JPS63258951A - Production of molded polyurethane resin product - Google Patents
Production of molded polyurethane resin productInfo
- Publication number
- JPS63258951A JPS63258951A JP9462487A JP9462487A JPS63258951A JP S63258951 A JPS63258951 A JP S63258951A JP 9462487 A JP9462487 A JP 9462487A JP 9462487 A JP9462487 A JP 9462487A JP S63258951 A JPS63258951 A JP S63258951A
- Authority
- JP
- Japan
- Prior art keywords
- polyurethane resin
- formulas
- resin molded
- molded product
- coating
- 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
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- -1 phosphoric acid ester compound Chemical class 0.000 claims abstract description 18
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 12
- 229920005862 polyol Polymers 0.000 claims abstract description 8
- 150000003077 polyols Chemical class 0.000 claims abstract description 8
- 239000004970 Chain extender Substances 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 239000012948 isocyanate Substances 0.000 claims abstract description 4
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 4
- 125000005037 alkyl phenyl group Chemical group 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 239000004604 Blowing Agent Substances 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract 1
- 239000004088 foaming agent Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 238000002845 discoloration Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 241000156978 Erebia Species 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 description 2
- HGXVKAPCSIXGAK-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine;4,6-diethyl-2-methylbenzene-1,3-diamine Chemical compound CCC1=CC(CC)=C(N)C(C)=C1N.CCC1=CC(C)=C(N)C(CC)=C1N HGXVKAPCSIXGAK-UHFFFAOYSA-N 0.000 description 2
- 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 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 239000001177 diphosphate Substances 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- PCTMTFRHKVHKIS-BMFZQQSSSA-N (1s,3r,4e,6e,8e,10e,12e,14e,16e,18s,19r,20r,21s,25r,27r,30r,31r,33s,35r,37s,38r)-3-[(2r,3s,4s,5s,6r)-4-amino-3,5-dihydroxy-6-methyloxan-2-yl]oxy-19,25,27,30,31,33,35,37-octahydroxy-18,20,21-trimethyl-23-oxo-22,39-dioxabicyclo[33.3.1]nonatriaconta-4,6,8,10 Chemical compound C1C=C2C[C@@H](OS(O)(=O)=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2.O[C@H]1[C@@H](N)[C@H](O)[C@@H](C)O[C@H]1O[C@H]1/C=C/C=C/C=C/C=C/C=C/C=C/C=C/[C@H](C)[C@@H](O)[C@@H](C)[C@H](C)OC(=O)C[C@H](O)C[C@H](O)CC[C@@H](O)[C@H](O)C[C@H](O)C[C@](O)(C[C@H](O)[C@H]2C(O)=O)O[C@H]2C1 PCTMTFRHKVHKIS-BMFZQQSSSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- RGBBCHBCGNDCRL-UHFFFAOYSA-N 3-n,4-dimethylbenzene-1,3-diamine Chemical compound CNC1=CC(N)=CC=C1C RGBBCHBCGNDCRL-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- RQEOBXYYEPMCPJ-UHFFFAOYSA-N 4,6-diethyl-2-methylbenzene-1,3-diamine Chemical compound CCC1=CC(CC)=C(N)C(C)=C1N RQEOBXYYEPMCPJ-UHFFFAOYSA-N 0.000 description 1
- WDTRNCFZFQIWLM-UHFFFAOYSA-N 4-benzylaniline Chemical compound C1=CC(N)=CC=C1CC1=CC=CC=C1 WDTRNCFZFQIWLM-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- UYANAUSDHIFLFQ-UHFFFAOYSA-N borinic acid Chemical compound OB UYANAUSDHIFLFQ-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000921 polyethylene adipate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 125000005624 silicic acid group Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012970 tertiary amine catalyst Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- 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、ポリウレタン樹脂成形品の製造方法に関し、
特に、表面に塗装を施した場合に当該塗装の変色の少な
いポリウレタン樹脂成形品の製造方法に関するものであ
る。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for producing a polyurethane resin molded product,
In particular, the present invention relates to a method for producing a polyurethane resin molded product that causes less discoloration of the coating when the surface is coated.
（従来の技術）
ポリウレタン樹脂は機械的特性に優れることから、バン
パー、スポイラ−、エアダムスカート。(Conventional technology) Polyurethane resin has excellent mechanical properties, so it is used in bumpers, spoilers, and air dam skirts.
フェンダその他の自動車用部品や電気製品等に広く利用
されている。It is widely used in fenders, other automobile parts, electrical products, etc.
そして近年需要者の高級化志向からこれらのポリウレタ
ン樹脂成形品は表面に塗装が施されることが多い。In recent years, as consumers have become more sophisticated, the surfaces of these polyurethane resin molded products are often coated.
ところで、近年、ポリウレタン樹脂の機械的特性をさら
に向上させる方策として鎖延長剤に従来のＥＧ （エチ
レングリコール）にかわってＤＩＥＴＤＡ（ジエチルト
リエンジアミン、１−メチル−３，５−ジエチル−２，
６−ジアツベンゼン又はその異性体）を代表とする芳香
族アミンを採用することが提唱され、（特公昭５４−１
７３５９号公報）、前記する表面塗装を有するポリウレ
タン樹脂成形品にも応用されつつある。By the way, in recent years, as a measure to further improve the mechanical properties of polyurethane resins, DIETDA (diethyltrienediamine, 1-methyl-3,5-diethyl-2,
It was proposed to use aromatic amines represented by 6-diatubenzene or its isomers, and
No. 7359), and it is also being applied to polyurethane resin molded products having the above-mentioned surface coating.
（発明が解決しようとする問題点）
しかしながら、表面塗装を有するポリウレタン樹脂成形
品に芳香族アミンの鎖延長剤を採用した場合、以下の如
き重大な問題のあることを知見した。(Problems to be Solved by the Invention) However, it has been found that when an aromatic amine chain extender is employed in a polyurethane resin molded product having a surface coating, the following serious problems occur.
すなわち、前記鎖延長剤を採用した表面塗装を有するポ
リウレタン樹脂成形品はその物性や加工性が向上する利
点を有するが、経時的に塗装が黄色に変色する欠点があ
り、この現象は、特に高温にさらされるバンパーやスポ
イラ−等の自動車部品について著しいことである。In other words, polyurethane resin molded products with a surface coating that employs the chain extender have the advantage of improved physical properties and processability, but have the disadvantage that the coating turns yellow over time, and this phenomenon is especially noticeable at high temperatures. This is particularly true for automobile parts such as bumpers and spoilers that are exposed to
この理由としては、経時的にウレタン樹脂内の芳香族ア
ミンが塗膜の層に移行し、かつ酸化して褐色に変色する
ためであると考えられる。The reason for this is thought to be that the aromatic amine in the urethane resin migrates to the coating layer over time, oxidizes, and discolors to brown.
そこで本発明は上述の問題点に着目し、鎖延長剤として
芳香族アミンを採用し、物性の向上を図りつつ塗装の変
色をも同時に防止することができるポリウレタン樹脂成
形品の製造方法を提供することを目的とするものである
。Therefore, the present invention focuses on the above-mentioned problems, and provides a method for manufacturing polyurethane resin molded products that uses an aromatic amine as a chain extender to improve physical properties and prevent discoloration of the coating at the same time. The purpose is to
（問題点を解決するための手段）
しかして上述の目的を達成するための本発明の特徴とす
るところはポリオール成分、有機イソシアネート成分及
び発泡剤を主体とし、鎖延長剤として芳香族アミンを使
用するとともに表面に塗装が施されるポリウレタン樹脂
成形品の製造方法において、前記ポリウレタン成分とし
て下記一般式（１） （２）あるいは（３）で示される
化合物からなる群より選ばれた少なくとも１つのリン酸
エステル化合物を添加したポリウレタン樹脂成形品の製
造方法である。(Means for Solving the Problems) To achieve the above-mentioned object, the present invention is characterized by mainly containing a polyol component, an organic isocyanate component, and a blowing agent, and using an aromatic amine as a chain extender. In the method for producing a polyurethane resin molded article, the surface of which is coated, at least one phosphorus selected from the group consisting of compounds represented by the following general formulas (1), (2), or (3) is used as the polyurethane component. This is a method for manufacturing a polyurethane resin molded article to which an acid ester compound is added.
ただし式中、Ｒ１、Ｒ１、Ｒ，、Ｒ，は同−又は異なる
炭素数１以上のアルキル基又はアルキルフェニル基であ
る。However, in the formula, R1, R1, R,, R, are the same or different alkyl groups or alkylphenyl groups having 1 or more carbon atoms.
ここで、上記本発明において使用される前記一般式（１
）で表わされる化合物の具体例としてはなどが挙げられ
る。Here, the general formula (1
Specific examples of compounds represented by ) include the following.
また、前記一般式（２）に表わされる化合物の例として
は、
但し Ｒ＝Ｃ，、〜ｃｐｓアルキル
があり、一般式（３）で表される化合物例としては、が
挙げられる。Examples of the compound represented by the general formula (2) include, where R=C, .about.cps alkyl, and examples of the compound represented by the general formula (3) include.
そして、当該化合物は、ポリオール１００重量部（ポリ
エーテルとＤＥＴＤＡの合計）に対して０．０５〜２．
０重量部添加することが好ましい。即ち含有量０．０５
以下は効果なく、２．０以上は効果横ばいとなり、何れ
も適当でない。The amount of the compound is 0.05 to 2.0 parts by weight based on 100 parts by weight of polyol (total of polyether and DETDA).
It is preferable to add 0 parts by weight. That is, the content is 0.05
Below, there is no effect, and above 2.0, the effect remains unchanged, and neither is appropriate.
次に本発明に係る前記化合物（１） （２） （３）は
その使用形態としてポリオール成分又はポリイソシアネ
ート成分に溶解又は分散状態で使用される。Next, the compounds (1), (2), and (3) according to the present invention are used in a dissolved or dispersed state in a polyol component or a polyisocyanate component.
本発明で使用するポリオール成分は、通常使用されてい
るので特に限定はないが、ポリエチレンエーテルグリコ
ール、ポリプロピレンエーテルグリコール、ポリテトラ
メチレンエーテルグリコール、ポリエチレンアジペート
ポリブチレンアジベート、ポリアクリロニトリルグラフ
ト化ポリプロピレンエーテルグリコール、ポリアクリロ
ニトリルポリスチレングラフト化ポリプロピレンエーテ
ルグリコールエチレングリコール、ｌ、４−ブタンジオ
ール、ジエチレングリコール等が好ましくこれらは単独
又は２種以上の混合系として用いられる。The polyol components used in the present invention are commonly used and are not particularly limited, but include polyethylene ether glycol, polypropylene ether glycol, polytetramethylene ether glycol, polyethylene adipate polybutylene adipate, polyacrylonitrile grafted polypropylene ether glycol, Polyacrylonitrile polystyrene grafted polypropylene ether glycol ethylene glycol, 1,4-butanediol, diethylene glycol and the like are preferred, and these may be used alone or as a mixture of two or more.
また、有機イソシアナート成分も通常よく使用されてい
るもので、ヘキサメチレンジイソシアナート（ＨＭＤＩ
）、４．４’−ジフェニルメタンジイソシアナート（Ｍ
ＤＩ） 、 ）ルエンジイソシアナー） （ＲＤＩ）
及びこれらの誘導体例えばプレポリマー、カルボジイミ
ド変成、イソシアヌレート変成等の１種又は数種の使用
が好適である。In addition, organic isocyanate components are also commonly used, such as hexamethylene diisocyanate (HMDI).
), 4,4'-diphenylmethane diisocyanate (M
DI), )ruene diisocyaner) (RDI)
It is preferable to use one or more of these derivatives, such as prepolymers, carbodiimide-modified products, isocyanurate-modified products, and the like.
一方、ポリウレタン樹脂の機械的性質、加工性を向上さ
せるために添加する芳香族アミンについては前記した特
公昭５４−１７３５９号公報に詳細に記載されているが
、例えば、２．４−及び２，６−ジアミツトルエン、２
，４′−及び４，４′−ジアミノ−ジフェニルメタン、
１．３−及び１．４−フェニレンジアミン、ナフチレン
−１，５−ジアミン、トリフェニルメタン−４，４’、
４“−トリアミン、４．４−ンー（メチルアミノ）
−ジフェニルメタン、１−メチル−２−メチルアミノ−
４−アミノベンゼン、ポリフェニル−ポリメチレンポリ
アミン、１．３−ジエチル−２，４−ジアミノベンゼン
２．４−ジアミノメシチレン、１−メチル−３，５−ジ
エチル−２，４−ジアミノベンゼン、１−メチル−３，
５−ジエチル−２，６−ジアミノベンゼン、１．３．５
−１−ジエチル−２゜６−ジアミノベンゼン及び３．５
．３’、 ５’−テトラエチル−４，４−ンアミノージ
フェニルメタン、１−メチル−３，５−ジエチル−２，
４−ジアミノベンゼンまたはこの化合物と１−メチル−
３，５−ジエチル−２，６−ジアミノ等が挙げられる。On the other hand, aromatic amines added to improve the mechanical properties and processability of polyurethane resins are described in detail in the above-mentioned Japanese Patent Publication No. 17359/1983, and examples include 2.4-, 2, 6-diamittoluene, 2
, 4'- and 4,4'-diamino-diphenylmethane,
1,3- and 1,4-phenylene diamine, naphthylene-1,5-diamine, triphenylmethane-4,4',
4"-triamine, 4.4-(methylamino)
-diphenylmethane, 1-methyl-2-methylamino-
4-aminobenzene, polyphenyl-polymethylene polyamine, 1,3-diethyl-2,4-diaminobenzene 2,4-diaminomesitylene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1- Methyl-3,
5-diethyl-2,6-diaminobenzene, 1.3.5
-1-diethyl-2゜6-diaminobenzene and 3.5
．． 3', 5'-tetraethyl-4,4-aminodiphenylmethane, 1-methyl-3,5-diethyl-2,
4-diaminobenzene or this compound and 1-methyl-
Examples include 3,5-diethyl-2,6-diamino.
また、発泡剤としては不活性液体、例えばフロンガス、
ハロゲン化炭化水素又は水が用いられる。In addition, as a blowing agent, an inert liquid such as chlorofluorocarbon gas,
Halogenated hydrocarbons or water are used.
更に、本発明では前記の外、ポリウレタンフォームの物
性改質剤として、ジブチルフタジーロジオクチルフタレ
ート等の可塑剤２石油樹脂、ポリブタジェン、エポキシ
樹脂等の樹脂類あるいは公知の充填剤（カーボンブラッ
ク、珪酸類、炭酸カルシウム等）を適宜必要により加え
ることもできる。Furthermore, in the present invention, in addition to the above, as a property modifier for polyurethane foam, plasticizers such as dibutyl phthalate, resins such as petroleum resins, polybutadiene, and epoxy resins, or known fillers (carbon black, silicic acids, etc. , calcium carbonate, etc.) may be added as appropriate.
（作用）
以上の本発明製造方法によれば上記一般式で示した本発
明の特徴をなす化合物はいずれもリン酸エステル化合物
であり、酸化防止効果を有するものである。(Function) According to the above-described production method of the present invention, the compounds characterized by the present invention represented by the above general formula are all phosphoric acid ester compounds, and have an antioxidant effect.
従って、上記リン酸エステル化合物は経時的にウレタン
成形品より塗膜層に移行した芳香族アミンに作用し、酸
化を防止して褐色に変色することを防ぎ、結果として塗
装の黄変を防止するべく作用する。Therefore, the above-mentioned phosphoric acid ester compound acts on the aromatic amine that has migrated from the urethane molded product to the coating layer over time, prevents oxidation and discoloration to brown, and as a result prevents the coating from yellowing. It works as expected.
以下、更に本発明製造方法につき、実施例を掲げる。Examples of the manufacturing method of the present invention will be further described below.
（実施例）
先ず、第−表ＡＢＣＤの４種類の配合を作成し、高圧Ｒ
ＩＭ注型機（ＫＲＡＵＳＳ ＭＡＦＦＥＩ ＭＫ−１６
タイプ）を用いて７０±５℃に温調された容積４５００
−のモールド内に吐出圧力１５０ｋｇ／ｃｉで注入し、
比重０．９０〜１．０５ｇ／ｃｄのウレタン樹脂成形品
を作成した。(Example) First, four types of formulations shown in Table ABCD were created, and high pressure R
IM casting machine (KRAUSS MAFFEI MK-16
Volume 4500 with temperature controlled at 70±5℃ using
- injected into the mold at a discharge pressure of 150 kg/ci,
A urethane resin molded product having a specific gravity of 0.90 to 1.05 g/cd was created.
そして、当該樹脂成形品を１．１．１−）リクロロエタ
ンで溶剤洗浄し、ｍ６００−１プライマ（日本ビーケミ
カル社製）塗付後８０℃の雰囲気温度で３０分乾燥し更
にソフレックス阻２００スーパーホワイト色（関西ペイ
ント社製）を塗布し８０℃で３０分乾燥して本発明のテ
ストピースを得た。Then, the resin molded product was washed with solvent using 1.1.1-)lichloroethane, coated with m600-1 primer (manufactured by Nippon B Chemical Co., Ltd.), dried for 30 minutes at an ambient temperature of 80°C, and further coated with Soflex Inhibi 200. Super White color (manufactured by Kansai Paint Co., Ltd.) was applied and dried at 80° C. for 30 minutes to obtain a test piece of the present invention.
一方、同様に本発明の特徴である化合物を含有しない配
合Ｅ、Ｆにより前記本発明の実施例と同一手段を経て比
較用テストピースを作成した。On the other hand, test pieces for comparison were similarly prepared using formulations E and F, which do not contain the compound characteristic of the present invention, through the same procedure as in the examples of the present invention.
第 １ 表
（単位：重量部）
但し、
（１） ポ’） ；ｋ −７１／ Ｉ ： ホー７
／ −ルＸＡｓ−１０８８８，０２（ダウケミカル社製
）
内部離型剤入り、ＰＰＧ
（２） ポリオール■：ボラノール４７０２ （ダウ
ケミカル社製）３官能９分子量
（３） ＤＥＴＤＡ ニジエチルトルエンジアミン
（１−メチル−３，５ジエチル−２，６−ジアミツベン
ゼン）
（４） タブコ３３ ＬＶ ： ３級アミン触媒（
日本乳化剤社製）
（５） スミジュールＰＦ ： ＭＤＩ変性プレポリ
マー（住友バイエルウレタン社
製） ＮＣ０２３％
（６） ＵＬ −２８：有機スズ系触媒（ウィットコ
社製）
（７） ＰＥ０−４Ｃニリン酸エステル（アデカアー
ガス（８）マーク１５００ ： リン酸エステル（アデ
カアーガス）
（９） マーク１１７８ ニリン酸エステル（アデカ
アーガス）
以上、作成したＡＢＣＤＥＦ６種の配合によるテストピ
ースについて、これを８０℃および９０℃の熱風循環オ
ーブン中に入れて２４０時間および５００時間経過後に
取り出し、色差計（スガ試験機製）を使用し変色の度合
ΔＥおよびΔＹＩを測定した。Table 1 (Unit: parts by weight) However, (1) Po') ;k -71/ I: Ho7
/ -L XAs-10888,02 (manufactured by Dow Chemical Company) Contains internal mold release agent, PPG (2) Polyol ■: Boranol 4702 (manufactured by Dow Chemical Company) Trifunctional 9 molecular weight (3) DETDA Nidiethyltoluenediamine (1- Methyl-3,5 diethyl-2,6-diamitbenzene) (4) Tabco 33 LV: Tertiary amine catalyst (
(manufactured by Nippon Nyukazai Co., Ltd.) (5) Sumidur PF: MDI modified prepolymer (manufactured by Sumitomo Bayer Urethane Co., Ltd.) NC023% (6) UL-28: Organotin catalyst (manufactured by Witco Co., Ltd.) (7) PE0-4C diphosphate ester (Adeka Argus (8) Mark 1500: Phosphate ester (Adeka Argus) (9) Mark 1178 Diphosphate ester (Adeka Argus) The test pieces prepared above with the six ABCDEF combinations were exposed to hot air at 80°C and 90°C. It was placed in a circulation oven and taken out after 240 hours and 500 hours, and the degrees of discoloration ΔE and ΔYI were measured using a color difference meter (manufactured by Suga Test Instruments).
結果は下記第２表の通りであった。The results are shown in Table 2 below.
以下余白
この結果より明白であるように、いずれの場合において
も本発明のポリウレタン樹脂成形品のテストピースは比
較的のテストピースよりも変色がはるかに小さいもので
あることが分かる。As is clear from the results, the test pieces of the polyurethane resin molded products of the present invention show much smaller discoloration than comparative test pieces in all cases.
（発明の効果）
以上のように本発明のポリウレタン樹脂成形品の製造方
法は、ウレタン材料中に少量の特定リン酸エステル化合
物を添加することにより経時的にウレタン成形品と表面
塗装膜の間ににじみ出た芳香族アミンの酸化を防止し、
これによって芳香族アミンの変色を防止することが可能
となり、従来、難点とされていた鎖延長剤として芳香族
アミンを採用した場合における物性の向上ならびに塗装
外表面の変色を防止することができる顕著な効果を有す
る。(Effects of the Invention) As described above, the method for manufacturing a polyurethane resin molded product of the present invention adds a small amount of a specific phosphoric acid ester compound to the urethane material, thereby creating a bond between the urethane molded product and the surface coating film over time. Prevents oxidation of aromatic amines that ooze out,
This makes it possible to prevent discoloration of aromatic amines, and when aromatic amines are used as chain extenders, which has been considered a problem in the past, the physical properties can be improved and the discoloration of the outer surface of the coating can be prevented. It has a great effect.
手続補正書印釦
１、事件の表示
昭和６２年特許願第９４６２４号
２、発明の名称
ポリウレタン樹脂成形品の製造方法
４、代理人
居所 大阪市南区南船場３丁目９番１０号６、補正の対
象 明細書の発明の詳細な説明の欄７、補正の内容
（１） 明細書第２頁１９行目の「ジエチルトリエン
」を「ジエチルトルエン」と補正する。Procedural amendment stamp button 1, Indication of case Patent Application No. 94624 of 1988 2, Title of invention Method for manufacturing polyurethane resin molded products 4, Agent residence 3-9-10-6, Minamisenba, Minami-ku, Osaka City, Amendment Subject Column 7 of the detailed explanation of the invention in the specification, Contents of amendment (1) "Diethyltriene" on page 2, line 19 of the specification is amended to "diethyltoluene."
（２）明細書第７頁最下行のｒ（ＲＤＩ） ｊをｒ（１
０１） Ｊと補正する。(2) r(RDI) j on the bottom line of page 7 of the specification is r(1
01) Correct as J.
（３）明細書第１１頁第１表中、左欄６段目のｒＰｔ！
Ｐ−ＡＣＪをｒＰＥＰ−ＡｃＪと補正する。(3) rPt in the 6th row of the left column in Table 1 on page 11 of the specification!
Correct P-ACJ with rPEP-AcJ.
（４）明細書第１２真１５行目のｒＰＥＯ−ＡＣＪをｒ
ＰＥＰ−ＡｃＪと補正する。(4) rPEO-ACJ on the 12th true line 15 of the specification
Correct with PEP-AcJ.
（５） 明細書第１４頁表下部３行目（下より７行目
）の「比較的」を「比較例」と補正する。(5) "Comparative" in the third line at the bottom of the table on page 14 of the specification (seventh line from the bottom) is corrected to "comparative example."
Claims (1)
剤を主体とし、鎖延長剤として芳香族アミンを使用する
とともに表面に塗装が施されるポリウレタン樹脂成形品
の製造方法において、前記ポリウレタン成分として下記
一般式（１）（２）又は（３）で示される群より選ばれ
た少なくとも１つのリン酸エステル化合物を添加するこ
とを特徴とするポリウレタン樹脂成形品の製造方法。 （１）▲数式、化学式、表等があります▼ （２）▲数式、化学式、表等があります▼ （３）▲数式、化学式、表等があります▼ ただし式中、Ｒ＿１、Ｒ＿２、Ｒ＿３、Ｒ＿４は同一又
は異なる炭素数１以上のアルキル基又はアルキルフェニ
ル基である。[Scope of Claims] 1. A method for producing a polyurethane resin molded product mainly comprising a polyol component, an organic isocyanate component, and a blowing agent, using an aromatic amine as a chain extender, and coating the surface, the method comprising: A method for producing a polyurethane resin molded article, which comprises adding at least one phosphoric acid ester compound selected from the group represented by the following general formulas (1), (2), or (3) as a component. (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (3) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ However, in the formula, R_1, R_2, R_3, R_4 are the same or different alkyl groups or alkylphenyl groups having 1 or more carbon atoms.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9462487A JPS63258951A (en) | 1987-04-16 | 1987-04-16 | Production of molded polyurethane resin product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9462487A JPS63258951A (en) | 1987-04-16 | 1987-04-16 | Production of molded polyurethane resin product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63258951A true JPS63258951A (en) | 1988-10-26 |
Family
ID=14115413
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9462487A Pending JPS63258951A (en) | 1987-04-16 | 1987-04-16 | Production of molded polyurethane resin product |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63258951A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999042525A1 (en) * | 1998-02-19 | 1999-08-26 | The Yokohama Rubber Co., Ltd. | One-can moisture-curing urethane compositions |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61123617A (en) * | 1984-11-19 | 1986-06-11 | Kao Corp | Production of polyurethane resin |
| JPS61128904A (en) * | 1984-11-28 | 1986-06-17 | 花王株式会社 | Shoe sole |
-
1987
- 1987-04-16 JP JP9462487A patent/JPS63258951A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61123617A (en) * | 1984-11-19 | 1986-06-11 | Kao Corp | Production of polyurethane resin |
| JPS61128904A (en) * | 1984-11-28 | 1986-06-17 | 花王株式会社 | Shoe sole |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999042525A1 (en) * | 1998-02-19 | 1999-08-26 | The Yokohama Rubber Co., Ltd. | One-can moisture-curing urethane compositions |
| US6180713B1 (en) | 1998-02-19 | 2001-01-30 | The Yokohama Rubber Co., Ltd. | One-can moisture-curing urethane compositions |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| BRPI0612033B1 (en) | thermoplastic polyurethane, processes for producing polyurethanes, for reaction of isocyanate thermoplastic polyurethanes, and for thermoplastic polyurethane injection molding, injection molded article, extruded article, and film | |
| ES2635038T3 (en) | Composition of crosslinked isocyanate and polyurethane prepolymer prepared therefrom | |
| CN110799502B (en) | Reactive ultraviolet light absorber and application thereof | |
| EP0799286A1 (en) | Mouldings made of polyurethane hot-melt-type adhesives | |
| KR20120029389A (en) | Polyurethane and manufacturing method therefor, master batch, ink binder, ink composition, thermoplastic polymer composition for molding, molded body, and compound molded body and manufacturing method therefor | |
| BRPI0709997A2 (en) | molded polyurethane part, method for its production and use | |
| KR20200057711A (en) | Polyurethane reactive heat melt with high strength and long opening time | |
| AU597859B2 (en) | Compatible polyol blends for high modulus polyurethane compositions | |
| CA2174596A1 (en) | Process for preparing tpu molding compositions | |
| BR112012024535A2 (en) | method of bonding melt adhesive, and, film, injection molded or extruded article. | |
| US5010133A (en) | Polyurethane molding composition, method and article | |
| JPH03212443A (en) | Polyoxymethylene resin composition | |
| EP3604445B1 (en) | Polyurethane resin composition and sealed object | |
| JPS63258951A (en) | Production of molded polyurethane resin product | |
| BR112015000928B1 (en) | polyol composition, process for preparing a flame retardant and a dissipative polyurethane elastomer and flame retardant and static dissipative polyurethane elastomer | |
| CN113316601B (en) | Method for producing hot melt adhesives with low monomeric isocyanate emissions | |
| US20230365838A1 (en) | Process of incorporating gelling and phase separation inhibitor into a filled polyurethane reactive hot melt adhesive | |
| IT8048255A1 (en) | IMPROVEMENT IN POLYURETHANE COMPOSITIONS. | |
| TW201927844A (en) | Chemical and stain resistant thermoplastic polyurethane composition | |
| JPH0262133B2 (en) | ||
| US4273912A (en) | Polyurethane floor varnish and floor materials coated therewith | |
| JPS63270783A (en) | Reaction injection molding product with insert | |
| EP4132987B1 (en) | Coated, printed substrate and its process of preparation | |
| JPH0458491B2 (en) | ||
| JPS6018514A (en) | Elastomer-forming composition |