JPS63203309A - Polyurethane reaction injection molding - Google Patents
Polyurethane reaction injection moldingInfo
- Publication number
- JPS63203309A JPS63203309A JP3816487A JP3816487A JPS63203309A JP S63203309 A JPS63203309 A JP S63203309A JP 3816487 A JP3816487 A JP 3816487A JP 3816487 A JP3816487 A JP 3816487A JP S63203309 A JPS63203309 A JP S63203309A
- Authority
- JP
- Japan
- Prior art keywords
- insert
- coating film
- resin layer
- solution
- isocyanate
- 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
- 239000004814 polyurethane Substances 0.000 title claims abstract description 20
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 20
- 238000010107 reaction injection moulding Methods 0.000 title description 2
- 239000011248 coating agent Substances 0.000 claims abstract description 35
- 238000000576 coating method Methods 0.000 claims abstract description 35
- 238000002347 injection Methods 0.000 claims abstract description 17
- 239000007924 injection Substances 0.000 claims abstract description 17
- 125000003158 alcohol group Chemical group 0.000 claims abstract description 15
- 238000004070 electrodeposition Methods 0.000 claims abstract description 11
- 239000003822 epoxy resin Substances 0.000 claims abstract description 10
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 10
- 239000003973 paint Substances 0.000 claims abstract description 8
- 238000000465 moulding Methods 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 125000002091 cationic group Chemical group 0.000 claims description 4
- 229920005989 resin Polymers 0.000 abstract description 18
- 239000011347 resin Substances 0.000 abstract description 17
- 229920005862 polyol Polymers 0.000 abstract description 16
- 150000003077 polyols Chemical class 0.000 abstract description 16
- 239000012948 isocyanate Substances 0.000 abstract description 13
- 150000002513 isocyanates Chemical class 0.000 abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 10
- 239000001257 hydrogen Substances 0.000 abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 7
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 2
- 229920001225 polyester resin Polymers 0.000 abstract description 2
- 239000004645 polyester resin Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 abstract 4
- 150000001768 cations Chemical class 0.000 abstract 1
- 239000000047 product Substances 0.000 description 28
- 239000007788 liquid Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 125000005442 diisocyanate group Chemical group 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 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 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 239000004604 Blowing Agent Substances 0.000 description 3
- 239000004970 Chain extender Substances 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 229910001335 Galvanized steel Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000008397 galvanized steel Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000012779 reinforcing material Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- -1 diethyltolylene diamine Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 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
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- IYXGSMUGOJNHAZ-UHFFFAOYSA-N Ethyl malonate Chemical compound CCOC(=O)CC(=O)OCC IYXGSMUGOJNHAZ-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- FBYUNLMTXMFAQK-UHFFFAOYSA-N butyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCCCC.CCCCCCCCCCCC(=O)OCCCC FBYUNLMTXMFAQK-UHFFFAOYSA-N 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 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
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 125000003198 secondary alcohol group Chemical group 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/68—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts by incorporating or moulding on preformed parts, e.g. inserts or layers, e.g. foam blocks
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
- B29C67/24—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 characterised by the choice of material
- B29C67/246—Moulding high reactive monomers or prepolymers, e.g. by reaction injection moulding [RIM], liquid injection moulding [LIM]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2063/00—Use of EP, i.e. epoxy resins or derivatives thereof, as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Mechanical Engineering (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
この発明はポリウレタン反応射出成形品に関し、特には
補強用等のインサートを内蔵したポリウレタン反応射出
成形品に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a polyurethane reaction injection molded product, and more particularly to a polyurethane reaction injection molded product having a built-in reinforcing insert.
（従来の技術）
近年、ポリウレタン反応射出成形品は種々の分野で利用
されており、その主たる分野の−として自動車部品の分
野がある。そしてその製品例にはバンパー、マッドガー
ド、エアスポイラ−等がある。(Prior Art) In recent years, polyurethane reaction injection molded products have been used in various fields, and one of the main fields is the field of automobile parts. Examples of these products include bumpers, mudguards, and air spoilers.
ところで、これら自動車部品は車体に固着する必要上、
通常その中に補強を兼ねてボルト等を立設した鋼板等の
補強材（通称インサート）が一体に埋設成形され、また
その用途が主に外装であるため該インサートには、亜鉛
メッキ等の防錆処理を施したものが使用されている。By the way, because these auto parts need to be fixed to the car body,
Normally, a reinforcing material (commonly known as an insert) such as a steel plate with bolts etc. placed upright therein is embedded and molded as an integral part of the reinforcing material, and since the purpose of the reinforcing material is mainly exterior, the insert is coated with protective material such as zinc plating. Rust-treated products are used.
（発明が解決しようとする問題点）
一方これら自動車部品は車体の色と合わせたり或いは逆
に対照的な色とするため塗装を施すことが５４行われ、
その塗膜の焼付のために塗装品を８０〜１２０ ℃のオ
ーブン中に入れることが行われる。(Problems to be Solved by the Invention) On the other hand, these automobile parts are often painted to match or contrast with the color of the car body54.
The coated product is placed in an oven at 80-120° C. for baking of the coating film.
しかしながら、前述の亜鉛メッキ鋼板等のインサートの
場合、該インサートとポリウレタン反応成形品との密着
力が弱く、前記塗膜の焼付時、或いは使用中にその界面
において剥離を生ずることがしばしばである。そこで一
部インサート等に孔を穿設したり、インサート表面を粗
面とすることにより、被覆するポリウレタン樹脂との物
理的固着を図ることも行われている。しかしインサート
等に多数の孔を有していたり、或いはインサートの表面
が粗面である場合には射出成形特被覆するポリウレタン
樹脂の流動が阻害されたり、複雑化して成形品表面に波
打ち、ヒケ等が生じたり、或いは空気を巻き込み、却っ
て成形品表面に欠陥が現れることもしばしばである。However, in the case of inserts such as the above-mentioned galvanized steel sheets, the adhesion between the insert and the polyurethane reaction molded product is weak, and peeling often occurs at the interface when the coating film is baked or during use. Therefore, some attempts have been made to form holes in the insert or to roughen the surface of the insert to ensure physical adhesion to the polyurethane resin that covers it. However, if the insert has a large number of holes or the surface of the insert is rough, the flow of the polyurethane resin used to cover the injection molding may be hindered, and the molded product surface may become wavy, sink, etc. This often results in air being trapped or defects appearing on the surface of the molded product.
（問題点を解決するための手段）
よって本発明はこのような問題点に鑑みなされたもので
あって、その要旨とするところは、インサートとしてア
ルコール基を有する塗料の電着塗膜を有するものを一体
成形したポリウレタン反応射出成形品にある。(Means for Solving the Problems) Therefore, the present invention has been made in view of the above problems, and its gist is to provide an insert having an electrodeposition coating film of a paint having an alcohol group. It is a polyurethane reaction injection molded product that is integrally molded with.
（作用）
ポリウレタン反応射出成形品は、基本的に活性水素を有
する三官能以上の化合物と同じく三官能以上のインシア
ネート基を有する化合物を混合反応させながら型内に射
出成形し、前記２成分の反応によるポリマー化を利用し
て所望の形状に成形したものである。その代表化合物例
は三官能以上のポリオールと二官能のジイソシアネート
との反応生成物である。以下、ポリオールとイソシアネ
ートとを主体に説明するが、本発明はこれに限るもので
はなく、ポリアミンとインシアネートとの組合せ、更に
はこれらに無機物の充填剤を加えたものであってもよい
。本発明はこれらを含めて広義にポリウレタン反応射出
成形品という。一方、インサートに施された電着塗膜は
アルコール基、すなわち活性水素を有するものであり、
該塗膜を有するインサートが型内に装置され、該インサ
ート上に前記活性水素を有する三官能以上の化合物と三
官能以上のインシアネート基を有する化合物との混合物
が圧入された場合には、これ゛ら二成分が反応してポリ
マー化すると共にその一部のイソシアネート基が塗膜中
のアルコール基と反応して塗膜と化学的に結合したもの
となる。すなわち塗膜と成形品とは極めて強固に一体化
したものとなる。他方該塗膜は荷電粒子とした塗料粒子
の電気泳動、付着を利用した電着によりインサート上に
形成されているものであるから該塗膜とインサートとの
結合も密であり強固な固着構造を有するものである。従
って成形されたポリウレタン反応射出成形品は樹脂層と
インサートとが塗膜を介して極めて強固に結合したもの
となる。(Function) Polyurethane reaction injection molded products are basically made by injection molding into a mold while mixing and reacting a trifunctional or higher functional compound having active hydrogen with a compound having a trifunctional or higher functional incyanate group. It is molded into a desired shape using polymerization through reaction. A typical example of such a compound is a reaction product of a trifunctional or higher functional polyol and a difunctional diisocyanate. Although polyol and isocyanate will be mainly described below, the present invention is not limited to this, and may also be a combination of polyamine and incyanate, or even a combination of these with an inorganic filler added. The present invention includes these products and is broadly referred to as polyurethane reaction injection molded products. On the other hand, the electrodeposition coating applied to the insert has alcohol groups, that is, active hydrogen,
When an insert having the coating film is placed in a mold and a mixture of the trifunctional or higher functional compound having active hydrogen and the compound having a trifunctional or higher functional incyanate group is press-fitted onto the insert, this The two components react to form a polymer, and some of the isocyanate groups react with the alcohol groups in the coating film to become chemically bonded to the coating film. In other words, the coating film and the molded article are extremely strongly integrated. On the other hand, since the coating film is formed on the insert by electrodeposition using electrophoresis and adhesion of paint particles as charged particles, the bond between the coating film and the insert is tight and has a strong adhesion structure. It is something that you have. Therefore, in the polyurethane reaction injection molded product, the resin layer and the insert are extremely firmly bonded via the coating film.
（実施例） 以下本発明を実施例に基いて説明する。(Example) The present invention will be explained below based on examples.
第１図は本発明実施例であるマッドガード１０（泥除け
）の正面図であり、第２図はそのＡ−Ａ線断面図である
。FIG. 1 is a front view of a mudguard 10 (mudguard) according to an embodiment of the present invention, and FIG. 2 is a cross-sectional view taken along the line A-A.
マッドガード１０は図示する如く所望の形状を有する鋼
板インサー［１、その上に施こされた電着塗膜１２およ
びこれらを被包するポリウレタ反応射出成形品脂層１３
とからなる。As shown in the figure, the mudguard 10 includes a steel plate insert [1] having a desired shape, an electrodeposited coating film 12 applied thereon, and a polyurethane reaction injection molded fat layer 13 covering these.
It consists of
鋼板インサート１１は脱脂処理され、更に好ましくは燐
酸塩等で表面処理されたものからなる。The steel plate insert 11 is made of a material that has been degreased and more preferably surface treated with phosphate or the like.
電着塗膜１２は、エポキシ樹脂をグリコール、ポリエス
テル樹脂等で変性、すなわちエポキシ樹脂に活性水素を
有するアルコール基を導入したちのを主展色剤とし０、
硬化剤としてブロックイソシアネートを添加したものを
主成分とする塗料からカチオン電着により前記インサー
ト１１上に形成された塗膜である。この塗膜１２の形成
は前記変性エポキシ樹脂とブロックイソシアネートとか
らなる塗料を水中にカチオン粒子として分散したエマル
ジョンから電着により前記インサート１１上に付着し、
これを８０〜１２０ ℃にて焼き付けることによってブ
ロックイソシアネートを解離させ、活性化したインシア
ネートでもって硬化させる。このときの硬化反応はウレ
タン化反応が主である。ここで使用できるインシアネー
トにはトリレンジイソシアネート、４．４’−ジフェニ
ルメタンジイソシアネート、キシレンジイソシアネート
、イソホロンジイソシアネート、ヘキサメチレンジイソ
シアネート等がある。またブロック化剤としてはアセト
酢酸エチルエステル、マロン酸ジエチルエステル、Ｐ−
ニトロフェノール、Ｐ−クロロフェノール等が使用でき
る。このイソシアネートによる硬化にふいて変性エポキ
シ樹脂中のアルコール基を全て反応させるのではなく僅
かに残しておくのが好ましい。その残存量は後述するポ
リウレタン反応樹脂の組成によって決定される。The electrodeposited coating film 12 is made by modifying an epoxy resin with glycol, polyester resin, etc., that is, introducing an alcohol group having active hydrogen into the epoxy resin as the main color vehicle.
This is a coating film formed on the insert 11 by cationic electrodeposition from a coating material containing as a main component a block isocyanate added as a curing agent. The coating film 12 is formed by depositing on the insert 11 by electrodeposition from an emulsion in which a coating material made of the modified epoxy resin and blocked isocyanate is dispersed in water as cationic particles.
By baking this at 80 to 120°C, the blocked isocyanate is dissociated, and the activated incyanate is cured. The curing reaction at this time is mainly a urethanization reaction. Incyanates that can be used here include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and the like. In addition, as blocking agents, acetoacetic acid ethyl ester, malonic acid diethyl ester, P-
Nitrophenol, P-chlorophenol, etc. can be used. During curing with this isocyanate, it is preferable to leave only a small amount of alcohol groups in the modified epoxy resin rather than reacting them all. The remaining amount is determined by the composition of the polyurethane reaction resin described below.
ポリウレタン反応射出成形樹脂層１３は、ポリオール、
イソシアネート、鎖延長剤（架橋剤）、触媒、発泡剤、
顔料等を成分とする液状原料、特にはポリオール成分を
主体とするＡ液とイソシアネート成分を主体とするＢ液
から反応射出成形されたものである。ポリオールとして
は、ポリエーテルポリオール、ポリマーポリオール、ポ
リブタジェンポリオール等アルコール基、好ましくは三
官能以上のアルコール基を有するものが好適に使用され
る。このポリオールには必要に応じて鎖延長剤、触媒更
には発泡剤が混合され、Ａ液とされる。The polyurethane reaction injection molded resin layer 13 is made of polyol,
Isocyanate, chain extender (crosslinking agent), catalyst, blowing agent,
It is reaction injection molded from liquid raw materials containing pigments and the like, particularly liquid A containing a polyol component as a main component and liquid B containing an isocyanate component as a main component. As the polyol, those having an alcohol group, preferably a trifunctional or higher functional alcohol group, such as polyether polyol, polymer polyol, polybutadiene polyol, etc., are suitably used. This polyol is mixed with a chain extender, a catalyst, and a blowing agent, if necessary, to form a liquid A.
鎖延長剤としては、３官能のグリセリン、２官能のエチ
レングリコール、１．４−ブタンジオールに代表される
グリコール類またはジエチルトリレンジアミン（略称Ｄ
ＥＴＯＡ） 、４ 、４ ’−ジアミノジフェニルメタ
ン（略称ＭＤＡ ）等の低分子アミン等が適宜使用され
る。また触媒としてはトリエチレンジアミン等の三級ア
ミン、ジブチル賜ジラウレート等の有機錫化合物が好適
に使用できる。発泡剤としてはフレオン−１１、メチレ
ンクロライド、水等が使用できる。As a chain extender, glycols represented by trifunctional glycerin, difunctional ethylene glycol, 1,4-butanediol, or diethyltolylene diamine (abbreviated as D
Low molecular weight amines such as ETOA), 4,4'-diaminodiphenylmethane (abbreviated as MDA), etc. are used as appropriate. As the catalyst, tertiary amines such as triethylene diamine and organic tin compounds such as dibutyl dilaurate can be suitably used. Freon-11, methylene chloride, water, etc. can be used as the blowing agent.
他方インシアソートとしては、トリレンジイソシアネー
ト（略称ＴＤＩ）、４．４’−ジフェニルメタンジイソ
シアネート（略称ＭＤＩ）系の三官能イソシアソート、
ポリメリックＭＤＩおよびポリオール類と反応させプレ
ポリマー化したインシアネート、カルボジイミド変性イ
ソシアネート等が適宜用途に応じ組合されて使用される
。このポリオールを主体とするＡ液とジイソシアネート
を主体とするＢ液は周知の如く高反応性であり、混合さ
れることにより主反応であるウレタン化反応を起こして
ポリマーとなる。またこの混合原料が所定の型中に射出
注入されることにより所定の成形品となる。なおこのポ
リオールとジイソシアネートとの反応は前述の塗膜１２
と同様にポリオール中の活性水素とイソシアネートとの
反応を主反応とするものである。他方この混合されたＡ
液とＢ液が射出注入される型中には、前述の塗膜１２を
有するインサート１１が装置れている。このインサート
１１の塗膜Ｉ２には前記の通り、同じく活性水素を有す
るアルコール基が存在することから該塗膜１２のアルコ
ール基と前記樹脂層１３を形成するインシアネートが反
応し、塗膜１２と形成される樹脂層１３とは化学的に一
体に結合したものとなる。従って該樹脂＠１３とインサ
ート１１とも強固に固着したものとなる。なお、上記に
おいては塗膜Ｉ２を構成する塗料を変性することにより
塗料中にアルコール基を導入した例について説明したが
、塗料そのものがアルコール基を有するものからなるも
の、例えば上記のエポキシ樹脂において、該エポキシ樹
脂がビスフェノールＡ型エポキシ樹脂である場合、すな
わちその主鎖中に２級アルコール基を有する場合には前
記変性は必ずしも必要なものではなく、変性するにして
も僅かに変性すればよいものである。他方ポリウレタン
反応樹脂も上記のポリオールとジイソネート反応物に限
るものではなく活性水素を有する化合物とジイソシアネ
ートとの反応物であればよいものである。活性水素を有
するその他の化合物としてはポリアミン等が挙げられる
。On the other hand, incyasate includes trifunctional isocyanate such as tolylene diisocyanate (abbreviated as TDI), 4,4'-diphenylmethane diisocyanate (abbreviated as MDI),
Polymeric MDI and incyanate made into a prepolymer by reacting with polyols, carbodiimide-modified isocyanate, etc. are used in combination depending on the purpose. As is well known, the A liquid mainly composed of polyol and the B liquid mainly composed of diisocyanate are highly reactive, and when mixed together, a urethanization reaction, which is the main reaction, occurs to form a polymer. Further, this mixed raw material is injected into a predetermined mold to form a predetermined molded product. Note that the reaction between this polyol and diisocyanate is similar to the above-mentioned coating film 12.
Similarly, the main reaction is the reaction between active hydrogen in the polyol and isocyanate. On the other hand, this mixed A
An insert 11 having the coating film 12 described above is placed in the mold into which the liquid and B liquid are injected. As mentioned above, the coating film I2 of this insert 11 also has alcohol groups having active hydrogen, so the alcohol groups of the coating film 12 react with the incyanate forming the resin layer 13, and the coating film 12 and The formed resin layer 13 is chemically bonded to the resin layer 13. Therefore, the resin @13 and the insert 11 are firmly fixed to each other. In addition, in the above, an example was explained in which an alcohol group was introduced into the paint by modifying the paint constituting the coating film I2. When the epoxy resin is a bisphenol A type epoxy resin, that is, when it has a secondary alcohol group in its main chain, the above-mentioned modification is not necessarily necessary, and even if it is modified, it only needs to be slightly modified. It is. On the other hand, the polyurethane reaction resin is not limited to the above-mentioned polyol and diisonate reaction product, but may be a reaction product of a compound having active hydrogen and a diisocyanate. Other compounds having active hydrogen include polyamines and the like.
次に本願発明に基いて成形した反応射出成形品の樹脂層
１３とインサート１１との接着強度を従来品と比較した
結果を次に示す。Next, the results of comparing the adhesive strength between the resin layer 13 and the insert 11 of the reaction injection molded product molded according to the present invention with a conventional product are shown below.
試験材料
従来品：脱脂処理した亜鉛引鋼板をインサートとして所
定の型中に装置し、ポリオールとジイソシアネートから
なるポリウレタン反応射出成形原料を前記インサートに
被覆した成形品
本発明品：脱脂処理した亜鉛引鋼板にエポキシ樹脂を主
成分とする塗料を約２０μの厚さにカチオン電着し、該
塗装品を従来品と同じ成形型に装置後同じ〈従来品と同
一の反応射出原料でもって前記塗装品に被覆した成形品
剥離強度
上記試料からＪＩＳ−Ｚ−０２３７に基づき試験片を調
製し、引張速度３００ｍｍ／分の速度で９０’剥離時の
剥離強度を求める。Test materials Conventional product: A molded product in which a degreased galvanized steel sheet is placed in a predetermined mold as an insert, and the insert is coated with a raw material for polyurethane reaction injection molding consisting of polyol and diisocyanate Inventive product: Degreased galvanized steel sheet A paint mainly composed of epoxy resin was cationically electrodeposited to a thickness of approximately 20μ, and the coated product was placed in the same mold as the conventional product using the same reaction injection raw material as the conventional product. Peel strength of coated molded product A test piece is prepared from the above sample according to JIS-Z-0237, and the peel strength at 90' peeling is determined at a tensile speed of 300 mm/min.
試験結果
剥離強度 備 考
従来品 ５．８ｋｇ／ａｍインサートと樹脂層の間で
剥離本発明品 ５２．９ｋｇ ／ ａｍ インサートと
ゆ膜との間で剥離（値は試験片１０個の平均値である）
（効果）
以上の如く本発明ポリウレタン反応射出成形品は、イン
サートとしてその表面にアルコール基を有する電着塗膜
を施したものを使用し、該インサートをポリウレタン反
応樹脂原料でもって被覆成形したものである。従ってイ
ンサート主体の鋼板等と被覆されたボリウレクン樹脂等
とは強固に結合されたものとなっている。そのため該成
形品に更に塗装等を施し、高温で焼付を行ってもインサ
ートと成形樹脂層間の剥離が殆ど生ずることなく塗装で
きるようになったものであり、またその塗膜の硬化も短
時間化できることとなったものである。更には使用にお
いてもインサートと樹脂層との剥離する虞は殆どなくな
ったものである。Test results Peel strength Remarks Conventional product 5.8 kg/am Peeling between insert and resin layer Inventive product 52.9 kg/am Peeling between insert and membrane (values are average values of 10 test pieces) ) (Effects) As described above, the polyurethane reaction injection molded product of the present invention uses an insert whose surface is coated with an electrodeposition coating having an alcohol group, and the insert is coated and molded with a polyurethane reaction resin raw material. It is. Therefore, the insert-based steel plate or the like and the polyurekne resin or the like coated thereon are firmly bonded. Therefore, even if the molded product is further coated and baked at high temperatures, there is almost no separation between the insert and the molded resin layer, and the coating can be cured in a shorter time. This is now possible. Furthermore, there is almost no possibility that the insert and the resin layer will separate during use.
第１図は本発明実施例品であるマッドガードの正面図、
第２図は第１図のＡ−Ａ線拡大断面図である。Figure 1 is a front view of a mudguard that is an example of the present invention.
FIG. 2 is an enlarged sectional view taken along the line A--A in FIG. 1.
Claims (3)
ンサートを一体に成形したことを特徴とするポリウレタ
ン反応射出成形品。(1) A polyurethane reaction injection molded product characterized by integrally molding an insert having an electrodeposition coating film of a paint having an alcohol group.
囲第１項記載のポリウレタン反応射出成形品。(2) The polyurethane reaction injection molded product according to claim 1, wherein the electrodeposition coating is a cationic electrodeposition coating.
ある特許請求の範囲第２項記載のポリウレタン反応射出
成形品。(3) The polyurethane reaction injection molded product according to claim 2, wherein the main component of the cationic electrodeposition coating film is a modified epoxy resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3816487A JPH0729323B2 (en) | 1987-02-20 | 1987-02-20 | Polyurethane reaction injection molded products |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3816487A JPH0729323B2 (en) | 1987-02-20 | 1987-02-20 | Polyurethane reaction injection molded products |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63203309A true JPS63203309A (en) | 1988-08-23 |
| JPH0729323B2 JPH0729323B2 (en) | 1995-04-05 |
Family
ID=12517762
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3816487A Expired - Lifetime JPH0729323B2 (en) | 1987-02-20 | 1987-02-20 | Polyurethane reaction injection molded products |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0729323B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004078464A1 (en) * | 2003-03-05 | 2004-09-16 | Krauss-Maffei Kunststofftechnik Gmbh | Method for producing parts having a compact polyurethane (pur) sealing layer |
| WO2013088765A1 (en) * | 2011-12-13 | 2013-06-20 | 豊田鉄工株式会社 | Vehicle bumper beam |
-
1987
- 1987-02-20 JP JP3816487A patent/JPH0729323B2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004078464A1 (en) * | 2003-03-05 | 2004-09-16 | Krauss-Maffei Kunststofftechnik Gmbh | Method for producing parts having a compact polyurethane (pur) sealing layer |
| WO2013088765A1 (en) * | 2011-12-13 | 2013-06-20 | 豊田鉄工株式会社 | Vehicle bumper beam |
| JP2013123927A (en) * | 2011-12-13 | 2013-06-24 | Toyoda Iron Works Co Ltd | Bumper beam for vehicle |
| CN104010886A (en) * | 2011-12-13 | 2014-08-27 | 丰田铁工株式会社 | Vehicle bumper beam |
| US8979146B2 (en) | 2011-12-13 | 2015-03-17 | Toyoda Iron Works Co., Ltd. | Vehicle bumper beam |
| CN104010886B (en) * | 2011-12-13 | 2016-05-04 | 丰田铁工株式会社 | Vehicular bumper beam |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0729323B2 (en) | 1995-04-05 |
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