JPS63113037A - Improved expandable polyolefin based resin particle - Google Patents
Improved expandable polyolefin based resin particleInfo
- Publication number
- JPS63113037A JPS63113037A JP25992586A JP25992586A JPS63113037A JP S63113037 A JPS63113037 A JP S63113037A JP 25992586 A JP25992586 A JP 25992586A JP 25992586 A JP25992586 A JP 25992586A JP S63113037 A JPS63113037 A JP S63113037A
- Authority
- JP
- Japan
- Prior art keywords
- particles
- foaming agent
- freon
- surface layer
- weight
- 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.)
- Granted
Links
- 239000002245 particle Substances 0.000 title claims abstract description 46
- 229920005672 polyolefin resin Polymers 0.000 title claims abstract description 18
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002344 surface layer Substances 0.000 claims abstract description 13
- 239000010410 layer Substances 0.000 claims abstract description 3
- 239000004604 Blowing Agent Substances 0.000 claims description 16
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000001273 butane Substances 0.000 claims description 7
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 7
- 239000001294 propane Substances 0.000 claims description 6
- DDMOUSALMHHKOS-UHFFFAOYSA-N 1,2-dichloro-1,1,2,2-tetrafluoroethane Chemical compound FC(F)(Cl)C(F)(F)Cl DDMOUSALMHHKOS-UHFFFAOYSA-N 0.000 claims description 5
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 claims description 4
- 235000019404 dichlorodifluoromethane Nutrition 0.000 claims description 4
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 claims description 4
- 239000004088 foaming agent Substances 0.000 abstract description 14
- 229920005989 resin Polymers 0.000 abstract description 9
- 239000011347 resin Substances 0.000 abstract description 9
- 238000004321 preservation Methods 0.000 abstract description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract 2
- 238000001704 evaporation Methods 0.000 abstract 1
- 230000008020 evaporation Effects 0.000 abstract 1
- 229920003020 cross-linked polyethylene Polymers 0.000 description 9
- 239000004703 cross-linked polyethylene Substances 0.000 description 9
- 239000008188 pellet Substances 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 6
- -1 polyethylene Polymers 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000006277 sulfonation reaction Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical compound C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 description 1
- 229920006248 expandable polystyrene Polymers 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229920002681 hypalon Polymers 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明は、粒子表面層が改質さhた発泡性ポリオレフィ
ン系樹脂粒子に関するものであり、更に詳しくは、含有
した易揮発性発泡剤の逸散が改質さhた表面層によって
抑制され、保存安定性に優れた発泡性ポリオレフィン系
樹脂粒子に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to expandable polyolefin resin particles whose surface layer has been modified. The present invention relates to expandable polyolefin resin particles that have excellent storage stability and whose dissipation is suppressed by a modified surface layer.
(従来の技術と問題点)
易揮発性発泡剤を含有し、表層部がスルホン化、クロル
スルホン化、又はクロルホスホン化されてなる発泡性ポ
リオレフィン系樹脂粒子は文献未記載の新規な物質であ
る。(Prior art and problems) Expandable polyolefin resin particles containing an easily volatile blowing agent and having a sulfonated, chlorosulfonated, or chlorophosphonated surface layer are a new substance that has not been described in any literature. .
従来、弾性に富む樹脂発泡体は、ポリエチレン、ポリプ
ロピレン、ポリスチレンにポリエチレンを配合した組成
物を原料樹脂として用い製造されている。しかしながら
、これらの原料ビーズは、易揮発性発泡剤を含有させた
場合、著しく発泡剤の保持性が悪く、従って発泡性ポリ
スチレンの様に原料ビーズとして販売できず、−置所定
倍率まで発泡させた予備発泡粒子か又は発泡済みの成形
体として市販されているのが現状である。Conventionally, highly elastic resin foams have been manufactured using polyethylene, polypropylene, and compositions in which polyethylene is blended with polystyrene as raw resins. However, when these raw material beads contain an easily volatile foaming agent, their retention of the foaming agent is extremely poor, and therefore they cannot be sold as raw material beads like expandable polystyrene; Currently, they are commercially available as pre-expanded particles or expanded molded bodies.
(問題点を解決する為の手段)
本発明は、かかる問題点を末質的に解決するものであり
、従来には全く無い新規な発泡性ポリオレフィン系樹脂
粒子を提供するものである。(Means for Solving the Problems) The present invention ultimately solves these problems and provides novel expandable polyolefin resin particles that have not existed in the past.
すなわち、本発明は、易揮発性発泡剤を含有し、表層部
がスルホン化、クロルスルホン化、又はクロルホスホン
化さhて成る発泡性ポリオレフィン系樹脂粒子を要旨と
する。That is, the gist of the present invention is to provide expandable polyolefin resin particles containing an easily volatile blowing agent and having a surface layer portion that is sulfonated, chlorosulfonated, or chlorophosphonated.
本発明にいうポリオレフィン系樹脂粒子とは、低密度ポ
リエチレン、高密度ポリエチレン、直鎖状低密度ポリエ
チレン、ポリプロピレン、エチレン−プロピレンランダ
ム共重合体、エチレン−at−Ml ヒ= k 共M
合体、エチレン−スチレングラフト共重合体、エチレン
−酢酸ピニルース4−vングラフト共重合体、塩素化ポ
リエチレン等であり、これらは単独又は相互に混合され
ていても良い。又、これらポリオレフィン系樹脂に、そ
の他の樹脂が混合されていても良い。この場合のポリオ
レフィン系樹脂は少なくとも50重量%以上である。又
、これらポリオレフィン系樹脂は過酸化物等により架橋
されていても良い。また樹脂の粒状化に関しては特に限
定されるものではない。粒状化に関する典型的な方法と
しては、押し出しベレット化がある。押し出しベレット
化の条件は、用いる樹脂により適宜選択され、特に限定
されるものではないが、好ましくは得られたベレットの
残存歪が少ない方が良い。又、粒子の径は何ら限定する
ものではないが通常11IIII程度のものが用いらh
る。The polyolefin resin particles referred to in the present invention include low-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, ethylene-propylene random copolymer, ethylene-at-Ml
These include ethylene-styrene graft copolymer, ethylene-acetate pinyloose 4-v graft copolymer, chlorinated polyethylene, etc., and these may be used alone or in admixture with each other. Further, other resins may be mixed with these polyolefin resins. In this case, the polyolefin resin is at least 50% by weight. Further, these polyolefin resins may be crosslinked with peroxide or the like. Furthermore, there are no particular limitations on the granulation of the resin. A typical method for granulation is extrusion pelletizing. The conditions for extrusion pelletizing are appropriately selected depending on the resin used and are not particularly limited, but it is preferable that the resulting pellet has less residual strain. In addition, the diameter of the particles is not limited in any way, but those of about 11III are usually used.
Ru.
しかして、本発明の特徴は、該ベレットの表層部をスル
ホン化、クロルスルホン化、又はクロルホスホン化スる
ことによって、ベレット中に含浸された易揮発性発泡剤
の逸散を低減し、保存安定性に優れた発泡性ポリオレフ
ィン系樹脂粒子を得ることにあり、スルホン化、クロル
スルホン化、又はクロルホスホン化は、従来知られてい
る反応を用いることができる。すなわち、スルホン化剤
として濃硫酸、発煙硫酸、クロロ硫酸等を用いて、室温
〜100°Cで反応させるスルホン化、クロルスルホン
化剤としてクロルスルホン酸ヲ用いる、あるいはスルホ
ン化した後、塩素化するクロルスルホン化、酸素の存在
下で三塩化リンを反応させるクロルホスホン化等の方法
である。Therefore, the feature of the present invention is that by sulfonating, chlorosulfonating, or chlorophosphonating the surface layer of the pellet, the escape of the easily volatile blowing agent impregnated into the pellet is reduced, and the preservation of the pellet is reduced. The aim is to obtain expandable polyolefin resin particles with excellent stability, and a conventionally known reaction can be used for sulfonation, chlorosulfonation, or chlorophosphonation. That is, sulfonation is carried out using concentrated sulfuric acid, fuming sulfuric acid, chlorosulfuric acid, etc. as a sulfonating agent at room temperature to 100°C, chlorosulfonic acid is used as a chlorosulfonating agent, or chlorination is carried out after sulfonation. These methods include chlorosulfonation and chlorophosphonation in which phosphorus trichloride is reacted in the presence of oxygen.
これらの方法によって改質される表面層の好ましい厚み
は、用いるポリオレフィン系樹脂粒子の大きさによるも
のの、一般にビーズ成形に用いられているがごとき平均
径0.5 aam以上の大きさの粒子の場合、粒子の表
面から1乃至200μの間が改質されていることが好ま
しい。1μ未満の薄い層のみの改質であれば発泡剤の逸
散を抑制する効果が小さく、200μ以上になると樹脂
の本来の特徴が損なわれるからである。The preferred thickness of the surface layer modified by these methods depends on the size of the polyolefin resin particles used, but in the case of particles with an average diameter of 0.5 aam or more, such as those commonly used in bead molding. It is preferable that the area between 1 and 200 μm from the surface of the particles is modified. This is because if only a thin layer of less than 1 μm is modified, the effect of suppressing the escape of the blowing agent is small, and if the thickness exceeds 200 μm, the original characteristics of the resin will be impaired.
本発明にいう易揮発性発泡剤としては、プロパン、プタ
ン、ペンタン、ヘキサン、ヘプタン等の脂肪族炭化水素
、フロン−11、フロン−12、フロン−114等の脂
肪族ハロゲン化炭化水素等の低沸点有機化合物が好適に
用いられるが、特に限定されるものではなく、これらは
単独もしくは混合して用いることができる。これら発泡
剤の含有量は、樹脂分に対して3〜3゜M量%の範囲に
あることが好ましい。3重量%未満では所望の発泡倍率
が得られず、30重量%をこえた含有量は所望の発泡倍
率を得るには用いる必要がない。Easily volatile blowing agents referred to in the present invention include aliphatic hydrocarbons such as propane, butane, pentane, hexane, and heptane, and aliphatic halogenated hydrocarbons such as Freon-11, Freon-12, and Freon-114. Boiling point organic compounds are preferably used, but are not particularly limited, and these can be used alone or in combination. The content of these blowing agents is preferably in the range of 3 to 3 M% based on the resin content. If the content is less than 3% by weight, the desired expansion ratio cannot be obtained, and if the content exceeds 30% by weight, it is not necessary to use it to obtain the desired expansion ratio.
しかして、これらの易揮発性発泡剤をベレット中に含有
せしめるには、例えば予め表層部を改質したベレットを
高温度の条件のもとて易揮発性発泡剤液に浸漬する等の
方法により可能である。In order to incorporate these easily volatile blowing agents into pellets, for example, a pellet whose surface layer has been modified in advance is immersed in a readily volatile blowing agent solution under high temperature conditions. It is possible.
かくして得られた発泡性ポリオレフィン系樹脂粒子は、
含有する発泡剤の保持性が良好で、長期間保存して置い
ても発泡能力を維持することが可能である。The expandable polyolefin resin particles thus obtained are
It has good retention of the foaming agent it contains, and can maintain its foaming ability even after long-term storage.
(実施例)
次に本発明の実施例を示すが、本発明は実施例のみに限
定されるものではない。(Example) Next, an example of the present invention will be shown, but the present invention is not limited only to the example.
実施例1
攪拌機付き耐圧反応器に高圧法ポリエチレン(密度0.
922、MI値1.5 ) 100重量部と水135重
量部を入れ、攪拌しつつ、ネオベレックス(界面活性剤
) o、 05重量部を含む水15重量部にジクミルパ
ーオキサイド0.45重量部を加温、攪拌下で可溶化乃
至微細分散せしめた系を加えた後、更にリン酸カルシウ
ム0.3重量部を含む水50重量部を加え、脱気後、窒
素置換して100°C12時間保持後、140°Cで4
時間保持した後、40°Cへ冷却し、内容物を取り出し
、水洗、乾燥して粒子同士の融着のない架橋ポリエチレ
ン粒を得た。この架橋ポリエチレンのゲル分率(沸騰キ
シレン中48時間での不溶分)は51重量%であった。Example 1 High-pressure polyethylene (density 0.
922, MI value 1.5) 100 parts by weight and 135 parts by weight of water were added, and while stirring, 0.45 parts by weight of dicumyl peroxide was added to 15 parts by weight of water containing 5 parts by weight of Neoverex (surfactant) O, 0. After adding the solubilized or finely dispersed system under heating and stirring, 50 parts by weight of water containing 0.3 parts by weight of calcium phosphate was added, and after degassing, the mixture was replaced with nitrogen and held at 100°C for 12 hours. , 4 at 140°C
After holding for a period of time, it was cooled to 40°C, the contents were taken out, washed with water, and dried to obtain crosslinked polyethylene particles with no fusion between particles. The gel fraction (insoluble matter in boiling xylene for 48 hours) of this crosslinked polyethylene was 51% by weight.
上記架橋ポリエチレン粒を50°C濃硫酸に120分間
浸漬した後、取り出し、水洗、乾燥して表面スルホン化
架橋ポリエチレン粒を得た。The crosslinked polyethylene particles were immersed in concentrated sulfuric acid at 50° C. for 120 minutes, taken out, washed with water, and dried to obtain surface-sulfonated crosslinked polyethylene particles.
得られた粒子のスルホン化の状態を、粒子断面に於る硫
黄元素の量として、X線マイクロアナライザーで調べた
ところ、硫黄は粒子の表面から50μmの内部まで分布
しており、又そのピークの最大は最外殻部分であって、
その濃度は8重量%であった。When the state of sulfonation of the obtained particles was examined using an X-ray microanalyzer as the amount of sulfur element in the cross section of the particles, it was found that sulfur was distributed from the surface of the particles to the inside of 50 μm, and that the peak The largest part is the outermost part,
Its concentration was 8% by weight.
次に、この表面スルホン化架橋ポリエチレン粒子100
重量部、0.5重量%ポリビニルアルコール水溶液12
0重量部及びプタン25重量部をオートクレーブに入れ
、攪拌しつつ100°Cに昇温6時間保持した後、冷却
、取り出し、乾燥を行ない発泡性粒子を得た。この発泡
性粒子の発泡剤保持性の経日性を23°C1開放の状態
で調べた。結果を表1に示した。Next, the surface sulfonated crosslinked polyethylene particles 100
Part by weight, 0.5% by weight polyvinyl alcohol aqueous solution 12
0 parts by weight and 25 parts by weight of butane were placed in an autoclave, and the temperature was raised to 100°C and maintained for 6 hours while stirring, then cooled, taken out, and dried to obtain expandable particles. The aging properties of the foaming agent retention properties of the foamable particles were examined at 23°C. The results are shown in Table 1.
比較例1
実施例1に於て、架橋ポリエチレン粒子の表層部スルホ
ン化を行なわず、他は同様にして発泡性粒子を得、実施
例1と同様の方法で発泡性粒子の発泡剤保持性の経日性
を調べた。結果を表1に示した。Comparative Example 1 Expandable particles were obtained in the same manner as in Example 1, except that the surface layer of the crosslinked polyethylene particles was not sulfonated. The chronology was investigated. The results are shown in Table 1.
実施例2
架橋ポリエチレン粒の濃硫酸による処理条件を70°C
で180分間とした以外は実施例1と同様にして発泡性
粒子を得た。結果を表1に示す。Example 2 Cross-linked polyethylene particles were treated with concentrated sulfuric acid at 70°C.
Expandable particles were obtained in the same manner as in Example 1, except that the heating time was 180 minutes. The results are shown in Table 1.
実施例5
架橋ポリエチレン粒の濃硫酸による処理条件を30°C
160分間とした以外は実施例1と同様にして発泡性粒
子を得た。結果を表1に示す。Example 5 Cross-linked polyethylene particles were treated with concentrated sulfuric acid at 30°C.
Expandable particles were obtained in the same manner as in Example 1 except that the heating time was 160 minutes. The results are shown in Table 1.
米1 含浸された発泡剤量は、発泡剤含浸直後のベレッ
トを100°Cの雰囲気下に1時間放置した間の重量減
量として求めた。Rice 1 The amount of blowing agent impregnated was determined as the weight loss during leaving the pellet immediately after impregnating the blowing agent in an atmosphere at 100° C. for 1 hour.
米2 初期含浸された発泡剤量に対する各時点での残存
率(重量%)で示す。123℃開放状態で保管。Rice 2 It is expressed as the residual rate (% by weight) at each time point relative to the amount of foaming agent that was initially impregnated. Stored in an open state at 123℃.
実施例4〜8
実施例1に於て、発泡剤として、プタンに変えて、夫々
、プロパン、ペンタン、フロン−11、フロン−12、
フロン−114を用いた結果を表2に示す。Examples 4 to 8 In Example 1, instead of butane as the blowing agent, propane, pentane, Freon-11, Freon-12, and
Table 2 shows the results using Freon-114.
比較例2〜6
比較例1に於て、発泡剤として、プタンに変えて、夫々
、プロパン、ペンタン、フロン−11、フロン−12、
フロン−114を用いた結果を表2に示す。Comparative Examples 2 to 6 In Comparative Example 1, instead of butane as the blowing agent, propane, pentane, Freon-11, Freon-12, and
Table 2 shows the results using Freon-114.
表 2
含浸された 発泡剤経日性c%)
発泡剤種 泡剤量
(重量%) 1時間 1日 7日 20日実施例4 プ
ロパン 23.5 90.2 84.A 66
57.1〃 5 ペンタン 22.1 9
1.1 82,1 61.5 53.4〃 6 フ
ロン−1224,894゜8 90.6 82
73.1〃 7 フロン−1121,891,2
82,360,652,3〃 8 フロン−114
24,593,888,781,270,5比較例2
プロパン 26.1 16.2 0 0
0〃 3 ペンタン 24,3 12.1 0
0 0〃 4 フロン−1226,52
6,0000〃 5 フロン−1123,323,2
000〃 6 フロン−11427,524,40
00実施例9
実施例1の架橋ポリエチレン粒5gを、クロルスルホン
酸の20%トリクレン溶液ニ、氷冷しながら徐々に加え
、その後、室温で60分攪拌した。得られたクロルスル
ホン化ポリエチレン粒を水洗乾燥後、X線マイクロアナ
ライザーで、その硫黄元素の分布を調べたところ、硫黄
は粒子の表面から50μmの内部まで分布しており、そ
のピークの最大は最外殻部分であって、その濃度は5重
量%であった。Table 2 Impregnated blowing agent aging c%) Blowing agent type Foaming agent amount (wt%) 1 hour 1 day 7 days 20 days Example 4 Propane 23.5 90.2 84. A 66
57.1 5 Pentane 22.1 9
1.1 82,1 61.5 53.4〃 6 Freon-1224,894゜8 90.6 82
73.1 7 Freon-1121,891,2
82,360,652,3 8 Freon-114
24,593,888,781,270,5 Comparative Example 2
Propane 26.1 16.2 0 0
0〃 3 Pentane 24.3 12.1 0
0 0〃 4 Freon-1226,52
6,0000〃 5 Freon-1123,323,2
000〃6 Freon-11427,524,40
00 Example 9 5 g of the crosslinked polyethylene particles of Example 1 were gradually added to a 20% trichlene solution of chlorsulfonic acid while cooling with ice, and then stirred at room temperature for 60 minutes. After washing and drying the obtained chlorosulfonated polyethylene particles, we examined the distribution of sulfur elements using an X-ray microanalyzer.We found that sulfur was distributed from the surface of the particles to the inside of 50 μm, and the maximum peak was at the maximum. The outer shell portion had a concentration of 5% by weight.
得られた粒子の発泡剤保持性を調べるべく、実施例1の
方法で、プタンを含浸した結果を表3に示した。In order to examine the foaming agent retention of the obtained particles, they were impregnated with butane using the method of Example 1, and the results are shown in Table 3.
実施例10
エチレン−プロピレンランダム共重合体(密度0.90
f/cmコ、MI値9、エチレン含有率約4.5%)1
00重量部及びパウダー状タルク0.05部を混合し、
該混合物を約1.5mの寸法のペレットに押し出した。Example 10 Ethylene-propylene random copolymer (density 0.90
f/cm, MI value 9, ethylene content approximately 4.5%) 1
00 parts by weight and 0.05 parts of powdered talc,
The mixture was extruded into pellets approximately 1.5 m in size.
得られたベレットを55℃の三塩化リン液中、酸素をバ
ブリングさせながら60分浸漬した後、水洗乾燥して表
面クロルホスホン化エチレン−プロピレンランダム共重
合体粒を得た。The obtained pellets were immersed in a phosphorous trichloride solution at 55° C. for 60 minutes while bubbling oxygen, then washed with water and dried to obtain ethylene-propylene random copolymer particles with surface chlorophosphonation.
得られた粒子のクロルホスホン化の状態を、粒子断面に
於るりン元素の量として、X線マイクロアナライザーで
調べたところ、リンは粒子の表面から80部mの内部ま
で分布しており、又、そのピークの最大は最外殻部分で
あって、その濃度は4重量%であった。When the state of chlorophosphonation of the obtained particles was examined using an X-ray microanalyzer as the amount of phosphorus element in the cross section of the particles, it was found that phosphorus was distributed from the surface of the particles to the inside of 80 parts m. The maximum peak was in the outermost shell portion, and its concentration was 4% by weight.
得られた粒子の発泡剤保持性を調べるべく、実施例1の
方法で、プタンを含浸した結果を表3に示した。In order to examine the foaming agent retention of the obtained particles, they were impregnated with butane using the method of Example 1, and the results are shown in Table 3.
表 3
(発明の効果)
実施例及び比較例の結果から明らかな通り、表面力、ス
ルホン化、クロルスルホン化、又はクロルホスホン化さ
れた本発明の発泡性ポリオレフィン系樹脂粒子は、易揮
発性発泡剤を含有させた場合、発泡剤経日保持性が飛躍
的に向上することが分かる。Table 3 (Effects of the Invention) As is clear from the results of Examples and Comparative Examples, the foamable polyolefin resin particles of the present invention, which have been subjected to surface strength, sulfonation, chlorosulfonation, or chlorophosphonation, are easily volatile and foamable. It can be seen that when the foaming agent is contained, the retention of the foaming agent over time is dramatically improved.
Claims (3)
クロルスルホン化、又はクロルホスホン化されて成る発
泡性ポリオレフイン系樹脂粒子。(1) Contains an easily volatile blowing agent, the surface layer is sulfonated,
Expandable polyolefin resin particles that are chlorosulfonated or chlorophosphonated.
請求の範囲第1項記載の発泡性ポリオレフィン系樹脂粒
子。(2) The expandable polyolefin resin particles according to claim 1, wherein the layer thickness of the surface layer portion is in the range of 1 to 200 μm.
、フロン−11、フロン−12、フロン−114のうち
の1種又は2種以上から成る特許請求の範囲第1項また
は第2項記載の発泡性ポリオレフイン系樹脂粒子。(3) Claims 1 or 2 in which the easily volatile blowing agent comprises one or more of propane, butane, pentane, Freon-11, Freon-12, and Freon-114. expandable polyolefin resin particles.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61259925A JPH0629333B2 (en) | 1986-10-31 | 1986-10-31 | Improved expandable polyolefin resin particles |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61259925A JPH0629333B2 (en) | 1986-10-31 | 1986-10-31 | Improved expandable polyolefin resin particles |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS63113037A true JPS63113037A (en) | 1988-05-18 |
JPH0629333B2 JPH0629333B2 (en) | 1994-04-20 |
Family
ID=17340832
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP61259925A Expired - Lifetime JPH0629333B2 (en) | 1986-10-31 | 1986-10-31 | Improved expandable polyolefin resin particles |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0629333B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5771793A (en) * | 1995-05-24 | 1998-06-30 | Voith Sulzer Finishing Gmbh | Calender having a control device |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60181139A (en) * | 1984-02-28 | 1985-09-14 | Japan Styrene Paper Co Ltd | Foamed particle of polypropylene resin |
-
1986
- 1986-10-31 JP JP61259925A patent/JPH0629333B2/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60181139A (en) * | 1984-02-28 | 1985-09-14 | Japan Styrene Paper Co Ltd | Foamed particle of polypropylene resin |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5771793A (en) * | 1995-05-24 | 1998-06-30 | Voith Sulzer Finishing Gmbh | Calender having a control device |
Also Published As
Publication number | Publication date |
---|---|
JPH0629333B2 (en) | 1994-04-20 |
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