JPS6369842A - Expandable thermoplastic resin particle - Google Patents
Expandable thermoplastic resin particleInfo
- Publication number
- JPS6369842A JPS6369842A JP21514686A JP21514686A JPS6369842A JP S6369842 A JPS6369842 A JP S6369842A JP 21514686 A JP21514686 A JP 21514686A JP 21514686 A JP21514686 A JP 21514686A JP S6369842 A JPS6369842 A JP S6369842A
- Authority
- JP
- Japan
- Prior art keywords
- resin particles
- thermoplastic resin
- expandable
- fatty acid
- particles
- 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
- 239000002245 particle Substances 0.000 title claims abstract description 54
- 229920005992 thermoplastic resin Polymers 0.000 title abstract description 15
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 19
- 239000000194 fatty acid Substances 0.000 claims abstract description 19
- 229930195729 fatty acid Natural products 0.000 claims abstract description 19
- 239000011248 coating agent Substances 0.000 claims abstract description 16
- 229920005989 resin Polymers 0.000 claims abstract description 16
- 239000011347 resin Substances 0.000 claims abstract description 16
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 14
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 14
- 238000009835 boiling Methods 0.000 claims abstract description 4
- -1 fatty acid ester Chemical class 0.000 claims description 11
- 239000012815 thermoplastic material Substances 0.000 claims 1
- 238000000465 moulding Methods 0.000 abstract description 13
- 150000004665 fatty acids Chemical class 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 12
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 abstract description 11
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 10
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 abstract description 8
- 238000000576 coating method Methods 0.000 abstract description 7
- 239000004793 Polystyrene Substances 0.000 abstract description 6
- 229920002223 polystyrene Polymers 0.000 abstract description 6
- 239000011324 bead Substances 0.000 abstract description 5
- 239000001273 butane Substances 0.000 abstract description 5
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 abstract description 5
- 229920000223 polyglycerol Polymers 0.000 abstract description 4
- 239000001294 propane Substances 0.000 abstract description 4
- 150000002148 esters Chemical class 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 239000004088 foaming agent Substances 0.000 abstract 2
- 239000000725 suspension Substances 0.000 abstract 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 20
- 239000004604 Blowing Agent Substances 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 235000019197 fats Nutrition 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229920001890 Novodur Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 150000002314 glycerols Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 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 2
- SKDFWEPBABSFMG-UHFFFAOYSA-N 1,2-dichloro-1,1-difluoroethane Chemical compound FC(F)(Cl)CCl SKDFWEPBABSFMG-UHFFFAOYSA-N 0.000 description 1
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- MMQZBEXYFLXHEN-UHFFFAOYSA-N OCC(O)CO.OCC(O)CO.OCC(O)CO.OCC(O)CO.OCC(O)CO.OCC(O)CO.CCCCCCCCCCCCCCCCCC(O)=O Chemical compound OCC(O)CO.OCC(O)CO.OCC(O)CO.OCC(O)CO.OCC(O)CO.OCC(O)CO.CCCCCCCCCCCCCCCCCC(O)=O MMQZBEXYFLXHEN-UHFFFAOYSA-N 0.000 description 1
- WTAYIFXKJBMZLY-XZABIIKCSA-N OCC(O)CO.OCC(O)CO.OCC(O)CO.OCC(O)CO.OCC(O)CO.OCC(O)CO.CCCCCCCC\C=C/CCCCCCCC(O)=O Chemical compound OCC(O)CO.OCC(O)CO.OCC(O)CO.OCC(O)CO.OCC(O)CO.OCC(O)CO.CCCCCCCC\C=C/CCCCCCCC(O)=O WTAYIFXKJBMZLY-XZABIIKCSA-N 0.000 description 1
- 244000007021 Prunus avium Species 0.000 description 1
- 235000010401 Prunus avium Nutrition 0.000 description 1
- 235000014441 Prunus serotina Nutrition 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003048 aphrodisiac agent Substances 0.000 description 1
- 230000002509 aphrodisiac effect Effects 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 229920006248 expandable polystyrene Polymers 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- KMNJKLJBUHNCQM-UHFFFAOYSA-N octadecanoic acid propane-1,2,3-triol Chemical compound OCC(O)CO.OCC(O)CO.OCC(O)CO.OCC(O)CO.OCC(O)CO.OCC(O)CO.CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O KMNJKLJBUHNCQM-UHFFFAOYSA-N 0.000 description 1
- BMANBDGYGRWCMJ-UHFFFAOYSA-N octadecanoic acid;propane-1,2,3-triol Chemical compound OCC(O)CO.OCC(O)CO.OCC(O)CO.OCC(O)CO.OCC(O)CO.OCC(O)CO.CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O BMANBDGYGRWCMJ-UHFFFAOYSA-N 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003751 zinc Chemical class 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〕
本発明は新規にして有用なる発泡性熱可塑性樹脂粒子に
関するものであり、さらに詳細にはポリグリセリン脂肪
酸エステルをコーティング剤として用いて、樹脂粒子の
表面を被覆せしめて得られる、とくに発泡性熱可塑性樹
脂粒子の成形工程における金型充填性、−滑性及び成形
サイクル性が改善された樹脂粒子に関するものである。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to novel and useful expandable thermoplastic resin particles, and more specifically, the present invention relates to novel and useful expandable thermoplastic resin particles. The present invention relates to resin particles which are obtained by coating the surface of foamable thermoplastic resin particles, and which have improved mold filling properties, slipperiness and molding cycle properties, particularly in the molding process of expandable thermoplastic resin particles.
ポリスチレンの如きスチレン系樹脂にプロパン、ブタン
、ペンタン、ヘキサンもしくはシクロヘキサンの如き炭
化水素発泡剤、またはモノクロルエタン、ジクロルエタ
ンモジくはジクロルジフルオルエタンの如きノ１０ゲン
化炭化水素発泡剤などをスチレン糸賀脂１００重量部に
対して１〜１５重量部含ませた形の発泡性スチレン系樹
脂粒子は既によく知られている。A hydrocarbon blowing agent such as propane, butane, pentane, hexane or cyclohexane, or a hydrogenated hydrocarbon blowing agent such as monochloroethane, dichloroethane modi or dichlorodifluoroethane is added to a styrenic resin such as polystyrene. Expandable styrenic resin particles containing 1 to 15 parts by weight per 100 parts by weight of styrene resin are already well known.
かかる組成になる発泡性樹脂粒子は、水蒸気などによシ
軟化点以上に加熱された場合、該粒子中に多数の小気泡
を生じて多孔体となシ、こうした多孔体の形で各種の緩
衝材、断熱材または容器などに利用されている。When expandable resin particles having such a composition are heated to a temperature above their softening point by water vapor, etc., many small bubbles are generated in the particles and the particles become porous. It is used for materials, insulation materials, containers, etc.
このように、かかる発泡性スチレン系樹脂粒子は、一般
に水蒸気などにより加熱されて内部に気泡を有する粒子
状の形態の、いわゆる発泡粒子に換えられるが、次いで
この均一に発泡した粒子は、小さな孔やスリットが設け
られている金型の中で更に加熱されて、これらの発泡粒
子が互いに融着して種々の成形物を与える。In this way, such expandable styrenic resin particles are generally heated with water vapor or the like and converted into so-called expanded particles that have air bubbles inside, but then these uniformly expanded particles have small pores. The foamed particles are further heated in a mold provided with molds and slits to fuse these foamed particles together to give various molded products.
そこでこうした多孔性の成形物を工業的に得るには、こ
れらの発泡性スチレン系樹脂粒子に山桜、水蒸気を接触
させて予め発泡した、いわゆる予備発泡粒子を調製し、
次いでこの予備発泡粒子を金型内に入れて目的とする成
形物となす方法が株られている。Therefore, in order to industrially obtain such porous molded products, so-called pre-expanded particles are prepared by contacting these expandable styrene resin particles with wild cherry blossoms and water vapor to pre-expand them.
There is a method in which the pre-expanded particles are then placed in a mold to form a desired molded product.
このような目的で使用される発泡性熱町塑性物（脂粒子
は、上記の如く成形される工程で種々の欠点が見い出さ
れるが、それらのうちで特に、（１１予備発泡機内で粒
子がブロッキングしやすい、（２）成形工程において金
型に充填された予備発泡粒子を加熱融着させ、更に冷却
して取り出す際に成形物を金型内で冷却する時間が長く
かかシ、このために成形サイクルが長く、成形生産性が
悪い、（３）上記（１）、（２）を改善しようとすると
、成形物の融着が悪くなる、等が大きな問題点であり、
改善が求められている。The foamable hot plastic particles (fat particles) used for such purposes have various drawbacks during the molding process as described above, but among them, (11) Blocking of the particles in the pre-foaming machine (2) In the molding process, the pre-expanded particles filled in the mold are heated and fused, and when they are further cooled and taken out, it takes a long time to cool the molded product in the mold. Major problems include long molding cycles and poor molding productivity; (3) attempts to improve the above (1) and (2) result in poor fusion of molded products;
Improvement is required.
これらの欠点を防止すべく脂肪酸のマグネシウム塩、カ
ルシウム塩、亜鉛塩を始め、ロジンの金属塩等の金属石
鹸類：タルク粉末：ワックス類：ｉ：用油を始め、それ
らの硬化油脂等の高級脂肪酸のグリセリンエステル類：
高級脂肪酸アマイド類やポリシロキサン等を単独或は組
合せ使用して、当該発泡性熱可塑性樹脂粒子の表面を＊
偵せしめるという方法も行われている。In order to prevent these drawbacks, magnesium salts, calcium salts, and zinc salts of fatty acids, metal soaps such as rosin metal salts, talc powder, waxes, i. Glycerin esters of fatty acids:
Using higher fatty acid amides, polysiloxane, etc. alone or in combination, the surface of the expandable thermoplastic resin particles*
Another method is to have them spy on you.
しかし、この種の表面被積剤が用いられたために、予備
発泡工程におけるブロッキングは解決出来たが、成形工
程に２いて一体的に粒子を融着せしめる段階で粒子間の
融着が阻害されたり、又、成形工程における成形サイク
ルが改善されたが、成形物の融着が阻害されたシという
問題が生じ、その結果として、目的とする発泡成形体の
機械的強度を始め、要求性能を低下させるという不都合
な事態を招来するに到っている。However, by using this type of surface coating agent, the blocking problem in the pre-foaming process was solved, but the fusion between the particles was inhibited during the molding process when the particles were fused together. In addition, although the molding cycle in the molding process has been improved, the problem arises that the fusion of the molded product is inhibited, and as a result, the required performance including the mechanical strength of the target foam molded product is reduced. This has led to an inconvenient situation where the
そこで本発明者らは、こうした諸々の事実を考慮に入れ
て鋭意検討した結果、発泡せしめるべき樹脂粒子の軟化
点よりも低い沸点を有する炭化水素類を発泡剤として含
有した発泡性熱可塑性樹脂粒子の表面を、ポリグリセリ
ン脂肪酸エステルを必須の成分として含んで成るコーテ
ィング剤で［９せしめると、前記目的に適合した発泡性
熱可塑性樹脂粒子が、ひいては発泡樹脂製品が得られる
ことを見出すに及んで、本発明を完成させるに到った。As a result of intensive studies taking these various facts into consideration, the present inventors have developed expandable thermoplastic resin particles containing as a blowing agent a hydrocarbon having a boiling point lower than the softening point of the resin particles to be foamed. It has been discovered that if the surface of , we have completed the present invention.
すなわち本発明は、発泡せしめるべき樹脂粒子の軟化点
よりも低い沸点を有する炭化水素類を含有し、かつポリ
グリセリン脂肪酸エステルを必須成分として含有するコ
ーティング剤で表面を被覆せしめてなることを特徴とす
る発泡性熱可塑性樹脂粒子を提供するものである。That is, the present invention is characterized in that the surface is coated with a coating agent containing hydrocarbons having a boiling point lower than the softening point of the resin particles to be foamed and containing polyglycerin fatty acid ester as an essential component. The present invention provides expandable thermoplastic resin particles.
ここにおいて上記した熱ＯＪ′塑性樹脂柁子としては、
スチレン系樹脂粒子が好ましく、例えばスチレンの単独
１合体（ポリスチレン）、メチルスチレンなどの如きア
ルキルスチレンの単独重合体、スチレンとアルキルスチ
レンとの共重合体：スチレンとアクリル酸もしくはメタ
クリル酸との共重合体；スチレンとアクリル酸エステル
もしくはメタクリル酸エステルとの共重合体；スチレン
とアクリロニトリルとの共重合体や上記スチレン糸重合
体とポリオレフィンとのブレンド物などの樹脂の粒状物
が挙げられ、なかでも懸濁重合法によって得られるビー
ズ状の重合体が特に好ましい。Here, as the thermal OJ' plastic resin resin mentioned above,
Styrene-based resin particles are preferred, such as single polymers of styrene (polystyrene), homopolymers of alkylstyrenes such as methylstyrene, copolymers of styrene and alkylstyrenes, and copolymers of styrene and acrylic acid or methacrylic acid. Coalescing; copolymers of styrene and acrylic esters or methacrylic esters; copolymers of styrene and acrylonitrile, and blends of the above-mentioned styrene thread polymers and polyolefins. Particularly preferred are bead-shaped polymers obtained by a turbidity polymerization method.
また発泡剤として用いる発泡せしめるべきｍ脂粒子の軟
化点よりも低い榔点を有する炭化水素類（以下、炭化水
素発泡剤と称す）とは、いわゆる易揮発性の炭化水素類
を指し、そのうち代表的なものを例示すれば、プロパン
、ブタン、ペンタン、ヘキサン、ヘプタンおよびそれら
の異性体Ｏ如き四状炭化水素類；シクロヘキサン、シク
ロペンタン等の環状炭化水素類：モノクロルエタン、ジ
クロルエタン、ジクロルフルオルメタンの如きハロゲン
化炭化水素類などがある。熱可塑性樹脂中に含有される
かかる炭化水素発泡剤の含有量としては、前記熱６ｆ塑
性便脂１００重量部に対して１〜１５重量部なる範囲内
が適当であり、炭化水素発泡剤は混合使用も出来る。In addition, hydrocarbons having a softening point lower than the softening point of the fat particles to be foamed (hereinafter referred to as hydrocarbon blowing agents) used as blowing agents refer to easily volatile hydrocarbons, among which For example, tetrahydrocarbons such as propane, butane, pentane, hexane, heptane and their isomer O; cyclic hydrocarbons such as cyclohexane, cyclopentane; monochloroethane, dichloroethane, dichlorofluoro; These include halogenated hydrocarbons such as methane. The content of the hydrocarbon blowing agent contained in the thermoplastic resin is suitably within the range of 1 to 15 parts by weight based on 100 parts by weight of the above-mentioned thermal 6f plastic stool fat, and the hydrocarbon blowing agent is mixed. It can also be used.
またプロパン、ブタン、ペンタン又はシクロヘキサン等
を単独或は混合で使用する場合には、トルエン、キシレ
ンエチルベンゼンの如き芳香族炭化水素糸や酢哨エチル
、酢酸ブチルの如きエステル系などの公知慣用の溶剤を
少量併用することも出来る。In addition, when using propane, butane, pentane, cyclohexane, etc. alone or in combination, known and commonly used solvents such as aromatic hydrocarbon threads such as toluene and xylene ethylbenzene, and esters such as ethyl acetate and butyl acetate are used. They can also be used together in small amounts.
かかる炭化水素発泡剤を前掲をれた如き各種の熱用塑性
側脂粒子中に含浸せしめるには、例えばオートクレーブ
中で相当程度、好ましくは８０％以上のを含率をもった
熱可塑性樹脂粒子、あるいは予め重合を終了して既に調
製された熱町塑何僧（脂粒子と炭化水素発泡剤とを、水
性懸濁液の状態で該樹脂粒子の軟化点以上の温度に加熱
して行うのがよい。In order to impregnate such hydrocarbon blowing agents into various types of thermoplastic side fat particles as mentioned above, thermoplastic resin particles having a considerable content, preferably 80% or more, in an autoclave, for example. Alternatively, it is possible to heat the resin particles and the hydrocarbon blowing agent, which have already been prepared by completing the polymerization in advance, in the form of an aqueous suspension to a temperature higher than the softening point of the resin particles. good.
本発明で用いるコーティング剤の必須成分たるポリグリ
セリン脂肪酸エステルとしては、ポリグリセリンと脂肪
酸とを反応させて得られる脂肪酸エステル構造を有する
ポリグリセリンが挙げられ、そのポリグリセリン構造の
縮合度、脂肪酸残基の棟類に特に制限はないが、なかで
もポリグリセリン構造の縮合度としては２〜１０、特に
３〜６が好ましく、脂肪酸残基の種類としては炭素数８
〜２４、特に１２〜２２のものが好ましい。又、エステ
ル化朋は必ずしも１００％である必要はない。The polyglycerin fatty acid ester that is an essential component of the coating agent used in the present invention includes polyglycerin having a fatty acid ester structure obtained by reacting polyglycerin and fatty acid, and the degree of condensation of the polyglycerin structure, fatty acid residues, etc. There is no particular restriction on the number of ridges, but the degree of condensation of the polyglycerin structure is preferably 2 to 10, particularly 3 to 6, and the type of fatty acid residue is preferably 8 to 8 carbon atoms.
-24, especially 12-22 are preferred. Further, the esterification rate does not necessarily have to be 100%.
ポリグリセリン脂肪酸エステルの具体例としては、テト
ラグリセリンペンタオレート、テトラグリセリンペンタ
ステアレート、テトラグリセリントリステアレート、テ
トラグリセリンモノオレート、テトラグリセリンモノス
テアレート、ヘキサグリセリンペンタオレート、ヘキサ
グリセリンペンタステアレート、ヘキサグリセリントリ
ステアレート、ヘキサグリセリンモノオレート、ヘキサ
グリセリンモノステアレート、デカグリセリンデカオレ
ート、デカグリセリンデカステアレート、デカグリセリ
ンペンタオレート、デカグリセリンペンタステアレート
、デカグリセリンモノオレート、デカグリセリンモノス
テアレート、テトグリセリンモノオレート等が挙げられ
る。Specific examples of polyglycerin fatty acid esters include tetraglycerin pentaolate, tetraglycerin pentastearate, tetraglycerin tristearate, tetraglycerin monooleate, tetraglycerin monostearate, hexaglycerin pentaolate, hexaglycerin pentastearate, hexa Glycerin tristearate, hexaglycerin monooleate, hexaglycerin monostearate, decaglycerin dekaolate, decaglycerin decastearate, decaglycerin pentaolate, decaglycerin pentastearate, decaglycerin monooleate, decaglycerin monostearate, Tet Examples include glycerin monooleate.
当該ポリグリセリン脂肪酸エステルは、使用に際して液
状であることが好ましく、粘度が２５℃で２，０ＯＯＯ
Ｐ以下の液状のものは通常そのまま用いるが、それ以外
のもの、例えばフレーク状、ペースト状、高粘度のもの
では水、アルコール、その他のｉ」溶な溶媒に溶解して
通常使用する。The polyglycerol fatty acid ester is preferably liquid when used, and has a viscosity of 2,000°C at 25°C.
Liquids with P or less are usually used as they are, but other types, such as flakes, pastes, and highly viscous ones, are usually used after being dissolved in water, alcohol, or other soluble solvents.
本発明においては、当該ポリグリセリン脂肪酸エステル
を必須成分として含有するコーティング剤を用いるが、
その他の成分として高級脂肪酸のグリセリンエステル類
、高級脂肪酸アマイド類、金属石鹸、メルク、炭酸カル
シウムなどの如き無機化合物Ｖ）体、シリコーン油等の
如き公知慣用のコーティング剤を併用してもよく、かが
る併用によって本発明の効果を一層向上せしめることが
出来る。In the present invention, a coating agent containing the polyglycerin fatty acid ester as an essential component is used, but
Other ingredients may be used in combination with glycerin esters of higher fatty acids, higher fatty acid amides, metal soaps, inorganic compounds such as Merck, calcium carbonate, etc., and known and commonly used coating agents such as silicone oil. The effects of the present invention can be further improved by the combined use.
当該コーティング剤の使用膣°としては、該コーティン
グ剤中に廿まれるポリグリセリン脂肪酸エステルの発泡
性熱可塑性樹脂粒子表面への被覆量が該樹脂粒子１００
重量部に対してｔＯ１量部具部以下ましくは［１，００
５〜［１５亜量部となる範囲が挙げられ、その被覆方法
としては、公知慣用の種々の方法が適用でき、特に節」
限はないが、研１常はドラムブレンダー、リボンミキサ
ー等により単に混合するだけでよい。The amount of coating of the polyglycerin fatty acid ester contained in the coating agent on the surface of the foamable thermoplastic resin particles is 100% of the amount of the coating agent used.
The amount of tO per part by weight or less or [1,00
A range of 5 to 15 parts is mentioned, and various well-known and commonly used methods can be applied as the coating method.
Although there are no limitations, the polishing process may be simply mixed using a drum blender, ribbon mixer, or the like.
その際、ポリグリセリン脂肪酸エステル含有コーティン
グ剤′（ｉｌ−被覆後に、前記高級脂肪酸のグリセリン
エステル類、高級脂肪酸アマイド類、金属石鹸あるいは
無機化合物粉末などを必要最少葉更に被覆せしめてもよ
い。In this case, after coating with a polyglycerol fatty acid ester-containing coating agent' (il-coating), the leaves may be further coated with the necessary minimum amount of glycerol esters of higher fatty acids, higher fatty acid amides, metal soap, or inorganic compound powder.
このようにして得られた本発明のｍａ済み発泡性熱可塑
性樹脂板子は、その予備発泡の際に発泡粒子同士が結合
し合い、集塊化することを著しく減少させることができ
るし、また成形金型内への充填を円滑に行うことも出来
る。更に成形工程における成形サイクルが著るしく短く
でき、しかも金型内での加熱によシ発泡粒子同士を強固
に融着せしめることか出来る。The thus obtained foamable thermoplastic resin board of the present invention can significantly reduce the bonding of foamed particles to each other and agglomeration during pre-foaming, and can also be molded. It is also possible to smoothly fill the mold. Furthermore, the molding cycle in the molding process can be significantly shortened, and the foamed particles can be firmly fused together by heating within the mold.
かくして得られた本発明の樹脂粒子は、魚類や農作物な
どを入れる容器として、電気部品や７ｕ気器具を収納し
運搬するさいの緩衝材として、あるいは建築用などの断
熱材として利用できる。The thus obtained resin particles of the present invention can be used as a container for storing fish or agricultural products, as a cushioning material when storing and transporting electrical parts or 7U air appliances, or as a heat insulating material for buildings.
次に本発明を実施例および比較例により具体的に説明す
るが、以下において部および％は判に断りのない限り、
すべて重量基準とする。Next, the present invention will be specifically explained with reference to Examples and Comparative Examples. In the following, unless otherwise specified, parts and percentages are as follows:
All measurements are based on weight.
実施例１〜６および比較例１〜４
重合槽にＷ！：、濁安定畑としての燐酸カルシウム１部
およびドデシルベンゼンスルホン酸ナトリウム［１，０
５部および純水１００部の混合物と、触媒としてのベン
ゾイルパーオキシド（１２５部およびｔｅｒ ｔ−ブチ
ルパーベンゾエート０．０５部をスチレン１００部に溶
解した溶液と、硬化ヤシ油０．０５部と、エポキシ化不
飽和脂肪酸メチルエステル１ＸＬ５部とを仕込み、８５
℃で重合を行い、重合率が９０％に達した時点で燐酸カ
ルシウム２部を追加し、さらに発泡剤としてのブタン７
部とシクロヘキサン上５部とを加えて１１５℃で重合を
完結させ、次いで冷却した彼、生成したビーズを取り出
し、脱水、乾燥、分級して、粒径Ｑ、９±α１篩なるポ
リスチレンビーズを侍た。Examples 1 to 6 and Comparative Examples 1 to 4 W! in the polymerization tank! :, 1 part calcium phosphate and sodium dodecylbenzenesulfonate [1,0
a mixture of 5 parts and 100 parts of pure water, a solution of 125 parts of benzoyl peroxide as a catalyst and 0.05 part of tert-butyl perbenzoate in 100 parts of styrene, and 0.05 part of hydrogenated coconut oil; Prepare 5 parts of epoxidized unsaturated fatty acid methyl ester 1XL, 85
Polymerization was carried out at ℃, and when the polymerization rate reached 90%, 2 parts of calcium phosphate was added, and 7 parts of butane as a blowing agent was added.
1 part and 5 parts of cyclohexane were added to complete the polymerization at 115°C, and then cooled. The formed beads were taken out, dehydrated, dried, and classified to obtain polystyrene beads with a particle size of Q and a sieve of 9±α1. Ta.
かくして侍られたポリスチレンビーズ２ゆをリボンミキ
サーに仕込み、次いで第１表に示される量の各種被穐剤
を添加順に従って加え、各々２分間攪拌して表面が被覆
された発泡性ポリスチレンピースを得た。Two volumes of the polystyrene beads prepared in this way were placed in a ribbon mixer, and then the amounts of various aphrodisiacs shown in Table 1 were added according to the order of addition, and each mixture was stirred for 2 minutes to obtain expandable polystyrene pieces whose surfaces were coated. Ta.
しかるのち、このポリスチレンビーズを攪拌バッチ式予
備発泡機中で６０倍に発泡せしめ、得られた予備発泡粒
子を縦横１０簡の篩でふるって、篩上に残存した予備発
泡粒子の量を計り、全予備発泡粒子に対する割合をブロ
ッキン重量として算出した。Thereafter, the polystyrene beads were expanded 60 times in a stirred batch type pre-expanding machine, the obtained pre-expanded particles were sieved through a sieve of 10 lengths and widths, and the amount of pre-expanded particles remaining on the sieve was measured. The ratio to the pre-expanded particles was calculated as the blocking weight.
次いで、かくして得られた篩を通過した予備発泡粒子を
３８Ｘ３０Ｘ３Ｇ＋ｌなる形状に成形し、予備発１ｍｆ
ａｔ子を充填する時点から金型内の圧力がｒ］、０４
ｋＩ？／（Ｍ＋２に至るまでの時間を成形サイクルとし
て測定した。Next, the pre-expanded particles that passed through the sieve thus obtained were molded into a shape of 38 x 30 x 3 G + l, and the pre-expanded particles were
From the time of filling the attenuator, the pressure inside the mold is r], 04
kI? /(The time up to M+2 was measured as a molding cycle.
更に、得られた成形物の半折して中央部を破壊し、その
破断面に現われている粒子のセルの接合割合（セルの中
心部で破壊している割合）を融着度として算出した。Furthermore, the obtained molded product was broken in half to destroy the central part, and the bonding ratio of the cells of the particles that appeared on the fractured surface (the ratio of cells broken at the center) was calculated as the degree of fusion. .
これらの結果を第１表に示す。These results are shown in Table 1.
／′/′
Claims (1)
する炭化水素類を含有し、かつポリグリセリン脂肪酸エ
ステルを必須成分として含有するコーティング剤で表面
を被覆せしめてなることを特徴とする発泡性熱可塑性樹
脂粒子。A foamable thermoplastic material whose surface is coated with a coating agent containing hydrocarbons having a boiling point lower than the softening point of the resin particles to be foamed and containing polyglycerin fatty acid ester as an essential component. resin particles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21514686A JPS6369842A (en) | 1986-09-12 | 1986-09-12 | Expandable thermoplastic resin particle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21514686A JPS6369842A (en) | 1986-09-12 | 1986-09-12 | Expandable thermoplastic resin particle |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6369842A true JPS6369842A (en) | 1988-03-29 |
Family
ID=16667441
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21514686A Pending JPS6369842A (en) | 1986-09-12 | 1986-09-12 | Expandable thermoplastic resin particle |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6369842A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009047289A (en) * | 2007-08-23 | 2009-03-05 | Mazda Motor Corp | Belt tensioner, and belt replacing method therein |
-
1986
- 1986-09-12 JP JP21514686A patent/JPS6369842A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009047289A (en) * | 2007-08-23 | 2009-03-05 | Mazda Motor Corp | Belt tensioner, and belt replacing method therein |
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