JP2004202978A - Process sheet and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inexpensive process sheet capable of being manufactured for a short time (high speed molding) while having sufficient adhesiveness without using an adhesive such as an anchor coating agent or the like, having high heat resistance and more enhanced in surface releasability, and its manufacturing method. <P>SOLUTION: In the process sheet 14 obtained by forming a surface layer 15 on a substrate 13 through an adhesive layer 16 without using the anchor coating agent, the surface layer 15 contains a 3-10C α-olefin homopolymer or copolymer as a main component and the adhesive layer 16 comprises a resin material containing 100-10 mass % of an ethylene (co)polymer (A) satisfying specific necessary conditions and 0-90 mass % of an other polyolefinic resin (B). <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【０１００】
上述したエチレン（共）重合体（Ａ）を用いて工程シートを作製した。
［使用材料］
（１）ポリプロピレン系樹脂：
ホモポリプロピレン（ＰＰ）
密度＝０.９０g/cm³、ＭＦＲ＝４２ｇ／10分
商品名＝ＰＨＡ０３Ａ サンアロマー（株）製
（２）ポリ−４−メチル−１−ペンテン樹脂（Ｐ４ＭｅＰ）：
メルトフローレート（２６０℃）１００ｇ／１０分
（３）基材：上質紙；紀州製紙（株）製 はまゆう ５０ｇ／ｍ^２
【０１０１】
［実施例１〜８］
表面層（III）１５μｍと、接着層（II）であるエチレン（共）重合体（Ａ）層１５μｍとを共押出した溶融樹脂フィルムのエチレン（共）重合体（Ａ）の表面をオゾン処理した。そして、アンカーコート剤を使用せずに、基材（Ｉ）である厚さ５０ｇ／ｍ²の上質紙の上に、溶融樹脂フィルムのオゾン処理面を押出ラミネートして工程シートを得た。その際、表面層（III）、接着層（II）、基材（Ｉ）には表２に示すものを使用し、接着層の表面は表２に示す条件でオゾン処理した。
ラミネート後４０℃、２時間をエージング後、得られた各積層体について基材（Ｉ）と接着層、接着層（II）と表面層（III）の間における各接着強度を測定した。結果を表２に示す。
なお、実施例５においては、表面層であるポリ−４−メチル−１−ペンテン樹脂層の厚さを５０μｍにした。
接着強度の測定は、１５ｍｍ幅の短冊状サンプルを切り出し、ＪＩＳ Ｋ６８５４に準拠して、引張速度３００ｍｍ／分の条件でＴ剥離により剥離強度を測定し、この剥離強度を接着強度とした。
また、表面酸化度（Ｏｒ）は、接着層（II）の、基材（Ｉ）と接している面において、表面ＦＴ−ＩＲ（ＡＴＲ）法による吸光度のスペクトルにおける１７２０ｃｍ^−１付近のピークの高さをＩ（１７２０）、１３７０（１３６９）ｃｍ^−１付近のピークの高さをＩ（１３７０）として（式８）で求めた。
（式８） Ｏｒ＝Ｉ（１７２０）／Ｉ（１３７０）
【０１０２】
【表２】

【０１０３】
［比較例１］
表３に示すように、上記エチレン（共）重合体（Ａ）を用いずに、表面層の片面をオゾン処理したこと以外は実施例１と同様にして工程シートを製造し、表面層（III）であるポリプロピレン系樹脂層と基材（Ｉ）との間の接着強度を測定した。結果を表３に示す。
【０１０４】
【表３】

【０１０５】
［比較例２、３］
比較例２においては、接着層（II）としてチーグラー系触媒によるエチレン共重合体（Ａ４）を用いたこと以外は実施例１と同様にして工程シートを製造し、その層間接着強度を測定した。結果を表４に示した。また、比較例３においては、接着層（II）として高圧ラジカル法低密度ポリエチレン（ＬＤＰＥ）を用いたこと以外は実施例１と同様にして工程シートを製造し、その層間接着強度を測定した。結果を表４に示す。
【０１０６】
【表４】

【０１０７】
［比較例４］
接着剤としてアンカーコート剤を用いて、表面層であるプロピレン−エチレンランダム共重合体層と基材（Ｉ）とからなる工程シートを製造し、その層間接着強度を測定した。結果を表５に示す。
この際、アンカーコート剤（ＡＣ剤）には、大日精化工業（株）製セイカダイン２７１０、セイカダイン２７１０Ｂ、市販の酢酸エチルの混合物（セイカダイン２７１０Ａ：セイカダイン２７１０Ｂ：酢酸エチル＝１：２：１５の質量比率）を用いた。
【０１０８】
［比較例５］
ドライラミネーションにより、表面層（III）であるプロピレン−エチレンランダム共重合体層と基材（Ｉ）とからなる工程シートを製造し、その層間接着強度を測定した。結果を表５に示す。
なお、上記ドライラミネーションでは、押出ラミネート機付属のＡＣコーターにて、プレーンロールを使用して、アンダーコート剤（東洋モートン（株）製ＡＤ−３０８Ａ：ＡＤ−３０８Ｂ：酢酸エチル１：１：３の比率でブレンド）を塗工量３ｇ／ｍ²でグラビアコートし、次いで、ドライヤー温度８０℃で乾燥し、圧着条件５０℃−４ｋｇ／ｍ²、３０ｍ/分でラミネートした。ラミネートした後、４０℃で２時間エージングしてから、接着強度を測定した。
【０１０９】
【表５】

【０１１０】
［実施例９］
エポキシ化大豆油（分子量：９３８、商品名；アデカサイザー、旭電化工業（株）製、以下、ＥＳＯと略す）を含浸（１００００ｐｐｍ）させた上記エチレン共重合体（Ａ１１）７０質量部に、上記ＬＤＰＥ３０質量部を配合し、タンブラーミキサーでドライブレンドした後、１７０℃でペレタイズして接着層（II）用の樹脂材料を調製した。
上記樹脂材料を用いて実施例１と同様にして工程シートを作製し、その接着強度を測定した。その結果を表６に示す。
【０１１１】
【表６】

【０１１２】
[評価結果]
上記表２〜５から明らかなように、実施例１〜９においては、接着層（II）が本願請求項１に範囲にあるため、基材（Ｉ）と表面層（III）との接着強度が極めて高かった。
一方、比較例１では、接着層（II）を設けなかったので、接着強度が低かった。また、比較例２では、チーグラー系触媒によるエチレン共重合体（Ａ４）を用い、比較例３では、高圧ラジカル法低密度ポリエチレン（ＬＤＰＥ）を用いたので、接着強度が低かった。
比較例４では、アンカーコート剤を用いたため、接着強度が低かった。比較例５では、ドライラミネーションにより製造したので、接着強度が低かった。
【０１１３】
【発明の効果】
以上説明したように、本発明によれば、特定のエチレン（共）重合体（Ａ）を用い、かつ望ましくは酸化処理することにより、アンカーコート剤を使用しなくても、基材（Ｉ）と表面層（III）との接着強度が高く、表面凹凸性やエンボス性に優れており、表面上の剥離性を安価により高めることができる。また、耐熱性に優れている。しかも、低温でのラミネート成形であっても短時間（高速成形）で製造することができる。
【図面の簡単な説明】
【図１】工程シートの層構成の一例を示す側断面図である。
【図２】本発明に係るエチレン（共）重合体（Ａ）の溶出温度−溶出量曲線を示すグラフである。
【図３】本発明に係るエチレン系共重合体（Ａ１）の溶出温度−溶出量曲線を示すグラフである。
【図４】メタロセン系触媒によるエチレン系共重合体の溶出温度−溶出量曲線を示すグラフである。
【図５】本発明に係るエチレン系共重合体（Ａ２）の溶出温度−溶出量曲線を示すグラフである。
【図６】工程シートの作製の一例を示す概略構成図である。
【図７】（ａ）ＥＳＣＡ測定用サンプルおよびＩＲ測定用サンプル作製方法の模式図、（ｂ）サンプル採取用紙を示す斜視図である。
【図８】合成皮革の製造例を示す概略構成図である。
【図９】合成皮革の製造の際、工程シートに合成皮革が接したときの断面図である。
【符号の説明】
１３ 基材
１４ 工程シート
１５ 表面層
１６ 接着層[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a process sheet used for producing synthetic leather and the like having excellent heat resistance and a method for producing the same.
[0002]
[Prior art]
2. Description of the Related Art As bindings and wall coverings for shoes, bags, belts, notebooks and the like, multilayer sheet materials in which a skin material made of a resin such as polyvinyl chloride or urethane is provided on various woven fabrics are widely used. These sheet materials are given a three-dimensional design by imparting a concavo-convex pattern (hereinafter referred to as embossed) on the surface, and are used as a synthetic leather to bring out the genuine leatheriness especially when used for shoes and bags. .
In order to apply embossing, it is common to transfer by pressing a press plate or roll engraved with an embossed pattern on the surface, especially when small lot production with a limited production volume is required. For the method, a method of molding using a process sheet (also referred to as process paper) having an embossed surface is adopted.
For example, on a process sheet, apply a solution mainly composed of polyvinyl chloride or polyurethane as a skin material, and after drying, apply an adhesive, attach a base fabric, heat-dry, and then apply the process sheet. By peeling off, a multilayer synthetic leather composed of a skin material and a base cloth is obtained. This process sheet can be used a plurality of times.
The process sheet used here usually has a process layer made of a resin in which the emboss is formed firmly and has heat resistance enough to withstand the heat in the embossing process, and which is easily peeled off from the skin material. 200g / cm²What is laminated on a paper base of a degree is used. Specifically, an inexpensive heat-resistant resin such as polypropylene is melted at about 300 ° C. by an extruder as a process layer, and is sandwiched between a cooling roll and a nip roll on a substrate to be bonded.
[0003]
[Patent Document 1]
JP-A-2000-108264
[Patent Document 2]
JP-A-2000-108266
[Patent Document 3]
JP 2000-108267 A
[Patent Document 4]
JP 2000-108268 A
[0004]
[Problems to be solved by the invention]
However, the adhesion strength of a homopolymer or a copolymer of an α-olefin having 3 or more carbon atoms such as a polypropylene resin (hereinafter, also referred to as an α-olefin polymer having 3 or more carbon atoms) to paper is low, and When subjected to embossing by pressing with a material, there is a risk of sticking to the skin material and peeling between the base material and the process layer, and it is important to further increase the adhesive strength between these. I have. In addition, there is a demand for manufacturing in a shorter time.
Generally, in extrusion lamination, it is known that in order to improve the bonding strength between layers, it is known that the temperature of the resin at the time of lamination should be increased, and the above requirement is mainly addressed by increasing the lamination temperature. Was.
However, raising the temperature of the resin causes problems such as (1) an increase in the influence on the working environment and the surrounding environment due to the generation of smoke, and (2) deterioration of the odor of the product due to oxidative deterioration at a high temperature.
In addition, in order to increase the molding speed while ensuring high adhesiveness, the resin temperature must be increased, and the above problem becomes serious.
In addition, it was difficult to secure sufficient adhesiveness even with the use of ozone treatment for high-speed molding. Further, as an attempt to improve the adhesiveness, a polyolefin-based resin composition in which a compound having an intramolecular unsaturated bond such as a polybutadiene resin is blended with a polyolefin-based resin in an adhesive layer has been proposed.
[0005]
In recent years, in particular, it has been attempted to make the skin material softer for the purpose of higher quality synthetic leather.
As a result, the skin material and the process sheet are more easily adhered to each other and are less likely to be peeled off, so that the productivity may be reduced or a defect may occur.
Further, when an anchor coating agent is used, since the anchor coating agent contains a solvent, there is a problem that the working environment is deteriorated by the volatile solvent. Also, since the solvent is handled, great care must be taken. In addition, it is necessary to arrange ventilation facilities, and there is a problem in that manufacturing costs increase due to the burden on such facilities.
It is also conceivable to interpose an adhesive layer between the base material and the surface layer composed of an α-olefin polymer having 3 or more carbon atoms. However, when low-density polyethylene is used as the adhesive layer, the adhesiveness to the substrate and the processability can be improved, but the adhesiveness to the α-olefin polymer having 3 or more carbon atoms and the heat resistance are not sufficient. Therefore, as the adhesive layer, a resin material in which polypropylene is blended with low-density polyethylene, or a resin material in which low-density polyethylene is blended with an α-olefin polymer having 3 or more carbon atoms as the surface layer may be used. Although it can be considered, the adhesiveness to the substrate and the moldability are still not satisfactory.
[0006]
The present invention has been made in order to solve the above problems, without using an adhesive such as an anchor coat agent, while maintaining the adhesion between the layers to a sufficiently satisfactory level, even in the case of lamination molding at low temperature An object of the present invention is to provide an inexpensive process sheet that can be manufactured in a short time (high-speed molding), has high heat resistance, and further enhances releasability on a surface, and a method for manufacturing the same.
[0007]
[Means for Solving the Problems]
The process sheet of the present invention is a process sheet in which a surface layer (III) is formed on a substrate (I) via an adhesive layer (II) without using an anchor coating agent,
The surface layer (III) contains a homopolymer or copolymer of an α-olefin having 3 to 10 carbon atoms as a main component,
The adhesive layer (II) contains 100 to 10% by mass of an ethylene (co) polymer (A) satisfying the following requirements (a) to (d) and 0 to 90% by mass of another polyolefin resin (B). It is characterized by being made of a resin material.
(A): density 0.86 to 0.97 g / cm³
(B): Melt flow rate is 0.01 to 100 g / 10 minutes
(C): molecular weight distribution (Mw / Mn) of 1.5 to 4.5
(D): Temperature T at which 25% of the total eluted determined from the integrated elution curve of the elution temperature-elution amount curve by the continuous heating elution fractionation method (TREF)₂₅And the temperature T at which 75% of the whole elutes₇₅Difference T from₇₅−T₂₅And the density d satisfies the relationship of the following (formula 1).
(Equation 1) T₇₅−T₂₅≦ −670 × d + 644
Here, it is preferable that the ethylene (co) polymer (A) further satisfies the following requirement (e).
(E): Temperature T at which 25% of the whole is eluted, obtained from an integrated elution curve of elution temperature-elution amount curve by continuous heating elution fractionation method (TREF).₂₅And the temperature T at which 75% of the whole elutes₇₅Difference T from₇₅−T₂₅And the density d satisfies the following relationship (Equation 2):
(Equation 2) d <0.950 g / cm³ When
T₇₅−T₂₅≧ −300 × d + 285
d ≧ 0.950 g / cm³When
T₇₅−T₂₅≧ 0
[0008]
Further, it is preferable that the ethylene (co) polymer (A) further satisfies (f) the mass average molecular weight of the o-dichlorobenzene (ODCB) -soluble component at 23 ° C. in the range of 8,000 to 30,000.
Further, the ethylene (co) polymer (A) is preferably an ethylene-based (co) polymer (A1) that further satisfies the following requirements (g) and (h).
(G): o-Dichlorobenzene (ODCB) soluble content X (mass%) at 25 ° C., density d and melt flow rate (MFR) satisfy the following formulas (formula 3) and (formula 4).
(Equation 3) When d−0.008 log MFR ≧ 0.93
X <2.0
(Equation 4) When d−0.008 log MFR <0.93
X <9.8 × 10³X (0.9300-d + 0.008 log MFR)²+2.0 (h): a plurality of peaks in the elution temperature-elution amount curve by continuous heating elution fractionation (TREF)
Alternatively, the ethylene (co) polymer (A) is preferably an ethylene (co) polymer (A2) that further satisfies the following requirements (i) and (j).
(I): One peak in the elution temperature-elution amount curve by the continuous heating elution fractionation method (TREF)
(J): one or more melting point peaks, and the highest melting point T among them_mlAnd the density d satisfy the relationship of the following (Equation 5)
(Equation 5) T_ml≧ 150 × d-19
It is preferable that the ethylene (co) polymer (A2) further satisfies the following requirement (k).
(K): Melt tension (MT) and melt flow rate (MFR) satisfy the following (formula 6).
(Equation 6) logMT ≦ −0.572 × logMFR + 0.3
Further, the resin material forming the adhesive layer (II) preferably contains an epoxy compound (C) having at least two epoxy groups in the molecule and having a molecular weight of 3000 or less.
[0009]
The process sheet manufacturing method of the present invention is a process sheet manufacturing method for forming a surface layer (III) on a substrate (I) via an adhesive layer (II) without using an anchor coating agent,
The surface layer (III) contains a homopolymer or copolymer of an α-olefin having 3 to 10 carbon atoms as a main component,
The adhesive layer (II) is 100 to 10% by mass of an ethylene (co) polymer (A) satisfying the following requirements (a) to (d), and the other polyolefin-based resin (B) is 0 to 90% by mass. Characterized by comprising a resin material containing
(A): density 0.86 to 0.97 g / cm³
(B): Melt flow rate is 0.01 to 100 g / 10 minutes
(C): molecular weight distribution (Mw / Mn) of 1.5 to 4.5
(D): Temperature T at which 25% of the total eluted determined from the integrated elution curve of the elution temperature-elution amount curve by the continuous heating elution fractionation method (TREF)₂₅And the temperature T at which 75% of the whole elutes₇₅Difference T from₇₅−T₂₅And the density d satisfies the relationship of the following (formula 1).
(Equation 1) T₇₅−T₂₅≦ −670 × d + 644
Here, the resin material forming the adhesive layer (II) preferably contains an epoxy compound (C) having at least two epoxy groups in the molecule and having a molecular weight of 3000 or less.
In the process sheet manufacturing method of the present invention, a homopolymer or a copolymer of a resin material forming the adhesive layer (II) and an α-olefin having 3 to 10 carbon atoms forming the surface layer (III) is formed. While forming a molten resin film by co-extrusion at a temperature of 200 to 350 ° C., the surface of the molten resin film which is in contact with the substrate (I) has (a) an oxygen atom concentration (Oc) of 1.8% by mass or more and (b) It is preferable to perform an oxidation treatment so that the surface oxidation degree (Or) becomes 0.10 or more, and laminate the molten resin film and the base material (I).
In the oxidation treatment, the molten resin film is preferably subjected to ozone treatment at a resin temperature of 200 to 350 ° C.
[0010]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
The process sheet in the present invention has at least a substrate (I) 13, an adhesive layer (II) 16, and a surface layer (III) 15, like a process sheet 14 shown in FIG.
[Base material (I)]
The substrate (I) in the present invention is appropriately selected depending on the application and is not limited, but generally, paper, woven fabric, and nonwoven fabric are applied. Examples of the paper include paperboard, woodfree paper, kraft paper, glassine paper, inorganic fiber mixed paper, and synthetic resin mixed paper.
[0011]
[Adhesive layer (II)]
The adhesive layer (II) in the present invention contains an ethylene (co) polymer (A) and another polyolefin resin (B). The other polyolefin-based resin (B) is an optional component and is contained as needed.
[0012]
[Ethylene (co) polymer (A)]
The ethylene (co) polymer (A) is obtained by copolymerizing ethylene with an α-olefin having 3 to 20, preferably 3 to 12 carbon atoms.
Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, and 1-dodecene. It is desirable that the content of these α-olefins is generally selected in a range of usually 30 mol% or less, preferably 3 to 20 mol% or less.
[0013]
The (a) density of the ethylene (co) polymer (A) is 0.86 to 0.97 g / cm.³ , Preferably 0.90 to 0.95 g / cm³ , More preferably 0.91 to 0.94 g / cm³ Range. 0.86 g / cm density³ If it is less than 1, rigidity (lumbar strength) and heat resistance are inferior. The density is 0.97 g / cm.³ If it exceeds 300, there is a possibility that the tear strength, impact resistance and the like may be insufficient. In addition, there is a problem that industrial productivity is reduced.
[0014]
The (b) melt flow rate (hereinafter, referred to as MFR) of the ethylene (co) polymer (A) is in the range of 0.01 to 100 g / 10 minutes, preferably 0.1 to 50 g / 10 minutes, and more preferably 0.1 to 50 g / 10 minutes. Preferably it is in the range of 0.5 to 30 g / min. If the MFR is less than 0.01 g / 10 minutes, there is a possibility that the moldability will be poor. On the other hand, if the MFR exceeds 100 g / 10 minutes, the tear strength and the like may be poor.
[0015]
The ethylene (co) polymer (A) further satisfies the following requirements (c) and (d).
(C) The molecular weight distribution (Mw / Mn) is 1.5 to 4.5. It is more preferably in the range of 2.0 to 4.0, and still more preferably in the range of 2.5 to 3.0. If Mw / Mn is less than 1.5, the moldability may be poor. If Mw / Mn exceeds 4.5, the tear strength, impact resistance, and the like may be insufficient.
Here, the molecular weight distribution (Mw / Mn) of the ethylene-based (co) polymer is obtained by determining the mass average molecular weight (Mw) and the number average molecular weight (Mn) by gel permeation chromatography (GPC), and calculating the ratio (Mw / Mn). Mw / Mn).
[0016]
As shown in FIG. 2, for example, as shown in FIG. 2, 25% of the ethylene (co) polymer (A) was obtained from the integrated elution curve of (d) elution temperature-elution amount curve by continuous temperature-elution fractionation (TREF). At which T elutes₂₅And the temperature T at which 75% of the whole elutes₇₅Difference T from₇₅−T₂₅And the density d satisfy the relationship of the following (Equation 1).
(Equation 1) T₇₅−T₂₅≦ −670 × d + 644
T₇₅−T₂₅If the density d and the density d do not satisfy the relationship of the above (Equation 1), there is a possibility that the low-temperature heat sealability may be inferior.
[0017]
The method of measuring TREF is as follows. First, a sample is added to o-dichlorobenzene (ODCB) to which an antioxidant (for example, butylhydroxytoluene) is added so that the sample concentration becomes 0.05% by mass, and heated and dissolved at 140 ° C. 5 ml of this sample solution is injected into a column filled with glass beads, cooled to 25 ° C. at a cooling rate of 0.1 ° C./min, and the sample is deposited on the surface of the glass beads. Next, the sample is sequentially eluted while raising the column temperature at a constant rate of 50 ° C./hr while flowing ODCB through the column at a constant flow rate. At this time, the concentration of the sample eluted in the solvent was 2925 cm, the wave number of the asymmetric stretching vibration of methylene.^-1Is continuously detected by measuring the absorption with respect to an infrared detector. From this value, the concentration of the ethylene (co) polymer in the solution is quantitatively analyzed to determine the relationship between the elution temperature and the elution rate.
According to the TREF analysis, the change in the elution rate with respect to the temperature change can be continuously analyzed with a very small amount of sample, so that relatively fine peaks that cannot be detected by the fractionation method can be detected.
[0018]
In addition, the ethylene (co) polymer (A) further elutes at a temperature T at which 25% of the whole is eluted from an integrated elution curve obtained by (e) elution temperature-elution amount curve by continuous temperature elution fractionation (TREF).₂₅And the temperature T at which 75% of the whole elutes₇₅Difference T from₇₅−T₂₅And the density d preferably satisfies the following relationship (Equation 2).
(Equation 2) d <0.950 g / cm³When
T₇₅−T₂₅≧ −300 × d + 285
d ≧ 0.950 g / cm³When
T₇₅−T₂₅≧ 0
T₇₅−T₂₅When the density and the density d satisfy the relationship of the above (Equation 2), the heat seal strength and the heat resistance are excellent.
[0019]
The ethylene (co) polymer (A) in the present invention preferably further satisfies (f) the mass average molecular weight of the ODCB-soluble component at 23 ° C. in the range of 8,000 to 30,000, more preferably 10,000 to 28,000. It is particularly preferably 13000 to 27000.
If the mass average molecular weight is less than 8000, it may cause stickiness and blocking of the molded product, and furthermore, the entanglement of the molecular chains hardly occurs, cohesive failure does not occur, and there is a possibility that it does not contribute to the improvement of the adhesive strength. is there. When the mass average molecular weight (Mw) exceeds 30,000, there is a concern that the adhesive strength is reduced.
[0020]
The ethylene (co) polymer (A) is an ethylene (co) polymer (A1) which further satisfies the requirements of (g) and (h) described below, or a copolymer of (i) and (j) further described below. It is preferably any of the ethylene (co) polymers (A2) satisfying the requirements.
[0021]
The ethylene-based (co) polymer (A1) has (g) the amount X (% by mass) of the ODCB-soluble component at 25 ° C., the density d, and the MFR satisfy the relationship of the following (formula 3) and (formula 4). I do.
(Equation 3) When d−0.008 log MFR ≧ 0.93,
X <2.0
(Equation 4) When d−0.008 log MFR <0.93,
X <9.8 × 10³X (0.9300-d + 0.008 log MFR)²+2.0
Preferably,
When d−0.008 log MFR ≧ 0.93,
X <1.0
When d−0.008 log MFR <0.93,
X <7.4 × 10³X (0.9300-d + 0.008 log MFR)²+2.0
Satisfy the relationship. More preferably,
When d−0.008 log MFR ≧ 0.93,
X <0.5
When d−0.008 log MFR <0.93,
X <5.6 × 10³X (0.9300-d + 0.008 log MFR)²+2.0
Satisfy the relationship.
[0022]
Here, the amount X of the ODCB-soluble component at 25 ° C. is measured by the following method. 0.5 g of the sample is heated at 135 ° C. for 2 hours in 20 ml of ODCB to completely dissolve the sample and then cooled to 25 ° C. After leaving this solution at 25 ° C. overnight, the solution is filtered through a Teflon (registered trademark) filter to collect a filtrate. The filtrate, which is a sample solution, was subjected to infrared spectroscopy to measure the asymmetric stretching vibration wave number of methylene at 2925 cm^-1The intensity of the nearby absorption peak is measured, and the sample concentration is calculated from a calibration curve created in advance. From this value, the ODCB-soluble content at 25 ° C. is determined.
[0023]
The ODCB-soluble component at 25 ° C. is a high branching degree component and a low molecular weight component contained in the ethylene (co) polymer, which causes a decrease in heat resistance and a sticky surface of a molded product, and causes a problem of hygiene and molding. It is desirable that this content be low because it causes blocking of the body surface. The amount of the ODCB-soluble component is affected by the α-olefin content and the molecular weight of the entire copolymer, that is, the density and the MFR. Therefore, the fact that the density and the amounts of MFR and ODCB-soluble component, which are these indices, satisfy the above relationship indicates that the uneven distribution of α-olefin contained in the whole copolymer is small.
[0024]
Further, the ethylene-based (co) polymer (A1) has a plurality of peaks in the elution temperature-elution amount curve obtained by (g) continuous temperature elution fractionation (TREF). It is particularly preferred that the peak on the high temperature side of the plurality of peak temperatures exists between 85 ° C and 100 ° C. The presence of this peak increases the melting point, increases the crystallinity, and improves the heat resistance and rigidity of the molded body.
[0025]
Here, as shown in FIG. 3, the ethylene-based (co) polymer (A1) has substantially a plurality of peaks in an elution temperature-elution amount curve obtained by a continuous heating elution fractionation method (TREF). It is a special ethylene (co) polymer. On the other hand, the ethylene-based (co) polymer shown in FIG. 4 is an ethylene-based (co) polymer having substantially one peak in an elution temperature-elution amount curve obtained by a continuous heating elution fractionation method (TREF). This corresponds to a conventional typical metallocene catalyst-based ethylene (co) polymer.
[0026]
As shown in FIG. 5, the ethylene-based (co) polymer (A2) in the present invention has one peak of an elution temperature-elution amount curve obtained by (h) continuous heating elution fractionation (TREF).
The ethylene (co) polymer (A2) having one peak of the elution temperature-elution amount curve by TREF has excellent heat resistance.
[0027]
Further, the ethylene (co) polymer (A2) in the present invention has (i) one or more melting point peaks and the highest melting point T among them._mlAnd the density d satisfy the relationship of the following (Equation 5).
(Equation 5) T_ml≧ 150 × d-19
If the melting point Tm1 and the density d do not satisfy the relationship of the above (Equation 5), the heat resistance may be deteriorated.
[0028]
Further, among the ethylene (co) polymers (A2), an ethylene (co) polymer that further satisfies the following requirement (j) is preferable.
(K) The melt tension (MT) and the melt flow rate (MFR) satisfy the following relationship (Equation 6).
(Equation 6) logMT ≦ −0.572 × logMFR + 0.3
When the MT and the MFR satisfy the relationship of the above (Equation 6), the moldability such as film molding becomes good.
[0029]
Here, as shown in FIG. 5, the ethylene copolymer (A2) has one TREF peak as shown in FIG. 5, but the ethylene copolymer based on a conventional typical metallocene catalyst has the above-mentioned formula (Formula 2). 2) is not satisfied, and is distinguished from an ethylene (co) polymer using a conventional typical metallocene catalyst.
[0030]
Such an ethylene (co) polymer (A) is a linear ethylene (co) polymer obtained by copolymerizing ethylene and an α-olefin in the presence of a single-site catalyst. Such a linear ethylene (co) polymer has excellent adhesion to a substrate or the like. Further, since the molecular weight distribution and the composition distribution are narrow, the polymer is excellent in mechanical properties, excellent in heat sealing property, heat blocking property, and the like, and has good heat resistance.
[0031]
Examples of the catalyst for producing the ethylene (co) polymer (A) in the present invention include a conventional typical metallocene catalyst, and include at least an organic cyclic compound having at least a conjugated double bond and a group IV of the periodic table. Single site catalysts containing transition metal compounds are preferred. As the single-site catalyst, it is particularly desirable to prepare a catalyst obtained by mixing the following compounds a1 to a4.
a1: General formula Me¹R¹ _pR² _q(OR³)_rX¹ _4-pqr A compound represented by the formula:¹ Represents zirconium, titanium and hafnium;¹ And R³ Is a hydrocarbon group having 1 to 24 carbon atoms, R² Are 2,4-pentanedionato ligands or derivatives thereof, benzoylmethanato ligands, benzoylacetonato ligands or derivatives thereof, X¹ Represents a halogen atom, and p, q and r are integers satisfying the ranges of 0 ≦ p ≦ 4, 0 ≦ q ≦ 4, 0 ≦ r ≦ 4, and 0 ≦ p + q + r ≦ 4, respectively.
a2: General formula Me²R⁴ _m(OR⁵)_nX² _zmn A compound represented by the formula:² Is a group I-III element of the periodic table, R⁴ And R⁵ Is a hydrocarbon group having 1 to 24 carbon atoms, X²Is a halogen atom or a hydrogen atom (however, X² When Me is a hydrogen atom,² Denotes a group III element of the periodic table), and z denotes Me² And m and n are integers satisfying the ranges of 0 ≦ m ≦ z and 0 ≦ n ≦ z, respectively, and 0 ≦ m + n ≦ z.
a3: Organic cyclic compound having a conjugated double bond
a4: Modified organic aluminum oxy compound and / or boron compound containing Al-O-Al bond
[0032]
The details are described below.
The general formula Me of the catalyst component a1¹R¹ _pR² _q(OR³)_rX¹ _4-pqr In the formula of the compound represented by¹ Represents zirconium, titanium, or hafnium, and the type of these transition metals is not limited, and a plurality of transition metals can be used. However, it is particularly preferable that zirconium having excellent weather resistance of the copolymer is contained. R¹ And R³ Is a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms. Specifically, alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group and butyl group; alkenyl groups such as vinyl group and allyl group; phenyl group, tolyl group, xylyl group, mesityl group, indenyl group and naphthyl group And an aralkyl group such as a benzyl group, a trityl group, a phenethyl group, a styryl group, a benzhydryl group, a phenylbutyl group, and a neophyl group. These may have branches. R² Represents a 2,4-pentanedionato ligand or a derivative thereof, a benzoylmethanato ligand, a benzoylacetonato ligand or a derivative thereof. X¹ Represents a halogen atom such as fluorine, iodine, chlorine and bromine. p, q and r are integers that satisfy the ranges of 0 ≦ p ≦ 4, 0 ≦ q ≦ 4, 0 ≦ r ≦ 4, and 0 ≦ p + q + r ≦ 4, respectively.
[0033]
Examples of the compound represented by the general formula of the catalyst component a1 include tetramethyl zirconium, tetraethyl zirconium, tetrabenzyl zirconium, tetrapropoxy zirconium, tripropoxy monochlorodisilconium, tetraethoxy zirconium, tetrabutoxy zirconium, tetrabutoxy titanium, tetrabutoxy titanium And Zr (OR) such as tetrapropoxyzirconium and tetrabutoxyzirconium.₄ Compounds are preferred, and they may be used in combination of two or more. Specific examples of the 2,4-pentanedionato ligand or derivative thereof, benzoylmethanato ligand, benzoylacetonato ligand or derivative thereof include tetra (2,4-pentanedionato) zirconium. , Tri (2,4-pentanedionato) chloride zirconium, di (2,4-pentanedionato) dichloride zirconium, (2,4-pentanedionato) trichloride zirconium, di (2,4-pentanedionato) Diethoxide zirconium, di (2,4-pentanedionato) di-n-propoxide zirconium, di (2,4-pentanedionato) di-n-butoxide zirconium, di (2,4-pentane Dionato) dibenzylzirconium, di (2,4-pentanedionato) dineophilzirconium, tetra ( Benzoylmethanato) zirconium, di (dibenzoylmethanato) dioxide zirconium, di (dibenzoylmethanato) di-n-propoxide zirconium, di (dibenzoylmethanato) di-n-butoxide zirconium, di (benzoyl) Examples thereof include (acetonato) dioxide zirconium, di (benzoylacetonato) di-n-propoxide zirconium, and di (benzoylacetonato) di-n-butoxide zirconium.
[0034]
The general formula Me of the catalyst component a2²R⁴ _m(OR⁵)_nX² _zmn In the formula of the compound represented by² Represents an element of Groups I to III of the periodic table, such as lithium, sodium, potassium, magnesium, calcium, zinc, boron, and aluminum. R⁴ And R⁵ Is a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, and more preferably 1 to 8 carbon atoms. Specifically, alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group and butyl group; alkenyl groups such as vinyl group and allyl group; phenyl group, tolyl group, xylyl group, mesityl group, indenyl group and naphthyl group And an aralkyl group such as a benzyl group, a trityl group, a phenethyl group, a styryl group, a benzhydryl group, a phenylbutyl group, and a neophyl group. These may have branches. X² Represents a halogen atom or a hydrogen atom such as fluorine, iodine, chlorine and bromine. Where X² When Me is a hydrogen atom,² Is limited to those of Group III elements of the periodic table exemplified by boron, aluminum and the like. Z is Me² And m and n are integers satisfying the ranges of 0 ≦ m ≦ z and 0 ≦ n ≦ z, respectively, and 0 ≦ m + n ≦ z.
[0035]
Examples of the compound represented by the general formula of the catalyst component a2 include organic lithium compounds such as methyl lithium and ethyl lithium; organic magnesium compounds such as dimethyl magnesium, diethyl magnesium, methyl magnesium chloride, and ethyl magnesium chloride; dimethyl zinc, diethyl Organic zinc compounds such as zinc; organic boron compounds such as trimethylboron and triethylboron; trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, tridecylaluminum, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum Sesquichloride, diethyl aluminum ethoxide, diethyl aluminum hydride Any derivative of an organic aluminum compound, and the like.
[0036]
The organic cyclic compound having a conjugated double bond of the catalyst component a3 is one or two or more rings having two or more, preferably two to four, more preferably two to three conjugated double bonds. A cyclic hydrocarbon compound having 4 to 24 carbon atoms, preferably 4 to 12 carbon atoms; wherein the cyclic hydrocarbon compound is partially a hydrocarbon residue having 1 to 6 carbon atoms (typically, 1 to 6 carbon atoms). A cyclic hydrocarbon compound substituted with 12 or more alkyl groups or aralkyl groups; having one or more rings having two or more, preferably two to four, more preferably two to three conjugated double bonds. An organosilicon compound having a cyclic hydrocarbon group having a total carbon number of 4 to 24, preferably 4 to 12; a hydrocarbon residue or an alkali metal salt (sodium) in which the cyclic hydrocarbon group is partially 1 to 6 Or lithium salt) The organosilicon compound is contained. Particularly preferably, those having a cyclopentadiene structure in any of the molecules are desirable.
[0037]
Examples of suitable compounds include cyclopentadiene, indene, azulene, and alkyl, aryl, aralkyl, alkoxy or aryloxy derivatives thereof. Further, a compound obtained by bonding (crosslinking) these compounds via an alkylene group (the number of carbon atoms of which is usually 2 to 8, preferably 2 to 3) is also preferably used.
[0038]
The organosilicon compound having a cyclic hydrocarbon group can be represented by the following general formula.
A_LSiR_4-L
Here, A represents the cyclic hydrogen group exemplified by a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, and a substituted indenyl group, and R represents a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group. An alkyl group such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group; an aryl group such as a phenyl group; an aryloxy group such as a phenoxy group; an aralkyl group such as a benzyl group; Represents 24 to 24, preferably 1 to 12 hydrocarbon residues or hydrogen, and L is 1 ≦ L ≦ 4, preferably 1 ≦ L ≦ 3.
[0039]
Specific examples of the organic cyclic hydrocarbon compound of the component a3 include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, propylcyclopentadiene, butylcyclopentadiene, 1,3-dimethylcyclopentadiene, and 1-methyl-3-ethylcyclopentadiene. , 1-methyl-3-propylcyclopentadiene, 1-methyl-3-butylcyclopentadiene, 1,2,4-trimethylcyclopentadiene, pentamethylcyclopentadiene, indene, 4-methyl-1-indene, 4,7- C5-C24 cyclopolyene or substituted cyclopolyene such as dimethylindene, cycloheptatriene, methylcycloheptatriene, cyclooctatetraene, azulene, fluorene, methylfluorene, monocyclope Tajienirushiran, biscyclopentadienyl silane, tris cyclopentadienyl silane, mono indenyl silane, bis indenyl silane, and tris indenyl silane.
[0040]
The modified organoaluminum oxy compound containing an Al—O—Al bond of the catalyst component a4 is obtained by reacting an alkylaluminum compound with water to obtain a modified organoaluminum oxy compound usually called aluminoxane. It usually contains 1 to 100, preferably 1 to 50 Al-O-Al bonds. The modified organic aluminum oxy compound may be linear or cyclic.
[0041]
The reaction between the organoaluminum and water is usually performed in an inert hydrocarbon. As the inert hydrocarbon, aliphatic, alicyclic, and aromatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, benzene, toluene, and xylene are preferable.
The reaction ratio (water / Al molar ratio) between water and the organoaluminum compound is usually from 0.25 / 1 to 1.2 / 1, preferably from 0.5 / 1 to 1/1.
[0042]
As the boron compound, triethylaluminum tetra (pentafluorophenyl) borate, triethylammonium tetra (pentafluorophenyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, dimethylaniliniumtetra (pentafluorophenyl) borate, butylammonium Tetra (pentafluorophenyl) borate, N, N-dimethylaniliniumtetra (pentafluorophenyl) borate, N, N-dimethylaniliniumtetra (3,5difluorophenyl) borate, trityltetrakispentafluoroborate, ferrocenium Examples include tetrakispentafluoroborate and trispentafluoroborane. Among them, N, N_-dimethylanilinium tetra (pentafluorophenyl) borate, trityltetrakispentafluoroborate, ferrocenium tetrakispentafluoroborate, and trispentafluoroborane are preferable.
[0043]
The above catalyst may be used by mixing and contacting a1 to a4, but it is preferable to use the catalyst by supporting it on an inorganic carrier and / or a particulate polymer carrier (a5).
Examples of the inorganic carrier and / or the particulate polymer carrier (a5) include a carbonaceous material, a metal, a metal oxide, a metal chloride, a metal carbonate, a mixture thereof, a thermoplastic resin, and a thermosetting resin. Suitable metals that can be used for the inorganic carrier include iron, aluminum, nickel and the like.
Specifically, SiO₂, Al₂O₃, MgO, ZrO₂, TiO₂, B₂O₃, CaO, ZnO, BaO, ThO₂And mixtures thereof.₂-Al₂O₃, SiO₂-V₂O₅, SiO₂-TiO₂, SiO₂-V₂O₅, SiO₂-MgO, SiO₂−Cr₂O₃And the like. Among them, SiO₂And Al₂O₃The main component is preferably at least one component selected from the group consisting of:
In addition, as the organic compound, any of a thermoplastic resin and a thermosetting resin can be used. Specifically, particulate polyolefin, polyester, polyamide, polyvinyl chloride, polymethyl (meth) acrylate, polystyrene, poly Examples include norbornene, various natural polymers, and mixtures thereof.
[0044]
The above-mentioned inorganic carrier and / or particulate polymer carrier can be used as they are, but preferably, as a preliminary treatment, these carriers are contact-treated with an organoaluminum compound or a modified organoaluminum compound containing an Al-O-Al bond. After that, it can be used as the component a5.
[0045]
The ethylene (co) polymer (A) is produced by a gas phase polymerization method, a slurry polymerization method, a solution polymerization method, or the like in the presence of the above-mentioned catalyst and substantially no solvent, and is substantially made of oxygen, water, or the like. In a state where the above-mentioned conditions have been refused, aliphatic hydrocarbons such as butane, pentane, hexane, and heptane; aromatic hydrocarbons such as benzene, toluene, and xylene; and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; It is produced in the presence or absence of an active hydrocarbon solvent. The polymerization conditions are not particularly limited, but the polymerization temperature is usually 15 to 350 ° C., preferably 20 to 200 ° C., more preferably 50 to 110 ° C., and the polymerization pressure is usually normal pressure to 70 kg / cm in the case of the low and medium pressure method.² G, preferably normal pressure to 20 kg / cm² G, usually 1500 kg / cm for high pressure method² G or less is desirable. The polymerization time is usually from 3 minutes to 10 hours, preferably from 5 minutes to 5 hours in the case of the low and medium pressure method. In the case of the high-pressure method, it is usually 1 minute to 30 minutes, preferably 2 minutes to 20 minutes. Further, the polymerization is not particularly limited to a one-stage polymerization method, but also to a two-stage or more multi-stage polymerization method in which polymerization conditions such as hydrogen concentration, monomer concentration, polymerization pressure, polymerization temperature, and catalyst are different from each other. As a particularly preferred production method, a method described in JP-A-5-132518 is exemplified.
[0046]
The ethylene (co) polymer (A) has a halogen concentration of at most 10 ppm, preferably at most 5 ppm, more preferably substantially at least, by using a catalyst having no halogen such as chlorine in the above-mentioned catalyst components. ND: 2 ppm or less (ND: Non-Detect).
By using such a halogen-free ethylene (co) polymer such as chlorine, there is no need to use an acid neutralizer (halogen absorber) as in the prior art, and it is excellent in chemical stability and the like. It becomes. Further, by using such a halogen-free state, there is no adverse effect of the acid neutralizer, and the adhesive strength can be improved.
[0047]
[Other polyolefin resin (B)]
The other polyolefin resin (B) is a polyolefin resin (B) other than the ethylene (co) polymer (A), and is a low-density polyethylene (LDPE) obtained by a high-pressure radical polymerization method, ethylene vinyl Ester copolymers, copolymers of ethylene with α, β-unsaturated carboxylic acids or derivatives thereof; having a density of 0.86 to 0.97 g / cm obtained from a Ziegler catalyst, a Phillips catalyst, or the like.³And other ethylene-based (co) polymers; polypropylene-based resins, poly-1-butene resins, poly-4-methyl-1-pentene resins, and mixtures thereof. By blending such another polyolefin-based resin (B), the moldability, heat resistance, and the like can be improved.
[0048]
The MFR of the LDPE is in the range of 0.01 to 100 g / 10 min, preferably 0.1 to 80 g / 10 min, and more preferably 0.5 to 50 g / 10 min. The density of LDPE is 0.91 to 0.94 g / cm.³ , More preferably 0.91 to 0.935 g / cm³ Range. Within this range, the melt tension is in an appropriate range, and the moldability is improved. The melt tension of LDPE is 1.5 to 25 g, preferably 3 to 20 g, and more preferably 3 to 15 g. The molecular weight distribution Mw / Mn of LDPE is 3.0 to 12, preferably 4.0 to 8.0.
[0049]
The ethylene-vinyl ester copolymer is a vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate, vinyl stearate, and trifluoroacetic acid containing ethylene produced as a main component by a high-pressure radical polymerization method. It is a copolymer with a vinyl ester monomer such as vinyl. Among them, particularly preferred is vinyl acetate. Further, a copolymer comprising 50 to 99.5% by mass of ethylene, 0.5 to 50% by mass of a vinyl ester, and 0 to 49.5% by mass of another copolymerizable unsaturated monomer is preferable. Particularly, the content of the vinyl ester is in the range of 3 to 30% by mass, preferably 5 to 25% by mass. The MFR of the ethylene / vinyl ester copolymer is in the range of 0.01 to 100 g / 10 minutes, preferably 0.1 to 50 g / 10 minutes, and more preferably 1.0 to 30 g / 10 minutes.
[0050]
Examples of the copolymer of ethylene and an α, β-unsaturated carboxylic acid or a derivative thereof include ethylene / (meth) acrylic acid and an alkyl ester copolymer thereof. These comonomers include acrylic acid and methacrylic acid. Acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, cyclohexyl acrylate, Examples thereof include cyclohexyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, glycidyl acrylate, and glycidyl methacrylate. Among these, particularly preferred are alkyl esters of (meth) acrylic acid such as methyl and ethyl. In particular, the content of the (meth) acrylate is in the range of 3 to 30% by mass, preferably 5 to 25% by mass. The MFR of a copolymer of ethylene and an α, β-unsaturated carboxylic acid or a derivative thereof has a MFR of 0.01 to 100 g / 10 min, preferably 0.05 to 50 g / 10 min, and more preferably 0.1 to 30 g / min. 10 minutes.
[0051]
[Compounding ratio of resin material]
The resin material forming the adhesive layer (II) contains 100 to 10% by mass of an ethylene (co) polymer (A) and 0 to 90% by mass of another polyolefin-based resin (B). It may be composed only of the (co) polymer (A). Preferably, the ethylene (co) polymer (A) is 50% by mass or more and the other polyolefin-based resin (B) is less than 50% by mass, and more preferably, the ethylene (co) polymer (A) is 65% by mass or more. And less than 35% by mass of the other polyolefin-based resin (B).
If the content of the ethylene (co) polymer (A) is less than 10% by mass and the content of the polyolefin-based resin (B) is 90% by mass or more, the adhesion and the like become insufficient.
[0052]
[Epoxy compound (C)]
The resin material forming the adhesive layer (II) may further contain an epoxy compound (C). When the epoxy compound (C) is contained, the adhesiveness can be further improved. As the epoxy compound (C), a polyvalent epoxy compound containing at least two or more epoxy groups (oxirane groups) in the molecule and having a molecular weight of 3000 or less is suitably used. When the epoxy compound has one epoxy group in the molecule, the effect of improving the adhesiveness to the base material cannot be expected much. The molecular weight of the epoxy compound is preferably 3000 or less, and particularly preferably 1500 or less. When the molecular weight exceeds 3,000, there is a possibility that a sufficient effect of improving adhesiveness may not be obtained when the composition is formed.
[0053]
Examples of such an epoxy compound (C) include diglycidyl phthalate, diglycidyl isophthalate, diglycidyl terephthalate, diglycidyl adipic ester, trimethylolpropane triglycidyl ether, polyglycerol polyglycidyl ether, Examples thereof include pentaerythritol polyglycidyl ether, butanediol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, phenol novolak polyglycidyl ether, and epoxidized vegetable oil. Among them, epoxidized vegetable oil is preferred from the viewpoint of ease of handling.
[0054]
Here, the epoxidized vegetable oil is obtained by epoxidizing an unsaturated double bond of a natural vegetable oil using a peracid or the like. For example, epoxidized soybean oil, epoxidized linseed oil, epoxidized olive oil, epoxidized safflower. Oil, epoxidized corn oil and the like. These epoxidized vegetable oils are commercially available as, for example, O-130P (epoxidized soybean oil), O-180A (epoxidized linseed oil) manufactured by Asahi Denka Kogyo KK.
It should be noted that the presence of an unepoxidized or insufficiently epoxidized oil component which is slightly produced as a by-product when epoxidizing vegetable oil does not hinder the function and effect of the present invention.
[0055]
The addition amount of the epoxy compound (C) is preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the resin component composed of the ethylene (co) polymer (A) and the other polyolefin-based resin (B). , More preferably 0.1 to 7 parts by mass, particularly preferably 0.2 to 5 parts by mass. When the addition amount of the epoxy compound (C) is less than 0.05 parts by mass, the effect of improving the adhesive strength to the base material may be insufficient. When the addition amount exceeds 10 parts by mass, the adhesiveness is improved, but due to stickiness. There is a possibility that adverse effects such as blocking or odor may occur.
[0056]
[Olefin resin having functional group]
Further, the resin material forming the adhesive layer (II) may further contain an olefin resin (D) having a functional group that reacts with an epoxy group in the molecule. The olefin-based resin (D) having a functional group that reacts with the epoxy group is not essential, but by adding this, the adhesion to the substrate can be further improved. This is because a reaction occurs between the functional group capable of reacting with the epoxy group and the epoxy compound, and the amount of the epoxy compound (C) grafted to the resin component increases.
[0057]
The amount of the olefin resin (D) having a functional group that reacts with the epoxy group is the total amount of the ethylene (co) polymer (A), the other polyolefin resin (B), and the olefin resin (D). It is preferably less than 30% by mass, more preferably 2 to 25% by mass, and still more preferably 5 to 20% by mass with respect to the mass. When the olefin-based resin (D) is added in an amount of 30% by mass or more, the effect of improving the adhesion is obtained but is not economical.
[0058]
Examples of the functional group that reacts with the epoxy group include a carboxyl group or a derivative thereof, an amino group, a phenol group, a hydroxyl group, and a thiol group. Among them, an olefin resin (D) having at least one group selected from the group consisting of an acid anhydride group, a carboxyl group, and a metal salt of a carboxylic acid in the molecule is preferably used in view of the balance between reactivity and stability.
Examples of a method for introducing a functional group that reacts with an epoxy group include a copolymerization method and a grafting method.
[0059]
For example, as the olefin-based resin (D) having a functional group that reacts with an epoxy group, which is produced by a copolymerization method, a binary or multi-component copolymer of ethylene and a compound capable of reacting with ethylene may be mentioned. Compounds used for the copolymerization include α, β-unsaturated carboxylic acids such as (meth) acrylic acid, α, β-unsaturated carboxylic acid metal salts such as sodium (meth) acrylate, maleic anhydride, and itaconic anhydride And unsaturated carboxylic acid anhydrides such as citraconic anhydride, hydroxyl-containing compounds such as hydroxyethyl (meth) acrylate and (meth) allyl alcohol, and unsaturated amino compounds such as allylamine. Further, in addition to these unsaturated compounds, a vinyl alcohol ester such as (meth) acrylate, vinyl acetate, vinyl propionate and the like may be copolymerized and used.
These compounds can be used as a mixture of two or more kinds in a copolymer with ethylene, and a copolymer of these compounds and ethylene can be used in combination of two or more kinds. For example, ethylene- (meth) acrylic acid copolymer, ethylene-maleic anhydride copolymer, ethylene-maleic anhydride-vinyl acetate copolymer, ethylene-maleic anhydride-acrylic acid ester copolymer and the like can be mentioned. .
[0060]
On the other hand, the olefin-based resin (D) into which a functional group capable of reacting with an epoxy group is introduced by graft modification allows a free radical generator such as a polyolefin and a peroxide and a compound for modification to act in a molten or solution state. It is common to manufacture it.
Examples of polyolefin resins used for graft modification include LDPE, linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE), polypropylene (PP), ethylene-propylene copolymer, propylene-butene-1 Copolymers, ethylene-vinyl acetate copolymer (EVA), ethylene- (meth) acrylic acid copolymer (E (M) A), ethylene-vinyl acetate- (meth) acrylate copolymer, and the like. Can be These can be used alone or in combination of two or more.
Further, for example, a copolymer which already contains an acid or a derivative thereof, such as an ethylene-maleic anhydride- (meth) acrylate copolymer, may be used after further graft modification.
[0061]
[Free radical generator]
The type of the free radical generator used at the time of graft modification is not particularly limited. For example, as the free radical generator, a common organic peroxide is used, and among them, from the viewpoint of good reactivity and easy handling. Dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3,1,3 -Bis (2-t-butylperoxyisopropyl) benzene, benzoyl peroxide and the like are preferably used.
[0062]
As the unsaturated compound for modification, the same unsaturated compound as the compound copolymerizable with ethylene used in the above copolymerization method is used, and a carboxylic acid group or a carboxylic acid anhydride group and a metal salt thereof, Basically, it can be used as long as it has a radically reactive unsaturated group such as a group or a hydroxyl group.
Examples of such an unsaturated compound for modification include unsaturated carboxylic acids such as (meth) acrylic acid, unsaturated carboxylic acid metal salts such as sodium (meth) acrylate, maleic anhydride or itaconic anhydride, Examples include unsaturated carboxylic anhydrides such as citraconic acid, unsaturated hydroxyl group-containing compounds such as hydroxyethyl (meth) acrylate and (meth) allyl alcohol, and unsaturated amino compounds such as allylamine, but are not limited thereto.
[0063]
If necessary, conventional additives such as antioxidants, plasticizers, lubricants, various stabilizers, antiblocking agents, antistatic agents, pigments, various inorganic and organic fillers may be added to the resin material forming the adhesive layer (II). It is also possible to add such known additives, but it is desirable that these known additives are not blended. By making such an additive-free, non-polar, polyethylene-based resin, such as polypropylene, which is considered to have low adhesion to a highly crystalline resin, the specific range of the ODCB-soluble component at 23 ° C. By using the ethylene (co) polymer (A) having a molecular weight, a strong adhesive strength can be obtained without using an anchor coat agent.
[0064]
The resin material forming the adhesive layer (II) may be a resin material comprising the ethylene (co) polymer (A) and another polyolefin resin (B) and / or an epoxy compound (C), if desired, The olefin-based resin (D) having a group can be obtained by mixing using an Henschel mixer, a ribbon mixer, or the like, or kneading the mixture using an open roll, a Banbury mixer, a kneader, an extruder, or the like. . The kneading temperature is usually from the melting point of the resin to 350 ° C.
[0065]
[Surface layer (III)]
The surface layer (III) in the present invention is mainly composed of a homopolymer or a copolymer of various α-olefins having 3 or more carbon atoms depending on the use. Here, the main component means that the content is 50% by mass or more. Examples of the homopolymer or copolymer of an α-olefin having 3 or more carbon atoms include, for example, a polypropylene resin and a polybutene-1 polymer resin obtained by low, medium, and high pressure polymerization using a Ziegler catalyst, a metallocene catalyst, or the like. , Poly-4-methyl-1-pentene resins and mixtures thereof. Among them, a polypropylene resin or a poly-4-methyl-1-pentene resin and a mixture thereof are preferable.
[0066]
[Polypropylene resin]
Examples of the polypropylene-based resin include a propylene homopolymer, a random copolymer of propylene and another α-olefin having 2 to 20 carbon atoms, a block copolymer, and the like. As the comonomer of the block copolymer or the random copolymer, α-olefins other than propylene such as ethylene, butene-1, pentene-1, and hexene-1 are used, and among them, ethylene is particularly preferable. The propylene content in these copolymers is preferably from 60 to 100 mol%, particularly preferably from 80 to 99 mol%. In a block copolymer using ethylene as the α-olefin, the ethylene-propylene block in the molecule is dispersed in the homopolypropylene block to exhibit rubber elasticity and function as a rubber component. The content of the rubber component is preferably 10 to 25% by mass of the block copolymer.
In the polypropylene resin, the melt flow rate at a load of 2.16 kg (230 ° C.) is preferably 0.001 to 1000 g / 10 minutes, more preferably 0.01 to 100 g / 10 minutes, and still more preferably. Is 0.1 to 50 g / 10 min. If the melt flow rate is too low or too high, the moldability may deteriorate. If the melt flow rate is too high, there is a concern that the strength of the product will decrease.
[0067]
[Poly-4-methyl-1-pentene resin]
Examples of the poly-4-methyl-1-pentene resin include 4-methyl-1-pentene homopolymer and copolymers thereof with one or more other α-olefins having 2 to 16 carbon atoms. Coalescence and the like.
In the poly-4-methyl-1-pentene resin, the melt flow rate at a load of 5.0 kg (260 ° C.) is preferably 20 to 500 g / 10 min, and more preferably 50 to 300 g / 10 min. . If the melt flow rate is too low or too high, the moldability is poor.
Further, a 4-methyl-1-pentene resin or a composition thereof can also be used. The composition contains a polyolefin such as a polyethylene resin or a polypropylene resin. Among them, a resin to which a polypropylene resin is added is particularly preferable from the viewpoints of heat resistance, peelability, and adhesive strength with an adhesive layer.
When a poly-4-methyl-1-pentene resin composition is used as the surface layer (III), the crystallization temperature of the poly-4-methyl-1-pentene resin is different from that of a polyolefin, particularly polypropylene. Thus, the extrusion lamination causes the poly-4-methyl-1-pentene resin having a low viscosity to segregate on the surface. As a result, in the obtained surface layer, the ratio of the poly-4-methyl-1-pentene-based resin increases on its surface, and only a small amount of the poly-4-methyl-1-pentene-based resin is blended. High releasability and heat resistance due to the poly-4-methyl-1-pentene resin are exhibited in the surface layer with high efficiency.
[0068]
The poly-4-methyl-1-pentene resin composition has a content of the poly-4-methyl-1-pentene resin of 95 to 50% by mass and the other polyolefin resin of 5 to 50% by mass. It is desired to be blended. More preferably, the poly-4-methyl-1-pentene-based resin component is 90 to 60% by mass, and the other polyolefin-based resin is 10 to 40% by mass. With such a configuration, the releasability or heat resistance is improved.
Further, as the whole poly-4-methyl-1-pentene resin composition in the present invention, the melt flow rate (230 ° C.) under a load of 2.16 kg is desirably 0.001 to 1000 g / 10 minutes. . It is more preferably 0.01 to 100 g / 10 minutes, and still more preferably 0.1 to 50 g / 10 minutes. If the melt flow rate is too low or too high, the moldability may deteriorate.
Further, the poly-4-methyl-1-pentene resin composition preferably has a melting point of 220 to 250C, more preferably 230 to 240C.
[0069]
A blending method for obtaining the composition can be performed by a usual mixing operation, for example, a tumbler mixer method, a Henschel mixer method, a Banbury mixer method, or an extrusion granulation method.
In obtaining the composition, a neutralizing agent, a dispersant, an antioxidant, a lubricant, a weather resistance improver, an antistatic agent, a pigment, a filler, and other additional components that do not impair the effects of the present invention. Can be blended.
[0070]
When the surface layer is composed of the poly-4-methyl-1-pentene resin composition, the heat resistance is extremely high, and the resilience of the emboss once applied is excellent, and the surface releasability is extremely excellent. It becomes an excellent process sheet.
[0071]
Although the above-described process sheet has been described with reference to a laminate having a three-layer structure of the base material (I), the adhesive layer (II), and the surface layer (III), the present invention is not limited to this. Other layers may be provided as long as the functions and effects of the invention are not impaired. For example, another arbitrary layer may be provided on the surface of the base material on which the adhesive layer is not formed, or the adhesive layer may be composed of a plurality of layers.
The thickness of each layer such as the adhesive layer and the base material is not limited, and is appropriately set within a range in which each layer functions.
[0072]
[Process sheet manufacturing method]
The process sheet manufacturing method of the present invention is a method of forming a surface layer (III) on a substrate (I) via an adhesive layer (II). If this method is followed, any method can be adopted, and examples thereof include an inflation method, an extrusion lamination method, a co-extrusion lamination method, and a sand lamination method. The method and the coextrusion lamination method are preferred. Since an anchor coating agent is not used when manufacturing the process sheet, there is an effect that there is no danger of environmental pollution and fire caused by a solvent and that the cost is low.
Further, according to the present invention, a process sheet having high interlayer strength can be laminated at a low temperature and can be manufactured by high-speed molding at 200 to 400 m / min.
[0073]
An example of the process sheet manufacturing method of the present invention will be described below. In this example, a process sheet is manufactured by an extrusion lamination method.
FIG. 6 is a schematic view showing a manufacturing apparatus by an extrusion lamination method. The manufacturing apparatus includes a feeder 30 for feeding the base material 13, an extruder 31 for extruding a resin a serving as an adhesive layer (II) and a resin b serving as a surface layer (III), The process sheet 14 is schematically configured to include a cooling roll 32 and a nip roll 33 for pressing the resin sheet a and the resin b therebetween, and a winder 34 for winding the obtained process sheet 14. In the manufacturing method using this manufacturing apparatus, the base material 13 made of paper or the like is fed at a predetermined speed from the feeder 30 and fed between the nip roll 33 and the cooling roll 32, and the molten resin film serving as an adhesive layer is provided. The resin a in a state and the resin b in a molten resin film state as a surface layer are co-extruded from an extruder 31 to a cooling roll 32 side between a nip roll 33 and a cooling roll 32 so that the adhesive layer comes into contact with the base material 13. , A laminate in which the adhesive layer 16 and the surface layer 15 are laminated on the base material 13 is manufactured. Thereafter, the obtained process sheet 14 including the base material 13, the adhesive layer 16 and the surface layer 15 is wound up by a winder 34.
[0074]
The resin temperature of the molten resin film in the extrusion lamination method or the like is preferably in the range of 200 to 350 ° C, preferably in the range of 240 to 330 ° C, and more preferably in the range of 260 to 320 ° C. In particular, in the present invention, molding can be performed at less than 300 ° C. If the temperature is lower than 200 ° C., the resulting laminate may have low adhesive strength with the substrate (I), the adhesive layer (II), and the surface layer (III). On the other hand, when the resin temperature of the molten resin film exceeds 350 ° C., the resin is deteriorated, so that desired characteristics may not be obtained.
[0075]
In the above-mentioned production method, the homopolymer or copolymer of the resin material forming the adhesive layer (II) and the α-olefin having 3 to 10 carbon atoms forming the surface layer (III) is formed at a molding temperature of 200 to 350. While forming a molten resin film by co-extrusion at 0 ° C., the surface of the molten resin film which is in contact with the substrate (I) has (A) an oxygen atom concentration (Oc) of 1.8% by mass or more and (B) a degree of surface oxidation. The molten resin film and the base material (I) can be laminated by performing an oxidation treatment so that (Or) becomes 0.10 or more.
Here, preferably, (a) the oxygen atom concentration (Oc) is 2.0 to 40% by mass and (b) the surface oxidation degree (Or) is 0.12 to 1.8, and more preferably (a) the oxygen atom concentration (Oc) is 2.2 to 40% by mass and (b) surface oxidation degree (Or) is 0.15 to 1.5, particularly preferably (a) oxygen atom concentration (Oc) is 2.5 to 40% by mass. And (b) the degree of surface oxidation (Or) is 0.20 to 1.2.
Within such a range, the amount of generation of oxygen-containing functional groups such as carbonyl groups contributing to adhesion will increase, so that the adhesive strength will be improved. Therefore, in this process sheet, it is not necessary to use an anchor coating agent, and there is little elution by a solvent or the like, and the sheet is clean. Further, by not using an anchor coating agent, the cost is reduced and the operation is simplified. Further, since no solvent is used, environmental problems and odor problems are eliminated. The ethylene (co) polymer (A) is easily oxidized and contains a high molecular weight component sufficient to cause cohesive failure.
[0076]
Here, the oxygen atom concentration (Oc) refers to the oxygen O1s corrected peak intensity: O and the carbon C1s corrected peak measured by the ESCA method on the surface of the adhesive layer (II) in contact with the substrate (I). Intensity: A value obtained by substituting C into (Equation 7). The amount of oxygen atoms introduced into the bonding surface can be quantified by the oxygen atom concentration.
(Equation 7) Oc = O / (C + O) × 100 (%)
[0077]
The surface oxidation degree (Or) refers to the oxygen-containing group such as a carbonyl group or an aldehyde group which is considered to contribute to the adhesion by the oxidation treatment on the surface of the adhesive layer (II) in contact with the substrate (I). Is a value indicating the degree to which a compound having The surface oxidation degree (Or) was determined to be 1720 cm by absorption of a carbonyl group in a spectrum of absorbance measured by a surface FT-IR (ATR) method.^-1The peak height in the vicinity is I (1720), 1370 (1369) cm due to the pitch absorption of the methylene group.^-1When the height of the nearby peak is I (1370), it can be obtained by (Equation 8).
(Equation 8) Or = I (1720) / I (1370)
Since this value is calculated based on the pitching absorption of the methylene group, it is difficult to compare polymers having different molecular weights. However, by measuring the above (a) together, more detailed information on surface oxidation can be obtained. can get.
[0078]
The measurement of the oxygen atom concentration (Oc) and the measurement of the degree of surface oxidation (Or) are performed after the laminating step, but the adhesion layer (II) is adhered to the base material (I) and the surface layer (III). Then, it becomes difficult to obtain a sample for measuring the oxidized surface of the adhesive layer (II). Therefore, during the laminating step, a sample for ESCA measurement and a sample for IR measurement should be obtained. In order to obtain an IR measurement sample, first, before laminating, as shown in FIG. 7A, a part of the surface of the base material 112 on which the molten resin film 111 is laminated is formed as shown in FIG. As shown in the figure, a sample collection sheet 115 having a vinylidene tetrafluoride adhesive tape 114 (non-adhesive surface) stuck on a paper 113 is placed on both sides such that the vinylidene tetrafluoride adhesive tape 114 is in contact with the molten resin film 111. Laminate using adhesive tape. Next, after laminating the molten resin film 111 on the base material 112 to obtain the process sheet 110, a portion of the process sheet 110 to which the sample collection paper 115 is bonded is cut out. The laminate at the bonded portion of the sample collection paper 115 is formed of a base material (I) made of paper 112, paper 113, an adhesive tape 114 made of vinylidene tetrafluoride, and an adhesive layer (II) formed by solidifying a molten resin film 111. Are stacked in this order. Here, since the adhesive tape 114 made of vinylidene tetrafluoride and the adhesive layer (II) are not adhered to each other, the adhesive layer (II) having a completely exposed oxidized surface can be obtained by separating the adhesive layer (II). Can be Using the adhesive layer (II) thus obtained as a sample for IR measurement, the IR of the oxidized surface is measured.
[0079]
As the sample for ESCA measurement, in the method for obtaining a sample for IR measurement described above, a polyethylene terephthalate (PET) film in which one surface is untreated and the other surface is corona-treated is used instead of the sample collection paper 115. . The corona surface of this PET film is stuck on the substrate 112, the untreated surface of the PET film is on the substrate (I) side, and a sample for ESCA measurement is obtained in the same manner as the sample for IR measurement described above. Then, the ESCA of the surface in contact with the PET film (untreated surface) is measured.
[0080]
The oxidation treatment is to bring oxygen or ozone into contact with the molten resin film. At that time, the oxidation treatment may be performed with oxygen or air, or the oxidation treatment may be forcibly performed using an oxidation treatment device.
Specific examples of the oxidation treatment method include an ozone treatment, an ultraviolet treatment, a plasma treatment, a corona treatment, and the like, but the ozone treatment is particularly preferable because of its efficiency. For example, in FIG. 6, ozone is sprayed on the surface of the resin a by the ozone generator 35 to oxidize the resin.
The temperature of the oxidation treatment is not particularly limited, but is preferably 200 to 350 ° C, preferably 260 to 310 ° C, and more preferably 290 to 310 ° C, which is preferably applied to a molten resin film because oxidation is easy and efficient. It is desirable to be in the range of 300 ° C.
When the substrate (I) and the surface layer (III) are laminated through the adhesive layer (II) by performing such an oxidation treatment, the laminate can be laminated firmly at a lower temperature, but more efficiently and more efficiently. It is particularly preferable to perform the ozone treatment at a temperature of the molten resin film in the range of 200 to 350 ° C. because the layer can be firmly laminated.
[0081]
The amount of ozone treatment in the oxidation treatment with ozone varies depending on the type and conditions of the base material, but is 5 g / Nm.³× 1Nm³/ Hr ~ 100g / Nm³× 20Nm³/ Hr (ie, 5-2000 g / hr), preferably 10 g / Nm³× 1.5Nm³/ Hr-70g / Nm³× 10Nm³/ Hr (ie, 15-700 g / hr), more preferably 15 g / Nm³× 2Nm³/ Hr ~ 50g / Nm³× 8Nm³/ Hr (i.e., 30 to 400 g / hr). When the ozone treatment amount is less than 5 g / hr, the oxidation treatment becomes insufficient, and there is a possibility that the adhesive strength between the base material (I) and the adhesive layer (II) does not improve. Things may deteriorate.
[0082]
In addition, the base material (I) and / or the surface layer (III) can be subjected to a surface treatment such as a preheat treatment, a corona treatment, a flame treatment, and a UV treatment. Preferably, the interlayer adhesion strength between the corona-treated substrate (I) and the ozone-treated adhesive layer (II) is extremely high. As the corona treatment, a corona discharger 36 shown in FIG.² It is preferable to process in the range of 10 to 100 W min / m²It is more preferable to perform processing within the range.
[0083]
In the extrusion laminating method, the wettability of the transfer surface can be controlled by adjusting the laminating temperature during the extrusion lamination step of the surface layer, and the releasability of the surface can be adjusted.
[0084]
The method of using the process sheet thus obtained will be described. In order to use the process sheet for embossing, for example, to manufacture synthetic leather, first, as shown in FIG. 8, a process sheet 14 having a predetermined embossed surface is fed from a feed roll 21. Then, it is introduced between the pinch roll 22 and the cooling roll 24 via the guide roll 20 and the like.
Further, the base cloth 12 is fed out from the feeding roll 18 and is similarly introduced between the pinch roll 22 and the cooling roll 24.
Further, a molten skin material 10 such as urethane resin or PVC is extruded from an extruder 28 equipped with a T-die or the like between the pinch roll 22 and the cooling roll 24 and between the process sheet 14 and the base fabric 12. To be introduced. The resin extrusion molding temperature at this time is in the range of 100 to 250 ° C.
[0085]
Then, the process sheet 14 / skin material 10 / base cloth 12 is pressed between the pinch roll 22 and the cooling roll 24, and the skin material 10 is embossed and simultaneously solidified by cooling, as shown in FIG. A multilayer synthetic leather 11 composed of a skin material 10 and a base cloth 12 is manufactured.
Thereafter, the multilayer synthetic leather 11 composed of the skin material 10 and the base cloth 12 is wound around a winding roll 19, and the process sheet 14 is drawn out in a direction different from that of the multilayer synthetic leather winding roll 19 and wound. It is wound on a roll 17. This process sheet 14 can be used a plurality of times. Thus, a multilayer synthetic leather is continuously produced.
Alternatively, urethane resin, PVC, or the like may be applied on a flattened process sheet, heated and cured to form a resin film, and then the resin film may be peeled off from the process sheet to form an emboss on the surface. Synthetic leather comprising the formed resin film can be manufactured.
[0086]
In the production of synthetic leather, the method of using embossed press plates and rolls on the surface requires the replacement of large press plates and rolls when their life is expired or when embossing is changed. Not only does it take a lot of effort, but it also increases costs. In addition, it is necessary to dry the resin after embossing and stabilize the resin, and it takes a long time to manufacture.
However, if a process sheet is used as in the method shown in FIG. 8 described above, various embossing processes can be performed only by replacing the process sheet 14, and the resin is instantaneously cooled and solidified, so that it is very simple and short. Multilayer synthetic leather can be manufactured in a short time at low cost.
The thickness of each layer of the multilayer synthetic leather manufactured as described above is not uniquely determined because it varies depending on the application. However, the thickness of the skin material is preferably at least 40 μm or more because embossing is performed. The maximum thickness is in the range of up to 500 μm from the viewpoint of moldability. On the other hand, the thickness of the base fabric is in the range of 10 μm to 500 μm. Further, depending on the use, it is also possible to further provide a layer other than the base cloth and the skin material, for example, a protective layer or the like, to form a laminate of three or more layers.
[0087]
Incidentally, as the process sheet, it is not always necessary to impart embossing to the surface layer, but when using as a transfer sheet such as embossing, pressing a press plate or roll on which a predetermined embossing is formed. Good.
It is preferable that the surface of the surface layer is subjected to a surface treatment with a silicone release agent or the like as necessary.
In such a process sheet, the ethylene (co) polymer (A) used for the adhesive layer is directly laminated on the surface layer (III) and the base material (I) by extrusion lamination, etc. It is not necessary to use an anchor coat agent in order to exhibit sufficient adhesive strength. Therefore, there is no contamination of the working environment due to the use of the solvent. Further, since the anchor coating agent is not used, the residual solvent in the process sheet is reduced. In addition, since a sufficient adhesive strength can be obtained without using an anchor coating agent, high-speed molding can be performed. Further, since there is no need to use an anchor coating agent, the cost is reduced.
[0088]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
[0089]
The test method in this example is as follows.
[density]
It conformed to JIS K6760.
[MFR]
It conformed to JIS K6760.
[Mw / Mn]
GPC (150C type manufactured by Waters) was used, and ODCB at 135 ° C. was used as a solvent. The column used was Shodex HT806M.
[0090]
[TREF]
First, a sample was added to ODCB to which an antioxidant (for example, butylhydroxytoluene) was added so that the sample concentration was 0.05% by mass, and was heated and dissolved at 140 ° C. 5 ml of this sample solution was injected into the column filled with glass beads while keeping the column at 135 ° C., cooled to 25 ° C. at a cooling rate of 0.1 ° C./min, and the sample was deposited on the surface of the glass beads. . Next, the samples were sequentially eluted while the column temperature was raised at a constant rate of 50 ° C./hr while flowing ODCB through the column at a constant flow rate. At this time, the concentration of the sample eluted in the solvent was 2925 cm, the wave number of the asymmetric stretching vibration of methylene.^-1Was continuously detected by measuring the absorption with respect to the infrared detector. From this value, the concentration of the ethylene (co) polymer in the solution was quantitatively analyzed to determine the relationship between the elution temperature and the elution rate.
[T by DSC_mlMeasurement]
A sheet having a thickness of 0.2 mm was formed by hot pressing, and a sample of about 5 mg was punched from the sheet. This sample was kept at 230 ° C. for 10 minutes and then cooled to 0 ° C. at 2 ° C./min. Thereafter, the temperature was raised again to 170 ° C. at a rate of 10 ° C./min._mlAnd
[0091]
[ODCB soluble content]
0.5 g of the sample was added to 20 ml of ODCB and heated at 135 ° C. for 2 hours to completely dissolve the sample and then cooled to 25 ° C. After leaving this solution at 25 ° C. overnight, the solution was filtered through a Teflon (registered trademark) filter to collect a filtrate. Using an infrared spectrometer, the wave number of the asymmetric stretching vibration of methylene in the filtrate as the sample solution was 2925 cm.^-1The intensity of the nearby absorption peak was measured, and the sample concentration in the filtrate was calculated from a calibration curve created in advance. From this value, the ODCB-soluble content at 25 ° C. was determined.
[0092]
[Melt tension (MT)]
The stress when the molten polymer was stretched at a constant speed was determined by measuring with a strain gauge. The measurement sample was granulated into pellets and measured using an MT measuring device manufactured by Toyo Seiki Seisaku-sho. The orifice used has a hole diameter of 2.09 mmφ and a length of 8 mm. The measurement conditions are a resin temperature of 190 ° C., a cylinder descending speed of 20 mm / min, and a winding speed of 15 m / min.
[0093]
[Halogen concentration]
It was measured by a fluorescent X-ray method, and when chlorine of 10 ppm or more was detected, this was used as an analysis value. When it was less than 10 ppm, it was measured with a TOX-100 type chlorine / sulfur analyzer manufactured by Dia Instruments Co., Ltd., and when it was 2 ppm or less, it was assumed that it was not substantially contained, and it was regarded as ND (non-detect).
[0094]
The ethylene copolymer (A11) was polymerized by the following method.
[Preparation of solid catalyst]
In a catalyst preparation device equipped with an electromagnetic induction stirrer, 1000 ml of toluene purified under nitrogen, tetrapropoxyzirconium (Zr (OPr)_Four ) 26 g, indene 22 g and methylbutylcyclopentadiene 88 g were added, 100 g of tripropylaluminum was added dropwise over 100 minutes while maintaining the temperature at 90 ° C., and then reacted at the same temperature for 2 hours. After cooling to 40 ° C., 2,424 ml of a toluene solution of methylalumoxane (concentration: 3.3 mmol / ml) was added, and the mixture was stirred for 2 hours. Next, silica (calculated at 450 ° C. for 5 hours)^Two / G) After adding 2000 g and stirring at room temperature for 1 hour, nitrogen blowing and drying under reduced pressure were performed at 40 ° C. to obtain a solid catalyst (a) having good fluidity.
[Gas phase polymerization]
Using a continuous fluidized bed gas phase polymerization apparatus, polymerization temperature 65 ° C, total pressure 20kgf / cm² G copolymerized ethylene and 1-hexene. The solid catalyst (a) was continuously supplied, and ethylene, 1-hexene, hydrogen, and the like were supplied so as to be maintained at a predetermined molar ratio to carry out polymerization to obtain an ethylene copolymer (A11). Table 1 shows the measurement results of the physical properties of the copolymer.
[0095]
The ethylene copolymer (A12) was polymerized by the following method.
[Preparation of solid catalyst]
In a catalyst preparation device equipped with an electromagnetic induction stirrer, 1000 ml of toluene purified under nitrogen, tetrabutoxyzirconium (Zr (OBu))_Four ) 31 g and indene 74 g were added, and while maintaining the temperature at 90 ° C, 127 g of triisobutylaluminum was added dropwise over 100 minutes, followed by a reaction at the same temperature for 2 hours. After cooling to 40 ° C., 2,424 ml of a toluene solution of methylalumoxane (concentration: 3.3 mmol / ml) was added, and the mixture was stirred for 2 hours. Next, silica (calculated at 450 ° C. for 5 hours)^Two/ G) After adding 2000 g and stirring at room temperature for 1 hour, nitrogen blowing and drying under reduced pressure were performed at 40 ° C. to obtain a solid catalyst (b) having good fluidity.
[Gas phase polymerization]
Using a continuous fluidized bed gas phase polymerization apparatus, polymerization temperature 70 ° C, total pressure 20kgf / cm^Two G copolymerized ethylene and 1-hexene. The solid catalyst (b) was continuously supplied, and polymerization was carried out by supplying ethylene, 1-hexene and hydrogen at a predetermined molar ratio to obtain an ethylene copolymer (A12). Table 1 shows the measurement results of the physical properties of the copolymer.
[0096]
The ethylene copolymer (A2) was polymerized by the following method.
[Preparation of solid catalyst]
In a catalyst preparation device equipped with an electromagnetic induction stirrer, 1000 ml of toluene purified under nitrogen, tetrapropoxyzirconium (Zr (OPr)_Four) 26 g, indene 74 g and methylpropylcyclopentadiene 78 g were added, 100 g of tripropylaluminum was added dropwise over 100 minutes while maintaining the temperature at 90 ° C., and then the mixture was reacted at the same temperature for 2 hours. After cooling to 40 ° C., 2133 ml of a toluene solution of methylalumoxane (concentration: 3.3 mmol / ml) was added, and the mixture was stirred for 2 hours. Next, silica (calculated at 450 ° C. for 5 hours)^Two/ G) After adding 2000 g and stirring at room temperature for 1 hour, nitrogen blowing and drying under reduced pressure were performed at 40 ° C. to obtain a solid catalyst (c) having good fluidity.
[Gas phase polymerization]
Using a continuous fluidized bed gas phase polymerization apparatus, polymerization temperature 80 ° C, total pressure 20kgf / cm^TwoG copolymerized ethylene and 1-hexene. The solid catalyst (c) was continuously supplied, and ethylene, 1-hexene and hydrogen were supplied so as to maintain a predetermined molar ratio to carry out polymerization, thereby obtaining an ethylene copolymer (A2). Table 1 shows the measurement results of the physical properties of the copolymer.
[0097]
The ethylene copolymer (A3) was polymerized by the following method.
[Production of ethylene-hexene-1 copolymer (A3) using metallocene catalyst]
Purified toluene was placed in a pressurized reactor equipped with a stirrer replaced with nitrogen, 1-hexene was added, and a mixed solution of bis (n-butylcyclopentadienyl) zirconium dichloride and methylalumoxane (MAO) was further added. (Al / Zr molar ratio = 200), the temperature was raised to 80 ° C., and a metallocene catalyst was charged. Then, ethylene was introduced, and the total pressure was 8 kg / cm while continuously polymerizing ethylene.^ThreeThe polymerization was carried out while maintaining the temperature to produce an ethylene / hexene-1 copolymer (A3). Table 1 shows the measurement results of the physical properties of the copolymer.
[0098]
[LLDPE with Ziegler catalyst]
The following ZLD-catalyzed LLDPE resin is shown in Table 1 as a sample (A4). Commercial LLDPE: density 0.910 g / cm³, MFR: 10.0 g / 10 min, comonomer: 4-methyl-pentene-1.
[0099]
[Table 1]

[0100]
A process sheet was prepared using the above-mentioned ethylene (co) polymer (A).
[Materials used]
(1) Polypropylene resin:
Homopolypropylene (PP)
Density = 0.90 g / cm^Three, MFR = 42g / 10min
Product name = PHA03A manufactured by Sun Allomer Co., Ltd.
(2) Poly-4-methyl-1-pentene resin (P4MeP):
Melt flow rate (260 ° C) 100g / 10min
(3) Base material: high-quality paper; Hamayu 50 g / m manufactured by Kishu Paper Co., Ltd.²
[0101]
[Examples 1 to 8]
The surface of the ethylene (co) polymer (A) of the molten resin film obtained by coextruding the surface layer (III) 15 μm and the ethylene (co) polymer (A) layer 15 μm as the adhesive layer (II) was subjected to ozone treatment. . Then, without using an anchor coating agent, the thickness of the substrate (I) of 50 g / m^TwoThe process sheet was obtained by extrusion laminating the ozone-treated surface of the molten resin film on high quality paper. At that time, those shown in Table 2 were used for the surface layer (III), the adhesive layer (II) and the base material (I), and the surface of the adhesive layer was subjected to ozone treatment under the conditions shown in Table 2.
After aging at 40 ° C. for 2 hours after lamination, each of the obtained laminates was measured for the adhesive strength between the substrate (I) and the adhesive layer, and between the adhesive layer (II) and the surface layer (III). Table 2 shows the results.
In addition, in Example 5, the thickness of the poly-4-methyl-1-pentene resin layer as the surface layer was set to 50 μm.
For the measurement of the adhesive strength, a strip sample having a width of 15 mm was cut out, and the peel strength was measured by T-peeling at a tensile speed of 300 mm / min according to JIS K 6854, and the peel strength was defined as the adhesive strength.
The degree of surface oxidation (Or) is determined by measuring the surface of the adhesive layer (II) in contact with the base material (I) at 1,720 cm in the spectrum of the absorbance measured by the surface FT-IR (ATR) method.^-1The heights of the nearby peaks are I (1720), 1370 (1369) cm^-1The height of a nearby peak was determined by (Equation 8) as I (1370).
(Equation 8) Or = I (1720) / I (1370)
[0102]
[Table 2]

[0103]
[Comparative Example 1]
As shown in Table 3, a process sheet was produced in the same manner as in Example 1 except that one surface of the surface layer was treated with ozone without using the ethylene (co) polymer (A). )) And the adhesive strength between the polypropylene resin layer and the substrate (I) were measured. Table 3 shows the results.
[0104]
[Table 3]

[0105]
[Comparative Examples 2 and 3]
In Comparative Example 2, a process sheet was manufactured in the same manner as in Example 1 except that an ethylene copolymer (A4) using a Ziegler catalyst was used as the adhesive layer (II), and the interlayer adhesive strength was measured. The results are shown in Table 4. In Comparative Example 3, a process sheet was produced in the same manner as in Example 1 except that the high-pressure radical method low-density polyethylene (LDPE) was used as the adhesive layer (II), and the interlayer adhesive strength was measured. Table 4 shows the results.
[0106]
[Table 4]

[0107]
[Comparative Example 4]
Using an anchor coat agent as an adhesive, a process sheet comprising a propylene-ethylene random copolymer layer as a surface layer and a substrate (I) was produced, and the interlayer adhesive strength was measured. Table 5 shows the results.
At this time, the anchor coating agent (AC agent) includes a mixture of Seikadyne 2710, Seikadyne 2710B manufactured by Dainichi Seika Kogyo Co., Ltd., and a commercially available mixture of ethyl acetate (Seikadyne 2710A: Seikadyne 2710B: Ethyl acetate = 1: 2: 15 mass). Ratio) was used.
[0108]
[Comparative Example 5]
A process sheet comprising a propylene-ethylene random copolymer layer as a surface layer (III) and a substrate (I) was produced by dry lamination, and the interlayer adhesion strength was measured. Table 5 shows the results.
In the dry lamination, an undercoat agent (AD-308A: AD-308B: Ethyl acetate 1: 1: 3, manufactured by Toyo Morton Co., Ltd.) was used with an AC coater attached to an extrusion laminator using a plain roll. 3g / m)^TwoAnd then dried at a dryer temperature of 80 ° C. under pressure bonding conditions of 50 ° C.-4 kg / m.^TwoAnd 30 m / min. After lamination, aging was performed at 40 ° C. for 2 hours, and then the adhesive strength was measured.
[0109]
[Table 5]

[0110]
[Example 9]
70 parts by mass of the ethylene copolymer (A11) impregnated (10000 ppm) with epoxidized soybean oil (molecular weight: 938, trade name; Adecaizer, manufactured by Asahi Denka Kogyo KK, hereinafter, abbreviated as ESO), After mixing 30 parts by mass of LDPE and dry blending with a tumbler mixer, the mixture was pelletized at 170 ° C. to prepare a resin material for the adhesive layer (II).
A process sheet was prepared using the resin material in the same manner as in Example 1, and the adhesive strength was measured. Table 6 shows the results.
[0111]
[Table 6]

[0112]
[Evaluation results]
As is clear from Tables 2 to 5, in Examples 1 to 9, since the adhesive layer (II) is within the scope of claim 1 of the present application, the adhesive strength between the substrate (I) and the surface layer (III). Was extremely high.
On the other hand, in Comparative Example 1, the adhesive strength was low because the adhesive layer (II) was not provided. Further, in Comparative Example 2, an ethylene copolymer (A4) using a Ziegler catalyst was used, and in Comparative Example 3, high-pressure radical method low-density polyethylene (LDPE) was used, so that the adhesive strength was low.
In Comparative Example 4, the adhesive strength was low because the anchor coating agent was used. In Comparative Example 5, the adhesive strength was low because it was manufactured by dry lamination.
[0113]
【The invention's effect】
As described above, according to the present invention, by using a specific ethylene (co) polymer (A) and desirably oxidizing treatment, the base material (I) can be prepared without using an anchor coat agent. And the surface layer (III) have high adhesive strength, excellent surface unevenness and embossability, and can enhance the peelability on the surface at low cost. Also, it has excellent heat resistance. In addition, it can be manufactured in a short time (high-speed molding) even in the case of lamination molding at a low temperature.
[Brief description of the drawings]
FIG. 1 is a side sectional view showing an example of a layer configuration of a process sheet.
FIG. 2 is a graph showing an elution temperature-elution amount curve of an ethylene (co) polymer (A) according to the present invention.
FIG. 3 is a graph showing an elution temperature-elution amount curve of the ethylene copolymer (A1) according to the present invention.
FIG. 4 is a graph showing an elution temperature-elution amount curve of an ethylene copolymer with a metallocene catalyst.
FIG. 5 is a graph showing an elution temperature-elution amount curve of the ethylene copolymer (A2) according to the present invention.
FIG. 6 is a schematic configuration diagram illustrating an example of manufacturing a process sheet.
FIG. 7A is a schematic diagram of a method for preparing a sample for ESCA measurement and a sample for IR measurement, and FIG. 7B is a perspective view showing a sample collection sheet.
FIG. 8 is a schematic configuration diagram showing a production example of synthetic leather.
FIG. 9 is a cross-sectional view when synthetic leather comes into contact with a process sheet in the production of synthetic leather.
[Explanation of symbols]
13 Substrate
14 Process sheet
15 Surface layer
16 Adhesive layer

Claims (11)

A process sheet in which a surface layer (III) is formed on a substrate (I) via an adhesive layer (II) without using an anchor coating agent,
The surface layer (III) contains a homopolymer or a copolymer of an α-olefin having 3 to 10 carbon atoms as a main component,
The adhesive layer (II) contains 100 to 10% by mass of an ethylene (co) polymer (A) satisfying the following requirements (a) to (d) and 0 to 90% by mass of another polyolefin resin (B). A process sheet, comprising: a resin material to be processed.
(A): Density 0.86 to 0.97 g / cm ³
(B): Melt flow rate is 0.01 to 100 g / 10 min. (C): Molecular weight distribution (Mw / Mn) is 1.5 to 4.5.
(D): elution temperature by continuous Atsushi Nobori elution fractionation (TREF) - the temperature _{T 75} to 75% of the total temperature _{T 25} to 25% of the total determined from the integral elution curve of elution amount curve is eluted elutes the difference _T 75 _{-T 25} and density d is, to satisfy the following relationship (equation 1) (equation _{1) T 75 -T 25 ≦ -670} × d + 644 The process sheet according to claim 1, wherein the ethylene (co) polymer (A) further satisfies the following requirement (e).
(E): elution temperature by continuous Atsushi Nobori elution fractionation (TREF) - the temperature _{T 75} to 75% of the total temperature _{T 25} to 25% of the total determined from the integral elution curve of elution amount curve is eluted elutes the difference _T 75 _{-T 25} and density d satisfy the following to satisfy the relation of (formula 2) (formula _{2) d <T 75 -T 25} ≧ -300 × d + 285 when 0.950 g / cm ³
When d ≧ 0.950 g / cm ³ , T ₇₅ −T ₂₅ ≧ 0 2. The ethylene (co) polymer (A), wherein (f) the o-dichlorobenzene (ODCB) soluble component at 23 ° C. has a mass average molecular weight of 8,000 to 30,000. 3. Or the process sheet according to 2. The ethylene (co) polymer (A) is an ethylene (co) polymer (A1) which further satisfies the following requirements (g) and (h). Process sheet described in Crab.
(G): o-Dichlorobenzene (ODCB) soluble content X (mass%), density d and melt flow rate (MFR) at 25 ° C. satisfy the following relations (Formula 3) and (Formula 4) ( Formula 3) When d−0.008 log MFR ≧ 0.93, X <2.0
(Equation 4) When d−0.008 log MFR <0.93, X <9.8 × 10 ³ × (0.9300−d + 0.008 log MFR) ² +2.0
(H): The presence of a plurality of peaks in the elution temperature-elution amount curve by the continuous heating elution fractionation method (TREF) The ethylene (co) polymer (A) is an ethylene (co) polymer (A2) that further satisfies the following requirements (i) and (j): Process sheet according to Crab.
(I): One peak of the elution temperature-elution amount curve by the continuous heating elution fractionation method (TREF). (J): One or more melting point peaks, and the highest melting point T _ml Density d satisfies the relationship of the following (Equation 5) (Equation 5) T _ml ≧ 150 × d−19 The process sheet according to claim 5, wherein the ethylene (co) polymer (A2) further satisfies the following requirement (k).
(K): Melt tension (MT) and melt flow rate (MFR) satisfy the following (Equation 6) (Equation 6) logMT ≦ −0.572 × logMFR + 0.3. The resin material constituting the adhesive layer (II) contains an epoxy compound (C) having at least two or more epoxy groups in a molecule and having a molecular weight of 3000 or less. The process sheet according to 1. A process for producing a process sheet for forming a surface layer (III) via an adhesive layer (II) on a substrate (I) without using an anchor coating agent,
The surface layer (III) contains a homopolymer or a copolymer of an α-olefin having 3 to 10 carbon atoms as a main component,
The adhesive layer (II) is 100 to 10% by mass of an ethylene (co) polymer (A) satisfying the following requirements (a) to (d), and the other polyolefin-based resin (B) is 0 to 90% by mass. A method for producing a process sheet, comprising a resin material containing:
(A): Density 0.86 to 0.97 g / cm ³
(B): Melt flow rate is 0.01 to 100 g / 10 min. (C): Molecular weight distribution (Mw / Mn) is 1.5 to 4.5.
(D): elution temperature by continuous Atsushi Nobori elution fractionation (TREF) - the temperature _{T 75} to 75% of the total temperature _{T 25} to 25% of the total determined from the integral elution curve of elution amount curve is eluted elutes the difference _T 75 _{-T 25} and density d is, to satisfy the following relationship (equation 1) (equation _{1) T 75 -T 25 ≦ -670} × d + 644 9. The process sheet according to claim 8, wherein the resin material forming the adhesive layer (II) contains an epoxy compound (C) having at least two epoxy groups in a molecule and a molecular weight of 3000 or less. Manufacturing method. A resin material forming the adhesive layer (II) and a homopolymer or copolymer of an α-olefin having 3 to 10 carbon atoms forming the surface layer (III) are coextruded at a molding temperature of 200 to 350 ° C. to form a molten resin film. While forming, the surface of the molten resin film that is in contact with the substrate (I) has (a) an oxygen atom concentration (Oc) of 1.8% by mass or more and (B) a surface oxidation degree (Or) of 0.10 or more. The method for producing a process sheet according to claim 8, wherein the molten resin film and the substrate (I) are laminated by oxidizing treatment so that The method for producing a process sheet according to any one of claims 8 to 10, wherein in the oxidation treatment, the molten resin film is subjected to ozone treatment at a resin temperature in a range of 200 to 350 ° C.

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