JPH01230652A - Resin composition - Google Patents
Resin compositionInfo
- Publication number
- JPH01230652A JPH01230652A JP5773388A JP5773388A JPH01230652A JP H01230652 A JPH01230652 A JP H01230652A JP 5773388 A JP5773388 A JP 5773388A JP 5773388 A JP5773388 A JP 5773388A JP H01230652 A JPH01230652 A JP H01230652A
- Authority
- JP
- Japan
- Prior art keywords
- ethylene
- polydiorganosiloxane
- resin composition
- weight
- meth
- 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
- 239000011342 resin composition Substances 0.000 title claims abstract description 18
- 125000000962 organic group Chemical group 0.000 claims abstract description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 7
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 5
- 238000010992 reflux Methods 0.000 claims abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 27
- 238000004898 kneading Methods 0.000 abstract description 17
- -1 phenyl vinyl Chemical group 0.000 abstract description 15
- 229920001577 copolymer Polymers 0.000 abstract description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 6
- 239000005977 Ethylene Substances 0.000 abstract description 6
- 150000003254 radicals Chemical class 0.000 abstract description 3
- 229920002554 vinyl polymer Polymers 0.000 abstract description 3
- 230000000704 physical effect Effects 0.000 description 13
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 9
- 239000005038 ethylene vinyl acetate Substances 0.000 description 7
- 229920005680 ethylene-methyl methacrylate copolymer Polymers 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000008188 pellet Substances 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 239000004416 thermosoftening plastic Substances 0.000 description 4
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明はポリジオルガノシロキサンとエチレン−（メタ
）アクリル酸エステル共重合体からなる樹脂組成物に関
するものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a resin composition comprising a polydiorganosiloxane and an ethylene-(meth)acrylic acid ester copolymer.
〈従来の技術〉
ポリジオルガノシロキサンとポリエチレンまたはエチレ
ン酢酸ビニルコポリマーとを混練して性質の新しい組合
せを達成することによって多くの有用な材料が得られて
いる。ポリマーは一般的には相溶性がないので、安定で
有用な混練物を得ることがしばしば困難である。このよ
うな場合、ブロック共重合あるいはグラフト共重合のよ
うな技法によって、ポリマー類に相溶性を持たせて安定
有用な混練物を得ることが行われている。PRIOR ART Many useful materials have been obtained by blending polydiorganosiloxanes with polyethylene or ethylene vinyl acetate copolymers to achieve new combinations of properties. Since polymers are generally not compatible, it is often difficult to obtain stable and useful blends. In such cases, techniques such as block copolymerization or graft copolymerization are used to make the polymers compatible and to obtain a stable and useful kneaded product.
特公昭５２−３６８９８号公報においてポリジオルガノ
シロキサンガムとポリエチレンとを混練することにより
、 また特公昭５６−１２０１号公報 においてポリジ
オルガノシロキサンガムとエチレン酢酸ビニルコボリマ
ーとを混練することにより加工性が良好で機械的に優れ
たグラフト共重合体が作られることが開示されている。Good workability was obtained by kneading polydiorganosiloxane gum and polyethylene in Japanese Patent Publication No. 52-36898, and by kneading polydiorganosiloxane gum and ethylene vinyl acetate copolymer in Japanese Patent Publication No. 56-1201. It has been disclosed that mechanically superior graft copolymers can be made.
ポリジオルガノシロキサンガムとエチレン酢酸ビニルコ
ポリマーとの混練生成物は、単独使用、又は他の熱可塑
性プラスチック等とのブレンドにより、これらの樹脂単
独では得られない各種の性質、たとえば耐衝撃性、耐薬
品性、潤滑性、剥離性、耐摩耗性、消耗性、耐老化性、
気体透過性等を付与することができる。The kneaded product of polydiorganosiloxane gum and ethylene vinyl acetate copolymer can be used alone or blended with other thermoplastics to provide various properties that cannot be obtained with these resins alone, such as impact resistance and chemical resistance. properties, lubricity, peelability, abrasion resistance, wear resistance, aging resistance,
Gas permeability etc. can be imparted.
しかしながら特公昭５６−１２０１号公報にも記載のご
とくポリジオルガノシロキサンガムとエチレン酢酸ビニ
ルコポリマーとの混練温度領域は、 １７０℃〜２３５
℃と狭＜ 、２３０℃の混練ですでに着色と物性の変化
を引き起こす。この現象はエチレン酢酸ビニルコポリマ
ーが熱的に不安定で、２３０℃以上で分解して酢酸を放
出することに起因する。この熱分解は混線機に対しても
腐食等を起こすので混練温度上限は厳密に守らねばなら
ない。However, as described in Japanese Patent Publication No. 56-1201, the kneading temperature range of polydiorganosiloxane gum and ethylene vinyl acetate copolymer is 170°C to 235°C.
℃ and narrowing, kneading at 230℃ already causes coloration and changes in physical properties. This phenomenon is caused by the fact that ethylene vinyl acetate copolymer is thermally unstable and decomposes at temperatures above 230° C., releasing acetic acid. This thermal decomposition also causes corrosion of the mixer, so the upper limit of the kneading temperature must be strictly observed.
また、加工時においても同様であり、ポリジオルガノシ
ロキサンガムとエチレン酢酸ビニルコポリマーの混練生
成物も２３５℃以上の温度で加工すると同様の脱酢酸反
応により着色、劣化を起こし、加工製品の物性的性質の
激しい悪化と着色を示す。また同様に加工機に対しても
腐食の影響は避けられないと言う欠点があった。The same thing applies during processing, and if the kneaded product of polydiorganosiloxane gum and ethylene vinyl acetate copolymer is processed at temperatures above 235°C, it will be colored and deteriorated due to the same deacetic acid reaction, resulting in the physical properties of the processed product. shows severe deterioration and discoloration. Similarly, processing machines also had the disadvantage of being unavoidably affected by corrosion.
〈発明が解決しようとする課題〉
かかる現状に鑑み、本発明の目的は混練時又は加工時に
おける熱安定性の良好なポリジオルガノシロキサンとエ
チレン−（メタ）アクリル酸エステル共重合体の樹脂組
成物を提供することである。<Problems to be Solved by the Invention> In view of the current situation, the object of the present invention is to provide a resin composition of polydiorganosiloxane and ethylene-(meth)acrylic acid ester copolymer that has good thermal stability during kneading or processing. The goal is to provide the following.
く課題を解決するための手段〉
本出願に係る発明は、次の様な構成要件を備えることを
特徴とする。 即ち、１０〜１７５重量部のポリジオル
ガノシロキサンと１００重量部のエチレン−（メタ）ア
クリル酸エステル共重合体との混練物であって、還流キ
シレン中で不溶である物質（以下ゲルという。）が混練
物合計の少なくとも１０重量％含有する樹脂組成物であ
る。Means for Solving the Problems> The invention according to the present application is characterized by having the following constituent elements. That is, it is a kneaded product of 10 to 175 parts by weight of polydiorganosiloxane and 100 parts by weight of ethylene-(meth)acrylic acid ester copolymer, which is a substance that is insoluble in refluxing xylene (hereinafter referred to as gel). It is a resin composition containing at least 10% by weight of the total kneaded material.
本発明に適するポリジオルガノシロキサンはウィリアム
ス可塑度が０．０２０インチより大きいトルエン可溶ガ
ムである。これらのガムは本質的にはジオルガノシロキ
サン単位から成り、従って珪素原子１個あたりの有機基
の比が約２．０となる。Polydiorganosiloxanes suitable for this invention are toluene soluble gums with a Williams plasticity greater than 0.020 inch. These gums consist essentially of diorganosiloxane units, resulting in a ratio of organic groups per silicon atom of about 2.0.
他のシロキサン単位としては末端基となるトリオルガノ
シロキサン単位またはジオルガノヒドロキシシロキサン
単位の他、少量でモノオルガノシロキサン単位、５ｉｎ
２シロキサン単位が存在してもよい。Other siloxane units include triorganosiloxane units or diorganohydroxysiloxane units that serve as terminal groups, and small amounts of monoorganosiloxane units, 5in.
Two siloxane units may be present.
これらのガムの有機基はメチル基、フェニル基、ビニル
基、及びアリル基から選ばれ、これはジメチルシロキサ
ン単位、メチルフェニルシロキサン単位、ジフェニルシ
ロキサン単位、メチルビニルシロキサン単位、メチルア
リルシロキサン単位、及びフェニルビニルシロキサン単
位のようなジオルガノシロキサン単位として存在する。The organic groups of these gums are selected from methyl, phenyl, vinyl, and allyl groups, which include dimethylsiloxane units, methylphenylsiloxane units, diphenylsiloxane units, methylvinylsiloxane units, methylallylsiloxane units, and phenyl Exists as diorganosiloxane units such as vinylsiloxane units.
存在する他のシロキサン単位はジオルガノシロキサン単
位と同じ有機単位を含む。ポリジオルガノシロキサン分
子はトリオルガノシロキサン単位またはヒドロキシル基
で末端封鎖されることが好ましい。しかし、高分子量分
子上の末端基の数は全ガム組成物について顕著な量を示
すものではないので、他の末端封鎖基でもよい。The other siloxane units present contain the same organic units as the diorganosiloxane units. Preferably, the polydiorganosiloxane molecules are end-capped with triorganosiloxane units or hydroxyl groups. However, since the number of end groups on the high molecular weight molecules does not represent a significant amount for the total gum composition, other end capping groups may be used.
本発明にとって適当なポリジオルガノシロキサンはビニ
ルまたはアリル、好ましくはビニルを含有する０、２モ
ル％〜１７モル％のシロキサン単位を有するものである
。Polydiorganosiloxanes suitable for the present invention are those having from 0.2 mole % to 17 mole % vinyl- or allyl-containing, preferably vinyl-containing siloxane units.
本発明において用いられるエチレン−（メタ）アクリル
酸エステル共重合体は、エチレンとラジカル共重合し得
るコモノマーとを有機過酸化物や酸素等の遊離基発生剤
を使用して共重合することによって得られるものである
。共重合反応は、通常１３０ないし３００℃の重合温度
下、５００ないし３０００ｋｇ／ｃｍ”の重合圧力下で
実施される。The ethylene-(meth)acrylic acid ester copolymer used in the present invention is obtained by copolymerizing ethylene and a comonomer capable of radical copolymerization using a free radical generator such as an organic peroxide or oxygen. It is something that can be done. The copolymerization reaction is usually carried out at a polymerization temperature of 130 to 300°C and a polymerization pressure of 500 to 3000 kg/cm''.
エチレン−（メタ）アクリル酸エステル共重合体として
は具体的には、エチレンとアクリル酸メチル、アクリル
酸エチル、アクリル酸ブチル、アクリル酸２−エチルヘ
キシル等との共重合体、及びエチレンとメタクリル酸メ
チル、メタクリル酸エチル、メタクリル酸ブチル、メタ
クリル酸２−エチルヘキシル等との共重合体があげられ
る。これらの共重合体は１種のみならず２種以上の混合
組成物を用いることもできる。Specifically, ethylene-(meth)acrylate copolymers include copolymers of ethylene and methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc., and ethylene and methyl methacrylate. , ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and the like. Not only one type of these copolymers may be used, but a mixed composition of two or more types can also be used.
本発明で用いるエチレン−（メタ）アクリル酸エステル
共重合体に含まれるコモノマーの含有量は５〜４０重量
％であり、特に１０〜３０重量％が好ましい。The content of the comonomer contained in the ethylene-(meth)acrylic acid ester copolymer used in the present invention is 5 to 40% by weight, particularly preferably 10 to 30% by weight.
コモノマーの含有量が５％より低いと、ゲル含量が組成
物合計の少なくとも１０重量％含有する樹脂組成物は得
られない。コモノマーの含有量が４０重量％より高いと
、本発明の効果は飽和に達すると共に、樹脂組成物が粘
着性を帯び、例えば造粒時のベレット化が困難になり実
用性に乏しい。If the comonomer content is lower than 5%, a resin composition with a gel content of at least 10% by weight of the total composition cannot be obtained. When the comonomer content is higher than 40% by weight, the effects of the present invention reach saturation and the resin composition becomes sticky, making it difficult to form pellets during granulation, resulting in poor practicality.
本発明で用いるエチレン−（メタ）アクリル酸エステル
共重合体のメルトフローレートは０．１ないし１００ｇ
／ １０ｍ ｉｎであり、５〜５０ｇ／１０ｍｉｎの範
囲にあることが好ましい。メルトフローレートが０．１
ｇ／ １０ｍｉｎより低いと、溶融粘度が高くなりすぎ
てポリジオルガノシロキサンとの相溶性に劣る。一方１
００ｇ／１０ｍｉｎより高いと、安定均質な混合組成物
を得ることは可能であるが、機械的強度のごとき実用物
性が劣り好ましくない。The melt flow rate of the ethylene-(meth)acrylic acid ester copolymer used in the present invention is 0.1 to 100 g.
/10 min, and is preferably in the range of 5 to 50 g/10 min. Melt flow rate is 0.1
If it is lower than g/10 min, the melt viscosity will be too high and the compatibility with polydiorganosiloxane will be poor. On the other hand 1
If it is higher than 00 g/10 min, it is possible to obtain a stable and homogeneous mixed composition, but practical physical properties such as mechanical strength are poor, which is not preferable.
本発明に用いられるエチレン−（メタ）アクリル酸エス
テル共重合体は、他の公知の配合剤、たとえば耐候安定
剤、酸化防止剤、帯電防止剤、滑剤、アンチブロッキン
グ剤、顔料、無機または有機の充填剤などを含有してい
てもよい。The ethylene-(meth)acrylic acid ester copolymer used in the present invention may contain other known compounding agents, such as weathering stabilizers, antioxidants, antistatic agents, lubricants, antiblocking agents, pigments, inorganic or organic additives, etc. It may also contain fillers and the like.
本発明の方法に於いては、１０〜１７５重量部のポリジ
オルガノシロキサンを１００重量部のエチレン−（メタ
）アクリル酸エステル共重合体と混合する。In the method of the invention, 10 to 175 parts by weight of polydiorganosiloxane are mixed with 100 parts by weight of ethylene-(meth)acrylate copolymer.
ポリジオルガノシロキサンが１７５重量部より多いとエ
チレン−（メタ）アクリル酸エステル共重合体との相溶
性の限界を越えるため、粘着性とベトッキを帯びた樹脂
組成物になるため、実用に供し得ない。If the polydiorganosiloxane is more than 175 parts by weight, it exceeds the limit of compatibility with the ethylene-(meth)acrylic acid ester copolymer, resulting in a resin composition that is sticky and sticky, and cannot be put to practical use. .
本発明の方法によって得られた組成物を他の熱可塑性プ
ラスチックスへの添加剤として使用するときには、１０
０〜１６０重量部のポリジオルガノシロキサン全１００
重最部のエチレン−（メタ）アクリル酸エステル共重合
体と混合することが好ましい。When the composition obtained by the method of the present invention is used as an additive to other thermoplastics, 10
0 to 160 parts by weight of polydiorganosiloxane total 100
It is preferable to mix it with the ethylene-(meth)acrylic acid ester copolymer in the heavymost part.
エチレン−（メタ）アクリル酸エステルとポリジオルガ
ノシロキサンとの組成物はある特定条件下でそれらを機
械的に混合することによってつくることができる。この
特定条件下で混練された組成物は、均質であり、常温に
於いてそれぞれの層へ分離することがない。又、一方の
物質が他方の物質からしみ出ることがなく、組成物がし
み出しあるいは分離を伴うことなく広範囲の加工温度範
囲にわたって使用できる。Compositions of ethylene-(meth)acrylate and polydiorganosiloxane can be made by mechanically mixing them under certain conditions. The composition kneaded under these specific conditions is homogeneous and does not separate into layers at room temperature. Also, one material does not ooze out from the other and the composition can be used over a wide processing temperature range without oozing or separation.
これらの安定な組成物をつくるには、ＩＱ ５ｅｃ−’
より大きい剪断速度をもつような条件で機械的に混練さ
れる。To create these stable compositions, IQ 5ec-'
It is mechanically kneaded under conditions such that it has a higher shear rate.
混練温度は、１７０℃〜３５０℃、望ましくは１７０℃
〜２８０℃である。１７０℃以下の温度においては、グ
ラフト化されに＜ ＜ 、３５０℃以上の温度において
は、変色と物理的性質の劣化が生じる。The kneading temperature is 170°C to 350°C, preferably 170°C.
~280°C. At temperatures below 170°C, grafting occurs, and at temperatures above 350°C, discoloration and deterioration of physical properties occur.
ポリジオルガノシロキサンとエチレン−（メタ）アクリ
ル酸エステル共重合体の機械的混練操作を、剪断下でか
つ適当な温度にふいて続けると、混練中の粘度はもとの
粘度をこえて上昇し最大粘度に達する。 この最大粘度
になった時に混練操作を停止する。この時、ゲル含量が
全混練物の少なくとも１０重量％含有しなければならな
い。ゲル含量が、１０重量％より少ないと、得られた樹
脂組成物がベトッキ感があり粘着性を帯びているため、
実用に供し得ない。When mechanical kneading of polydiorganosiloxane and ethylene-(meth)acrylic acid ester copolymer is continued under shear and at an appropriate temperature, the viscosity during kneading increases beyond the original viscosity and reaches a maximum. Viscosity is reached. The kneading operation is stopped when this maximum viscosity is reached. At this time, the gel content must be at least 10% by weight of the entire kneaded product. If the gel content is less than 10% by weight, the resulting resin composition will feel sticky and sticky.
It cannot be put to practical use.
本発明の適当な混線機としては、バンバリーミキサ−、
ブラベンダープラスチーコーダー、混練押出機等が使用
できる。Suitable mixers for the present invention include Banbury mixers,
Brabender plastic chicoder, kneading extruder, etc. can be used.
この方法により製造された組成物は安定で均質な組成物
であって、乾燥状で非粘着性のベレットへ容易に成形さ
れる。このペレットは通常の加工技術によって容易に処
理できる。この組成物は、良好な電気的性質、ガス透過
性、他の熱可塑性プラスチックスとの相溶性、可撓性を
有し、有機パーオキサイド、紫外線照射、ガンマ線照射
などにより架橋できる等の優れた性質をを有しているた
め、電線及びケーブルの被覆、医療用途、他の熱可塑性
プラスチックスの改質剤のような用途に使用することが
できる。The compositions produced by this method are stable, homogeneous compositions that are easily formed into dry, non-tacky pellets. This pellet can be easily processed using conventional processing techniques. This composition has excellent electrical properties, gas permeability, compatibility with other thermoplastics, flexibility, and can be crosslinked with organic peroxide, ultraviolet irradiation, gamma ray irradiation, etc. Due to its properties, it can be used in applications such as coating electric wires and cables, medical applications, and as a modifier for other thermoplastics.
〈実施例〉 以下の実施例によって本発明をさらに詳しく説明する。<Example> The invention will be explained in more detail by the following examples.
尚、実施例及び比較例において各物性の評価方法は次の
方法によった。In addition, in the Examples and Comparative Examples, each physical property was evaluated by the following method.
（１）メルトフローレート （ＭＦＲ）ＪＩＳ −Ｋ
６７３０に準拠した。(1) Melt flow rate (MFR) JIS-K
Compliant with 6730.
得られた樹脂組成物のＭＦＲが、用いたエチレン−（メ
タ）アクリル酸エステル共重合自身のＭＦＲより高いと
グラフト反応が不十分であるか、又は熱安定性の悪い樹
脂組成物が得られていると判定される。If the MFR of the resulting resin composition is higher than the MFR of the ethylene-(meth)acrylate copolymer itself used, the graft reaction may be insufficient or a resin composition with poor thermal stability may be obtained. It is determined that there is.
（２）引張強さ、伸び ＪＩＳ −Ｋ ６７３０に準拠した。(2) Tensile strength, elongation Compliant with JIS-K 6730.
（３）硬度（ショアーＡ） ＡＳＴ！、！ ２２４０に準拠した。(3) Hardness (Shore A) AST! ,! Compliant with 2240.
（４）加工性
混練造粒された樹脂組成物が、乾燥状でかつ非粘着性ペ
レットの形態で得られるものを゛良°そうでないものを
゛不良° として判定した。(4) Processability The kneaded and granulated resin composition obtained in the form of dry, non-adhesive pellets was judged as "good", and the ones that were not so good were judged as "poor".
（５）ゲル含量（還流キシレン不溶物含有量）混練造粒
された樹脂組成物を還流キシレン中で２０時間抽出する
ことによって、得られる不溶物質の組成物全体に対する
割合を重量％で示す。(5) Gel content (content of insoluble matter in refluxing xylene) The ratio of the insoluble matter obtained by extracting the kneaded and granulated resin composition in refluxing xylene for 20 hours to the total composition is expressed in weight %.
（６）外観
樹脂組成物の熱安定性の尺度として、着色度の目視判定
、臭気官能テストを行い、白色で臭気のないものを正常
、その他は異常と判定される。(6) Appearance As a measure of the thermal stability of the resin composition, a visual judgment of the degree of coloration and an odor sensory test are conducted, and those that are white and odorless are judged as normal, and the others as abnormal.
（７）ウィリアムス可塑度 、 ＡＳＴＭ ０９２６に準拠した。(7) Williams plasticity , Compliant with ASTM 0926.
実施例−１
珪素原子あたり２．０８モル％のビニル基をもち、約０
．０６インチのウィリアムス可塑度をもち、かつ９８モ
ル％のジメチルシロキサン単位と２モル％のメチルビニ
ルシロキサン単位であるジメチルビニルシロキサン基で
末端封鎖されたトルエン可溶ポリジオルガノシロキサン
の２７００ｇと、エチレン−メタクリル酸メチル共重合
体（ＭＦＲ＝ ７ ｇ／１０ｍｉｎ 、メタクリル酸メ
チル含有量１０重量％）の１８００ｇをＯ型インテンシ
ブミキサー（容量４．５β）で１９０℃、７５ｒｐｍで
１５分間混練した後、Ｐ６５−１６ＡＤ型押出造粒機で
造粒した混練組成物について物性を測定した。Example-1 2.08 mol% vinyl group per silicon atom, about 0
．． 2700 g of a toluene soluble polydiorganosiloxane having a Williams plasticity of 0.06 inch and end-capped with dimethylvinylsiloxane groups, 98 mole percent dimethylsiloxane units and 2 mole percent methylvinylsiloxane units, and ethylene-methacrylate. After kneading 1800 g of acid methyl copolymer (MFR = 7 g/10 min, methyl methacrylate content 10% by weight) using an O-type intensive mixer (capacity 4.5β) at 190°C and 75 rpm for 15 minutes, P65-16AD was mixed. The physical properties of the kneaded composition granulated using an extrusion granulator were measured.
第１表にその結果を示した。Table 1 shows the results.
比較例−１
実施例−１と同−試料及び同一の組成のポリジオルガノ
シロキサンとエチレン−メタクリル酸メチル共重合体を
、混練時間を５分間にした以外は実施例−１と同様に調
整した混練組成物について物性を測定した。第１表にそ
の結果を示した。Comparative Example-1 Same as Example-1 - Kneading prepared in the same manner as in Example-1 except that the sample and the same composition of polydiorganosiloxane and ethylene-methyl methacrylate copolymer were kneaded for 5 minutes. Physical properties of the composition were measured. Table 1 shows the results.
実施例−２
実施例−１のエチレン−メタクリル酸メチル共重合体の
代わりに、エチレン−アクリル酸エチル共重合体（ＭＦ
Ｒ・７ｇ／１０ｍｉｎ 、アクリル酸エチル含有量＝１
８重量％）を用いて実施例−１と同一の条件で調整した
混練組成物について物性を測定した。Example-2 Instead of the ethylene-methyl methacrylate copolymer of Example-1, ethylene-ethyl acrylate copolymer (MF
R・7g/10min, ethyl acrylate content=1
The physical properties of a kneaded composition prepared under the same conditions as in Example-1 using 8% by weight) were measured.
比較例−２
珪素原子１個あたり０．１２モル％のビニル基を含むポ
リジオルガノシロキサンを用いた以外は実施例−２と同
様に調整した混練組成物について物性を測定した。第２
表にその結果を示した。Comparative Example-2 Physical properties were measured for a kneaded composition prepared in the same manner as in Example-2 except that polydiorganosiloxane containing 0.12 mol % of vinyl groups per silicon atom was used. Second
The results are shown in the table.
第２表
実施例−３
実施例−１と同−試料及び同一組成のポリジオルガノシ
ロキサンとエチレン−メタクリル酸メチル共重合体を、
混線温度２５０℃にした以外は実施例−１と同様に調整
した混練組成物について物性を測定した。 第３表にそ
の結果を示した。Table 2 Example-3 Same sample as Example-1 and polydiorganosiloxane and ethylene-methyl methacrylate copolymer of the same composition,
Physical properties were measured for a kneaded composition prepared in the same manner as in Example-1 except that the mixing wire temperature was 250°C. The results are shown in Table 3.
比較例−３
実施例−３のエチレン−メタクリル酸メチル共重合体の
代わりに、エチレン−酢酸ビニール共重合体（ＭＦＲ＝
７ ｇ／１０ｍｉｎ 、酢酸ビニール含有量＝１０重
量％）を用いて実施例−３と同一条件で調整した混練組
成物について物性を測定した。Comparative Example-3 Instead of the ethylene-methyl methacrylate copolymer of Example-3, ethylene-vinyl acetate copolymer (MFR=
7 g/10 min, vinyl acetate content = 10% by weight) under the same conditions as in Example 3. The physical properties of the kneaded composition were measured.
第３表にその結果を示した。The results are shown in Table 3.
第３表
実施例−４
実施例−１と同−試料及び同一組成のポリジオルガノシ
ロキサンとエチレン−メタクリル酸メチル共重合体を、
混練温度３００℃にした以外は実施例−１と同様に調整
した混練組成物について物性を測定した。 第３表にそ
の結果を示した。Table 3 Example-4 Same sample as Example-1 and polydiorganosiloxane and ethylene-methyl methacrylate copolymer of the same composition,
The physical properties of a kneaded composition prepared in the same manner as in Example-1 except that the kneading temperature was 300°C were measured. The results are shown in Table 3.
比較例−４
実施例−４のエチレン−メタクリル酸メチル共重合体の
代わりに、エチレン−酢酸ビニール共重合体（ＭＦＲ＝
７ ｇ／１０ｍｉｎ 、酢酸ビニール含有量＝１０重
量％）を用いて実施例−４と同一条件で調整した混練組
成物について物性を測定した。Comparative Example-4 Instead of the ethylene-methyl methacrylate copolymer of Example-4, ethylene-vinyl acetate copolymer (MFR=
7 g/10 min, vinyl acetate content = 10% by weight) under the same conditions as in Example 4. The physical properties of the kneaded composition were measured.
第４表にその結果を示した。Table 4 shows the results.
第４表
〈発明の効果〉
本発明による樹脂組成物によって混練時の熱安定性が著
しく改善された。又、当該組成物の加工時の熱安定性も
著しく改善された。Table 4 (Effects of the Invention) The resin composition according to the invention significantly improved thermal stability during kneading. The thermal stability of the composition during processing was also significantly improved.
Claims (3)
と１００重量部のエチレン−（メタ）アクリル酸エステ
ル共重合体との混練物であって、還流キシレン中で不溶
である物質が混練物合計の少なくとも１０重量％含有す
ることを特徴とする樹脂組成物。(1) A kneaded product of 10 to 175 parts by weight of polydiorganosiloxane and 100 parts by weight of an ethylene-(meth)acrylic acid ester copolymer, in which a substance insoluble in refluxing xylene is at least A resin composition characterized by containing 10% by weight.
り大きいウイリアムス可塑度をもつトルエン可溶ガムで
あり、珪素原子１個あたりの有機基の比が約２であって
、その際それら有機基はメチル基、フェニル基、ビニル
基及びアリル基から選ばれ、０．２〜１７モル％までの
ケイ素原子はビニル基又はアリル基をもち、かつフェニ
ル基は有機基の５０％以下で存在する請求項１に記載の
樹脂組成物。(2) the polydiorganosiloxane is a toluene soluble gum with a Williams plasticity greater than 0.020 inches, and the ratio of organic groups per silicon atom is about 2, where the organic groups are methyl groups; , phenyl group, vinyl group and allyl group, 0.2 to 17 mol% of the silicon atoms have a vinyl group or allyl group, and the phenyl group is present in not more than 50% of the organic groups. The resin composition described.
はコモノマー含有率が５〜４０重量％、メルトフローレ
ートが０．１〜１００ｇ／１０ｍｉｎである請求項１に
記載の樹脂組成物。(3) The resin composition according to claim 1, wherein the ethylene-(meth)acrylic acid ester copolymer has a comonomer content of 5 to 40% by weight and a melt flow rate of 0.1 to 100 g/10 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63057733A JP2585051B2 (en) | 1988-03-10 | 1988-03-10 | Resin composition and additive for resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63057733A JP2585051B2 (en) | 1988-03-10 | 1988-03-10 | Resin composition and additive for resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01230652A true JPH01230652A (en) | 1989-09-14 |
| JP2585051B2 JP2585051B2 (en) | 1997-02-26 |
Family
ID=13064119
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63057733A Expired - Lifetime JP2585051B2 (en) | 1988-03-10 | 1988-03-10 | Resin composition and additive for resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2585051B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0321612A (en) * | 1989-06-19 | 1991-01-30 | Nippon Unicar Co Ltd | Formable kneaded resin mixture |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57195757A (en) * | 1981-05-29 | 1982-12-01 | Shin Etsu Chem Co Ltd | Rubber composition |
| JPS6198755A (en) * | 1984-10-22 | 1986-05-17 | Japan Synthetic Rubber Co Ltd | Rubber composition |
| JPS61188439A (en) * | 1985-02-18 | 1986-08-22 | Shin Etsu Chem Co Ltd | Rubber composition |
| JPS61195162A (en) * | 1985-02-26 | 1986-08-29 | Bridgestone Corp | Flexible article |
-
1988
- 1988-03-10 JP JP63057733A patent/JP2585051B2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57195757A (en) * | 1981-05-29 | 1982-12-01 | Shin Etsu Chem Co Ltd | Rubber composition |
| JPS6198755A (en) * | 1984-10-22 | 1986-05-17 | Japan Synthetic Rubber Co Ltd | Rubber composition |
| JPS61188439A (en) * | 1985-02-18 | 1986-08-22 | Shin Etsu Chem Co Ltd | Rubber composition |
| JPS61195162A (en) * | 1985-02-26 | 1986-08-29 | Bridgestone Corp | Flexible article |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0321612A (en) * | 1989-06-19 | 1991-01-30 | Nippon Unicar Co Ltd | Formable kneaded resin mixture |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2585051B2 (en) | 1997-02-26 |
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