JPH04331241A - Production of water-crosslinked resin molding - Google Patents
Production of water-crosslinked resin moldingInfo
- Publication number
- JPH04331241A JPH04331241A JP13066791A JP13066791A JPH04331241A JP H04331241 A JPH04331241 A JP H04331241A JP 13066791 A JP13066791 A JP 13066791A JP 13066791 A JP13066791 A JP 13066791A JP H04331241 A JPH04331241 A JP H04331241A
- Authority
- JP
- Japan
- Prior art keywords
- water
- crosslinking
- molded product
- crosslinked resin
- resin
- 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
- 229920005989 resin Polymers 0.000 title claims abstract description 44
- 239000011347 resin Substances 0.000 title claims abstract description 44
- 238000000465 moulding Methods 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 238000004132 cross linking Methods 0.000 claims abstract description 59
- 239000000203 mixture Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 55
- 238000000034 method Methods 0.000 abstract description 14
- 238000009792 diffusion process Methods 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 230000003712 anti-aging effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- -1 unsaturated silane compound Chemical class 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 2
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- 239000003707 silyl modified polymer Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical class C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229920001112 grafted polyolefin Polymers 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Heating, Cooling, Or Curing Plastics Or The Like In General (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、水架橋樹脂成形物の製
造方法に関し、さらに詳しくは、水架橋時間を大幅に短
縮することができ、生産性向上と製造コスト低減を可能
とする水架橋樹脂成形物の製造方法に関する。本発明の
製造方法は、特に、水架橋樹脂被覆電線（絶縁電線）や
絶縁チューブ等の製造に好適である。[Industrial Application Field] The present invention relates to a method for producing a water-crosslinked resin molded product, and more specifically, the present invention relates to a method for producing a water-crosslinked resin molded product, and more specifically, a water-crosslinking method that can significantly shorten the water-crosslinking time, improve productivity, and reduce manufacturing costs. The present invention relates to a method for manufacturing a resin molded product. The manufacturing method of the present invention is particularly suitable for manufacturing water-crosslinked resin-coated wires (insulated wires), insulated tubes, and the like.
【０００２】0002
【従来の技術】従来、ケーブルの被覆材やチューブなど
の樹脂成形物は、耐熱性の向上や亀裂防止などの目的で
、架橋が行なわれている。架橋方法としては、水によっ
て架橋する水架橋、電子線照射による架橋、過酸化物に
よる化学架橋などの各種方法があり、製品サイズや製造
コスト等により使い分けられている。これらの中でも、
水架橋は、水架橋可能な樹脂成形物を水分の存在下に加
水分解・脱水縮合させることにより架橋する方法であり
、その簡便さから注目されている。2. Description of the Related Art Conventionally, resin molded products such as cable sheathing materials and tubes have been crosslinked for the purpose of improving heat resistance and preventing cracks. There are various crosslinking methods such as water crosslinking using water, crosslinking using electron beam irradiation, and chemical crosslinking using peroxide, which are used depending on the product size, manufacturing cost, etc. Among these,
Water crosslinking is a method of crosslinking a water crosslinkable resin molded product by subjecting it to hydrolysis and dehydration condensation in the presence of water, and is attracting attention because of its simplicity.
【０００３】水架橋可能な樹脂としては、例えば、オレ
フィン系ポリマーに、ビニルトリメトキシシランなどの
不飽和シラン化合物を遊離ラジカル発生剤の存在下に反
応させたシラングラフトポリオレフィン、あるいはオレ
フィン−不飽和シラン化合物共重合体などの、加水分解
可能なシラン基を有する各種ポリマーが用いられている
。Examples of water-crosslinkable resins include silane-grafted polyolefins obtained by reacting an olefin polymer with an unsaturated silane compound such as vinyltrimethoxysilane in the presence of a free radical generator, or olefin-unsaturated silanes. Various polymers having hydrolyzable silane groups, such as compound copolymers, have been used.
【０００４】水架橋による架橋方法では、水架橋可能な
樹脂に、所望によりシラノール縮合触媒や老化防止剤、
充填剤、難燃剤等を混合した組成物を、先ず、導体上に
押出被覆して被覆電線を成形したり、あるいはチューブ
等の所望の形状に成形した後、これらの成形物を水分の
存在下で加水分解・縮合させる。この水架橋は、常温で
も可能であるが、一般的には、成形物を高温水槽に漬浸
したり、あるいは高温高湿槽に放置することにより行な
われている。[0004] In the crosslinking method using water crosslinking, a silanol condensation catalyst, an antiaging agent,
First, a composition mixed with fillers, flame retardants, etc. is extruded and coated onto a conductor to form a covered electric wire, or after being formed into a desired shape such as a tube, these molded products are heated in the presence of moisture. Hydrolyze and condense. Although this water crosslinking is possible at room temperature, it is generally carried out by immersing the molded product in a high-temperature water tank or leaving it in a high-temperature and high-humidity tank.
【０００５】ところで、水架橋による架橋方法は、他の
架橋方法と比べて架橋に長時間を要するという問題があ
る。例えば、被覆電線の水架橋は、加水分解可能なシラ
ン基を有するシラン変成ポリエチレンなどの水架橋可能
な樹脂を導体上に押出被覆して被覆電線を製造した後、
該被覆電線をドラムに巻き取り、次いでこのドラムを高
温高湿槽に放置することにより行われている。水架橋可
能な樹脂の水架橋は、該樹脂中のシラン変成部分が水分
と接触することにより生じるが、この場合、水分の被覆
電線の被覆層の厚さ方向への拡散が比較的緩やかに進行
するため、架橋に多大の時間を必要とする。チューブ等
の成形物の場合も同様に成形物内部への水の拡散が緩や
かなために架橋に長時間を必要とする。[0005] However, the crosslinking method using water crosslinking has a problem in that it takes a longer time for crosslinking than other crosslinking methods. For example, water-crosslinking of a covered electric wire is carried out by extruding and coating a conductor with a water-crosslinkable resin such as silane-modified polyethylene having a hydrolyzable silane group, and then manufacturing a covered electric wire.
This is carried out by winding the coated wire onto a drum, and then leaving the drum in a high-temperature, high-humidity tank. Water crosslinking of a water-crosslinkable resin occurs when the silane-modified portion in the resin comes into contact with moisture, but in this case, the diffusion of moisture in the thickness direction of the coating layer of the covered wire progresses relatively slowly. Therefore, a large amount of time is required for crosslinking. Similarly, in the case of molded products such as tubes, crosslinking takes a long time because water diffuses slowly into the molded product.
【０００６】従来、水架橋時間の短縮のために、例えば
、変成用のシラン化合物や触媒、助剤等の開発が進めら
れているが（特開昭５７−２０８００６号、特開昭６２
−１０６９４７号）、これらの方法は、加水分解反応を
効率良く進行させようとするものであって、水の成形物
内部への拡散を進行させるものではないため、架橋時間
の短縮には限界がある。また、水架橋樹脂被覆電線・ケ
ーブルの架橋時に、水分との接触を高める方法もいくつ
か提案されているが（特開昭６０−２５４５２０号、特
開昭６０−２６５１０号）、やはり成形物内部への水の
拡散を進行させるものではない。Conventionally, in order to shorten the water crosslinking time, for example, silane compounds, catalysts, auxiliaries, etc. for modification have been developed (Japanese Patent Application Laid-open Nos. 57-208006, 1983).
-106947), these methods aim to advance the hydrolysis reaction efficiently, but do not promote the diffusion of water into the molded product, so there is a limit to shortening the crosslinking time. be. In addition, several methods have been proposed to increase contact with water when crosslinking water-crosslinkable resin-coated wires and cables (Japanese Patent Application Laid-open Nos. 60-254520 and 60-26510); It does not promote the diffusion of water into the water.
【０００７】[0007]
【発明が解決しようとする課題】本発明の目的は、架橋
時に、水架橋樹脂成形物内部への水の拡散を促進して、
水架橋反応に要する時間を大幅に短縮することのできる
水架樹脂成形物の製造方法を提供することにある。本発
明者らは、前記従来技術の有する問題点を克服するため
に鋭意研究した結果、水架橋可能な樹脂を含む組成物を
所望の形状に成形した後、水分の存在下に水架橋する際
、超音波雰囲気中で水架橋することにより、水架橋樹脂
成形物内部への水の拡散が促進され、上記目的を達成で
きることを見いだし、その知見に基づいて本発明を完成
するに至った。[Problems to be Solved by the Invention] An object of the present invention is to promote the diffusion of water into the interior of a water-crosslinked resin molded product during crosslinking.
It is an object of the present invention to provide a method for producing a water-crosslinked resin molded product that can significantly shorten the time required for a water-crosslinking reaction. As a result of intensive research to overcome the problems of the prior art, the present inventors found that after molding a composition containing a water-crosslinkable resin into a desired shape, when water-crosslinking it in the presence of water, It was discovered that water crosslinking in an ultrasonic atmosphere promotes the diffusion of water into the interior of a water crosslinked resin molded product, thereby achieving the above object, and based on this knowledge, the present invention was completed.
【０００８】[0008]
【課題を解決するための手段】かくして本発明によれば
、水架橋可能な樹脂を含む組成物を成形する工程と、得
られた成形物を水架橋する工程を含む水架橋樹脂成形物
の製造方法において、水架橋する工程の少なくとも一部
を超音波雰囲気中で行なうことを特徴とする水架橋樹脂
成形物の製造方法が提供される。[Means for Solving the Problems] Thus, according to the present invention, the production of a water-crosslinkable resin molded product includes a step of molding a composition containing a water-crosslinkable resin, and a step of water-crosslinking the obtained molded product. There is provided a method for producing a water-crosslinked resin molded article, characterized in that at least a part of the water-crosslinking step is carried out in an ultrasonic atmosphere.
【０００９】以下、本発明について詳述する。本発明に
おいて使用する水架橋可能な樹脂は、特に限定されない
が、例えば、樹脂状またはゴム状のポリマーに、炭素−
炭素不飽和二重結合を有するアルコキシシラン化合物を
遊離ラジカル発生剤の存在下にグラフト重合させたシラ
ン変成樹脂、あるいはオレフィン−不飽和シラン化合物
共重合体などの、加水分解可能なシラン基を有する各種
樹脂を挙げることができる。The present invention will be explained in detail below. The water-crosslinkable resin used in the present invention is not particularly limited, but for example, a resin-like or rubber-like polymer, carbon-
Silane-modified resins made by graft polymerizing alkoxysilane compounds with carbon unsaturated double bonds in the presence of free radical generators, or olefin-unsaturated silane compound copolymers, which have hydrolyzable silane groups. Examples include resins.
【００１０】シラン変成するポリマーとしては、例えば
、高・低、中密度ポリエチレン、線状低密度ポリエチレ
ン、エチレン−酢酸ビニル共重合体、エチレン−エチル
アクリレート共重合体、エチレン−アクリル酸共重合体
、エチレン−プロピレン共重合体（ランダムおよびブロ
ック共重合体）、ポリブテン、ポリペンテン、ポリヘキ
セン、ポリ４−メチルペンテン、エチレン−ブテン共重
合体、塩素化ポリエチレン等のオレフィン系ポリマー、
あるいはエチレンプロピレンゴムやエチレン−プロピレ
ン−ジエン共重合体ゴムなどのゴムを挙げることができ
る。Examples of the silane-modified polymers include high/low and medium density polyethylene, linear low density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, Olefinic polymers such as ethylene-propylene copolymers (random and block copolymers), polybutene, polypentene, polyhexene, poly4-methylpentene, ethylene-butene copolymers, chlorinated polyethylene,
Alternatively, rubbers such as ethylene propylene rubber and ethylene-propylene-diene copolymer rubber can be used.
【００１１】シラン化合物としては、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−メタクリロキシプロピルト
リメトキシシラン、ビニルトリス（２−メトキシエトキ
シ）シラン等のエチレン性不飽和シラン化合物を挙げる
ことができる。Examples of the silane compound include ethylenically unsaturated silane compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, γ-methacryloxypropyltrimethoxysilane, and vinyltris(2-methoxyethoxy)silane. can be mentioned.
【００１２】これらの水架橋可能な樹脂は、それぞれ単
独で、あるいは２種以上を組み合わせて使用することが
できる。また、所望により、シラン変成されていないポ
リマーをブレンドすることもできる。さらに、有機錫化
合物などの加水分解を促進するシラノール縮合触媒、老
化防止剤、難燃剤、充填剤、発泡剤、着色剤、滑剤等の
配合剤を配合してもよい。このほか、過酸化物を添加し
て、過酸化物架橋を併用してもよい。These water-crosslinkable resins can be used alone or in combination of two or more. Further, if desired, a non-silane modified polymer may be blended. Furthermore, compounding agents such as a silanol condensation catalyst, an anti-aging agent, a flame retardant, a filler, a blowing agent, a coloring agent, a lubricant, etc. that promote hydrolysis of organic tin compounds may be added. In addition, peroxide crosslinking may also be carried out by adding a peroxide.
【００１３】したがって、本発明における水架橋可能な
樹脂とは、樹脂状およびゴム状のポリマーを含み、また
、水架橋可能な樹脂を含む組成物とは、シラン変成樹脂
単独の場合と、他の樹脂やゴム、配合剤等を配合した組
成物を意味する。本発明においては、特に、水架橋可能
な樹脂に加水分解を促進する触媒等を配合した組成物が
有効である。[0013] Therefore, the water-crosslinkable resin in the present invention includes resin-like and rubber-like polymers, and the composition containing the water-crosslinkable resin includes a case in which a silane-modified resin is used alone, and a case in which a silane-modified resin is used alone. It means a composition containing resin, rubber, compounding agents, etc. In the present invention, a composition in which a water-crosslinkable resin is blended with a catalyst that promotes hydrolysis is particularly effective.
【００１４】本発明の水架橋樹脂成形物の製造方法では
、通常、押出成形により水架橋可能な樹脂を含む組成物
を所望の形状、例えば、導体に被覆して被覆電線とした
り、あるいはチューブ等に成形した後に、水中に浸漬す
るか、あるいは水蒸気の存在する雰囲気にさらして水架
橋を行なうが、この水架橋工程を超音波雰囲気中で行な
う点に特徴を有する。この場合、押し出した成形物が自
重等により潰れやすい時には、予め室温や成形物が変形
しない温度で予備的に水架橋を進行させた後、超音波雰
囲気中での水架橋を行なってもよい。In the method for producing a water-crosslinkable resin molded product of the present invention, a composition containing a water-crosslinkable resin is usually formed into a desired shape by extrusion molding, for example, a conductor is coated to form a covered electric wire, a tube, etc. After molding, water crosslinking is performed by immersing it in water or exposing it to an atmosphere in which water vapor is present, and the feature is that this water crosslinking step is performed in an ultrasonic atmosphere. In this case, if the extruded molded product is likely to collapse due to its own weight, water crosslinking may be carried out in an ultrasonic atmosphere after preliminary water crosslinking is performed at room temperature or a temperature at which the molded product does not deform.
【００１５】前記したとおり、水架橋樹脂成形物の水架
橋は、樹脂中のシラン変成部分が水と接触することによ
り生じるため、成形物の表面は比較的速く架橋するが、
その内部は水の拡散が遅いため架橋に時間がかかる。本
発明では、この水の拡散を促進し、架橋反応に要する時
間を大幅に短縮するために、超音波雰囲気中で水架橋を
行なう。As mentioned above, water crosslinking of a water-crosslinked resin molded product occurs when the silane-modified moiety in the resin comes into contact with water, so the surface of the molded product crosslinks relatively quickly.
Crosslinking takes time because water diffuses slowly inside it. In the present invention, water crosslinking is performed in an ultrasonic atmosphere in order to promote the diffusion of this water and significantly shorten the time required for the crosslinking reaction.
【００１６】超音波とは、周波数が可聴周波領域を越え
る弾性波である。超音波雰囲気中で水架橋を行なうには
、水架橋工程において、水分の存在する箇所、例えば、
高温水槽や高温高湿槽に、超音波発生器を付設し、水分
および超音波雰囲気中に水架橋樹脂成形物をさらす方法
により行なう。[0016] Ultrasound is an elastic wave whose frequency exceeds the audio frequency range. In order to perform water crosslinking in an ultrasonic atmosphere, in the water crosslinking process, a place where moisture exists, for example,
This is carried out by attaching an ultrasonic generator to a high-temperature water tank or a high-temperature, high-humidity tank, and exposing the water-crosslinked resin molded product to a moisture and ultrasonic atmosphere.
【００１７】超音波雰囲気中で水架橋が迅速に進行する
理由は、超音波により微視的に樹脂が振動するため、水
分が樹脂成形物中に侵入し易く、かつ、架橋反応を促進
するためであると考えることができ、その結果、成形物
内部の架橋が速く進行する。ここでいう水分の存在下と
は、成形物が水中に浸漬されている状態、水蒸気雰囲気
中にさらされている状態、あるいは水を吸収している状
態などをいう。The reason why water crosslinking progresses rapidly in an ultrasonic atmosphere is that the resin is microscopically vibrated by the ultrasonic waves, which makes it easy for water to enter the resin molding and promotes the crosslinking reaction. As a result, crosslinking inside the molded product progresses rapidly. The presence of moisture herein refers to a state in which the molded product is immersed in water, exposed to a steam atmosphere, or absorbs water.
【００１８】本発明で利用できる超音波の周波数は、成
形物の劣化を起こさず、水の拡散を促進できる周波数の
範囲であればよく、特に限定されるものではない。具体
例としては、工業的に利用されている周波数の２．４６
ＧＨＺや１３．５６ＭＨＺ、さらに、超音波水槽などに
利用されているＰＺＴ振動子、フェライト磁歪型振動子
、トランジスターによる自動発振などの振動子の周波数
１０ｋＨＺ〜数百ｋＨＺの範囲を挙げることができる。The frequency of the ultrasonic waves that can be used in the present invention is not particularly limited, as long as it does not cause deterioration of the molded product and can promote water diffusion. As a specific example, the frequency used industrially is 2.46.
Examples include GHZ, 13.56 MHZ, and the frequency range of 10 kHz to several hundred kHz of vibrators such as PZT vibrators used in ultrasonic water tanks, ferrite magnetostrictive vibrators, and automatic oscillation by transistors.
【００１９】本発明においては、水架橋する工程の少な
くとも一部を超音波雰囲気中で行なうことが必要であり
、例えば、水架橋工程の前段あるいは後段などで、通常
の水架橋を行なうことを排除するものではない。また、
所望により、過酸化物架橋や電子線照射架橋を併用して
もよい。[0019] In the present invention, it is necessary to perform at least a part of the water crosslinking step in an ultrasonic atmosphere, and for example, it is unnecessary to perform ordinary water crosslinking before or after the water crosslinking step. It's not something you do. Also,
If desired, peroxide crosslinking or electron beam irradiation crosslinking may be used in combination.
【００２０】[0020]
【実施例】以下、本発明について、実施例および比較例
を挙げて具体的に説明するが、本発明は、これらの実施
例のみに限定されるものではない。[Examples] The present invention will be specifically explained below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
【００２１】［実施例１］シラン変成ポリエチレン（三
菱油化製、商品名リンクロンＸＦ８００）１００重量部
に、触媒（三菱油化製、商品名リンクロン ＬＺ０１
３Ｓ）５重量部、重炭酸カルシウム３０重量部、および
老化防止剤２重量部を配合した樹脂組成物を用い、押出
により外径１１ｍｍ、内径８ｍｍのチューブを作製した
。[Example 1] A catalyst (manufactured by Mitsubishi Yuka, trade name Linkron LZ01) was added to 100 parts by weight of silane-modified polyethylene (manufactured by Mitsubishi Yuka, trade name Linkron LZ01).
A tube having an outer diameter of 11 mm and an inner diameter of 8 mm was produced by extrusion using a resin composition containing 5 parts by weight of 3S), 30 parts by weight of calcium bicarbonate, and 2 parts by weight of an anti-aging agent.
【００２２】作製したチューブを、７０℃の超音波温水
槽中に漬浸して放置し、チューブのゲル分率が６０％に
到達した時間を測定し、架橋進行程度を調べた。この時
用いた超音波の周波数は４２ｋＨＺである。また、ゲル
分率は、ソックスレー抽出器を用いてキシレンの沸点で
１０時間キシレン抽出を行なった時の不溶分の割合を示
す。結果を表１に示す。The produced tube was immersed in an ultrasonic hot water bath at 70° C. and left to stand, and the time required for the gel fraction of the tube to reach 60% was measured to examine the degree of crosslinking progress. The frequency of the ultrasonic waves used at this time was 42 kHz. Moreover, the gel fraction indicates the proportion of insoluble matter when xylene extraction is performed for 10 hours at the boiling point of xylene using a Soxhlet extractor. The results are shown in Table 1.
【００２３】［実施例２］シラン変成エチレン酢酸ビニ
ル共重合体（三菱油化製、商品名リンクロンＶＥ８００
Ｎ）１００重量部に、触媒（三菱油化製、商品名リンク
ロン ＶＥ０１０Ｚ）５重量部、重炭酸カルシウム３
０重量部、および老化防止剤２重量部を配合した樹脂組
成物を用い、押出により外径１１ｍｍ、内径８ｍｍのチ
ューブを作製した。このようにして作製したチューブを
実施例１と同様に７０℃の超音波温水中に浸漬した後、
チューブのゲル分率が６０％を越える時間を測定し、架
橋の進行程度を調べた。結果を表１に示す。[Example 2] Silane-modified ethylene-vinyl acetate copolymer (manufactured by Mitsubishi Yuka, trade name: Linkron VE800)
N) 100 parts by weight, 5 parts by weight of catalyst (manufactured by Mitsubishi Yuka, trade name Linkron VE010Z), 3 parts by weight of calcium bicarbonate
A tube having an outer diameter of 11 mm and an inner diameter of 8 mm was produced by extrusion using a resin composition containing 0 parts by weight of anti-aging agent and 2 parts by weight of an anti-aging agent. After immersing the thus prepared tube in ultrasonic hot water at 70°C in the same manner as in Example 1,
The time required for the gel fraction of the tube to exceed 60% was measured to examine the extent of crosslinking. The results are shown in Table 1.
【００２４】［比較例１］水架橋を７０℃の温水中に浸
漬して行なったこと以外は、実施例１と同様にした。結
果を表１に示す。[Comparative Example 1] The same procedure as in Example 1 was carried out except that water crosslinking was carried out by immersion in hot water at 70°C. The results are shown in Table 1.
【００２５】［比較例２］水架橋を７０℃の温水中に浸
漬して行なったこと以外は、実施例２と同様にした。結
果を表１に示す。[Comparative Example 2] The same procedure as Example 2 was carried out except that the water crosslinking was carried out by immersion in hot water at 70°C. The results are shown in Table 1.
【００２６】[0026]
【表１】[Table 1]
【００２７】表１から明らかなように、ゲル分率６０％
到達時間は、実施例１では６時間であるのに対して、比
較例１では４０時間であり、架橋時間を約７倍短縮する
ことができた。また、実施例２におけるゲル分率６０％
到達時間は２時間であり、比較例２の温水中での架橋と
比較して、約３倍の時間が短縮可能となった。As is clear from Table 1, the gel fraction is 60%.
The arrival time was 6 hours in Example 1, while it was 40 hours in Comparative Example 1, meaning that the crosslinking time could be shortened by about 7 times. In addition, the gel fraction in Example 2 was 60%.
The arrival time was 2 hours, which was about 3 times shorter than the crosslinking in hot water in Comparative Example 2.
【００２８】[0028]
【発明の効果】本発明の製造方法によれば、水架橋する
工程の少なくとも一部を超音波雰囲気中で行なうことに
より、従来長時間を要していた水架橋時間を大幅に短縮
することができ、製品の生産性の向上、製造コストの低
減が可能であり、特に、被覆電線、チューブなどの工業
製品の製造に好適である。[Effects of the Invention] According to the manufacturing method of the present invention, at least a part of the water crosslinking step is carried out in an ultrasonic atmosphere, thereby making it possible to significantly shorten the water crosslinking time, which conventionally required a long time. It is possible to improve product productivity and reduce manufacturing costs, and is particularly suitable for manufacturing industrial products such as covered electric wires and tubes.
Claims (1)
する工程と、得られた成形物を水架橋する工程を含む水
架橋樹脂成形物の製造方法において、水架橋する工程の
少なくとも一部を超音波雰囲気中で行なうことを特徴と
する水架橋樹脂成形物の製造方法。Claim 1. A method for producing a water-crosslinkable resin molded product comprising a step of molding a composition containing a water-crosslinkable resin and a step of water-crosslinking the obtained molded product, wherein at least part of the water-crosslinking step is performed. A method for producing a water-crosslinked resin molded article, characterized in that the step is carried out in an ultrasonic atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13066791A JPH04331241A (en) | 1991-05-02 | 1991-05-02 | Production of water-crosslinked resin molding |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13066791A JPH04331241A (en) | 1991-05-02 | 1991-05-02 | Production of water-crosslinked resin molding |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04331241A true JPH04331241A (en) | 1992-11-19 |
Family
ID=15039735
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13066791A Pending JPH04331241A (en) | 1991-05-02 | 1991-05-02 | Production of water-crosslinked resin molding |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04331241A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6812262B2 (en) | 2002-04-18 | 2004-11-02 | Tosoh Corporation | Silane-crosslinking expandable polyolefin resin composition and crosslinked foam |
-
1991
- 1991-05-02 JP JP13066791A patent/JPH04331241A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6812262B2 (en) | 2002-04-18 | 2004-11-02 | Tosoh Corporation | Silane-crosslinking expandable polyolefin resin composition and crosslinked foam |
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