as the block copolymer (A) is high, the TREF has a T (A1) peak exceeding 90 ° C., and T (A4) also exceeds 92 ° C. Furthermore, the case where the component (A1) does not contain ethylene is shown. At this time, there is almost no suitability for high-frequency welder, it is unsuitable for high-frequency seal processing, and inferior in flexibility and impact resistance.
Comparative Example-2 shows a case where the quantity ratio of the component (A2) is too large as the block copolymer (A). At this time, the block copolymer (A) has high-frequency welder suitability, but has no heat resistance and poor transparency. , Stickiness and bleed out are prominent.
Comparative Example-3 shows a case where components (A1) and (A2) are phase-separated as a block copolymer (A) and Tg does not take a single peak, and at this time, it has high-frequency welder suitability. The transparency is remarkably deteriorated and the glossiness is inferior.
Comparative Example 4 shows a case where a conventional propylene-ethylene random copolymer polymerized with a metallocene catalyst, which does not contain the component (A2) in the surface layer, is used. The time required to reach a sufficient area exceeding 2000 g / 15 mm is as long as 3 seconds, the seal processability is poor, and the flexibility and impact resistance are also poor.
In Comparative Example-5, the same polymerization as in each Example was performed using a Ziegler-Natta catalyst. However, even if the component (A1) had the same ethylene content, T (A1) was sufficiently reduced. In addition, the suitability for high-frequency welder is considerably inferior, the glossiness is also poor, and stickiness and bleedout are markedly deteriorated.
From the above comparative evaluation, various properties such as transparency, gloss, flexibility, heat resistance, etc. are all well-balanced, especially compared to the polyolefin-based multilayer sheet of the present invention having good high-frequency welder suitability. The example polyolefin-based multilayer sheet is inferior in performance and highlights the excellence of the present invention.

It is a graph which shows the TREF elution amount curve and elution amount integration in PP-1. It is a graph which shows the solid viscoelasticity measurement in PP-1. It is a graph which shows the solid viscoelasticity measurement in PP-5.

Claims (8)

Propylene-ethylene random block copolymer comprising components (A1) and (A2) satisfying the following conditions (Ai) to (A-iv) on a base material layer comprising a polar group-containing ethylene resin (B) A polyolefin-based multilayer film or a polyolefin-based multilayer sheet, characterized in that (A) is laminated.
(Ai) TREF obtained as a plot of the elution amount (dwt% / dT) against temperature by the temperature rising elution fractionation method (TREF) in the temperature range of −15 ° C. to 140 ° C. using an o-dichlorobenzene solvent In the elution curve, the peak T (A1) observed on the high temperature side is in the range of 65 ° C. to 90 ° C., and the peak T (A2) observed on the low temperature side is below 50 ° C., or the peak T (A2) (If no peak is observed, the component (A2) is eluted into the solvent and the concentration is observed at −15 ° C., the lower limit of the measurement temperature.) (A-ii) In the TREF elution curve, the component (A ) The temperature T (A4) at which 99 wt% of the whole elutes is 92 ° C. or less (A-iii) In the TREF elution curve, peaks T (A1) and T (A2) (component (A2) is the peak If not shown, T (A2) is −15 ° C. which is the lower limit of the measurement temperature.) The integrated amount W (A2) of the component eluted until the temperature T (A3) at the midpoint of both peaks is 30 to 70% by weight, and the integrated amount W (A1) of the component eluted at T (A3) or higher is 70 to 30% by weight (A-iv) Temperature-loss tangent (tan δ) obtained by solid viscoelasticity measurement (DMA) ) In the curve, the tan δ curve has a single peak below 0 ° C 2. The polyolefin-based multilayer according to claim 1, wherein a propylene-ethylene random block copolymer (A) is laminated on an outer surface layer and an inner surface layer on an intermediate layer made of a polar group-containing ethylene resin (B). Film or polyolefin multilayer sheet. The propylene-ethylene random block copolymer (A) uses a metallocene catalyst, the propylene-ethylene random copolymer containing 1-7 wt% ethylene in the first step is 30-70 wt%, and the first step is the second step. The propylene-ethylene random block copolymer obtained by sequentially polymerizing 70-30 wt% of a propylene-ethylene random copolymer containing 6-12 wt% more ethylene than in the process, A polyolefin-based multilayer film or a polyolefin-based multilayer sheet according to claim 2. The polar group-containing ethylene-based resin (B) is an ethylene-vinyl acetate copolymer, the vinyl acetate content is 15 wt% or more, and the melt flow rate (MFR: 190 ° C., 2.16 kg load) is 0.1 to 100 g / 10. The polyolefin-based multilayer film or polyolefin-based multilayer sheet according to any one of claims 1 to 3, wherein the polyolefin-based multilayer film is a minute. The polyolefin-based multilayer film or polyolefin-based multilayer according to any one of claims 1 to 4, wherein the propylene-ethylene random block copolymer (A) satisfies the following conditions (A-v): Sheet.
(Av) The weight average molecular weight Mw of the block copolymer (A) obtained by gel permeation chromatography (GPC) measurement is in the range of 100,000 to 400,000, and the weight average molecular weight is 5,000. The following component amount W (Mw ≦ 5,000) is 0.8 wt% or less in the block copolymer (A). The polyolefin-based multilayer film or polyolefin-based multilayer according to any one of claims 1 to 5, wherein the propylene-ethylene random block copolymer (A) satisfies the following condition (A-vi): Sheet.
(A-vi) The intrinsic viscosity [η] cxs measured in 135 ° C. decalin of the 23 ° C. xylene soluble component is in the range of 1 to 2 (dl / g). It is composed of a surface layer made of a propylene-ethylene random block copolymer (A) and a base material layer made of a polar group-containing ethylene resin (B), and the thickness of the surface layer is 20% or less with respect to the thickness of the entire multilayer sheet. Or it is 70 micrometers or less, The polyolefin-type multilayer film or polyolefin-type multilayer sheet in any one of Claims 1-6 characterized by the above-mentioned. A molded product, wherein the polyolefin-based multilayer film or polyolefin-based multilayer sheet according to any one of claims 1 to 7 is molded by high-frequency welder processing.

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