JPS63304051A - Polyurethane polymer composition - Google Patents
Polyurethane polymer compositionInfo
- Publication number
- JPS63304051A JPS63304051A JP13940087A JP13940087A JPS63304051A JP S63304051 A JPS63304051 A JP S63304051A JP 13940087 A JP13940087 A JP 13940087A JP 13940087 A JP13940087 A JP 13940087A JP S63304051 A JPS63304051 A JP S63304051A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- carbonate
- comparative example
- polyurethane resin
- oxide
- 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
- 229920002635 polyurethane Polymers 0.000 title abstract description 10
- 239000004814 polyurethane Substances 0.000 title abstract description 10
- 229920000642 polymer Polymers 0.000 title abstract description 6
- 239000000203 mixture Substances 0.000 title abstract 3
- 239000003063 flame retardant Substances 0.000 claims abstract description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 9
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 7
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 7
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 150000002367 halogens Chemical class 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 229920005749 polyurethane resin Polymers 0.000 claims description 34
- 239000011342 resin composition Substances 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 14
- 229920000728 polyester Polymers 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000292 calcium oxide Substances 0.000 abstract description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 abstract description 3
- 229920005906 polyester polyol Polymers 0.000 abstract description 3
- 230000001588 bifunctional effect Effects 0.000 abstract description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 abstract 1
- OUHCLAKJJGMPSW-UHFFFAOYSA-L magnesium;hydrogen carbonate;hydroxide Chemical compound O.[Mg+2].[O-]C([O-])=O OUHCLAKJJGMPSW-UHFFFAOYSA-L 0.000 abstract 1
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 36
- 229920005862 polyol Polymers 0.000 description 13
- 150000003077 polyols Chemical class 0.000 description 13
- -1 phosphate ester Chemical class 0.000 description 11
- 238000000034 method Methods 0.000 description 8
- 125000005442 diisocyanate group Chemical group 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 229920001610 polycaprolactone Polymers 0.000 description 5
- 239000004632 polycaprolactone Substances 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 2
- UGQQAJOWXNCOPY-AOHCVTONSA-N (1R,2R,5S,6S,9S,10R,13S,14S)-1,6,7,8,9,14,15,16,17,17,18,18-dodecachloropentacyclo[12.2.1.16,9.02,13.05,10]octadeca-7,15-diene Chemical compound ClC1=C(Cl)[C@@]2(Cl)[C@@H]3CC[C@H]4[C@@H](CC[C@@H]3[C@@]1(Cl)C2(Cl)Cl)[C@@]1(Cl)C(Cl)=C(Cl)[C@]4(Cl)C1(Cl)Cl UGQQAJOWXNCOPY-AOHCVTONSA-N 0.000 description 1
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920000562 Poly(ethylene adipate) Polymers 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000921 polyethylene adipate Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- LUVCTYHBTXSAMX-UHFFFAOYSA-N tris(2-chloroethyl) phosphite Chemical compound ClCCOP(OCCCl)OCCCl LUVCTYHBTXSAMX-UHFFFAOYSA-N 0.000 description 1
- XAOIGBAYYHYZQA-UHFFFAOYSA-N tris(2-chloroethyl)phosphane Chemical compound ClCCP(CCCl)CCCl XAOIGBAYYHYZQA-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
Abstract
Description
【発明の詳細な説明】
（技術分野）
本発明は耐水性に優れたポリエステル系ポリウレタン樹
脂組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Technical Field) The present invention relates to a polyester polyurethane resin composition having excellent water resistance.
（従来技術の問題点）
ポリウレタンとは、ポリエステルジオール又はポリエス
テルジオールなどのポリオールに、ジイソシアネート等
とを反応させて得られるポリマーで、ゴムとプラスチッ
クとの両特性を兼備したものであり、チーープ、電線被
覆、シートの他、数多くの製品に使用されている。そし
て得られた製品の耐熱性、耐水性、耐油性といった特性
については、ポリウレタンを構成するポリオール成分に
よって定まる事が知られておシ、例えば、ポリエステル
系ポリウレタンは、主鎖のエステル基が加水分解を受は
易い事から、耐水性に劣るというものであった。(Problems with the prior art) Polyurethane is a polymer obtained by reacting polyester diol or a polyol such as polyester diol with diisocyanate, etc. It has the characteristics of both rubber and plastic, and it is used for cheap and electric wires. In addition to coatings and sheets, it is used in many other products. It is known that the properties such as heat resistance, water resistance, and oil resistance of the resulting product are determined by the polyol components that make up the polyurethane.For example, in polyester polyurethane, the ester groups in the main chain are hydrolyzed. It was said that the water resistance was poor because it was easily susceptible to water damage.
又、近年防災的見地から難燃化が要求され、前記ポリウ
レタンにハロゲン系難燃剤（例えば、ハロゲン含有リン
酸エステル系難燃剤）を配合して利用するが、この場合
には難燃剤が分解して生ずるハロゲン化水素（例えばＨ
Ｃ；ｔ ）によって加水分解が加速され、耐水性はより
悪化する。In recent years, flame retardancy has been required from a disaster prevention perspective, and halogen-based flame retardants (for example, halogen-containing phosphate ester flame retardants) are blended with the polyurethane, but in this case the flame retardant decomposes. Hydrogen halides (e.g. H
C; t) accelerates hydrolysis and further deteriorates water resistance.
（発明の構成）
本発明は、ポリエステル系ポリウレタン樹脂即ちエステ
ル結合を有するポリウレタン樹脂の耐水性を改良する為
に種々検討を行った結果、ブルカリ土金属の炭酸塩もし
くは酸化物を配合することによって組成物の耐水性が大
巾に改善出来る事を見い出した。(Structure of the Invention) As a result of various studies conducted to improve the water resistance of polyester-based polyurethane resins, that is, polyurethane resins having ester bonds, the present invention was developed by incorporating carbonates or oxides of burkari earth metal. We have discovered that the water resistance of objects can be greatly improved.
即ち、本発明は
エステル結合を有するポリウレタン樹脂を５０重量％以
上配合した樹脂組成物において、前記、ポリウレタン樹
脂１００重量部に対して、アルカリ土金属の酸化物、も
しくは炭酸塩またはこれらを含有した化合物が０．０１
〜１！ｌＯ重量部の割合で配合したことを特徴とするポ
リウレタン樹脂組成物に関するものである。That is, the present invention provides a resin composition containing 50% by weight or more of a polyurethane resin having an ester bond, in which an oxide or carbonate of an alkaline earth metal, or a compound containing these, is added to 100 parts by weight of the polyurethane resin. is 0.01
~1! The present invention relates to a polyurethane resin composition characterized in that it is blended in a proportion of 10 parts by weight.
この発明に於いて用いられるポリウレタン樹脂とは、２
官能ポリエステルポリオールとジインシアネートとを反
応させて得られるものである。即ち、２官能ポリエステ
ルポリオール、例えばポリ（エチレンアジペート）、ポ
リ（Ｌ４−ブチルアジペート）、ポリ（１６−ヘキサン
アジペート）、ポリ−１−カプロラクトン、ポリ（ヘキ
サメチレンカーボネート）などのポリエステルジオール
と鎖延長剤としてのグリコール例えばＬ４−ブチレンク
リコール、Ｌ６−ヘキサンジオール、エチレングリコー
ルなどと、ジイソシアネート、例えばヰ。The polyurethane resin used in this invention is 2
It is obtained by reacting a functional polyester polyol and a diincyanate. That is, bifunctional polyester polyols, such as polyester diols such as poly(ethylene adipate), poly(L4-butyl adipate), poly(16-hexane adipate), poly-1-caprolactone, poly(hexamethylene carbonate), and a chain extender. glycols such as L4-butylene glycol, L6-hexanediol, ethylene glycol, etc. and diisocyanates such as diisocyanates.
１１′−ジフェニルメタンジイソシアネート、４．４’
−ジシクロヘキシルメタンジイソ７アネート、イソホロ
ンジイソシアネートなどとを反応させて、上記ポリオー
ルとジイソシアネートからなるソフトブロックと、グリ
コールとジイソシアネートにより構成されるハードブロ
ックにより組立てて得られるポリマーであシ熱可塑性を
有するものである。11'-diphenylmethane diisocyanate, 4.4'
- A thermoplastic polymer obtained by reacting dicyclohexylmethane diiso7anate, isophorone diisocyanate, etc. and assembling a soft block consisting of the above polyol and diisocyanate and a hard block consisting of glycol and diisocyanate. It is.
又、該ポリエステル系ポリウレタン樹脂に対して相溶性
があり、物理的にブレンド可能な他のポリマー、例えば
、ポリエーテル系ポリウレタン樹脂、エチレン−酢酸ビ
ニル共重合体、ポリエチレン樹脂、アクリロニトリル−
ブタジェン−スチレン共重合体、ナイロン、塩化ビニル
、などを適量混合して用いる場合にも適する。In addition, other polymers that are compatible with and physically blendable with the polyester polyurethane resin, such as polyether polyurethane resin, ethylene-vinyl acetate copolymer, polyethylene resin, acrylonitrile-
It is also suitable for mixing appropriate amounts of butadiene-styrene copolymer, nylon, vinyl chloride, etc.
そして、上述したポリマーブレンドにおいては、該ポリ
エステル系ポリウレタン樹脂が５０重量パーセント以上
の場合に、その効果が発揮される。In the above-mentioned polymer blend, the effect is exhibited when the content of the polyester-based polyurethane resin is 50% by weight or more.
次に必要に応じ配合されるハロゲン系難燃剤とシテハ、
トリス（２−クロロエチル）７オスフエート、トリス（
ジクロログロビル）フォスフェートなどの塩素含有リン
酸エステル、トリス（２，５−ジゾ計フロビル）フォス
フェートなどの臭素含有リン酸エステル、又はドデカク
ロロドデカヒドロジメタノジベンゾシクロオクテンなど
の芳香族系臭素化合物、又はデカプロモージフェニルオ
キサイドなどの芳香族系塩素化合物、及びこれらに他の
例えば三酸化アンチモンなどの難燃剤を併用した難燃系
にも適用出来る。そしてこれらの難燃剤は、ウレタン樹
脂１００電食部に対して５〜２０重量部の範囲で添加さ
れるのが一般的であり、これを分散性良く樹脂に配合す
る為には、例えば液状ハロゲン含有リン酸エステル難燃
剤をその合成の段階で添加することが望ましいが、成形
の段階でウレタン樹脂にまぶすか又は粉末状であればマ
スターバッチ化して配合する事も出来る。Next, halogen-based flame retardant and Shiteha are added as necessary.
Tris (2-chloroethyl) 7 phosphate, Tris (
Chlorine-containing phosphate esters such as dichloroglobil) phosphate, bromine-containing phosphate esters such as tris(2,5-dizofurobyl) phosphate, or aromatic systems such as dodecachlorododecahydrodimethanodibenzocyclooctene It can also be applied to flame retardant systems using aromatic chlorine compounds such as bromine compounds or decapromodiphenyl oxide, and other flame retardants such as antimony trioxide. These flame retardants are generally added in an amount of 5 to 20 parts by weight per 100 parts of electrolytically eroded urethane resin. It is desirable to add the phosphoric acid ester flame retardant at the stage of synthesis, but it can also be blended by sprinkling it on the urethane resin at the stage of molding, or by forming it into a master batch if it is in powder form.
この発明において、アルカリ土金属の酸化物、もしくは
炭酸塩とは化学式ＸＯのＸをアルカリ土金属で置き換え
た例えば酸化カルシウム、酸化マグネシウムなどで又炭
酸塩とはＨＣＯ，のＨをアルカリ土金属で置き換えた例
えば炭酸力ルンウム、炭酸バリウム、炭酸マグネシウム
などであり、更にこれらを含んだ化合物としては例えば
ヒドロオキシ炭酸マグネシウムＭｇＣＯ５・Ｍｇ （Ｏ
Ｈ） ｔ・２Ｈ宜０などが挙げられる。In this invention, an oxide or carbonate of an alkaline earth metal refers to a chemical formula XO in which X is replaced with an alkaline earth metal, such as calcium oxide or magnesium oxide, and a carbonate is HCO, in which H is replaced with an alkaline earth metal. Examples include carbonate, barium carbonate, magnesium carbonate, etc. Compounds containing these include, for example, hydroxymagnesium carbonate MgCO5.Mg (O
H) t・2H 0 and the like.
そしてこれらの添加量はポリエステル系ポリウレタン樹
脂１００重量部に対して０．０１〜１５．０重量部が好
ましい。なぜなら０．０１重量部未満であるとその効果
は発揮されないし、１５１重量部以上であると、製品外
観にぶつ、肌荒れが見られる様になって好ましくない。The amount of these additives added is preferably 0.01 to 15.0 parts by weight per 100 parts by weight of the polyester polyurethane resin. This is because if the amount is less than 0.01 parts by weight, the effect will not be exhibited, and if it is more than 151 parts by weight, the appearance of the product will be affected and the skin will become rough, which is not preferable.
そして、これらをポリウレタン樹脂に配合する手段とし
ては、押出機、射出成形機等による成形段階で、該ポリ
ウレタン樹脂にまぶすか、もしくはマスターバッチ化し
て配合する方法、又はポリオール成分とジイソシアネー
ト成分とを反応させポリウレタン樹脂を合成する段階に
て配合する方法等、いずれでも選択する事が出来る。These can be blended into the polyurethane resin by sprinkling them on the polyurethane resin or by blending them into a master batch during the molding step using an extruder, injection molding machine, etc., or by reacting the polyol component with the diisocyanate component. Any method can be selected, such as the method of blending at the stage of synthesizing the polyurethane resin.
特に後者の場合には、ジインシアネート及びジオ−ルと
酸化物及び炭酸基との反応が合成時に進まないよう合成
条件を選定すれば差し支えない。Particularly in the latter case, there is no problem as long as the synthesis conditions are selected so that the reaction between the diincyanate and diol and the oxide and carbonate group does not proceed during the synthesis.
本発明樹脂組成物に対しては、その特性を変えない範囲
で常用される助剤、例えばカーボンブラック、発泡剤、
酸化防止剤、防ばい剤、着色剤などを添加し得る。そし
て、これら助剤は上記のポリオールとジイソシアネート
の合成反応を阻害するものでなければいずれの段階でも
添加して良いが、そのような阻害作用を有するものであ
れば成形時に添加する事が望ましい。For the resin composition of the present invention, commonly used auxiliary agents such as carbon black, blowing agents,
Antioxidants, fungicides, colorants, etc. may be added. These auxiliaries may be added at any stage as long as they do not inhibit the synthesis reaction of the polyol and diisocyanate, but if they have such an inhibiting effect, they are preferably added during molding.
（作 用）
この発明の作用は必ずしも全てを明らかに成し得た訳で
はないが、以下に説明する。(Function) Although not all of the functions of this invention have been achieved clearly, they will be explained below.
ポリエステル系ポリウレタンのエステル結合ヲ有する分
子鎖は以下の様な構造を有し、水による加水分解を生じ
る。The molecular chain having ester bonds in polyester polyurethane has the following structure and is hydrolyzed by water.
分解により生じた脂肪酸は、酸性を有する為、加水分解
の触媒になって更に劣化速度をはやめる。Since fatty acids produced by decomposition have acidity, they act as catalysts for hydrolysis, further slowing down the rate of deterioration.
これに本発明の一例である酸化カルシウム又は炭酸カル
シウムを添加すると、次式で示す反応が進行するものと
考えられる。When calcium oxide or calcium carbonate, which is an example of the present invention, is added to this, the reaction shown by the following formula is considered to proceed.
又ハロゲン系難燃剤を添加したポリウレタンに対しては
難燃剤が分解して発生するノ・ロゲ／化水素この様にア
ルカリ土金属の炭酸塩は、加水分解の触媒作用を有する
脂肪酸、更にはノ・ロゲン化水素を不活性化する働きを
示し、これによって耐水性を向上せしめる事が可能とな
る。In addition, for polyurethane containing halogenated flame retardants, carbonates of alkaline earth metals, which are generated by decomposition of the flame retardant and hydrogen hydride, can be used as a catalyst for fatty acids that have a catalytic effect on hydrolysis.・It shows the function of inactivating hydrogen halogenide, which makes it possible to improve water resistance.
（実施例） 以下実施例によシ、本発明を具体的に説明する。(Example) EXAMPLES The present invention will be specifically explained below with reference to Examples.
比較例Ｌ
ポリエチレンアジペートをポリオール成分としたショア
ーＡ９０のポリウレタン樹脂１００重量％を使用して射
出成形機にて２慎厚のシートを作成した。Comparative Example L A 2-inch thick sheet was produced using an injection molding machine using 100% by weight Shore A90 polyurethane resin containing polyethylene adipate as a polyol component.
そして得られたシートをＪＩＳ ３号ダンベルで打ち
抜き１００℃温水中に浸漬して、経過日数に伴う機械強
度（抗張力と伸び）を測定して絶対伸び５０チに至る日
数を求めた。Then, the obtained sheet was punched out with a JIS No. 3 dumbbell and immersed in hot water at 100° C., and the mechanical strength (tensile strength and elongation) was measured over the elapsed number of days to determine the number of days until the absolute elongation reached 50 inches.
比較例２、
ポリカプロラクトンをポリオール成分としたショアーＡ
９８のポリウレタン樹脂を用いた以外は比較例りと同様
に行なった。Comparative Example 2: Shore A containing polycaprolactone as a polyol component
The same procedure as in Comparative Example was conducted except that No. 98 polyurethane resin was used.
比較例ｊ
ポリカーボネートをポリオール成分としたショアーＡ８
０のポリウレタン樹脂を用いた以外は比較例１と同様に
行った。Comparative example j Shore A8 with polycarbonate as the polyol component
Comparative Example 1 was carried out in the same manner as in Comparative Example 1 except that No. 0 polyurethane resin was used.
比較例ヰ。Comparative example.
ポリカプロラクトン・をポリオール成分としたショアー
Ａ９８のポリウレタン樹脂７５重量パーセントにショア
ーＡ９８のポリエーテル系ポリウレタン樹脂２５重量パ
ーセントを使用した以外は、比較例１と同様に行った。Comparative Example 1 was carried out in the same manner as in Comparative Example 1, except that 25 weight percent of Shore A98 polyether polyurethane resin was used in 75 weight percent of Shore A98 polyurethane resin containing polycaprolactone as the polyol component.
比較例５゜
ポリカプロラクトンをポリオール成分としたショアーＡ
９８のポリウレタン樹脂１１０重ｉ％にショアーＡ９Ｂ
のポリエーテル系ポリウレタン樹脂６０重量％を使用し
た以外は比較例１と同様に行った。Comparative Example 5 Shore A containing polycaprolactone as a polyol component
98 polyurethane resin 110% by weight Shore A9B
Comparative Example 1 was carried out in the same manner as in Comparative Example 1, except that 60% by weight of the polyether polyurethane resin was used.
比較例６゜
ポリカプロラクトンをポリオール成分としたショアーＤ
６１＋のポリウレタン樹脂１００重量部に同様に行った
。Comparative Example 6 Shore D using polycaprolactone as a polyol component
The same procedure was applied to 100 parts by weight of 61+ polyurethane resin.
比較例７゜
ポリカーボネートをポリオール成分としたショアーＡ９
８のポリウレタン樹脂１００重量部にトリス（２−クロ
ロエチル）フォスファイト１０重量部が配合された樹脂
を用いた以外は比較例１と同様に行った。Comparative Example 7 Shore A9 with polycarbonate as the polyol component
Comparative Example 1 was carried out in the same manner as in Comparative Example 1, except that a resin in which 100 parts by weight of the polyurethane resin No. 8 and 10 parts by weight of tris(2-chloroethyl)phosphite was blended was used.
比較例＆
ポリカプロラクトンをポリオール成分としたショアーＤ
６４のポリウレタン樹脂７０ 重ｉＬ％’、！：アクリ
ロエトリルースチレンーブタジエン共重合体５０重量％
から成る樹脂に、トリス（２−クロロエチル）フォスフ
アイ）１０重量部が配合された樹脂を用いた以外は比較
例１と同様に行った。Comparative example & Shore D with polycaprolactone as a polyol component
64 polyurethane resin 70 weight iL%',! : Acryloethryl-styrene-butadiene copolymer 50% by weight
Comparative Example 1 was carried out in the same manner as in Comparative Example 1, except that a resin containing 10 parts by weight of tris(2-chloroethyl) phosphor was used.
以上比較例１〜８の結果を第１表に示す。The results of Comparative Examples 1 to 8 are shown in Table 1.
実施例１〜８
比較例１〜８に記載のポリエステル系ポリウレタン樹脂
１００重量部に対して炭酸カルシウムを１重量部配合し
た以下は比較例１と同様に行った。Examples 1 to 8 The same procedure as in Comparative Example 1 was carried out except that 1 part by weight of calcium carbonate was added to 100 parts by weight of the polyester polyurethane resin described in Comparative Examples 1 to 8.
得られた結果を第゛２表に示す。The results obtained are shown in Table 2.
実施例９
比較例１のポリウレタン樹脂１００重量部に対して酸化
マグネシウムを５重量部配合した以外は比較例１と同様
に行った。得られた結果を第２表に示す。Example 9 The same procedure as in Comparative Example 1 was carried out except that 5 parts by weight of magnesium oxide was added to 100 parts by weight of the polyurethane resin of Comparative Example 1. The results obtained are shown in Table 2.
実施例１０
比較例１のポリウレタン樹脂１００重量部に対して炭酸
カルシウムを１０重量部配合した以外は比較例１と同様
に行った。得られた結果を第２表に示す。Example 10 The same procedure as in Comparative Example 1 was carried out except that 10 parts by weight of calcium carbonate was added to 100 parts by weight of the polyurethane resin of Comparative Example 1. The results obtained are shown in Table 2.
実施例１１
比較例１のポリウレタン樹脂１００重量部に対して炭酸
カルシウムを０．０１重量部を配合した以外は比較例１
と同様に行った。得られた結果を第２表に示す。Example 11 Comparative Example 1 except that 0.01 parts by weight of calcium carbonate was blended with 100 parts by weight of the polyurethane resin of Comparative Example 1.
I did the same thing. The results obtained are shown in Table 2.
比較例９
比較例１のポリウレタン樹脂１００重量部に対して炭酸
カルシウムを１７重量部配合した以外は比較例１と同様
に行った。得られた結果を第２表に示す。Comparative Example 9 The same procedure as Comparative Example 1 was carried out except that 17 parts by weight of calcium carbonate was added to 100 parts by weight of the polyurethane resin of Comparative Example 1. The results obtained are shown in Table 2.
比較例１０
比較例１のポリウレタン樹脂１００重量部に対して炭酸
カルシウムをＯ，ＯＯ５重量部配合した以外は比較例１
と同様に行った。得られた結果を第２表に示す。Comparative Example 10 Comparative Example 1 except that 5 parts by weight of calcium carbonate O, OO was blended with 100 parts by weight of the polyurethane resin of Comparative Example 1.
I did the same thing. The results obtained are shown in Table 2.
以上、実施例１〜１１及び比較例９〜１０にて得られた
結果を第２表に示す。The results obtained in Examples 1 to 11 and Comparative Examples 9 to 10 are shown in Table 2.
（効 果）
以上、実施例と比較例とを対比すれば明らかな如く、本
発明のポリウレタン樹脂組成物は優れた耐水特性を保有
するものであシ、その実用的価値は極めて大きいもので
ある。(Effects) As is clear from comparing the Examples and Comparative Examples, the polyurethane resin composition of the present invention has excellent water resistance properties, and its practical value is extremely large. .
Claims (1)
％以上配合した樹脂組成物において、前記ポリウレタン
樹脂１００重量部に対して、アルカリ土金属の酸化物、
もしくは炭酸塩又これらを含有した化合物が０．０１〜
１５．０重量部の割合で配合した事を特徴とするポリウ
レタン樹脂組成物。 ２、樹脂組成物がハロゲン系難燃剤を含有することを特
徴とする特許請求の範囲第１項記載のポリウレタン樹脂
組成物。[Scope of Claims] 1. In a resin composition containing 50% by weight or more of a polyurethane resin having an ester bond, an oxide of an alkaline earth metal,
Or carbonate or a compound containing these is 0.01~
A polyurethane resin composition characterized in that it is blended in a proportion of 15.0 parts by weight. 2. The polyurethane resin composition according to claim 1, wherein the resin composition contains a halogen flame retardant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13940087A JPS63304051A (en) | 1987-06-03 | 1987-06-03 | Polyurethane polymer composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13940087A JPS63304051A (en) | 1987-06-03 | 1987-06-03 | Polyurethane polymer composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63304051A true JPS63304051A (en) | 1988-12-12 |
Family
ID=15244392
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13940087A Pending JPS63304051A (en) | 1987-06-03 | 1987-06-03 | Polyurethane polymer composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63304051A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2659083A1 (en) * | 1990-03-02 | 1991-09-06 | Atochem | Flame-retarded thermoplastic resin composition with an improved heat resistance |
| WO2011022582A1 (en) * | 2009-08-21 | 2011-02-24 | Lubrizol Advanced Materials, Inc. | Hydrolytically stable polyurethane nanocomposites |
| JP2021501824A (en) * | 2017-11-03 | 2021-01-21 | ビーエイエスエフ・ソシエタス・エウロパエアＢａｓｆ Ｓｅ | Flame-retardant composition, method for preparing the flame-retardant composition, and products obtained from the same. |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4976993A (en) * | 1972-11-27 | 1974-07-24 | ||
| JPS5734155A (en) * | 1980-08-08 | 1982-02-24 | Dainippon Ink & Chem Inc | Composite stabilizer for polyurethane |
| JPS57108155A (en) * | 1973-04-03 | 1982-07-06 | Uniroyal Inc | Flame retardant composition |
| JPS57121022A (en) * | 1981-01-22 | 1982-07-28 | Dainippon Ink & Chem Inc | Flame-retardant thermoplastic resin composition |
| JPS59133248A (en) * | 1983-01-20 | 1984-07-31 | Asahi Chem Ind Co Ltd | Polyurethane composition |
| JPS60188455A (en) * | 1984-03-08 | 1985-09-25 | Mitui Toatsu Chem Inc | Moisture-curing, one-component polyurethane composition |
| JPS61197655A (en) * | 1985-02-27 | 1986-09-01 | Dainichi Seika Kogyo Kk | Flame-retardant polyurethane resin composition |
-
1987
- 1987-06-03 JP JP13940087A patent/JPS63304051A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4976993A (en) * | 1972-11-27 | 1974-07-24 | ||
| JPS57108155A (en) * | 1973-04-03 | 1982-07-06 | Uniroyal Inc | Flame retardant composition |
| JPS57108141A (en) * | 1973-04-03 | 1982-07-06 | Uniroyal Inc | Flame retardant composition |
| JPS5734155A (en) * | 1980-08-08 | 1982-02-24 | Dainippon Ink & Chem Inc | Composite stabilizer for polyurethane |
| JPS57121022A (en) * | 1981-01-22 | 1982-07-28 | Dainippon Ink & Chem Inc | Flame-retardant thermoplastic resin composition |
| JPS59133248A (en) * | 1983-01-20 | 1984-07-31 | Asahi Chem Ind Co Ltd | Polyurethane composition |
| JPS60188455A (en) * | 1984-03-08 | 1985-09-25 | Mitui Toatsu Chem Inc | Moisture-curing, one-component polyurethane composition |
| JPS61197655A (en) * | 1985-02-27 | 1986-09-01 | Dainichi Seika Kogyo Kk | Flame-retardant polyurethane resin composition |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2659083A1 (en) * | 1990-03-02 | 1991-09-06 | Atochem | Flame-retarded thermoplastic resin composition with an improved heat resistance |
| WO2011022582A1 (en) * | 2009-08-21 | 2011-02-24 | Lubrizol Advanced Materials, Inc. | Hydrolytically stable polyurethane nanocomposites |
| JP2013502494A (en) * | 2009-08-21 | 2013-01-24 | ルブリゾル アドバンスド マテリアルズ， インコーポレイテッド | Hydrolysis-stable polyurethane nanocomposites |
| JP2021501824A (en) * | 2017-11-03 | 2021-01-21 | ビーエイエスエフ・ソシエタス・エウロパエアＢａｓｆ Ｓｅ | Flame-retardant composition, method for preparing the flame-retardant composition, and products obtained from the same. |
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