JPH054411B2 - - Google Patents
Info
- Publication number
- JPH054411B2 JPH054411B2 JP58141734A JP14173483A JPH054411B2 JP H054411 B2 JPH054411 B2 JP H054411B2 JP 58141734 A JP58141734 A JP 58141734A JP 14173483 A JP14173483 A JP 14173483A JP H054411 B2 JPH054411 B2 JP H054411B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- crosslinking
- swellable
- swelling
- rubber
- 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.)
- Expired - Lifetime
Links
- 238000004132 cross linking Methods 0.000 claims description 44
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000010894 electron beam technology Methods 0.000 claims description 17
- 230000005855 radiation Effects 0.000 claims description 12
- 229920001971 elastomer Polymers 0.000 claims description 11
- 239000005060 rubber Substances 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 230000002522 swelling effect Effects 0.000 description 10
- 230000008961 swelling Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- NPERTKSDHFSDLC-UHFFFAOYSA-N ethenol;prop-2-enoic acid Chemical compound OC=C.OC(=O)C=C NPERTKSDHFSDLC-UHFFFAOYSA-N 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000035515 penetration Effects 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- -1 wire mesh Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- 239000005662 Paraffin oil Substances 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- CPGFMWPQXUXQRX-UHFFFAOYSA-N 3-amino-3-(4-fluorophenyl)propanoic acid Chemical compound OC(=O)CC(N)C1=CC=C(F)C=C1 CPGFMWPQXUXQRX-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- FOCUNENRNMMOKC-UHFFFAOYSA-N [S].C1=CC=C2SC(S)=NC2=C1 Chemical compound [S].C1=CC=C2SC(S)=NC2=C1 FOCUNENRNMMOKC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229940116901 diethyldithiocarbamate Drugs 0.000 description 1
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
水膨潤製品は、シーラント、止水材、防水シー
ト、ガスケツト、生理用品、農業用保水材などに
用いられている。これら水膨潤製品は、吸水性高
分子を含む樹脂やゴムなどからなる複合体であ
り、多くの用途で、架橋という化学反応を行なつ
て製品としている。この架橋は、吸水性高分子自
身を架橋させる場合と、吸水性高分子を含むマト
リツクス側の樹脂またはゴムを架橋させる場合と
がある。特に従来、吸水性高分子を含むマトリツ
クス側の樹脂またはゴムの架橋は、熱空気または
加熱された加圧金型により加熱して達成されてい
た。
本発明者らは、水膨潤製品の架橋法について鋭
意検討した結果、本発明に到達したものであり、
本発明の方法は、従来の加熱方式とはまつたく異
なる大きな特徴ないし利点を有している。
すなわち本発明は、水膨潤製品を製造する際の
架橋処理に、赤外線、電子線および放射線から選
ばれる架橋手段を使用する水膨潤製品製造方法を
提供するものである。これら架橋手段を水非膨潤
製品へ応用すること、あるいは含水状態のポリビ
ニルアルコールに放射線を照射して吸水性高分子
自体を製造することは公知であるが、本発明のよ
うに吸水性高分子を含む複合体からなる水膨潤製
品へ放射線などの架橋手段を応用した例はまつた
く見あたらない。また、従来の吸水性高分子自体
の製造に放射線を適用するのと異なり、本発明で
は、吸水性高分子と樹脂またはゴムとの複合体か
らなる水膨潤製品に対して、実質的に無水状態
で、赤外線、電子線または放射線を照射する。
本発明でいう赤外線、電子線または放射線は、
それぞれ赤外線加熱装置、電子線架橋装置または
放射線架橋装置により供給されるが、いずれも、
従来水膨潤製品に用いられた架橋法（熱空気、加
熱された金型などによる加熱架橋法）に比べ、短
時間に架橋を達成することができるという大きな
特徴を有している。とりわけ、電子線または放射
線による架橋は、数秒といつた短時間で架橋でき
るうえ、架橋による発熱がなく、また架橋のため
の加熱が行なわれないので、架橋後の水膨潤製品
は室温状態にあり、特別な冷却を必要としない。
赤外線加熱は、両者に比べ架橋には長時間を要す
るが、装置の価格が安いという利点を有する。
赤外線加熱装置として一般には、無機材を用い
た加熱炉の壁部に赤外線放射体を取り付けたもの
が用いられているが、本発明では、反射面付赤外
線加熱装置が特に好ましく用いられる。この装置
は、楕円面または放物面を有する反射面の焦点に
赤外線放射体を配置したものであり、他の通常の
赤外線加熱装置に比べてエネルギーロスが少な
く、したがつて昇温効果が大きく、架橋時間も大
幅に短くてすむことから、消費電力量も少なく、
製造コストの低減をはかることができるという大
きな特徴を有しているため、特に好ましい。
さらに本発明は、水膨潤製品に対し、部分的ま
たは限定的な架橋を容易かつ迅速に行なうことが
できるという大きな特徴を有し、この特徴を利用
して、水膨潤製品の水膨潤特性を抑制できるとい
う実用上非常に有益な効果が達成できる。
水膨潤製品は、吸水することにより体積が増加
し、形状が大きくなる。通常この膨潤は、任意の
方向へ均等である。しかしながら多くの用途で、
特定の箇所や特定の方向への膨潤を抑制する必要
のある場合が多い。従来こうした場合には、水膨
潤しない素材と複合化する方法などが用いられて
いた。これら水膨潤ないし素材としては、紙、繊
維、布、金網、水膨潤性物質を含まない樹脂やゴ
ムのシートなどが例示される。しかしながらこう
した複合化には、特別な成形加工機を必要とした
り、生産性の低下や原料コストのアツプにつなが
るといつた多くの問題が含まれていた。そのうえ
こうした複合化は、複合界面での接着や粘着が弱
いのに加えて、一方が吸水により膨潤するのに対
し、他方が膨潤しないため、両者の界面では非常
に応力が不均一となり、界面剥離現象が生じやす
いという重大かつ不可避な難問題を抱えていた。
本発明により、水膨潤製品の部分的または限定的
膨潤抑制についてまつたく新しい手段を提供でき
たことは、特に注目すべき意義ある点である。
水膨潤製品は、架橋を密にすることにより膨潤
特性が低下することはよく知られている。しかし
ながら従来の架橋は、熱空気加熱、金型加熱など
により行なわれていたため、部分的加熱は困難で
あり、したがつて部分的または限定的に架橋を行
なうことはできなかつた。仮に、なんらかの手段
で部分的または限定的架橋をある程度可能ならし
めたとしても、不必要な部分へ熱が伝動して他の
部分も架橋が行なわれ、必要な部分における水膨
潤性の変化が損なわれることになる。
本発明は、赤外線、電子線または放射線を利用
して架橋を達成するものである。電子線および放
射線は、それぞれの架橋装置から水膨潤製品の限
定された部分に対し、連続的または断続的に照射
することができる。その照射は瞬間的であり、か
つ架橋が瞬時に行なわれるため、非照射部での架
橋はまつたく進行しない。さらにまた、電子の加
速電圧などを適切に選択すれば、水膨潤製品への
浸透力（透過力）をコントロールでき、ごく表面
近傍だけを架橋させることも可能である。
一方、赤外線加熱、それも特に反射面付赤外線
加熱装置によるものは、赤外線を一箇所に集光さ
せることができ、加熱昇温速度が極めて速いた
め、水膨潤製品を加熱した場合に、他の不必要な
部分へ熱が伝わる前に必要な部分のみの架橋を完
了することができる。
以上のように、本発明によれば部分的に架橋を
進行させることができ、したがつて水膨潤製品の
膨潤を部分的に抑制することができる。例えばシ
ート状の製品に対し、上面および下面の両面を部
分的に薄い層として架橋処理を行なえば、水平面
方向への膨潤が抑制され、膨潤の実質的に厚さ方
向にのみ起こさせることができる。
本発明でいうところの水膨潤製品は、エチレン
−ビニルエステル−アクリル酸エステルのケン化
物、アクリル酸−アクリル酸塩共重合体の架橋物
など公知の吸水性高分子を含む樹脂またはゴムと
の複合体である。ゴムおよび樹脂としては、天然
ゴム、スチレンブタジエンゴム、エチレン−αオ
レフインまたはエチレン−αオレフイン−ジエン
共重合体（αオレフインとしてプロピレンが代表
的であり、エチレンプロピレンゴムと称される）、
クロロプレンゴム、ブチルゴム、ポリエチレン、
ポリ塩化ビニル、ポリエチレンビニルアセテート
などが例示される。また必要に応じて、カーボン
ブラツク、白色充填剤、プロセスオイル、加工助
剤、架橋剤、架橋促進剤、発泡済、発泡助剤、老
化防止剤、粘着付与剤、顔料などが併用される。
電子線架橋または放射線架橋の場合には、架橋剤
がなくても架橋できることから、架橋剤は必ずし
も使用しなくてもよい。
以下に実施例を示すが、これらは本発明を限定
するものではない。
実施例 １
電子線架橋の例を示す。
〈配合〉
エスプレン501A 100重量部
〔ムーニー粘度43M1+4（100℃）のエチレ
ン・プロピレンゴム、住友化学工業(株)製〕
クレー 100 〃
パラフイン油 30 〃
界面活性剤 ３ 〃
スミカゲルSP−520 40 〃
〔ビニルアルコール・アクリル酸ソーダ共重
合体系の吸水性高分子、住友化学工業(株)製〕
〈混練〉
BR型バンバリーを使用して混練した。ただし
スミカゲルは、10インチロールにて添加した。
〈試料調製〉
10インチロールを用いて、0.5mmのシートを作
成した。
〈水膨潤特性〉
電子線照射後のシートより40mmφの試験片を採
収し、一定時間水中に放置して体積増加率を求め
た。
〈結果〉
Water-swellable products are used in sealants, waterproof materials, waterproof sheets, gaskets, sanitary products, agricultural water retaining materials, etc. These water-swellable products are composites made of resins, rubbers, etc. containing water-absorbing polymers, and are used in many applications by undergoing a chemical reaction called crosslinking. This crosslinking may be performed by crosslinking the water-absorbing polymer itself or by cross-linking the resin or rubber on the matrix side containing the water-absorbing polymer. In particular, crosslinking of the resin or rubber on the matrix side containing the water-absorbing polymer has heretofore been achieved by heating with hot air or a heated press mold. The present inventors have arrived at the present invention as a result of intensive studies on crosslinking methods for water-swellable products.
The method of the present invention has significant features and advantages that are significantly different from conventional heating methods. That is, the present invention provides a method for producing a water-swellable product using a crosslinking means selected from infrared rays, electron beams, and radiation in the crosslinking treatment when producing the water-swellable product. It is known to apply these crosslinking means to non-water-swellable products or to produce water-absorbing polymers themselves by irradiating water-containing polyvinyl alcohol with radiation. There are no examples of applying cross-linking methods such as radiation to water-swellable products made of composites containing the following. Furthermore, unlike the conventional method of applying radiation to the production of water-absorbing polymers themselves, in the present invention, water-swellable products consisting of composites of water-absorbing polymers and resins or rubbers are produced in a substantially anhydrous state. irradiate with infrared rays, electron beams, or radiation. The infrared rays, electron beams, or radiations referred to in the present invention are
Each is supplied by an infrared heating device, an electron beam crosslinking device, or a radiation crosslinking device, but in each case,
Compared to the crosslinking method conventionally used for water-swellable products (thermal crosslinking method using hot air, heated molds, etc.), it has the great feature of being able to achieve crosslinking in a shorter time. In particular, crosslinking using electron beams or radiation can be crosslinked in a short time, such as a few seconds, and there is no heat generation due to crosslinking, and since no heating is performed for crosslinking, the water-swollen product after crosslinking can be kept at room temperature. , does not require special cooling.
Although infrared heating requires a longer time for crosslinking than both methods, it has the advantage that the equipment is inexpensive. Generally, an infrared heating device is used, which is a heating furnace made of inorganic material with an infrared radiator attached to the wall, but in the present invention, an infrared heating device with a reflective surface is particularly preferably used. This device has an infrared radiator placed at the focal point of a reflective surface that has an elliptical or parabolic surface, and has less energy loss than other ordinary infrared heating devices, so it has a large temperature-raising effect. , as the crosslinking time is significantly shorter, power consumption is also lower.
It is particularly preferable because it has the great feature of being able to reduce manufacturing costs. Furthermore, the present invention has a major feature in that it is possible to easily and quickly perform partial or limited crosslinking on water-swellable products, and this feature is utilized to suppress the water-swelling properties of water-swellable products. A very useful effect in practice can be achieved. Water-swollen products increase in volume and shape by absorbing water. Usually this swelling is uniform in any direction. However, in many applications,
There are many cases where it is necessary to suppress swelling in a specific location or in a specific direction. Conventionally, in such cases, methods such as compounding with materials that do not swell with water have been used. Examples of these water-swellable materials include paper, fibers, cloth, wire mesh, and resin or rubber sheets that do not contain water-swellable substances. However, such compositing has many problems, such as requiring special molding machines, lowering productivity, and increasing raw material costs. Furthermore, in addition to weak adhesion and adhesion at the composite interface, one side of the composite swells due to water absorption while the other does not, resulting in extremely uneven stress at the interface between the two, resulting in interfacial peeling. There was a serious and unavoidable problem in that this phenomenon was likely to occur.
It is particularly noteworthy and significant that the present invention provides a completely new means for partially or limited swelling suppression of water-swellable products. It is well known that water-swellable products have reduced swelling properties due to denser crosslinking. However, since conventional crosslinking was carried out by hot air heating, mold heating, etc., partial heating was difficult, and therefore it was not possible to carry out crosslinking partially or limitedly. Even if partial or limited crosslinking is made possible to some extent by some means, heat will be transferred to unnecessary parts and crosslinking will occur in other parts, impairing the change in water swelling properties in the necessary parts. It will be. The present invention utilizes infrared rays, electron beams, or radiation to achieve crosslinking. Electron beams and radiation can be irradiated continuously or intermittently from each crosslinking device to a limited portion of the water-swollen product. Since the irradiation is instantaneous and crosslinking occurs instantaneously, crosslinking does not proceed rapidly in non-irradiated areas. Furthermore, by appropriately selecting the electron accelerating voltage, etc., it is possible to control the penetration power (penetration power) into the water-swollen product, and it is also possible to crosslink only the very vicinity of the surface. On the other hand, infrared heating, especially those using infrared heating devices with reflective surfaces, can concentrate infrared rays in one place and have an extremely fast heating rate, so when water-swollen products are heated, other Crosslinking can be completed in only the necessary areas before heat is transferred to unnecessary areas. As described above, according to the present invention, crosslinking can be partially progressed, and therefore, swelling of water-swellable products can be partially suppressed. For example, if a sheet-shaped product is cross-linked with partially thin layers on both the top and bottom surfaces, swelling in the horizontal direction can be suppressed, and swelling can substantially only occur in the thickness direction. . The water-swellable product referred to in the present invention is a composite product with a resin or rubber containing a known water-absorbing polymer, such as a saponified product of ethylene-vinyl ester-acrylic acid ester, or a cross-linked product of acrylic acid-acrylate copolymer. It is the body. Rubbers and resins include natural rubber, styrene-butadiene rubber, ethylene-α-olefin or ethylene-α-olefin-diene copolymer (propylene is a typical α-olefin and is called ethylene propylene rubber);
Chloroprene rubber, butyl rubber, polyethylene,
Examples include polyvinyl chloride and polyethylene vinyl acetate. Further, if necessary, carbon black, white filler, process oil, processing aid, crosslinking agent, crosslinking accelerator, foamed foam, foaming aid, anti-aging agent, tackifier, pigment, etc. are used in combination.
In the case of electron beam crosslinking or radiation crosslinking, crosslinking can be performed without a crosslinking agent, so a crosslinking agent does not necessarily have to be used. Examples are shown below, but these are not intended to limit the invention. Example 1 An example of electron beam crosslinking is shown. <Formulation> Esprene 501A 100 parts by weight [Ethylene-propylene rubber with Mooney viscosity 43M 1+4 (100℃), manufactured by Sumitomo Chemical Co., Ltd.] Clay 100 Paraffin oil 30 Surfactant 3 Sumikagel SP-520 40 [Water-absorbing polymer based on vinyl alcohol/sodium acrylate copolymer, manufactured by Sumitomo Chemical Co., Ltd.] <Kneading> Kneading was carried out using a BR type Banbury. However, Sumikagel was added using a 10-inch roll. <Sample Preparation> A 0.5 mm sheet was prepared using a 10 inch roll. <Water swelling properties> A 40 mmφ test piece was collected from the sheet after electron beam irradiation, and left in water for a certain period of time to determine the volume increase rate. <result>
【表】
本実施例は、電子線を用いることにより物性に
優れた水膨潤ゴムを製造しうることを示してい
る。照射量とともに物性（TB）が向上すること
がわかる。なお、照射量とともに水膨潤特性は低
下するが、必要に応じてスミカゲルを増量すれば
改良することができる。
実施例 ２
反射面付赤外線加熱装置を用いた例を示す。
〈配合〉
エスプレン510A 100重量部
〔実施例１で用いたものと同じ〕
クレー 100 〃
パラフイン油 30 〃
界面活性剤 ３ 〃
亜鉛華 ５ 〃
ステアリン酸 １ 〃
スミカゲルSP−520 30 〃
〔実施例１で用いたものと同じ〕
酸化カルシウム ６ 〃
ソクシノールBZ ２ 〃
〔ジ−ｎ−ブチルジチオカルバミン酸亜鉛〕
ソクシノールTT 0.5 〃
〔テトラメチルチウラムジスルフイド〕
ソクシノールTRA 0.5 〃
〔ジペンタメチレンチウラムテトラスルフイ
ド〕
ソクシノールＭ １ 〃
〔２−メルカプトベンゾチアゾール〕
イオウ 0.75 〃
〈混練〉
BR型バンバリーを使用して混練した。ただし
上記配合に示したスミカゲル以下は、10インチロ
ールにて添加した。
〈試料調製〉
45mmφ押出機にて、１×20mmのリボン状サンプ
ルを作成した。
〈架橋〉
放物四面型有効長24cmの反射面は赤外線加熱装
置中に、１ｍ／minの速度で通して架橋した。
〈測定〉
物性：JISK6301に準拠して、２号ダンベルを
用い、引張速度500mm／minで測定した。
水膨潤特性：長さ３cmのリボン状試験片を一定
時間水中に放置し、体積増加を測定した。
〈結果〉[Table] This example shows that water-swellable rubber with excellent physical properties can be produced by using an electron beam. It can be seen that the physical properties (T B ) improve with the irradiation dose. Note that the water swelling property decreases with the irradiation dose, but it can be improved by increasing the amount of sumica gel as necessary. Example 2 An example using an infrared heating device with a reflective surface is shown. <Formulation> Esprene 510A 100 parts by weight [Same as that used in Example 1] Clay 100 [Paraffin oil 30] Surfactant 3 [Zinc white 5] Stearic acid 1 [Sumikagel SP-520 30] [In Example 1 Same as used] Calcium oxide 6 Soccinol BZ 2 [Zinc di-n-butyldithiocarbamate] Soccinol TT 0.5 [Tetramethylthiuram disulfide] Soccinol TRA 0.5 [Dipentamethylenethiuram tetrasulfide] Soccinol M 1 [2-Mercaptobenzothiazole] Sulfur 0.75 <Kneading> Kneaded using a BR type Banbury. However, Sumikagel shown in the above formulation was added using a 10-inch roll. <Sample Preparation> A 1×20 mm ribbon sample was prepared using a 45 mmφ extruder. <Crosslinking> The parabolic tetrahedral reflecting surface with an effective length of 24 cm was passed through an infrared heating device at a speed of 1 m/min for crosslinking. <Measurement> Physical properties: Measured at a tensile speed of 500 mm/min using a No. 2 dumbbell in accordance with JISK6301. Water swelling properties: A ribbon-shaped test piece with a length of 3 cm was left in water for a certain period of time, and the increase in volume was measured. <result>
【表】
＊ 参考例
実施例 ３
部分的に水膨潤特性を抑制する目的で検討を行
なつた例を示す。
〈配合、混練〉
エスプレン505〔ムーニー粘度75M1+4（100℃）
のエチレン・プロピレンゴム、住友化学工業(株)
製〕を用い、ソクシノールTE〔ジエチルジチオカ
ルバミン酸テルル〕0.8重量部を併用した他は、
実施例２に同じ。
〈試料調製〉
45mmφ押出機を用い、厚さ１mm、巾15mmのリボ
ンの中央上部に、外径15mm、内径９mmのチユーブ
が一体化している第１図に示す断面形状をもつサ
ンプルを作成し、120℃オーブン中にて40分加硫
成形した。得られたサンプルの下部リボン部に対
し、電子線または赤外線により架橋処理を行なつ
た。
〈測定〉
リボン部およびチユーブ部より、巾１cm、長さ
３cmの試験片を採取し、水中５日放置後の体積増
加率（％）を求めた。
〈結果〉[Table] *Reference Example Example 3 This is an example in which studies were conducted for the purpose of partially suppressing water swelling characteristics. <Blending, kneading> Esprene 505 [Mooney viscosity 75M 1+4 (100℃)
Ethylene/propylene rubber, Sumitomo Chemical Co., Ltd.
In addition to using 0.8 parts by weight of Soccinol TE [tellurium diethyldithiocarbamate],
Same as Example 2. <Sample Preparation> Using a 45mmφ extruder, a sample with the cross-sectional shape shown in Figure 1 was prepared, in which a tube with an outer diameter of 15mm and an inner diameter of 9mm was integrated in the upper center of a ribbon with a thickness of 1mm and a width of 15mm. Vulcanization molding was performed in an oven at 120°C for 40 minutes. The lower ribbon portion of the obtained sample was subjected to crosslinking treatment using an electron beam or infrared rays. <Measurement> Test pieces with a width of 1 cm and a length of 3 cm were taken from the ribbon portion and the tube portion, and the volume increase rate (%) after being left in water for 5 days was determined. <result>
【表】
＊ 参考例
サンプルをそのままオーブン中で処理した場合
には、熱空気によりリボン部とチユーブ部が同時
に加熱されるため、両者とも水膨潤特性が抑制さ
れる。これに対し、放物一面型反射面付赤外線加
熱装置を用いた場合、赤外線の輻射熱によりリボ
ン部のみが加熱され、チユーブ部は加熱されない
ため、リボン部の水膨潤特性が抑制される反面、
チユーブ部の水膨潤特性は保持される。電子線架
橋の場合も、電子線の透過力が１mm程度となる加
速電圧では、電子がチユーブ部まで到達すること
ができず、架橋が進行しないため、リボン部は水
膨潤特性が抑制されるが、チユーブ部は影響を受
けず、水膨潤特性が保持される。
赤外線を反射面で集光させて部分的に強熱加熱
したり、電子線を部分的にあてたり、加速電圧を
調整して透過力を調整することにより、水膨潤ゴ
ム製品の膨潤特性を部分的または選択的に抑制で
きることが、本実施例からわかる。なお、赤外線
または電子線により膨潤特性が抑制された部分は
架橋が密になつており、物性（TB）が向上する
ことはいうまでもない。[Table] *Reference Example When the sample is processed in an oven as it is, the ribbon part and tube part are simultaneously heated by hot air, so the water swelling properties of both are suppressed. On the other hand, when using an infrared heating device with a parabolic one-sided reflective surface, only the ribbon portion is heated by infrared radiant heat and the tube portion is not heated, so the water swelling characteristics of the ribbon portion are suppressed.
The water swelling properties of the tube portion are maintained. In the case of electron beam crosslinking, at an accelerating voltage where the penetration power of the electron beam is about 1 mm, the electrons cannot reach the tube part and crosslinking does not proceed, so the water swelling properties of the ribbon part are suppressed. , the tube part is not affected and the water swelling properties are maintained. By concentrating infrared rays on a reflective surface and heating the parts with high heat, applying electron beams to parts, and adjusting the penetration power by adjusting the accelerating voltage, the swelling characteristics of water-swellable rubber products can be adjusted locally. This example shows that it can be suppressed selectively or selectively. It goes without saying that the portions whose swelling properties are suppressed by infrared rays or electron beams are densely crosslinked, and the physical properties (T B ) are improved.
第１図は、実施例３で用いたサンプルの断面図
である。
FIG. 1 is a cross-sectional view of the sample used in Example 3.
Claims (1)
体に、実質的に無水状態で、赤外線、電子線また
は放射線を部分的に照射して架橋処理し、当該複
合体の水膨潤特性を部分的または限定的に抑制す
ることを特徴とする水膨潤製品製造方法。 ２ 赤外線を反射面付赤外線加熱装置により照射
する特許請求の範囲第１項記載の水膨潤製品製造
方法。[Scope of Claims] 1. A composite material containing a water-absorbing polymer and a resin or rubber is partially irradiated with infrared rays, electron beams, or radiation in a substantially anhydrous state to undergo crosslinking treatment, and the composite material is crosslinked. A method for producing a water-swellable product characterized by partially or limitedly suppressing water-swelling properties. 2. The water-swellable product manufacturing method according to claim 1, wherein infrared rays are irradiated by an infrared heating device with a reflective surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14173483A JPS6032830A (en) | 1983-08-01 | 1983-08-01 | Manufacture of article swelling with water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14173483A JPS6032830A (en) | 1983-08-01 | 1983-08-01 | Manufacture of article swelling with water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6032830A JPS6032830A (en) | 1985-02-20 |
| JPH054411B2 true JPH054411B2 (en) | 1993-01-20 |
Family
ID=15298961
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14173483A Granted JPS6032830A (en) | 1983-08-01 | 1983-08-01 | Manufacture of article swelling with water |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6032830A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60173055A (en) * | 1984-02-20 | 1985-09-06 | Dainichi Seika Kogyo Kk | Photosensitive resin composition |
| JPH0647626B2 (en) * | 1986-07-01 | 1994-06-22 | 三菱油化株式会社 | Method for manufacturing water-absorbent composite material |
| JPH02168681A (en) * | 1988-12-21 | 1990-06-28 | Nec Corp | Combination system of piezoelectric ceramic element and secondary cell |
| WO1991016380A1 (en) * | 1990-04-20 | 1991-10-31 | Arakawa Chemical Industries Ltd. | Molding of water-absorbent resin, production thereof, use thereof, and production of water-absorbent resin |
| JPH0564636A (en) * | 1990-11-27 | 1993-03-19 | Arakawa Chem Ind Co Ltd | Auxiliary sheet for nmr diagnosis |
| CN101262943A (en) | 2005-09-16 | 2008-09-10 | 株式会社日本触媒 | Method for production of water absorbing agent |
| JP5748677B2 (en) * | 2012-01-23 | 2015-07-15 | 株式会社クラレ | Method for producing ethylene-vinyl alcohol copolymer resin |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5193992A (en) * | 1975-02-15 | 1976-08-18 | Bifunjogansuigeruno seizohoho | |
| JPS5399333A (en) * | 1977-02-10 | 1978-08-30 | Agency Of Ind Science & Technol | Regulator of intraocular pressure |
| JPS5633032A (en) * | 1979-08-27 | 1981-04-03 | Sumitomo Chem Co Ltd | Material having water absorbing and water-holding capacity |
| JPS581746A (en) * | 1981-06-03 | 1983-01-07 | ジヨンソン・エンド・ジヨンソン | Manufacture of absorptive polymer |
| JPS59129232A (en) * | 1983-01-12 | 1984-07-25 | Nippon Synthetic Chem Ind Co Ltd:The | Production of highly water-absorptive resin |
-
1983
- 1983-08-01 JP JP14173483A patent/JPS6032830A/en active Granted
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5193992A (en) * | 1975-02-15 | 1976-08-18 | Bifunjogansuigeruno seizohoho | |
| JPS5399333A (en) * | 1977-02-10 | 1978-08-30 | Agency Of Ind Science & Technol | Regulator of intraocular pressure |
| JPS5633032A (en) * | 1979-08-27 | 1981-04-03 | Sumitomo Chem Co Ltd | Material having water absorbing and water-holding capacity |
| JPS581746A (en) * | 1981-06-03 | 1983-01-07 | ジヨンソン・エンド・ジヨンソン | Manufacture of absorptive polymer |
| JPS59129232A (en) * | 1983-01-12 | 1984-07-25 | Nippon Synthetic Chem Ind Co Ltd:The | Production of highly water-absorptive resin |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6032830A (en) | 1985-02-20 |
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