JP2023152647A - Method for producing crosslinked molding - Google Patents
Method for producing crosslinked molding Download PDFInfo
- Publication number
- JP2023152647A JP2023152647A JP2022198036A JP2022198036A JP2023152647A JP 2023152647 A JP2023152647 A JP 2023152647A JP 2022198036 A JP2022198036 A JP 2022198036A JP 2022198036 A JP2022198036 A JP 2022198036A JP 2023152647 A JP2023152647 A JP 2023152647A
- Authority
- JP
- Japan
- Prior art keywords
- silane
- modified polyolefin
- crosslinking
- crosslinked
- molded article
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- 238000000465 moulding Methods 0.000 title claims abstract description 18
- 229920000098 polyolefin Polymers 0.000 claims abstract description 129
- 239000000203 mixture Substances 0.000 claims abstract description 55
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- 238000010894 electron beam technology Methods 0.000 claims abstract description 29
- 230000001678 irradiating effect Effects 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- 238000009833 condensation Methods 0.000 claims description 20
- 230000005494 condensation Effects 0.000 claims description 20
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 14
- 238000004132 cross linking Methods 0.000 abstract description 76
- 150000001875 compounds Chemical class 0.000 abstract description 4
- -1 unsaturated silane compound Chemical class 0.000 description 26
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- 239000002994 raw material Substances 0.000 description 15
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- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 2
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- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000010690 paraffinic oil Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
Abstract
Description
本発明は、シラン変性ポリオレフィンの架橋方法に関するものである。
本発明はまた、シラン変性ポリオレフィン又はシラン変性ポリオレフィンを含むポリオレフィン組成物よりなる成形体と、この成形体を用いた架橋成形体に関する。
The present invention relates to a method for crosslinking silane-modified polyolefins.
The present invention also relates to a molded article made of a silane-modified polyolefin or a polyolefin composition containing a silane-modified polyolefin, and a crosslinked molded article using this molded article.
従来より、電線やケーブルの被覆材料として、ポリオレフィンを架橋した架橋ポリオレフィンが使用されている。ポリオレフィンの架橋に使用される架橋方式としては、電子線照射架橋、化学架橋、水架橋方式が知られている。 BACKGROUND ART Crosslinked polyolefins, which are crosslinked polyolefins, have been used as coating materials for electric wires and cables. As crosslinking methods used for crosslinking polyolefins, electron beam irradiation crosslinking, chemical crosslinking, and water crosslinking are known.
化学架橋は、架橋剤として、ジクミルペルオキレドのような過酸化物を配合したポリオレフィン組成物を加熱することで架橋反応させるものである。化学架橋では、架橋反応を完結させるためには、一度、成形加工した製品を、再度、過酸化物を分解させるために過酸化物の分解温度以上に加熱し、反応終了後に冷却させる工程が必要であることから、非常に長い大型の設備を必要とする。また、化学架橋は反応のコントロールが難しく生産性が悪い。
電子線照射架橋は、ポリオレフィン組成物に電子線照射することで架橋反応させるものである。
また、水架橋は、ビニルトリメトキシシラン等によりポリオレフィンをシラン変性したシラン変性ポリオレフィンに有機スズ化合物等の架橋触媒（シラノール縮合触媒）などを配合し、温水あるいは水蒸気等の存在下で架橋させるものである（特許文献１参照）。
In chemical crosslinking, a polyolefin composition containing a peroxide such as dicumyl peroxide as a crosslinking agent is heated to cause a crosslinking reaction. In chemical crosslinking, in order to complete the crosslinking reaction, it is necessary to heat the molded product once again to a temperature above the peroxide decomposition temperature in order to decompose the peroxide, and then cool it after the reaction is complete. Therefore, it requires very long and large equipment. In addition, chemical crosslinking is difficult to control and has poor productivity.
In electron beam irradiation crosslinking, a polyolefin composition is irradiated with an electron beam to cause a crosslinking reaction.
In addition, water crosslinking is a process in which a crosslinking catalyst (silanol condensation catalyst) such as an organic tin compound is added to a silane-modified polyolefin obtained by modifying a polyolefin with vinyltrimethoxysilane or the like, and the crosslinking is performed in the presence of hot water or steam. Yes (see Patent Document 1).
電子線照射架橋や水架橋を用いる方法は、化学架橋と比較して、架橋反応のコントロールが比較的容易であり、生産性もよいため、被覆電線の製造方法として一般的に用いられている。 A method using electron beam irradiation crosslinking or water crosslinking is generally used as a method for producing covered electric wires because it is relatively easy to control the crosslinking reaction and has good productivity compared to chemical crosslinking.
水架橋は、所望の性能を発現させる架橋状態を得るまでに、長時間（数十時間）を要することがあり、生産性の観点で課題を有する場合がある。また、水架橋で架橋触媒として通常使用される有機スズ化合物は、環境負荷への懸念があり、この点においても水架橋は好ましくない。
電子線照射架橋は、架橋触媒を用いる必要がなく、また、所望の架橋状態を得るまでの時間を短縮でき、生産性に優れるものの、所望の架橋状態を得るために、照射強度を上げると、得られる架橋ポリオレフィン組成物の成形体の物性が低下したり、外観が劣化する場合があった。また、照射強度を上げずに架橋度を上げる方法として、架橋助剤を増やす手段も考えられるが、架橋助剤を増やすと架橋ポリオレフィン組成物の成形体から架橋助剤そのものがブリードする場合があった。
このように、従来において、有機スズ化合物等の架橋触媒を用いることなく、生産性と、得られる架橋成形体の物性の双方に優れる架橋成形体の製造方法は提供されていない。
Water crosslinking may require a long time (several tens of hours) to obtain a crosslinked state that exhibits desired performance, which may pose a problem in terms of productivity. Furthermore, organic tin compounds that are commonly used as crosslinking catalysts in water crosslinking have concerns about environmental impact, and water crosslinking is not preferred in this respect as well.
Although electron beam irradiation crosslinking does not require the use of a crosslinking catalyst and can shorten the time required to obtain the desired crosslinked state, resulting in excellent productivity, increasing the irradiation intensity in order to obtain the desired crosslinked state The physical properties of the resulting crosslinked polyolefin composition molded product may deteriorate or the appearance may deteriorate. In addition, increasing the crosslinking aid may be considered as a method to increase the degree of crosslinking without increasing the irradiation intensity, but increasing the amount of the crosslinking aid may cause the crosslinking aid itself to bleed from the molded article of the crosslinked polyolefin composition. Ta.
As described above, conventionally, there has been no method for producing a crosslinked molded product that is excellent in both productivity and physical properties of the resulting crosslinked molded product without using a crosslinking catalyst such as an organic tin compound.
本発明の目的は、上記従来技術の課題を解決し、有機スズ化合物等の架橋触媒を必要とすることなく、生産性と機械物性と耐熱物性に優れる架橋成形体を可能とする架橋成形体の製造方法と、成形体及び架橋成形体を提供することにある。 The purpose of the present invention is to solve the above-mentioned problems of the prior art, and to produce a crosslinked molded product that is excellent in productivity, mechanical properties, and heat-resistant properties without requiring a crosslinking catalyst such as an organic tin compound. The object of the present invention is to provide a manufacturing method, a molded article, and a crosslinked molded article.
本発明者は、上記課題に鑑み鋭意検討を行った結果、シラン変性ポリオレフィン乃至はシラン変性ポリオレフィンを含むポリオレフィン組成物を成形した成形体に電子線照射する製造方法により、架橋触媒不要の電子線架橋において、生産性を向上できるとともに、機械物性、耐熱物性に優れた架橋成形体を得ることができることを見出した。
即ち、本発明は以下の特徴を有する。
As a result of intensive studies in view of the above-mentioned problems, the inventors of the present invention have developed a method for electron beam cross-linking that does not require a cross-linking catalyst, using a manufacturing method in which a molded article formed from a silane-modified polyolefin or a polyolefin composition containing a silane-modified polyolefin is irradiated with an electron beam. It has been found that productivity can be improved and a crosslinked molded article with excellent mechanical properties and heat-resistant properties can be obtained.
That is, the present invention has the following features.
［１］ シラン変性ポリオレフィンを得る工程、該シラン変性ポリオレフィンを成形して成形体を得る工程、該成形体に電子線照射する工程、を有する架橋成形体の製造方法。 [1] A method for producing a crosslinked molded body, which includes the steps of obtaining a silane-modified polyolefin, molding the silane-modified polyolefin to obtain a molded body, and irradiating the molded body with an electron beam.
［２］ シラン変性ポリオレフィンを含むポリオレフィン組成物を得る工程、該ポリオレフィン組成物を成形して成形体を得る工程、該成形体に電子線照射する工程、を有する架橋成形体の製造方法。 [2] A method for producing a crosslinked molded article, comprising the steps of obtaining a polyolefin composition containing a silane-modified polyolefin, molding the polyolefin composition to obtain a molded article, and irradiating the molded article with an electron beam.
［３］ ［１］または［２］に記載の架橋成形体の製造方法により製造した架橋成形体よりなる電線被覆材を製造する電線被覆材の製造方法。 [3] A method for manufacturing an electric wire covering material, which comprises manufacturing an electric wire covering material made of a crosslinked molded product produced by the method for manufacturing a crosslinked molded product according to [1] or [2].
［４］ ［３］に記載の電線被覆材の製造方法により製造された電線被覆材により電線を被覆する被覆電線の製造方法。 [4] A method for manufacturing a covered electric wire, comprising covering an electric wire with an electric wire sheathing material manufactured by the method for manufacturing an electric wire sheathing material according to [3].
［５］ シラン変性ポリオレフィン又はシラン変性ポリオレフィンを含むポリオレフィン組成物よりなる成形体であって、該成形体のシラノール縮合触媒由来の金属含有率が１ｐｐｍ未満である成形体。 [5] A molded article made of a silane-modified polyolefin or a polyolefin composition containing a silane-modified polyolefin, the molded article having a metal content derived from a silanol condensation catalyst of less than 1 ppm.
［６］ ［５］に記載の成形体を用いた架橋成形体。 [6] A crosslinked molded article using the molded article according to [5].
本発明によれば、生産性と機械物性と耐熱物性に優れる架橋成形体を可能とする架橋成形体の製造方法を提供することができる。
また、本発明によれば、有機スズ化合物等の架橋触媒不要の電子線架橋により架橋成形体を得ることができるため、有機スズ化合物等のシラノール縮合触媒由来の金属化合物を含まない、或いは、シラノール縮合触媒由来の金属含有率、例えばスズ含有率が著しく低い成形体から架橋成形体を得ることができる。
According to the present invention, it is possible to provide a method for producing a crosslinked molded product that enables a crosslinked molded product with excellent productivity, mechanical properties, and heat-resistant properties.
Further, according to the present invention, a crosslinked molded article can be obtained by electron beam crosslinking without the need for a crosslinking catalyst such as an organotin compound. A crosslinked molded body can be obtained from a molded body having a significantly low metal content derived from the condensation catalyst, for example, a tin content.
以下に本発明の実施の形態を詳細に説明するが、本発明は以下の説明に限定されるものではなく、本発明の要旨を逸脱しない範囲において、任意に変形して実施することができる。
尚、本明細書において、「～」を用いてその前後に数値又は物性値を挟んで表現する場合、その前後の値を含むものとして用いることとする。
Embodiments of the present invention will be described in detail below, but the present invention is not limited to the following description, and can be implemented with arbitrary modifications within the scope of the gist of the present invention.
In this specification, when "~" is used to express a numerical value or physical property value before and after it, it is used to include the values before and after it.
［シラン変性ポリオレフィン］
本発明において、シラン変性ポリオレフィンは、架橋ポリオレフィンとして要求される機械特性と電気特性を発揮するために必要となる。
[Silane-modified polyolefin]
In the present invention, the silane-modified polyolefin is necessary to exhibit the mechanical properties and electrical properties required as a crosslinked polyolefin.
本発明におけるシラン変性ポリオレフィンは、シラン変性ポリオレフィンを架橋したシラン架橋ポリオレフィンとは区別される。すなわち、シラン変性ポリオレフィンとは、架橋されていないシラン変性のオレフィン重合体を意味する。 The silane-modified polyolefin in the present invention is distinguished from a silane-crosslinked polyolefin obtained by crosslinking a silane-modified polyolefin. That is, the silane-modified polyolefin means a silane-modified olefin polymer that is not crosslinked.
シラン変性ポリオレフィンは、例えば、以下に挙げる原料となるオレフィン重合体に不飽和シラン化合物をグラフト化して変性することによって得られる。 A silane-modified polyolefin can be obtained, for example, by grafting an unsaturated silane compound onto an olefin polymer as a raw material listed below to modify it.
シラン変性ポリオレフィンの原料として用いるオレフィン重合体（以下、「原料オレフィン重合体」と称す場合がある。）は特に限定されないが、例えば、エチレン、プロピレン、１－ブテン等の炭素数２～８程度のα－オレフィンの単独重合体、これらのα－オレフィンとエチレン、プロピレン、１－ブテン、３－メチル－１－ブテン、１－ペンテン、４－メチル－１－ペンテン、１－ヘキセン、１－オクテン、１－デセン等の炭素数２～２０程度の他のα－オレフィンや、酢酸ビニル、（メタ）アクリル酸、（メタ）アクリル酸エステル等との共重合体が挙げられる。ここで、「（メタ）アクリル酸」とは「アクリル酸」と「メタクリル酸」の一方又は双方を示す。後述の「（メタ）アクリロイル」、「（メタ）アクリレート」についても同様である。 The olefin polymer used as a raw material for the silane-modified polyolefin (hereinafter sometimes referred to as "raw material olefin polymer") is not particularly limited, but examples include ethylene, propylene, 1-butene, etc. having about 2 to 8 carbon atoms. Homopolymers of α-olefins, these α-olefins and ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, Examples include other α-olefins having about 2 to 20 carbon atoms such as 1-decene, and copolymers with vinyl acetate, (meth)acrylic acid, (meth)acrylic esters, and the like. Here, "(meth)acrylic acid" refers to one or both of "acrylic acid" and "methacrylic acid." The same applies to "(meth)acryloyl" and "(meth)acrylate" described below.
上記原料オレフィン重合体の具体例としては、分岐状又は直鎖状の低密度ポリエチレン、分岐状又は直鎖状の中密度ポリエチレン、分岐状又は直鎖状の高密度ポリエチレン等のエチレン単独重合体、エチレン・プロピレン共重合体、エチレン・１－ブテン共重合体、エチレン・４－メチル－１－ペンテン共重合体、エチレン・１－ヘキセン共重合体、エチレン・１－オクテン共重合体、エチレン・酢酸ビニル共重合体、エチレン・（メタ）アクリル酸共重合体、エチレン・（メタ）アクリル酸エチル共重合体等のエチレン系重合体、プロピレン単独重合体、プロピレン・エチレン共重合体、プロピレン・１－ブテン共重合体、プロピレン・エチレン・１－ブテン共重合体、プロピレン・４－メチル－１－ペンテン共重合体等のプロピレン系重合体、及び、１－ブテン単独重合体、１－ブテン・エチレン共重合体、１－ブテン・プロピレン共重合体等の１－ブテン系重合体が挙げられる。
これらの原料オレフィン重合体は、１種類を用いても２種類以上を併用してもよい。
Specific examples of the raw material olefin polymer include ethylene homopolymers such as branched or linear low-density polyethylene, branched or linear medium-density polyethylene, and branched or linear high-density polyethylene; Ethylene/propylene copolymer, ethylene/1-butene copolymer, ethylene/4-methyl-1-pentene copolymer, ethylene/1-hexene copolymer, ethylene/1-octene copolymer, ethylene/acetic acid Ethylene polymers such as vinyl copolymers, ethylene/(meth)acrylic acid copolymers, ethylene/(meth)ethyl acrylate copolymers, propylene homopolymers, propylene/ethylene copolymers, propylene/1- Propylene polymers such as butene copolymer, propylene/ethylene/1-butene copolymer, propylene/4-methyl-1-pentene copolymer, 1-butene homopolymer, 1-butene/ethylene copolymer, etc. Polymers and 1-butene-based polymers such as 1-butene/propylene copolymers can be mentioned.
These raw material olefin polymers may be used alone or in combination of two or more.
ここで、エチレン系重合体、プロピレン系重合体、１－ブテン系重合体とは、それぞれ、エチレン単位、プロピレン単位、又は１－ブテン単位を、重合体を構成する全モノマー単位中で最も多く含有する重合体のことを言い、好ましくは５０質量％を超える割合で含有する重合体を言う。
これらの中でも、シラン変性ポリオレフィンの原料に用いるオレフィン重合体としては、以下の理由から、エチレン系重合体が好ましく、エチレン系重合体の中でも、エチレン・１－ブテン共重合体、エチレン・１－ヘキセン共重合体、エチレン・１－オクテン共重合体、エチレン・酢酸ビニル共重合体、エチレン・（メタ）アクリル酸メチル共重合体が特に好ましい。
Here, ethylene polymer, propylene polymer, and 1-butene polymer each contain the largest amount of ethylene units, propylene units, or 1-butene units among all monomer units constituting the polymer. It refers to a polymer that contains 50% by mass, preferably in a proportion exceeding 50% by mass.
Among these, ethylene polymers are preferred as the olefin polymers used as raw materials for silane-modified polyolefins for the following reasons. Among ethylene polymers, ethylene/1-butene copolymers, ethylene/1-hexene copolymers, etc. Particularly preferred are copolymers, ethylene/1-octene copolymers, ethylene/vinyl acetate copolymers, and ethylene/methyl (meth)acrylate copolymers.
本発明におけるシラン変性ポリオレフィンは、後述する通り、例えば、遊離ラジカル発生剤によるグラフト反応で原料オレフィン重合体に対して不飽和シラン化合物をグラフトさせることにより得られるが、重合槽で不飽和シラン化合物を添加しオレフィンと共重合させたものを用いてもよい。
グラフト反応でシラン変性ポリオレフィンを得る場合、原料オレフィン重合体が、エチレン系重合体であれば、グラフト化を好適に行うことができるので好ましい。また、原料オレフィン重合体がエチレン系重合体であれば、本発明の製造方法により得られる架橋成形体を電線被覆用に用いた場合に、耐熱性が良好となるので好ましい。
The silane-modified polyolefin in the present invention can be obtained, for example, by grafting an unsaturated silane compound onto a raw olefin polymer in a graft reaction using a free radical generator, as described below. It may be added and copolymerized with olefin.
When obtaining a silane-modified polyolefin by grafting reaction, it is preferable that the raw material olefin polymer is an ethylene polymer because grafting can be suitably performed. Further, it is preferable that the raw material olefin polymer is an ethylene polymer, since the crosslinked molded product obtained by the production method of the present invention will have good heat resistance when used for covering electric wires.
原料オレフィン重合体を不飽和シラン化合物によりグラフト変性してシラン変性ポリオレフィンを得るには、通常、公知の方法で原料オレフィン重合体を有機過酸化物等の遊離ラジカル発生剤の存在下にエチレン性不飽和シラン化合物のグラフト反応工程に供してグラフト変性することが行われる。
例えば、原料オレフィン重合体に所定量の不飽和シラン化合物と遊離ラジカル発生剤を混合し、８０～２５０℃の温度で溶融混練する方法を用いることができる。なお、この際、水を含んでいると、水架橋反応が進行するので、水を含まない状態で溶融混練することが好ましい。
To obtain a silane-modified polyolefin by graft-modifying a raw material olefin polymer with an unsaturated silane compound, the raw material olefin polymer is usually graft-modified with an ethylenic compound in the presence of a free radical generator such as an organic peroxide using a known method. Graft modification is carried out by subjecting the saturated silane compound to a graft reaction step.
For example, a method can be used in which a predetermined amount of an unsaturated silane compound and a free radical generator are mixed with a raw olefin polymer, and the mixture is melt-kneaded at a temperature of 80 to 250°C. Note that, at this time, if water is included, the water crosslinking reaction will proceed, so it is preferable to melt-knead in a state that does not contain water.
グラフト変性に用いる不飽和シラン化合物としては、下記一般式（Ｉ）で表されるエチレン性不飽和シラン化合物が挙げられる。
Ｒ１ＳｉＲ２
ｎＹ３－ｎ …（Ｉ）
Examples of the unsaturated silane compound used for graft modification include ethylenically unsaturated silane compounds represented by the following general formula (I).
R 1 SiR 2 n Y 3-n ...(I)
上記式（Ｉ）中、Ｒ１はエチレン性不飽和炭化水素基又はハイドロカーボンオキシ基を表し、Ｒ２は炭化水素基を表し、Ｙは加水分解可能な有機基を表し、ｎは０～２の整数である。 In the above formula (I), R 1 represents an ethylenically unsaturated hydrocarbon group or a hydrocarbonoxy group, R 2 represents a hydrocarbon group, Y represents a hydrolyzable organic group, and n is 0 to 2 is an integer.
ここで、Ｒ１としては、炭素数が２～６のエチレン性不飽和炭化水素基又はハイドロカーボンオキシ基、例えば、ビニル基、プロペニル基、ブテニル基、シクロヘキセニル基、γ－（メタ）アクリロイルオキシプロピル基が挙げられる。また、Ｒ２としては、炭素数が１～１０の炭化水素基、例えば、メチル基、エチル基、プロピル基、デシル基、フェニル基が挙げられる。さらに、Ｙとしては、例えば、メトキシ基、エトキシ基、ホルミルオキシ基、アセトキシ基、プロピオニルオキシ基、アルキルアミノ基、アリールアミノ基が挙げられる。 Here, R 1 is an ethylenically unsaturated hydrocarbon group or hydrocarbonoxy group having 2 to 6 carbon atoms, such as vinyl group, propenyl group, butenyl group, cyclohexenyl group, γ-(meth)acryloyloxy Propyl group is mentioned. Examples of R 2 include a hydrocarbon group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a decyl group, and a phenyl group. Furthermore, examples of Y include a methoxy group, an ethoxy group, a formyloxy group, an acetoxy group, a propionyloxy group, an alkylamino group, and an arylamino group.
このようなエチレン性不飽和シラン化合物の具体例としては、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリアセトキシシラン、γ－メタクリロイルオキシプロピルトリメトキシシランが挙げられる。これらの中でも、臭気等の観点から、ビニルトリメトキシシランが好適に用いられる。
不飽和シラン化合物は、１種類を用いても２種類以上を併用してもよい。
Specific examples of such ethylenically unsaturated silane compounds include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, and γ-methacryloyloxypropyltrimethoxysilane. Among these, vinyltrimethoxysilane is preferably used from the viewpoint of odor and the like.
One type of unsaturated silane compound may be used or two or more types may be used in combination.
前記不飽和シラン化合物の使用量は限定されず、生産性と得られる架橋成形体の機械物性を向上させる観点から多いほうが望ましいが、加工性の観点からは少ないほうが望ましい。具体的には、原料オレフィン重合体１００質量部に対して、好ましくは０．５質量部以上、より好ましくは１．０質量部以上であり、一方、好ましくは１０質量部以下、より好ましくは５質量部以下である。 The amount of the unsaturated silane compound to be used is not limited, and from the viewpoint of improving productivity and the mechanical properties of the resulting crosslinked molded product, a larger amount is desirable, but from the viewpoint of processability, a smaller amount is desirable. Specifically, it is preferably 0.5 parts by mass or more, more preferably 1.0 parts by mass or more, and preferably 10 parts by mass or less, more preferably 5 parts by mass, based on 100 parts by mass of the raw material olefin polymer. Parts by mass or less.
前記遊離ラジカル発生剤としては、原料オレフィン重合体に対して不飽和シラン化合物をグラフト化可能であれば限定されないが、ジクミルパーオキサイト、２，５－（ｔｅｒｔ－ブチルペルオキシ）ヘキシン－３、１，３－ビス（ｔｅｒｔ－ブチルペルオキシイソプロピル）ベンゼンなどの有機過酸化物が主として使用できる。これらの有機過酸化物も、１種類を用いても２種類以上を併用してもよい。 The free radical generator is not limited as long as it can graft an unsaturated silane compound to the raw olefin polymer, but examples include dicumyl peroxide, 2,5-(tert-butylperoxy)hexine-3, Organic peroxides such as 1,3-bis(tert-butylperoxyisopropyl)benzene can primarily be used. These organic peroxides may be used alone or in combination of two or more.
前記遊離ラジカル発生剤の使用量は限定されず、不飽和シラン化合物が原料オレフィン重合体に十分にグラフト共重合し十分な架橋効果を得るためには多いほうが望ましいが、加工性の観点からは少ないほうが望ましい。具体的には、原料オレフィン重合体１００質量部に対し、好ましくは０．０１質量部以上、より好ましくは０．０２質量部以上であり、一方、好ましくは０．２質量部以下、より好ましくは０．１質量部以下である。 The amount of the free radical generator used is not limited, and it is desirable to use a large amount in order to sufficiently graft copolymerize the unsaturated silane compound to the raw material olefin polymer and obtain a sufficient crosslinking effect, but from the viewpoint of processability, it is desirable to use a large amount. It is more desirable. Specifically, it is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, and on the other hand, preferably 0.2 parts by mass or less, more preferably It is 0.1 part by mass or less.
本発明で用いるシラン変性ポリオレフィンは、密度が０．８５０～０．９７０ｇ／ｃｍ３であることが好ましく、より好ましくは０．８７０～０．９５０ｇ／ｃｍ３である。密度が高くなるほど、得られる架橋成形体の耐熱性、耐薬品性、耐摩耗性、耐屈曲性等が良好となり、一方で、密度が低くなるほど、柔軟性が良好となる。前記の範囲内とすることにより、得られる架橋成形体の耐熱性、耐薬品性、耐摩耗性、耐屈曲性が十分に向上すると共に、十分な柔軟性を得ることができる。 The silane-modified polyolefin used in the present invention preferably has a density of 0.850 to 0.970 g/cm 3 , more preferably 0.870 to 0.950 g/cm 3 . The higher the density, the better the heat resistance, chemical resistance, abrasion resistance, bending resistance, etc. of the crosslinked molded product obtained, while the lower the density, the better the flexibility. By setting it within the above range, the heat resistance, chemical resistance, abrasion resistance, and bending resistance of the crosslinked molded product obtained can be sufficiently improved, and sufficient flexibility can be obtained.
前記シラン変性ポリオレフィンの、ＪＩＳ Ｋ７２１０に従って測定した１９０℃、２．１６ｋｇ荷重におけるメルトフローレート（ＭＦＲ）は、成形性の点では大きい方が好ましく、機械的特性の点では小さい方が好ましい。具体的には、シラン変性ポリオレフィンの１９０℃、２．１６ｋｇ荷重におけるＭＦＲが０．１ｇ／１０ｍｉｎ以上であることが好ましく、１ｇ／１０ｍｉｎ以上であることがより好ましく、一方、２０ｇ／１０ｍｉｎ以下であることが好ましく、１０ｇ／１０ｍｉｎ以下であることがより好ましい。これらの範囲内とすることにより、成形性と機械的特性をバランスよく発現させることができる。 The melt flow rate (MFR) of the silane-modified polyolefin measured according to JIS K7210 at 190° C. and a load of 2.16 kg is preferably larger in terms of moldability, and smaller in terms of mechanical properties. Specifically, the MFR of the silane-modified polyolefin at 190° C. and a load of 2.16 kg is preferably 0.1 g/10 min or more, more preferably 1 g/10 min or more, and on the other hand, 20 g/10 min or less. It is preferably 10 g/10 min or less, and more preferably 10 g/10 min or less. By setting it within these ranges, moldability and mechanical properties can be expressed in a well-balanced manner.
前記シラン変性ポリオレフィンは、１種のみを用いてもよく、モノマー組成や物性等の異なるものの２種以上を混合して用いてもよい。 The silane-modified polyolefin may be used alone or in a mixture of two or more different monomer compositions and physical properties.
前記シラン変性ポリオレフィンとしては市販品を用いることもでき、例えば、三菱ケミカル（株）製、商品名「リンクロン」やＢｏｒｅａｌｉｓ社製、商品名「Ｖｉｓｉｃｏ」を好適に用いることができる。 As the silane-modified polyolefin, commercially available products can be used, and for example, products such as those manufactured by Mitsubishi Chemical Corporation under the trade name "Linklon" and manufactured by Borealis under the trade name "Visico" can be suitably used.
［シラン変性ポリオレフィン組成物］
本発明において、上記のシラン変性ポリオレフィンは単独でも使用することができるし、他の成分と組み合わせたシラン変性ポリオレフィンを含むポリオレフィン組成物（以下、「シラン変性ポリオレフィン組成物」と称す場合がある。）として使用することもできる。シラン変性ポリオレフィン組成物として用いる場合、シラン変性ポリオレフィン組成物全体に対するシラン変性ポリオレフィンの含有率は、好ましくは１０質量％以上、より好ましくは１５質量％以上、更に好ましくは２０質量％以上、特に好ましくは３０質量％以上である。
一方、シラン変性ポリオレフィン組成物全体に対するシラン変性ポリオレフィンの含有率は、好ましくは１００質量％未満、より好ましくは９０質量％以下である。
シラン変性ポリオレフィン組成物中のシラン変性ポリオレフィンの含有率が上記下限以上であれば、電子線照射での十分な架橋効果が得られ、良好な機械物性を発現しやすくなる。また、シラン変性ポリオレフィン組成物中のシラン変性ポリオレフィンの含有率を上記上限以下とすることで、押出負荷が増えすぎることにより加工性が悪くなり外観荒れを起こすことを抑制しやすい傾向となる。
[Silane-modified polyolefin composition]
In the present invention, the above-mentioned silane-modified polyolefin can be used alone, or a polyolefin composition containing the silane-modified polyolefin in combination with other components (hereinafter sometimes referred to as "silane-modified polyolefin composition"). It can also be used as When used as a silane-modified polyolefin composition, the content of the silane-modified polyolefin in the entire silane-modified polyolefin composition is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, particularly preferably It is 30% by mass or more.
On the other hand, the content of the silane-modified polyolefin in the entire silane-modified polyolefin composition is preferably less than 100% by mass, more preferably 90% by mass or less.
When the content of the silane-modified polyolefin in the silane-modified polyolefin composition is at least the above-mentioned lower limit, a sufficient crosslinking effect can be obtained by electron beam irradiation, and good mechanical properties can be easily exhibited. Furthermore, by controlling the content of the silane-modified polyolefin in the silane-modified polyolefin composition to be below the above-mentioned upper limit, it tends to be easy to prevent the processability from worsening and the appearance from becoming rough due to an excessive increase in extrusion load.
＜難燃剤＞
本発明で用いるシラン変性ポリオレフィン組成物は、難燃剤を含有していてもよい。
難燃剤は、ハロゲン系難燃剤と非ハロゲン系難燃剤に大別されるが、非ハロゲン系難燃剤が好ましい。非ハロゲン系難燃剤としては、金属水酸化物難燃剤、リン系難燃剤、窒素含有化合物（メラミン系、グアニジン系）難燃剤及び無機系化合物（硼酸塩、モリブデン化合物）難燃剤が挙げられる。これらの中でも金属水酸化物が好適に用いられる。
金属水酸化物の種類は限定されないが、具体的には、水酸化マグネシウム、水酸化アルミニウム、水酸化カルシウム、ハイドロタルサイトが挙げられ、中でも、水酸化マグネシウム、水酸化アルミニウムが好適に用いられる。
これら難燃剤は、１種類を用いても２種類以上を併用してもよい。
<Flame retardant>
The silane-modified polyolefin composition used in the present invention may contain a flame retardant.
Flame retardants are broadly classified into halogen flame retardants and non-halogen flame retardants, with non-halogen flame retardants being preferred. Examples of non-halogen flame retardants include metal hydroxide flame retardants, phosphorus flame retardants, nitrogen-containing compound (melamine, guanidine) flame retardants, and inorganic compound (borates, molybdenum compounds) flame retardants. Among these, metal hydroxides are preferably used.
Although the type of metal hydroxide is not limited, specific examples include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, and hydrotalcite, and among them, magnesium hydroxide and aluminum hydroxide are preferably used.
These flame retardants may be used alone or in combination of two or more.
本発明で用いるシラン変性ポリオレフィン組成物において、難燃剤として金属水酸化物を用いる場合の含有率は、シラン変性ポリオレフィン組成物全体に対して、好ましくは３０質量％以上、より好ましくは４０質量％以上であり、一方、好ましくは８０質量％以下、より好ましくは７０質量％以下である。金属水酸化物の含有率が上記下限以上であれば、難燃性能を十分に得ることができる。一方、金属水酸化物の含有率が上記上限以下であれば、押出負荷が増大することによる生産性の低下や、機械的特性の低下を防止することができる。 In the silane-modified polyolefin composition used in the present invention, when a metal hydroxide is used as a flame retardant, the content is preferably 30% by mass or more, more preferably 40% by mass or more, based on the entire silane-modified polyolefin composition. On the other hand, it is preferably 80% by mass or less, more preferably 70% by mass or less. If the content of the metal hydroxide is at least the above lower limit, sufficient flame retardant performance can be obtained. On the other hand, if the content of the metal hydroxide is below the above upper limit, it is possible to prevent a decrease in productivity and a decrease in mechanical properties due to an increase in extrusion load.
＜その他の成分＞
本発明で用いるシラン変性ポリオレフィン組成物には、必要に応じて、本発明の効果を著しく妨げない範囲で、上述のシラン変性ポリオレフィンと難燃剤以外の重合体類等や添加剤を「その他の成分」として含んでいてもよい。その他の成分は、１種類のみを用いても、２種類以上を任意の組合せと比率で併用してもよい。
<Other ingredients>
If necessary, the silane-modified polyolefin composition used in the present invention may contain polymers and additives other than the above-mentioned silane-modified polyolefin and flame retardant to the extent that the effects of the present invention are not significantly impaired. ” may be included. As for the other components, only one type may be used, or two or more types may be used in combination in any combination and ratio.
（重合体類）
前述のシラン変性ポリオレフィン以外の重合体類については特に制限はないが、未変性エチレン系重合体のような未変性オレフィン重合体類を使用することができる。この重合体類は、前記シラン変性ポリオレフィンを用いるシラン変性ポリオレフィン組成物、その成形体、及び架橋成形体における機械的特性や成形性を向上させるための成分として用いられる。
(Polymers)
There are no particular limitations on the polymers other than the above-mentioned silane-modified polyolefin, but unmodified olefin polymers such as unmodified ethylene polymers can be used. These polymers are used as a component for improving the mechanical properties and moldability of silane-modified polyolefin compositions using the silane-modified polyolefin, molded products thereof, and crosslinked molded products.
前記未変性オレフィン重合体類とは、各種のポリエチレンや共重合により官能基が導入されたエチレン共重合体等のエチレン系重合体や、ポリプロピレンや共重合により官能基が導入されたプロピレン共重合体等のプロピレン系重合体等であって、シランカップリング剤や官能基などにより変性されていない重合体をいう。
ここで、エチレン系重合体、プロピレン系重合体とは、それぞれ、エチレン単位、プロピレン単位を、重合体を構成する全モノマー単位中に最も多く含有する重合体のことを言い、好ましくは５０質量％を超える割合で含有する重合体を言う。
The unmodified olefin polymers include various polyethylenes and ethylene copolymers such as ethylene copolymers into which functional groups have been introduced through copolymerization, and polypropylene and propylene copolymers into which functional groups have been introduced through copolymerization. This refers to propylene-based polymers such as, etc., which have not been modified with silane coupling agents or functional groups.
Here, the ethylene polymer and propylene polymer refer to a polymer containing the largest amount of ethylene units and propylene units, respectively, in all monomer units constituting the polymer, preferably 50% by mass. refers to a polymer containing a proportion exceeding .
前記エチレン系重合体の例としては、エチレンと、プロピレン、１－ブテン、３－メチル－１－ブテン、１－ペンテン、４－メチル－１－ペンテン、１－ヘキセン、１－オクテン、１－デセン等の炭素数３～２０程度の他のα－オレフィンとの共重合体や、エチレンと、酢酸ビニル、（メタ）アクリル酸、（メタ）アクリル酸エステル等との共重合体を挙げることができる。 Examples of the ethylene polymer include ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, and 1-decene. copolymers with other α-olefins having about 3 to 20 carbon atoms, and copolymers of ethylene with vinyl acetate, (meth)acrylic acid, (meth)acrylic acid ester, etc. .
前記未変性エチレン系重合体は、密度が０．８５０～０．９７０ｇ／ｃｍ３のものが好ましく用いられる。密度が０．８５０ｇ／ｃｍ３以上であれば、得られる架橋成形体の耐熱性、耐薬品性、耐摩耗性、耐屈曲性等が良好となり、密度が０．９７０ｇ／ｃｍ３以下であれば、柔軟性が良好となる。
前記未変性エチレン系重合体は、ＪＩＳ Ｋ７２１０に従って測定した１９０℃、２．１６ｋｇ荷重におけるＭＦＲが１～１０ｇ／１０ｍｉｎであることが好ましい。未変性ポリエチレンのＭＦＲは、シラン変性ポリオレフィンのＭＦＲの規定と同様に、成形性の点では大きい方が好ましく、単位時間当たりの生産量を向上させることができ、機械的特性や耐熱性の点では小さい方が好ましい。
The unmodified ethylene polymer preferably has a density of 0.850 to 0.970 g/cm 3 . If the density is 0.850 g/cm 3 or more, the resulting crosslinked molded product will have good heat resistance, chemical resistance, abrasion resistance, bending resistance, etc., and if the density is 0.970 g/cm 3 or less, , the flexibility is good.
The unmodified ethylene polymer preferably has an MFR of 1 to 10 g/10 min at 190° C. and a load of 2.16 kg, as measured according to JIS K7210. Similar to the MFR of silane-modified polyolefin, the MFR of unmodified polyethylene is preferably larger in terms of moldability, can improve production volume per unit time, and is better in terms of mechanical properties and heat resistance. Smaller is preferable.
前記未変性エチレン系重合体は、１種のみを用いてもよく、モノマー組成や物性等の異なるものの２種以上を混合して用いてもよい。 The unmodified ethylene polymer may be used alone or in a mixture of two or more different monomer compositions, physical properties, etc.
シラン変性ポリオレフィン、未変性エチレン系重合体以外の前記重合体類としては、前述の未変性プロピレン系重合体の他、例えば、無水マレイン酸などの不飽和カルボン酸及び／又はその無水物（不飽和カルボン酸成分）により変性されたポリオレフィン、フェニレンエーテル系重合体；カーボネート重合体；ナイロン６６、ナイロン１１等のポリアミド；ポリエチレンテレフタレート、ポリブチレンテレフタレート等のエステル系重合体、ポリスチレン等のスチレン系重合体、ポリメチル（メタ）アクリレート等の（メタ）アクリル系重合体といった熱可塑性重合体や各種熱可塑性エラストマーが挙げられる。 Examples of the polymers other than silane-modified polyolefins and unmodified ethylene polymers include the aforementioned unmodified propylene polymers, as well as unsaturated carboxylic acids such as maleic anhydride and/or their anhydrides (unsaturated polyolefins and phenylene ether polymers modified with carboxylic acid components; carbonate polymers; polyamides such as nylon 66 and nylon 11; ester polymers such as polyethylene terephthalate and polybutylene terephthalate; styrene polymers such as polystyrene; Examples include thermoplastic polymers such as (meth)acrylic polymers such as polymethyl (meth)acrylate, and various thermoplastic elastomers.
本発明で用いるシラン変性ポリオレフィン組成物が、シラン変性ポリオレフィン以外の重合体類を含有する場合、該重合体類の含有率は、シラン変性ポリオレフィン組成物全体に対して、好ましくは１質量％以上、より好ましくは３質量％以上であり、一方、好ましくは３０質量％以下、より好ましくは４０質量％以下である。重合体類の含有率が上記下限以上であれば、得られる架橋成形体の耐熱性、耐薬品性、耐摩耗性、耐屈曲性、引張強度等が良好となり、上記上限以下であれば、押出負荷が増大することによる生産性の低下や、機械的特性の低下を防止することができる。 When the silane-modified polyolefin composition used in the present invention contains polymers other than silane-modified polyolefin, the content of the polymers is preferably 1% by mass or more based on the entire silane-modified polyolefin composition, It is more preferably 3% by mass or more, on the other hand, preferably 30% by mass or less, more preferably 40% by mass or less. If the content of the polymers is above the above lower limit, the resulting crosslinked molded product will have good heat resistance, chemical resistance, abrasion resistance, bending resistance, tensile strength, etc., and if it is below the above upper limit, extrusion is possible. It is possible to prevent a decrease in productivity and a decrease in mechanical properties due to an increase in load.
（炭化水素系ゴム用軟化剤）
本発明で用いるシラン変性ポリオレフィン組成物は、炭化水素系ゴム用軟化剤を含有していてもよい。炭化水素系ゴム用軟化剤としては、鉱物油系又は合成樹脂系の軟化剤が好ましく、鉱物油系軟化剤がより好ましい。
前記鉱物油系軟化剤は、一般的に、芳香族炭化水素、ナフテン系炭化水素及びパラフィン系炭化水素の混合物であり、全炭素原子の５０％以上がパラフィン系炭化水素であるものがパラフィン系オイル、全炭素原子の３０～４５％程度以上がナフテン系炭化水素であるものがナフテン系オイル、全炭素原子の３５％以上が芳香族系炭化水素であるものが炭素原子芳香族系オイルと各々呼ばれている。
(Softener for hydrocarbon rubber)
The silane-modified polyolefin composition used in the present invention may contain a softener for hydrocarbon rubber. As the softener for hydrocarbon rubber, mineral oil-based or synthetic resin-based softeners are preferred, and mineral oil-based softeners are more preferred.
The mineral oil softener is generally a mixture of aromatic hydrocarbons, naphthenic hydrocarbons, and paraffinic hydrocarbons, and those in which 50% or more of all carbon atoms are paraffinic hydrocarbons are called paraffinic oils. , those in which about 30 to 45% or more of all carbon atoms are naphthenic hydrocarbons are called naphthenic oils, and those in which 35% or more of all carbon atoms are aromatic hydrocarbons are called carbon-aromatic oils. It is.
前記合成樹脂系軟化剤としては、パラフィン系オイル、ナフテン系オイル、及び芳香族系オイルから選択される何れかを用いることが好ましい。これらのうち、色相が良好であることから、パラフィン系オイルを用いることがより好ましい。合成樹脂系軟化剤としては、ポリブテン及び低分子量ポリブタジエン等が挙げられる。 As the synthetic resin softener, it is preferable to use one selected from paraffin oils, naphthenic oils, and aromatic oils. Among these, it is more preferable to use paraffin oil because of its good hue. Examples of the synthetic resin softener include polybutene and low molecular weight polybutadiene.
炭化水素系ゴム用軟化剤は、１種類を用いても２種類以上を併用してもよい。 The softeners for hydrocarbon rubber may be used alone or in combination of two or more.
本発明で用いるシラン変性ポリオレフィン組成物が、炭化水素系ゴム用軟化剤を含有する場合、炭化水素系ゴム用軟化剤の含有率は、シラン変性ポリオレフィン組成物全体に対して、好ましくは０．５質量％以上、より好ましくは１質量％以上であり、一方、好ましくは３０質量％以下、より好ましくは４０質量％以下である。炭化水素系ゴム用軟化剤の含有率が上記下限以上であれば柔軟性を十分に得ることができ、上記上限以下であれば得られる架橋成形体の機械的特性の低下を防止することができる。 When the silane-modified polyolefin composition used in the present invention contains a hydrocarbon rubber softener, the content of the hydrocarbon rubber softener is preferably 0.5 with respect to the entire silane-modified polyolefin composition. It is at least 1% by mass, more preferably at least 1% by mass, and on the other hand, preferably at most 30% by mass, more preferably at most 40% by mass. If the content of the softener for hydrocarbon rubber is at least the above-mentioned lower limit, sufficient flexibility can be obtained, and if it is below the above-mentioned upper limit, deterioration in the mechanical properties of the resulting crosslinked molded product can be prevented. .
（架橋助剤）
本発明で用いるシラン変性ポリオレフィン組成物は、架橋助剤を含有していてもよい。
架橋助剤としては、重合性官能基を１分子中に２以上有するモノマーを使用することができ、典型的には、例えば、ジビニルベンゼン、及びトリアリルシアヌレートなどの多官能性ビニルモノマー；エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、及びアリル（メタ）アクリレートなどの多官能性（メタ）アクリレートモノマー；などであってよい。
前記架橋助剤は、１種のみを用いてもよく、異なるものの２種以上を混合して用いてもよい。
(Crosslinking aid)
The silane-modified polyolefin composition used in the present invention may contain a crosslinking aid.
As the crosslinking aid, monomers having two or more polymerizable functional groups in one molecule can be used, typically polyfunctional vinyl monomers such as divinylbenzene and triallyl cyanurate; ethylene. Polyfunctional compounds such as glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and allyl(meth)acrylate (meth)acrylate monomer; etc.
The crosslinking aids may be used alone or in combination of two or more different ones.
架橋助剤は、架橋度を高める観点では、配合量を増やすことが好ましい。一方、架橋後の成形体から架橋助剤そのもののブリード抑制の観点からは配合量が少ない方が好ましい。 From the viewpoint of increasing the degree of crosslinking, it is preferable to increase the amount of the crosslinking aid. On the other hand, from the viewpoint of suppressing bleeding of the crosslinking aid itself from the molded article after crosslinking, it is preferable that the blending amount is small.
本発明で用いるシラン変性ポリオレフィン組成物が、架橋助剤を含有する場合、架橋度を高める一方で、架橋助剤のブリードを抑制する観点から、架橋助剤の含有率は、シラン変性ポリオレフィン組成物全体に対して、好ましくは０．１質量％以上、より好ましくは０．３質量％以上であり、一方、好ましくは４質量％以下、より好ましくは５質量％以下である。 When the silane-modified polyolefin composition used in the present invention contains a crosslinking auxiliary agent, the content of the crosslinking auxiliary agent is determined from the viewpoint of increasing the degree of crosslinking and suppressing bleeding of the crosslinking auxiliary agent. It is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, based on the whole, and preferably 4% by mass or less, more preferably 5% by mass or less.
（その他の添加剤）
上記以外のその他の添加剤としては、具体的には、加工助剤、可塑剤、結晶核剤、衝撃改良剤、難燃助剤、架橋触媒、帯電防止剤、酸化防止剤、滑剤、充填材、相溶化剤、熱安定剤、光安定剤、紫外線吸収剤、カーボンブラック、着色剤が挙げられる。
(Other additives)
Other additives other than those listed above include processing aids, plasticizers, crystal nucleating agents, impact modifiers, flame retardant aids, crosslinking catalysts, antistatic agents, antioxidants, lubricants, and fillers. , compatibilizers, heat stabilizers, light stabilizers, ultraviolet absorbers, carbon black, and colorants.
一般に、シラン変性ポリオレフィンを水架橋する場合には、架橋触媒として、シラノール縮合触媒が好適に使用される。シラノール縮合触媒として、具体的には、ジブチルスズジラウレート、ジオクチルスズジラウレート、ジブチルスズジアセテート、ジブチルスズジオクタエート、酢酸第１スズ、カプリル酸第１スズ、カプリル酸亜鉛、ナフテン酸鉛、ナフテン酸コバルト等の金属脂肪酸塩が挙げられる。本発明においては、水架橋工程を必須としないため、架橋触媒は任意成分であり、架橋触媒を含有しない実施形態が好ましい。
ここで、架橋触媒を含有しないとは、シラン変性ポリオレフィン組成物中の架橋触媒に由来する金属換算の含有率として５ｐｐｍ以下、例えば０～２ｐｐｍ、好ましくは０ｐｐｍであることをさす。なお、この金属換算の含有率は、得られる成形体及び架橋成形体中の架橋触媒由来の金属含有率に等しい。
Generally, when silane-modified polyolefin is water-crosslinked, a silanol condensation catalyst is preferably used as the crosslinking catalyst. Examples of silanol condensation catalysts include dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, dibutyltin dioctaate, stannous acetate, stannous caprylate, zinc caprylate, lead naphthenate, cobalt naphthenate, etc. Examples include metal fatty acid salts. In the present invention, since the water crosslinking step is not essential, the crosslinking catalyst is an optional component, and embodiments that do not contain the crosslinking catalyst are preferred.
Here, "not containing a crosslinking catalyst" means that the content of metal derived from the crosslinking catalyst in the silane-modified polyolefin composition is 5 ppm or less, for example 0 to 2 ppm, preferably 0 ppm. Note that this content in terms of metal is equal to the metal content derived from the crosslinking catalyst in the obtained molded body and crosslinked molded body.
前記の熱安定剤及び酸化防止剤としては、例えば、ヒンダードフェノール類、リン化合物、ヒンダードアミン、イオウ化合物、銅化合物、アルカリ金属のハロゲン化物が挙げられる。 Examples of the heat stabilizer and antioxidant include hindered phenols, phosphorus compounds, hindered amines, sulfur compounds, copper compounds, and alkali metal halides.
前記の充填材は、有機充填材と無機充填材に大別される。有機充填材としては、例えば、澱粉、セルロース微粒子、木粉、おから、モミ殻、フスマ等の天然由来のポリマーやこれらの変性品が挙げられる。また、無機充填材としては、例えば、タルク、炭酸カルシウム、炭酸亜鉛、ワラストナイト、シリカ、アルミナ、酸化マグネシウム、ケイ酸カルシウム、アルミン酸ナトリウム、アルミン酸カルシウム、アルミノ珪酸ナトリウム、珪酸マグネシウム、ガラスバルーン、カーボンブラック、酸化亜鉛、三酸化アンチモン、ゼオライト、ハイドロタルサイト、金属繊維、金属ウイスカー、セラミックウイスカー、チタン酸カリウム、窒化ホウ素、グラファイト、炭素繊維が挙げられる。 The fillers mentioned above are broadly classified into organic fillers and inorganic fillers. Examples of the organic filler include naturally occurring polymers such as starch, cellulose particles, wood flour, okara, rice husks, and bran, and modified products thereof. Examples of inorganic fillers include talc, calcium carbonate, zinc carbonate, wollastonite, silica, alumina, magnesium oxide, calcium silicate, sodium aluminate, calcium aluminate, sodium aluminosilicate, magnesium silicate, and glass balloon. , carbon black, zinc oxide, antimony trioxide, zeolite, hydrotalcite, metal fiber, metal whisker, ceramic whisker, potassium titanate, boron nitride, graphite, and carbon fiber.
［シラン変性ポリオレフィン組成物を得る工程］
本発明で用いるシラン変性ポリオレフィン組成物を得る工程には特に制限はなく、シラン変性ポリオレフィンと上記した金属水酸化物やその他の成分を含有するポリオレフィン組成物が得られるように製造することができればよい。本発明で用いるシラン変性ポリオレフィン組成物は、例えば、各材料を同時に又は任意の順序で混合することで製造することができる。酸化防止剤や着色剤などのその他の成分は、均一に分散させることができればどのタイミングで加えても良い。
[Step of obtaining silane-modified polyolefin composition]
There is no particular restriction on the process for obtaining the silane-modified polyolefin composition used in the present invention, as long as it can be produced so as to obtain a polyolefin composition containing the silane-modified polyolefin, the above-mentioned metal hydroxide, and other components. . The silane-modified polyolefin composition used in the present invention can be produced, for example, by mixing each material simultaneously or in any order. Other components such as antioxidants and colorants may be added at any timing as long as they can be uniformly dispersed.
前記の各原料成分を混合する際の装置に限定はないが、ニーダー、バンバリーミキサー、ロール、一軸押出機、二軸押出機などの汎用のものが使用できる。溶融混合時の温度は、各原料成分の少なくとも一つが溶融状態となる温度であればよいが、通常は用いる全成分が溶融する温度が選択され、一般には１５０～２５０℃で行われる。 Although there is no limitation on the equipment used to mix the raw material components, general-purpose equipment such as a kneader, Banbury mixer, roll, single-screw extruder, and twin-screw extruder can be used. The temperature during melt mixing may be any temperature at which at least one of the raw material components is in a molten state, but the temperature at which all the components used are usually melted is selected, and is generally carried out at a temperature of 150 to 250°C.
［成形体を得る工程］
シラン変性ポリオレフィン又はシラン変性ポリオレフィン組成物を成形して成形体を得る工程は、押出成形、圧縮成形、射出成形など特に限定するものではないが、シラン変性ポリオレフィン又はシラン変性ポリオレフィン組成物の溶融状態での流動性の観点から押出成形が望ましい。また成形温度はシラン変性ポリオレフィン又はシラン変性ポリオレフィン組成物の溶融温度より高温であれば限定されないが、１５０～２２０℃が望ましい。成形温度が上記下限以上であれば、溶融したシラン変性ポリオレフィン又はシラン変性ポリオレフィン組成物の流動性が高く、目的の形状の成形体を得やすい。一方、成形温度が上記上限以下であれば金属水酸化物の分解等による発泡による外観の悪化が起こりにくい。
[Process of obtaining a molded body]
The process of molding a silane-modified polyolefin or a silane-modified polyolefin composition to obtain a molded product is not particularly limited to extrusion molding, compression molding, injection molding, etc. Extrusion molding is desirable from the viewpoint of fluidity. Further, the molding temperature is not limited as long as it is higher than the melting temperature of the silane-modified polyolefin or silane-modified polyolefin composition, but it is preferably 150 to 220°C. When the molding temperature is equal to or higher than the above lower limit, the melted silane-modified polyolefin or silane-modified polyolefin composition has high fluidity, and it is easy to obtain a molded article in the desired shape. On the other hand, if the molding temperature is below the above upper limit, deterioration of the appearance due to foaming due to decomposition of the metal hydroxide is unlikely to occur.
［成形体のシラノール縮合触媒由来の金属含有率］
本発明に係るシラン変性ポリオレフィン又はシラン変性ポリオレフィン組成物を成形して得られる本発明の成形体は、シラノール縮合触媒由来の金属含有率、例えばスズ含有率が１ｐｐｍ未満であることを特徴とする。
即ち、本発明においては、電子線架橋を行うことから、環境負荷が懸念される有機スズ化合物等の架橋触媒を用いる必要はなく、得られる成形体は、シラノール縮合触媒としての金属化合物由来の金属含有率は１ｐｐｍ未満、好ましくは０ｐｐｍ（金属非含有）のものとすることができる。
[Metal content derived from silanol condensation catalyst in molded body]
The molded article of the present invention obtained by molding the silane-modified polyolefin or the silane-modified polyolefin composition according to the present invention is characterized in that the metal content derived from the silanol condensation catalyst, for example, the tin content, is less than 1 ppm.
That is, in the present invention, since electron beam crosslinking is carried out, there is no need to use a crosslinking catalyst such as an organic tin compound, which is a concern for environmental impact, and the obtained molded article is a metal compound derived from a metal compound as a silanol condensation catalyst. The content can be less than 1 ppm, preferably 0 ppm (no metals).
なお、成形体のシラノール縮合触媒由来の金属含有率、例えばスズ含有率は、後掲の実施例の項に記載の方法で測定される。
実施例においては、シラノール縮合触媒由来の金属含有率として架橋成形体のスズ含有率を測定しているが、架橋成形体の金属含有率は架橋前の成形体の金属含有率に等しいため、架橋成形体の金属含有率を成形体の金属含有率とすることができる。
Note that the metal content derived from the silanol condensation catalyst, such as the tin content, of the molded body is measured by the method described in the Examples section below.
In the examples, the tin content of the crosslinked molded body is measured as the metal content derived from the silanol condensation catalyst, but since the metal content of the crosslinked molded body is equal to the metal content of the molded body before crosslinking, The metal content of the molded body can be defined as the metal content of the molded body.
［電子線照射する工程］
上記シラン変性ポリオレフィン又はシラン変性ポリオレフィン組成物を成形して成形体を得る工程により得られた成形体である本発明の成形体に電子線照射することによって、耐熱性、機械的特性に優れた架橋成形体を得ることができる。
電子線照射する工程では、照射強度が好ましくは６０ｋＧｙ以上、より好ましくは８０ｋＧｙ以上になるように電子線照射を行う。上記照射強度が得られれば、加速電圧や速度は任意で構わない。
電子線照射による架橋処理に要する時間は、目的の照射強度に依存するが、通常数秒から数分程度である。水架橋に要する架橋時間が通常１０～２４時間であるのに対して、電子線照射による架橋処理であれば大幅に架橋処理時間を短縮することができる。
[Process of electron beam irradiation]
The molded product of the present invention, which is the molded product obtained by molding the silane-modified polyolefin or silane-modified polyolefin composition to obtain a molded product, is crosslinked with excellent heat resistance and mechanical properties by irradiating it with an electron beam. A molded body can be obtained.
In the electron beam irradiation step, the electron beam irradiation is performed so that the irradiation intensity is preferably 60 kGy or more, more preferably 80 kGy or more. As long as the above irradiation intensity is obtained, the accelerating voltage and speed may be arbitrary.
The time required for crosslinking treatment by electron beam irradiation depends on the desired irradiation intensity, but is usually about several seconds to several minutes. While the crosslinking time required for water crosslinking is usually 10 to 24 hours, crosslinking treatment using electron beam irradiation can significantly shorten the crosslinking treatment time.
［架橋成形体のシラノール縮合触媒由来の金属含有率］
シラノール縮合触媒由来の金属含有率１ｐｐｍ未満の本発明の成形体を用いて得られる本発明の架橋成形体は、本発明の成形体と同様シラノール縮合触媒由来の金属含有率１ｐｐｍ未満、好ましくはシラノール縮合触媒由来の金属含有率０ｐｐｍ（金属非含有）であり、その製造工程から得られる製品に到るまで、環境負荷が低く安全性の高い架橋成形体である。
本発明の架橋成形体は、具体的には上記の電子線照射する工程により、本発明の成形体に電子線を照射することにより製造される。
[Metal content derived from silanol condensation catalyst in crosslinked molded body]
The crosslinked molded article of the present invention obtained using the molded article of the present invention having a metal content of less than 1 ppm derived from a silanol condensation catalyst, preferably having a metal content of less than 1 ppm derived from a silanol condensation catalyst, is similar to the molded article of the present invention. The metal content derived from the condensation catalyst is 0 ppm (metal free), and from the manufacturing process to the product obtained, the crosslinked molded product has a low environmental impact and is highly safe.
Specifically, the crosslinked molded article of the present invention is manufactured by irradiating the molded article of the present invention with an electron beam in the step of irradiating the molded article with an electron beam.
［架橋成形体の用途］
本発明の架橋成形体の製造方法により製造される本発明の架橋成形体の用途は特に限定するものではないが、優れた耐熱性、機械的特性を併せ持ち、外観に優れ、しかも環境負荷が懸念されるスズ含有の問題もなく、絶縁体、シースとして電線・ケーブルに好適に用いることができる。更には、複数の樹脂被覆電線を束ねるチューブの他、各種絶縁フィルム、絶縁パイプ、電源ボックス等に好適に使用することができる。以上に挙げたものの中でも本発明の架橋成形体の製造方法により製造される本発明の架橋成形体は電線被覆材として、これを電線に用い、電線被覆材を被覆した被覆電線として用いることが特に好ましい。
[Applications of crosslinked molded bodies]
The use of the crosslinked molded product of the present invention produced by the method for producing a crosslinked molded product of the present invention is not particularly limited, but it has excellent heat resistance and mechanical properties, has an excellent appearance, and is concerned about environmental burden. There is no problem of tin content, and it can be suitably used as an insulator or sheath for electric wires and cables. Furthermore, it can be suitably used for various insulating films, insulating pipes, power supply boxes, etc. in addition to tubes for bundling a plurality of resin-coated electric wires. Among the above-mentioned products, the crosslinked molded product of the present invention produced by the method for producing a crosslinked molded product of the present invention is particularly preferably used as an electric wire coating material, and used as a covered electric wire coated with an electric wire coating material. preferable.
以下、実施例を用いて本発明の具体的態様を更に詳細に説明するが、本発明はその要旨を超えない限り、以下の実施例によって限定されるものではない。尚、以下の実施例における各種の製造条件や評価結果の値は、本発明の実施態様における上限又は下限の好ましい値としての意味をもつものであり、好ましい範囲は前記した上限又は下限の値と、下記実施例の値又は実施例同士の値との組み合わせで規定される範囲であってもよい。 Hereinafter, specific embodiments of the present invention will be explained in more detail using Examples, but the present invention is not limited by the following Examples unless the gist thereof is exceeded. In addition, the values of various manufacturing conditions and evaluation results in the following examples have the meaning as preferable upper or lower limits in the embodiments of the present invention, and the preferable ranges are different from the above-mentioned upper or lower limits. , it may be a range defined by the values of the following examples or a combination of values of the examples.
［原料］
以下の実施例及び比較例では、以下の原料を用いた。
[material]
In the following Examples and Comparative Examples, the following raw materials were used.
＜ポリエチレン＞
ポリエチレン－１：
エチレン・１－ブテン共重合体、商品名：ＥＮＧＡＧＥ７２５６（ダウ・ケミカル日本（株）製、ＭＦＲ：２．５ｇ／１０ｍｉｎ、密度：０．８８５ｇ／ｃｍ３）
ポリエチレン－２：
ポリエチレン、商品名：ＮＯＶＡＴＥＣ ＨＹ３５０（日本ポリエチレン(株)製、ＭＦＲ：２．５ｇ／１０ｍｉｎ、密度：０．９５１／ｃｍ３）
<Polyethylene>
Polyethylene-1:
Ethylene/1-butene copolymer, trade name: ENGAGE7256 (manufactured by Dow Chemical Japan Co., Ltd., MFR: 2.5 g/10 min, density: 0.885 g/cm 3 )
Polyethylene-2:
Polyethylene, product name: NOVATEC HY350 (manufactured by Japan Polyethylene Co., Ltd., MFR: 2.5 g/10 min, density: 0.951/cm 3 )
＜シラン変性ポリオレフィン＞
シラン変性ポリオレフィン－１：
「ポリエチレン－１」１００質量部に対し、不飽和シラン化合物としてビニルトリメトキシシランを２質量部、遊離ラジカル発生剤としてジクミルパーオキサイトを０．０４４質量部添加して配合し、これを２６ｍｍφの２軸押出機（Ｌ／Ｄ＝４９）にて押出樹脂温度２００℃で押出した。押出したストランドをペレタイザーでペレット化して「シラン変性ポリオレフィン－１」を製造した。得られたシラン変性ポリエチレン－１のＭＦＲは２．０ｇ／１０ｍｉｎ、密度は０．８９０ｇ／ｃｍ３であった。
<Silane-modified polyolefin>
Silane modified polyolefin-1:
2 parts by mass of vinyltrimethoxysilane as an unsaturated silane compound and 0.044 parts by mass of dicumyl peroxide as a free radical generator were added to 100 parts by mass of "Polyethylene-1", and this was mixed into a 26 mmφ It was extruded using a twin-screw extruder (L/D=49) at an extrusion resin temperature of 200°C. The extruded strand was pelletized using a pelletizer to produce "silane-modified polyolefin-1". The MFR of the obtained silane-modified polyethylene-1 was 2.0 g/10 min, and the density was 0.890 g/cm 3 .
＜難燃剤＞
難燃剤：
合成水酸化アルミニウム 平均粒子径：２．０μｍ、表面処理のないもの。
<Flame retardant>
Flame retardants:
Synthetic aluminum hydroxide Average particle size: 2.0 μm, without surface treatment.
＜その他樹脂・添加剤＞
ＥＶＡ：
エチレン・酢酸ビニル共重合体、商品名：エバフレックスＥＶ３６０（三井ダウポリケミカル（株）製、ＭＦＲ：２．０ｇ／１０ｍｉｎ、密度：０．９５０ｇ／ｃｍ３）
鉱油：
出光興産社製、「ダイアナプロセスオイル ＰＷ９０」（鉱物油系炭化水素）
架橋助剤：
新中村化学工業社製、「トリメチロールプロパントリ（メタ）アクリレート（ＴＭＰＴＭＡ）」
シラノール縮合触媒ＭＢ：
「ポリエチレン－２」１００質量部に対し、０．１質量部のスズ触媒（ジオクチルスズジラウレート）添加して配合し、これを２６ｍｍφの２軸押出機（Ｌ／Ｄ＝４９）にて押出樹脂温度２００℃で押出した。押出したストランドをペレタイザーでペレット化して「シラノール縮合触媒ＭＢ」を製造した。得られたシラノール縮合触媒ＭＢのＭＦＲは３．５ｇ／１０ｍｉｎ、密度は０．９５０ｇ／ｃｍ３であった。
<Other resins/additives>
EVA:
Ethylene/vinyl acetate copolymer, trade name: Evaflex EV360 (manufactured by Mitsui Dow Polychemical Co., Ltd., MFR: 2.0 g/10 min, density: 0.950 g/cm 3 )
Mineral oil:
Manufactured by Idemitsu Kosan, "Diana Process Oil PW90" (mineral oil hydrocarbon)
Crosslinking aid:
"Trimethylolpropane tri(meth)acrylate (TMPTMA)" manufactured by Shin Nakamura Chemical Industry Co., Ltd.
Silanol condensation catalyst MB:
0.1 parts by mass of a tin catalyst (dioctyltin dilaurate) was added to 100 parts by mass of "Polyethylene-2" and blended, and this was extruded using a 26 mmφ twin screw extruder (L/D=49) at a resin temperature of It was extruded at 200°C. The extruded strands were pelletized using a pelletizer to produce "silanol condensation catalyst MB." The MFR of the obtained silanol condensation catalyst MB was 3.5 g/10 min, and the density was 0.950 g/cm 3 .
［評価］
＜機械物性試験＞
架橋処理を行った押出シート（厚さ１ｍｍ）を用い、ＪＩＳ Ｃ－３００５に準拠して
破断点強度及び破断点伸びの測定を行った。試験片は３号ダンベルを用い、引張速度は２００ｍｍ／分とした。
破断点強度及び破断点伸びの何れも、値が高い方が好ましいが、引張強度は１０ＭＰａ以上を合格とし、引張伸度は１００％以上を合格とした。
[evaluation]
<Mechanical property test>
Using a crosslinked extruded sheet (thickness: 1 mm), strength at break and elongation at break were measured in accordance with JIS C-3005. A No. 3 dumbbell was used as the test piece, and the tensile speed was 200 mm/min.
For both the strength at break and the elongation at break, higher values are preferred; however, a tensile strength of 10 MPa or more was considered a pass, and a tensile elongation of 100% or more was considered a pass.
＜耐熱物性試験＞
架橋処理を行った押出シート（厚さ１ｍｍ）を用い、ＩＥＣ６０８１１－２－１を参考にして、ホットセット試験を行った。測定温度は２５０℃、荷重は２０Ｎ／ｃｍ２とした。
荷重時伸び、永久伸びの何れも、値が低い方が好ましいが、十分な架橋効果が得られている場合は、破断しない。
<Heat-resistant physical property test>
A hot set test was conducted using an extruded sheet (thickness: 1 mm) that had been crosslinked, with reference to IEC60811-2-1. The measurement temperature was 250° C. and the load was 20 N/cm 2 .
Lower values for both elongation under load and permanent elongation are preferred, but if a sufficient crosslinking effect is obtained, no breakage occurs.
＜スズ含有率＞
測定試料として架橋処理を行った押出シート（厚さ１ｍｍ）を用い、蛍光エックス線分析装置を用い、散乱線ファンダメンタルパラメーター法により架橋成形体のスズ含有率を求めた。なお、スズの検出の積算時間は、３００秒とした。
<Tin content>
Using an extruded sheet (thickness: 1 mm) that had been crosslinked as a measurement sample, the tin content of the crosslinked molded product was determined by the scattered radiation fundamental parameter method using a fluorescent X-ray analyzer. Note that the cumulative time for detecting tin was 300 seconds.
［実施例１］
内容量１．０Ｌの加圧ニーダーに、シラン変性ポリオレフィン－１を６０質量部、ＥＶＡを４０質量部、難燃剤を１８０質量部、鉱油を５質量部投入し、加圧ニーダーの設定温度１００℃で１５分間混練した。得られた混練物をペレット化してシラン変性ポリオレフィンを含むポリオレフィン組成物を作製した。
得られた樹脂組成物を単軸押出機を用いて２００℃で押出成形し、幅５０ｍｍ×厚さ１ｍｍの押出シート（架橋前の成形体）を得た。
得られた押出シートを、所定の照射強度（１００ｋＧｙ）で電子線照射処理を行い、シラン変性ポリオレフィン組成物の架橋成形体を得た。
得られた架橋成形体の機械物性試験及び耐熱物性試験の結果を表１に示す。
[Example 1]
60 parts by mass of silane-modified polyolefin-1, 40 parts by mass of EVA, 180 parts by mass of flame retardant, and 5 parts by mass of mineral oil were put into a pressure kneader with an internal capacity of 1.0 L, and the temperature of the pressure kneader was set at 100°C. The mixture was kneaded for 15 minutes. The obtained kneaded material was pelletized to prepare a polyolefin composition containing a silane-modified polyolefin.
The obtained resin composition was extrusion-molded at 200° C. using a single-screw extruder to obtain an extruded sheet (a molded article before crosslinking) having a width of 50 mm and a thickness of 1 mm.
The obtained extruded sheet was subjected to electron beam irradiation treatment at a predetermined irradiation intensity (100 kGy) to obtain a crosslinked molded product of the silane-modified polyolefin composition.
Table 1 shows the results of the mechanical property test and heat resistance property test of the obtained crosslinked molded product.
［実施例２～４、比較例１～５、参考例１］
表１、２に示す配合に従い、表１、２に示す電子線照射強度で実施例１と同様にして架橋成形体を得、実施例１と同様に機械物性試験及び耐熱物性試験を実施した。結果を表１、２に示す。
なお、参考例１は、電子線照射架橋処理しない場合を示す。
[Examples 2 to 4, Comparative Examples 1 to 5, Reference Example 1]
A crosslinked molded article was obtained in the same manner as in Example 1 according to the formulations shown in Tables 1 and 2 and at the electron beam irradiation intensity shown in Tables 1 and 2, and mechanical property tests and heat resistance tests were conducted in the same manner as in Example 1. The results are shown in Tables 1 and 2.
Note that Reference Example 1 shows the case where no electron beam irradiation crosslinking treatment was performed.
［参考例２］
表１に示す配合に従い、実施例１と同様にして得られた押出シートを、８５℃８５％ＲＨの恒温恒湿下で２４時間の加熱処理（水架橋）を行って架橋成形体を得、実施例１と同様に機械物性試験及び耐熱物性試験を実施した。結果を表１に示す。
[Reference example 2]
According to the formulation shown in Table 1, the extruded sheet obtained in the same manner as in Example 1 was heat-treated (water-crosslinked) for 24 hours at a constant temperature and humidity of 85° C. and 85% RH to obtain a crosslinked molded product. A mechanical property test and a heat resistance property test were conducted in the same manner as in Example 1. The results are shown in Table 1.
また、実施例１～４及び参考例２の架橋成形体についてスズ含有率を測定した。結果を表１，２に示す。 Furthermore, the tin content of the crosslinked molded bodies of Examples 1 to 4 and Reference Example 2 was measured. The results are shown in Tables 1 and 2.
［結果］
表１，２より次のことが分かる。
実施例１は、電子線照射により十分な架橋効果が得られ、引張物性ならびに耐熱物性の向上が認められた。これに対し、シラン変性ポリオレフィンを含まない比較例１～２は、機械物性と耐熱物性に劣るものであった。これは、十分な架橋効果が得られていないためと推察される。
また、電子線照射強度６０ｋＧｙと低い場合における実施例２～４は、十分な機械強度や耐熱物性を発現し、物性向上に改善がみられた。一方、シラン変性ポリオレフィンを含まない比較例３～５は、架橋助剤を添加しても、機械物性と耐熱物性に劣るものであった。これは、十分な架橋効果が得られていないためと推察される。
参考例２は、シラノール縮合触媒として有機スズ化合物を用いて水架橋を行った例であるが、架橋処理に２４時間もの長時間を有する。架橋処理時間が不十分であると、十分に架橋反応が進行せず、得られた架橋成形体は耐熱物性に劣る。しかも、この架橋成形体はスズを含み、環境面で好ましくない。
[result]
The following can be seen from Tables 1 and 2.
In Example 1, a sufficient crosslinking effect was obtained by electron beam irradiation, and improvements in tensile properties and heat-resistant properties were observed. On the other hand, Comparative Examples 1 and 2, which did not contain silane-modified polyolefin, had poor mechanical properties and heat-resistant properties. This is presumably because a sufficient crosslinking effect was not obtained.
Further, Examples 2 to 4 in which the electron beam irradiation intensity was as low as 60 kGy exhibited sufficient mechanical strength and heat-resistant physical properties, and an improvement in physical properties was observed. On the other hand, Comparative Examples 3 to 5, which did not contain silane-modified polyolefin, had poor mechanical properties and heat-resistant properties even if a crosslinking aid was added. This is presumably because a sufficient crosslinking effect was not obtained.
Reference Example 2 is an example in which water crosslinking was performed using an organic tin compound as a silanol condensation catalyst, but the crosslinking process took as long as 24 hours. If the crosslinking treatment time is insufficient, the crosslinking reaction will not proceed sufficiently, and the resulting crosslinked molded product will have poor heat resistance properties. Moreover, this cross-linked molded product contains tin, which is unfavorable from an environmental standpoint.
以上の結果から、本発明によれば、生産性と機械物性及び耐熱物性に優れ、しかもスズ等のシラノール縮合触媒由来の金属含有の問題がなく、環境負荷が低く安全性の高い架橋成形体を提供することができることが分かる。
From the above results, according to the present invention, a crosslinked molded product with excellent productivity, mechanical properties, and heat-resistant properties, without the problem of containing metals derived from silanol condensation catalysts such as tin, and with a low environmental impact and high safety. I know that I can provide it.
Claims (6)
A crosslinked molded article using the molded article according to claim 5.
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