JPH01284550A - Composite resin composition - Google Patents
Composite resin compositionInfo
- Publication number
- JPH01284550A JPH01284550A JP11609188A JP11609188A JPH01284550A JP H01284550 A JPH01284550 A JP H01284550A JP 11609188 A JP11609188 A JP 11609188A JP 11609188 A JP11609188 A JP 11609188A JP H01284550 A JPH01284550 A JP H01284550A
- Authority
- JP
- Japan
- Prior art keywords
- polyurethane
- resin composition
- chlorine
- composite resin
- acid
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 15
- 239000000805 composite resin Substances 0.000 title claims abstract description 7
- 239000004814 polyurethane Substances 0.000 claims abstract description 29
- 229920002635 polyurethane Polymers 0.000 claims abstract description 29
- 239000011347 resin Substances 0.000 claims abstract description 13
- 229920005989 resin Polymers 0.000 claims abstract description 13
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 8
- SDQROPCSKIYYAV-UHFFFAOYSA-N 2-methyloctane-1,8-diol Chemical compound OCC(C)CCCCCCO SDQROPCSKIYYAV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000002009 diols Chemical class 0.000 claims abstract description 4
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 4
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000460 chlorine Substances 0.000 claims description 14
- 229910052801 chlorine Inorganic materials 0.000 claims description 14
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 abstract description 10
- 239000004014 plasticizer Substances 0.000 abstract description 6
- 239000001361 adipic acid Substances 0.000 abstract description 5
- 235000011037 adipic acid Nutrition 0.000 abstract description 5
- -1 adipic acid) Chemical compound 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 239000003381 stabilizer Substances 0.000 abstract description 3
- 239000003086 colorant Substances 0.000 abstract description 2
- 239000000945 filler Substances 0.000 abstract description 2
- 239000000314 lubricant Substances 0.000 abstract description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 abstract 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920005862 polyol Polymers 0.000 description 6
- 150000003077 polyols Chemical class 0.000 description 6
- 239000004800 polyvinyl chloride Substances 0.000 description 6
- 229920000915 polyvinyl chloride Polymers 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- HGAZMNJKRQFZKS-UHFFFAOYSA-N chloroethene;ethenyl acetate Chemical compound ClC=C.CC(=O)OC=C HGAZMNJKRQFZKS-UHFFFAOYSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N trans-stilbene Chemical group C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000010618 wire wrap Methods 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 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
本発明はポリウレタンと塩素含有樹脂とからなる複合樹
脂組成物に関する3゜
従来の技術
従来、ポリ塩化ビニル(以下、塩ビと略記することもあ
る)で代表さrLる塩素含有樹脂の可塑剤としてはンタ
ル酸エステル等の低分子エステル、ボリフ゛テレンア、
ンペートボリオールまたはポリへキプメナレンアジベー
トと有機ポリインシアネートからのポリウレタン等が挙
げられるが、最も広く用いられているのはジオクチルフ
タレートを始めとするフタル酸エステル誘導体である。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a composite resin composition comprising polyurethane and a chlorine-containing resin. Typical plasticizers for chlorine-containing resins include low-molecular esters such as talic acid esters, boroplasticizers,
Examples include polyurethanes made from polyester polyol or polyhecypmenalene adipate and organic polyinsyanate, but the most widely used are phthalic acid ester derivatives such as dioctyl phthalate.
これらのンタル酸エステルは曖れた可塑化性能を有して
いる反面、抽出性、移行性等が大きくガソリン、オイル
またはその他の有機薬品によ如容易に抽出される。その
ため従来からも前記ポリウレタンをポリ塩化ビニルとブ
レンドしたシ捷たは共重合したりIノで、上i己のよう
な容易な抽出、移行を伴なう塩ビrIf塑剤を使用しな
いで十分軟質のポリ環化ビニル組成物が得らノ1.るこ
とか知られている。Although these tantalic acid esters have vague plasticizing properties, they have high extractability, migration properties, etc., and are easily extracted by gasoline, oil, or other organic chemicals. Therefore, conventionally, polyurethane is blended or copolymerized with polyvinyl chloride. A polycyclized vinyl composition of No.1 is obtained. It is known that
発明が解決しよ′ する課題
上記小す9レクンを塩ビの可塑剤として用いた場合、該
ポリワレクンはその可塑化能が丑だ十分でなく、軟質塩
ビ組成物を得るにはかなり多量のポリウレタンを使用す
るかあるいはその他の低分子可塑剤と併用するかし7.
とければならなかった。Problems to be Solved by the Invention When the above-mentioned polyurethane is used as a plasticizer for PVC, the plasticizing ability of the polyurethane is insufficient, and a considerably large amount of polyurethane is required to obtain a soft PVC composition. 7. Use or combination with other low molecular weight plasticizers.
I had to get over it.
さらに可塑剤として使用さルるポリウレタンの耐加水分
解性が劣るため、その複合樹脂組成物の性能の経時変化
があシ好ましくなかった。Furthermore, since the polyurethane used as a plasticizer has poor hydrolysis resistance, the performance of the composite resin composition tends to change over time, which is undesirable.
また、上記のポリウレタンを含有するポリ塩化ビニル組
成物は低温雰囲気下での柔軟性(以下、低温柔軟性と記
す)において十分満足しえたものでなかった。Further, the polyvinyl chloride composition containing the above-mentioned polyurethane was not sufficiently satisfactory in flexibility under a low temperature atmosphere (hereinafter referred to as low temperature flexibility).
本発明の目的は従来見られなかった様な優t′Lfc可
塑化能を有する特殊なポリウレタンと塩ビとの複合によ
シ抽出性、移行性が無く長期にわたシ優れた未軟性を有
する成員熱可塑性樹脂組成物を提供することにある。The purpose of the present invention is to create a composite of a special polyurethane with excellent t'Lfc plasticizing ability, which has never been seen before, and vinyl chloride. An object of the present invention is to provide a thermoplastic resin composition.
課題を解決するための手段
本発明によれば上記目的は塩素含有樹脂およびHa
分子内に一〇CH2C)I(CH2)60−基を有する
ボ11ウレタンからなる組成物により達成される。Means for Solving the Problems According to the present invention, the above objects are achieved by a composition comprising a chlorine-containing resin and a polyurethane having 10CH2C)I(CH2)60- groups in the Ha molecule.
本発明において用いられるポリウレタンは上記の基を含
む平均分子11000〜10000のポリエステルポリ
オールと有機ポリインシアナートとを反応はぜることに
よシ製造される。該ポリウレタンは必要により鎖伸長剤
等を併用することは自由である。The polyurethane used in the present invention is produced by reacting a polyester polyol containing the above groups and having an average molecular weight of 11,000 to 10,000 with an organic polyincyanate. The polyurethane may be used in combination with a chain extender, if necessary.
C1]3
?
分子内に一0CR2CH(CH2)60−基を有する平
均分子111000〜10000のポリオールとは具体
的には2−メチル−1,8−オクタンジオールまたはこ
れを含有する低分子ポリオールとアジピン酸、コハク酸
、グルタル酸、ピメリン酸、セパチン酸、アゼフィン酸
、テレフタル酸、インフタル酸、マレイン酸、フタール
酸等のジカルボン酸よシ合成されるポリエステルポリオ
ールである。C1]3? Specifically, the polyol having an average molecular weight of 111,000 to 10,000 and having 10CR2CH(CH2)60- group in the molecule is 2-methyl-1,8-octanediol or a low-molecular polyol containing it, adipic acid, and succinic acid. It is a polyester polyol synthesized from dicarboxylic acids such as , glutaric acid, pimelic acid, sepacic acid, azefinic acid, terephthalic acid, inphthalic acid, maleic acid, and phthalic acid.
2−メチル−1,8−オクタンジオールと併用すること
のできる低分子ポリオールとしては、1,6−ヘキサン
ンオール、2−)fルー1.3−7’ロバンジオール、
1,4−ブタンジオール、3−メチル−1,5−ベンタ
ンジオール、1.9−ノナンジオール等が好−ましい。Examples of low-molecular polyols that can be used in combination with 2-methyl-1,8-octanediol include 1,6-hexaneol, 2-)f-1,3-7'lovandiol,
1,4-butanediol, 3-methyl-1,5-bentanediol, 1,9-nonanediol and the like are preferred.
本発明において、ポリエステルポリオールの合成に用い
られる低分子ポリオール中に2−メチル−1,8−オク
タンジオールを多量に用いるのが好ましい。一般に低分
子ポリオール9之0
上用いるのがよい。上記ポリエステルポリオールは通常
ポリウレタンの製造に用いられ他のポリオールを併用す
ることもできる。In the present invention, it is preferable to use a large amount of 2-methyl-1,8-octanediol in the low-molecular-weight polyol used to synthesize the polyester polyol. Generally, it is preferable to use a low molecular weight polyol. The above-mentioned polyester polyol is usually used in the production of polyurethane, and other polyols can also be used in combination.
本発明で使用される有機ポリイソシアナートとしては、
例えばジフェニルメタンジイソシアナート、2. 4
− )リレンジイソシアナート、2. 6 − )リレ
ンジイソシアナート、フェニレンジインシアナート、1
,5−ナフチレンジイソシアナート、3。The organic polyisocyanate used in the present invention includes:
For example diphenylmethane diisocyanate, 2. 4
-) lylene diisocyanate, 2. 6-) lylene diisocyanate, phenylene diisocyanate, 1
, 5-naphthylene diisocyanate, 3.
3′−ジクロロ−4,4′−ジフェニルメタンジイソシ
アナート、キシリレンジインシアナート、トルイレンジ
インシアナート等の芳香族ジインシアナートや、ヘキサ
メチレンジインシアナート、インホロンジイソシアナー
ト、4.4’−ジシクロヘキシルメタンジインシアナー
ト、水添化キシリレンジイソシアナート等の脂肪族また
は脂環族ジイソシアナートが挙げられる。好ましいジイ
ンシアナートは脂肪族または脂環族ジインシアナートで
あシ、特に好ましいのはへキシリレンジインシアナート
、4.4’−ジシクロヘキシルメタンジインシアナート
である。これらの2インシアナートは単独で用いても、
また混合して用いてもよい。Aromatic diincyanates such as 3'-dichloro-4,4'-diphenylmethane diisocyanate, xylylene diinocyanate, toluylene diinocyanate, hexamethylene diinocyanate, inphorone diisocyanate, 4.4'- Examples include aliphatic or alicyclic diisocyanates such as dicyclohexylmethane diisocyanate and hydrogenated xylylene diisocyanate. Preferred diincyanates are aliphatic or cycloaliphatic diincyanates, particularly preferred are hexylylene diincyanate and 4,4'-dicyclohexylmethane diincyanate. Even if these two incyanates are used alone,
Alternatively, they may be used in combination.
塩素含有樹脂とポリウレタンとの複合樹脂組成物を製造
する方法としては
(1)熱可塑性ポリウレタンと塩素含有樹脂をいわゆる
ポリマーブレンドという手法によシボリマー同志を押出
機ロール等の混合装置を使用して混合、分散させる方法
による
(2)塩素含有ビニル七ツマ−に可溶な熱可塑性ポリウ
レタンを塩化とニルモノマーに溶解し、次で塩素含有ビ
ニルモノマーをラジカル重合させる方法
(8) 粉末状の塩素含有樹脂を攪拌下にポリウレタ
ンの原料となるポリエステルポリオールt−含浸させ、
これにポリイソシアナートを添加し塩素含有樹脂中でポ
リウレタンを生成せしめる方法
(4) 塩素含有樹脂エマルジョンとポリウレタンエマ
ルジョンの混合エマルジョンよりlA造する方法
等が挙げられる。The method for producing a composite resin composition of chlorine-containing resin and polyurethane is as follows: (1) thermoplastic polyurethane and chlorine-containing resin are mixed together using a mixing device such as an extruder roll, using a method called polymer blending. (2) A method in which a thermoplastic polyurethane soluble in a chlorine-containing vinyl monomer is dissolved in a chlorine-containing monomer, and then the chlorine-containing vinyl monomer is subjected to radical polymerization (8) A method in which a powdered chlorine-containing resin is Impregnated with polyester polyol, which is a raw material for polyurethane, while stirring,
Method (4) of adding polyisocyanate to this to produce polyurethane in a chlorine-containing resin. Examples include a method of producing 1A from a mixed emulsion of a chlorine-containing resin emulsion and a polyurethane emulsion.
本発明では塩素含有樹脂成分100重量部に対しウレタ
ン成分が10〜200重量部である。In the present invention, the urethane component is 10 to 200 parts by weight per 100 parts by weight of the chlorine-containing resin component.
なお本発明で使用する塩素含有樹脂とは好ましくは塩化
ビニル含有重合体で重合度600以上のポリ塩化ビニル
単独重合体もしくは塩化ビニルを主成分とする共重合体
、例えば塩化ビニル−酢酸ビニル重合体、塩化ビニル−
エチレン酢酸ビニル(EVA)共重合体などを挙げるこ
とができる。The chlorine-containing resin used in the present invention is preferably a vinyl chloride-containing polymer with a degree of polymerization of 600 or more, such as a polyvinyl chloride homopolymer or a copolymer mainly composed of vinyl chloride, such as a vinyl chloride-vinyl acetate polymer. , vinyl chloride
Examples include ethylene vinyl acetate (EVA) copolymer.
本発明の複合回脂の製造においで予め安定剤、滑剤、充
填剤、可塑剤、着色剤等を配合しておくことができる。In the production of the composite relipid of the present invention, stabilizers, lubricants, fillers, plasticizers, colorants, etc. can be added in advance.
本発明組成物は熱可塑性ポリウレタンの強靭性、耐摩耗
性、耐溶剤性等の緒特性及び塩化ビニル重合体の耐候性
、易成形加工性などの両特性を兼備すると共にすぐnた
反発弾性と透明性を有するものであるから、フィルム、
シート、レザー、チュ一ブ、ホース、ラップフィルム、
バッキング、電線被榎、おもちや、接着剤、コーティン
グ剤、バインダー、塗料前のきわめて広汎な利用分野を
有する。The composition of the present invention has both the toughness, abrasion resistance, and solvent resistance of a thermoplastic polyurethane, and the weather resistance and easy moldability of a vinyl chloride polymer, as well as excellent impact resilience. Because it has transparency, film,
Seats, leather, tubes, hoses, wrap films,
It has an extremely wide range of applications including backing, wire wrapping, toys, adhesives, coatings, binders, and paints.
実施例 以下、実施例によシ本発明をさらに具体的に説明する。Example Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例および比較例中の部は重量部を示す。実施例およ
び比較例中の各物性は次の試験法によシ測定した。その
結果を表1にまとめた。Parts in Examples and Comparative Examples indicate parts by weight. Each physical property in Examples and Comparative Examples was measured by the following test method. The results are summarized in Table 1.
試験方法;
(1)低温柔軟性
厚さ0.4咽の試験片をつくり東洋側器■製直胱式動的
粘弾性測定器パイブロンModeLDD V −II
(IIOH2)によるTαを6川定する。1hが小さい
ほど低温柔軟性に優れる。。Test method: (1) A test piece with a low temperature flexibility thickness of 0.4 mm was prepared using a direct bladder type dynamic viscoelasticity measuring device Pybron ModeLDD V-II manufactured by Toyo Saiki.
Determine Tα due to (IIOH2) in six rivers. The smaller 1h is, the better the low-temperature flexibility is. .
(2) 柔軟性の経時変化率
成形11−1後、JISK−6の引張り試験法に準じて
引張シ速さを5 Q mm 7分としプζ場合の20%
モジュラスを測足し、該モジュラスをA、成型後60日
経過した時の20%モジュ=8−
ラスをAsoとし次式によシ経時変化率を求め/ヒ。(2) Change rate of flexibility over time After molding 11-1, the tensile speed was set to 5 Q mm 7 minutes and 20% of that of ζ according to JISK-6 tensile test method.
The modulus is measured, the modulus is A, the 20% modulus when 60 days have passed after molding = 8-, and the rate of change over time is calculated using the following formula.
経時変化4.(チ) =((A60−At)/At )
XIUO実施例1
2−メチル−1,8−オクタンジオールと1,9−ノナ
ンジオール(8/2)の混合ジオールとアジピン酸から
の平均分子13000のポリエステルグリコールにヘキ
サメチレンジインシアナー)1.1モルを攪拌下に加え
、高速攪拌のの5140℃の乾燥機中のズットの上へ広
げ30分間反応し反応を完結した。このポリウレタン1
00部に重合度1.000の粉末状ポリ塩化ビニル10
0部を混ぜてのち150℃で10分間混練した後、所定
厚さのシートにプレスした。Change over time 4. (ch) = ((A60-At)/At)
XIUO Example 1 Polyester glycol with an average molecular weight of 13000 from a mixed diol of 2-methyl-1,8-octanediol and 1,9-nonanediol (8/2) and adipic acid (hexamethylene diyne cyanur) 1.1 mol was added under stirring, spread on top of a suttle in a dryer at 5140° C. under high speed stirring, and reacted for 30 minutes to complete the reaction. This polyurethane 1
00 parts to 10 parts of powdered polyvinyl chloride with a degree of polymerization of 1.000
After mixing 0 parts, the mixture was kneaded at 150°C for 10 minutes, and then pressed into a sheet of a predetermined thickness.
実施例2
分子1t3000のポリ(β−メチル−δ−バレロラク
トン)グリコール0.1モルと2−メチル−1゜8−オ
クタンジオールとアジピン酸から得られる分子1300
0のポリエステルグリコール0.9モルの混合グリコー
ルにヘキサメチレンゾインンアナ− ) 1.05モル
を加えて高速攪拌ののち140℃の乾燥器のバットの中
にひろげ30分間反応を行ない、−40℃に冷却後粉砕
した。このポリウレタン100部、塩化ビニルモノマー
100部、水300部、α、α′−アゾビスインブチロ
ニトリル0.3部、ポリビニルアルコール0.5部をオ
ートクレーブに仕込み室温で3時間攪拌しポリウレタン
を溶解後、次いで60℃で10時間重合した。得られた
懸濁状の生成物を減圧F140℃で乾燥しパウダーを得
た。これにステアリン酸カルンウム、ステアリン酸亜鉛
の安定剤を加えたのちロール上で5分間混練し、シート
状に成形した。Example 2 Molecules 1t3000 molecules obtained from 0.1 mol of poly(β-methyl-δ-valerolactone) glycol, 2-methyl-1°8-octanediol and adipic acid
1.05 mol of hexamethylenezoin analyte (1.05 mol) was added to 0.9 mol of mixed glycol of 0.0 polyester glycol, and after stirring at high speed, it was spread in a vat of a dryer at 140°C and reacted for 30 minutes. After cooling to ℃, it was crushed. 100 parts of this polyurethane, 100 parts of vinyl chloride monomer, 300 parts of water, 0.3 part of α, α'-azobisin butyronitrile, and 0.5 part of polyvinyl alcohol were placed in an autoclave and stirred at room temperature for 3 hours to dissolve the polyurethane. After that, polymerization was carried out at 60° C. for 10 hours. The obtained suspended product was dried at reduced pressure F140°C to obtain a powder. After adding stabilizers such as carunium stearate and zinc stearate, the mixture was kneaded for 5 minutes on a roll and formed into a sheet.
比較例1
実施例1におけるポリウレタンのソフトセグメントだけ
を1,6−ヘキサンジオールとアジピン酸からの分子f
f14= 3000のポリエステルグリコールに変え、
その他は実施例1と同様にしてシートを作成し、た。Comparative Example 1 Only the soft segment of the polyurethane in Example 1 was replaced with a molecule f from 1,6-hexanediol and adipic acid.
Change to f14 = 3000 polyester glycol,
A sheet was produced in the same manner as in Example 1 in other respects.
比較例2
実施例2におけるポリウレタンの71フトセグメントだ
けを分子′ik3000のポリカプロラクトングリコー
ルに変え、その他は実施例2と同様にしてシートを作成
した。Comparative Example 2 A sheet was prepared in the same manner as in Example 2, except that only the 71 foot segment of the polyurethane in Example 2 was replaced with polycaprolactone glycol having a molecule of 3000 ik.
表 1
発明の効果
本発明のポリ塩化ビニル−ポリウレタン複合樹脂組成物
は、低温柔軟性に優れ、かつ耐加水分解性に優れるので
長期間にわたシ優れた柔軟性を有する。Table 1 Effects of the Invention The polyvinyl chloride-polyurethane composite resin composition of the present invention has excellent low-temperature flexibility and hydrolysis resistance, so it has excellent flexibility over a long period of time.
特Wト出願人 株式会社 り ラ しSpecial W applicant: RiRashi Co., Ltd.
Claims (2)
等があります▼ 基を有するポリウレタンからなる複合樹脂組成物。(1) A composite resin composition consisting of a chlorine-containing resin and polyurethane with ▲ mathematical formulas, chemical formulas, tables, etc. in the molecule.
オールを単独または該ジオールを20モル%以上含有す
る混合ジオールとジカルボン酸から得られた平均分子量
1000〜10000のポリエステルポリオールと有機
ポリイソシアナートを反応させることにより得られたポ
リウレタンである特許請求の範囲第1項記載の組成物。(2) The polyurethane contains 2-methyl-1,8-octanediol alone or a mixed diol containing 20 mol% or more of the diol and a polyester polyol with an average molecular weight of 1000 to 10000 obtained from dicarboxylic acid and an organic polyisocyanate. The composition according to claim 1, which is a polyurethane obtained by reacting.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11609188A JPH01284550A (en) | 1988-05-12 | 1988-05-12 | Composite resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11609188A JPH01284550A (en) | 1988-05-12 | 1988-05-12 | Composite resin composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH01284550A true JPH01284550A (en) | 1989-11-15 |
Family
ID=14678488
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP11609188A Pending JPH01284550A (en) | 1988-05-12 | 1988-05-12 | Composite resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH01284550A (en) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6222817A (en) * | 1985-07-23 | 1987-01-31 | Kuraray Co Ltd | Production of polyurethane |
JPS6264861A (en) * | 1985-09-17 | 1987-03-23 | Kuraray Co Ltd | Polyvinylchloride-polyurethane composite resin composition |
-
1988
- 1988-05-12 JP JP11609188A patent/JPH01284550A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6222817A (en) * | 1985-07-23 | 1987-01-31 | Kuraray Co Ltd | Production of polyurethane |
JPS6264861A (en) * | 1985-09-17 | 1987-03-23 | Kuraray Co Ltd | Polyvinylchloride-polyurethane composite resin composition |
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