JPS63182391A - Impregnating agent for porous rigid material - Google Patents
Impregnating agent for porous rigid materialInfo
- Publication number
- JPS63182391A JPS63182391A JP1339387A JP1339387A JPS63182391A JP S63182391 A JPS63182391 A JP S63182391A JP 1339387 A JP1339387 A JP 1339387A JP 1339387 A JP1339387 A JP 1339387A JP S63182391 A JPS63182391 A JP S63182391A
- Authority
- JP
- Japan
- Prior art keywords
- impregnating agent
- impregnating
- formula
- porous rigid
- rigid material
- 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
- 239000000463 material Substances 0.000 title abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 38
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000000178 monomer Substances 0.000 abstract description 17
- 239000011148 porous material Substances 0.000 abstract description 15
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002685 polymerization catalyst Substances 0.000 abstract description 7
- 238000006116 polymerization reaction Methods 0.000 abstract description 7
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000004014 plasticizer Substances 0.000 abstract description 4
- 239000003112 inhibitor Substances 0.000 abstract description 3
- VCUMSCGTOGXRMY-UHFFFAOYSA-N 4-ethenyl-1-ethyl-3,5,8-trioxabicyclo[2.2.2]octane Chemical compound C1OC2(C=C)OCC1(CC)CO2 VCUMSCGTOGXRMY-UHFFFAOYSA-N 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 abstract 1
- 238000005470 impregnation Methods 0.000 description 11
- -1 acrylic ester Chemical class 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 230000002950 deficient Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000005266 casting Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010720 hydraulic oil Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- LAQYHRQFABOIFD-UHFFFAOYSA-N 2-methoxyhydroquinone Chemical compound COC1=CC(O)=CC=C1O LAQYHRQFABOIFD-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000010538 cationic polymerization reaction Methods 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000006187 pill Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D31/00—Cutting-off surplus material, e.g. gates; Cleaning and working on castings
- B22D31/002—Cleaning, working on castings
- B22D31/005—Sealing or impregnating porous castings
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Powder Metallurgy (AREA)
- Porous Artificial Stone Or Porous Ceramic Products (AREA)
- Sealing Material Composition (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は多孔性剛性物体の新規な含浸剤、更に詳細には
アルミニウム合金、亜鉛合金、マグネシウム合金、銅合
金、鉄合金等の鋳造物又は粉末冶金焼結体並びにセラミ
ック等の多孔性剛性物体の表面及び内部に有する細孔に
含浸させた後、硬化させて、これを封入・密閉する含浸
剤に関する。Detailed Description of the Invention [Field of Industrial Application] The present invention is a novel impregnating agent for porous rigid objects, more particularly for castings of aluminum alloys, zinc alloys, magnesium alloys, copper alloys, iron alloys, etc. The present invention relates to an impregnating agent that impregnates the surface and pores of porous rigid objects such as powder metallurgy sintered bodies and ceramics, and then hardens them to encapsulate and seal them.
鋳造あるいは焼結金属は自動車の各種部品、電気機械材
料として広い範囲で使用されているが、これらは一般に
表面及び内部に各種形状のひけ巣といわれる細孔が存在
するため、使用にあたっては、これらの漏洩を惹き起こ
す原因となる細孔はシールしなければならない。又、鋳
造品や焼結体に電気メッキまたは化学メッキを行なう場
合、表面に露出している欠陥部を密封しておく必要があ
る。Cast or sintered metals are widely used as various automobile parts and electromechanical materials, but since these metals generally have pores of various shapes called shrinkage cavities on their surfaces and insides, they must be used carefully. Pores that cause leakage must be sealed. Furthermore, when performing electroplating or chemical plating on a cast product or a sintered body, it is necessary to seal the defective parts exposed on the surface.
従来、上記多孔性剛性物体の細孔をシールする方法とし
ては種々の方法が行なわれているが、就中、含浸剤とし
て不飽和エステル、工？キシド、シリコン、フェノール
、シフ １フル７タレート等の熱硬化性樹脂原料を使用
し、細孔中で重合硬化させてこれをシールする方法が一
般に行なわれている。しかしながら、これら含浸剤は粘
度あるいは硬化条件等において種々の欠点を有しており
、必ずしも満足し得るものではなかった。Conventionally, various methods have been used to seal the pores of the above-mentioned porous rigid object, but among them, unsaturated esters, esters, etc. are used as impregnating agents. A commonly used method is to use a thermosetting resin raw material such as oxide, silicone, phenol, or Schiff 1flu7talate, polymerize and harden it in the pores, and then seal it. However, these impregnating agents have various drawbacks in terms of viscosity, curing conditions, etc., and are not always satisfactory.
一方、近年少量の多官能性アクリルエステルモノマー及
び実質的に大部分の（メタ）アクリル酸エステルモノマ
ーを含有する含浸剤が開発された（例えば英国特許第１
，２９７，１０３号、特公昭５０−２０９８９号、特公
昭５４−３６４５号等）。これらの含浸剤は低粘度で浸
透力を持ち、剛性物体表面に付着し先金浸液を水で容易
に洗浄できるという利点を有すると共に、更に適当な触
媒及び抑制剤を組み合わせて使用すれば、比較的低温で
容易に硬化させることができる。On the other hand, impregnating agents containing small amounts of polyfunctional acrylic ester monomers and substantially the majority of (meth)acrylic ester monomers have been developed in recent years (for example, British Patent No.
, No. 297, 103, Special Publication No. 50-20989, Special Publication No. 3645-1974, etc.). These impregnating agents have the advantage of having low viscosity and penetrating power, adhering to the surface of rigid objects, and allowing the pre-metal impregnation liquid to be easily washed away with water. It can be easily cured at relatively low temperatures.
しかし、斯かる（メタ）アクリル酸エステル系含浸剤を
用いて細孔を有する鋳物を含浸処理し、気密性を付与す
る中で、うまくこれを封孔することのできない場合があ
る。すなわち、鋳巣は発生原因によってその形状も多種
多様で、かつ複雑であるが、例えば湯境によって起因す
る欠陥は含浸が劣シ、このような部品の封孔合格率は極
めて悪い場合がある。However, when a casting having pores is impregnated with such a (meth)acrylic acid ester impregnating agent to impart airtightness, it may not be possible to seal the pores successfully. That is, the shapes of blowholes are diverse and complex depending on the cause of their occurrence, but defects caused by hot melting, for example, have poor impregnation, and the sealing success rate of such parts may be extremely poor.
又、欠陥部分のひけ巣の大きさを正副試験のガス漏れ量
（加圧ガス、 ｔｄ ／ ｍＩ ｎ ）で表わすならば
、漏れ量が数百１！ｌｌ／ｍｉｎ以上の不良部品は、含
浸処理しても合格しない場合がある。Furthermore, if the size of the shrinkage cavity at the defective part is expressed in terms of the amount of gas leakage (pressurized gas, td/mI n ) in the primary and secondary tests, the amount of leakage is several hundred! A defective part with a rate of 1 liter/min or more may not pass the test even if it is impregnated.
この様な大きな漏れ量をもつ不良部品にあっては、含浸
処理前に特大の漏れであった部品が含浸処理後は中漏れ
に１大大漏れであった部品が小漏れに、大漏れであった
部品が微量漏れに改善されるという一般的な傾向が６Ｄ
、−回の含浸処理では合格とならない。その上、仮に特
大の漏れが封孔合格することがあっても耐久性が乏しく
、例えば自動車部品であれば、装着後、予想外に早い漏
れを生じる結果を来たす。この様々事例は有機含浸液の
場合、硬化時のひび割れ、硬化物の応力ひずみ、剛性物
体との密接性、含浸剤の巣孔からの流出、硬化物の体積
収縮など、直接に含浸液組成の性能に起因する。For defective parts with such a large amount of leakage, parts that had an extra-large leak before impregnation treatment became medium leaks, parts with large leaks became small leaks, and parts with large leaks became large leaks after the impregnation treatment. There is a general tendency that parts with small leakage are improved by 6D.
, − times of impregnation treatment will not pass the test. Moreover, even if an oversized leak were to pass the sealing process, the durability would be poor, and for example, in the case of automobile parts, leakage would occur unexpectedly quickly after installation. In the case of organic impregnating liquids, these various cases can be directly affected by the composition of the impregnating liquid, such as cracks during curing, stress strain of the cured product, closeness to rigid objects, outflow of the impregnant from pores, and volumetric shrinkage of the cured product. Due to performance.
ひけ巣を有する圧漏れ鋳造部品は、そのすべてが含浸対
象となるのではなく、救済されるものはその欠陥の直接
の原因であるひけ巣の直径の大きさによっておのずと一
定の限界があるものとされている。つまシ、一定量以上
の圧漏れ部品は含浸対象から除外するとか、−回の含浸
で合格しない部品は、再度含浸しないで、溶解されてい
る。Not all pressure leakage cast parts that have shrinkage cavities are subject to impregnation, but there is a certain limit to what can be repaired depending on the diameter of the shrinkage cavity that is the direct cause of the defect. has been done. However, parts that leak more than a certain amount are excluded from the impregnating target, and parts that do not pass the impregnation process are dissolved without being impregnated again.
重合硬化物のひび割れは、主剤のメタクリル酸エステル
並びに架橋剤等の組成モノマーの反応性比あるいは重合
速度の相違に基づいて生じる内部応力のひずみに起因す
るものである。また、接触する金属に対する重合硬化物
の密着性は、含有上ツマ−と金属との間の固有の親和力
に基づくものである。更に、メタクリル酸エステル系樹
脂は、一般のビニルモノマーと同様に、重合する際に大
きな収縮を伴うことが知られておシ、ビニルモノマーの
重合時の体積収縮率の例を挙げると、スチレン１４．５
％、アクリロニトリル３１％、酢酸ビニル２１％、メタ
クリル酸エチル１７．８％、メタクリル酸メチル２１．
２％、シアリルフタレート１１．８％である。この現象
は材料科学の観点から大きな問題となっているが、とり
わけ多孔性剛性物体を含浸処理して気密性を付与する含
浸剤にとって、硬化時の体積収縮率はその性能に重要な
影響を有する。Cracks in the polymerized cured product are caused by internal stress distortion caused by differences in the reactivity ratio or polymerization rate of the methacrylic acid ester as the main ingredient and the composition monomers such as the crosslinking agent. Further, the adhesion of the polymerized cured product to the metal it comes into contact with is based on the inherent affinity between the contained material and the metal. Furthermore, it is known that methacrylic acid ester resins, like general vinyl monomers, undergo large shrinkage during polymerization. .5
%, acrylonitrile 31%, vinyl acetate 21%, ethyl methacrylate 17.8%, methyl methacrylate 21.
2%, and sialyl phthalate 11.8%. This phenomenon is a big problem from the perspective of materials science, but especially for impregnants that impregnate porous rigid objects to make them airtight, the volumetric shrinkage rate during curing has an important effect on their performance. .
〔問題点を解決するための手段〕
斯かる実状において、本発明者は鋭意研究を行った結果
、非収縮性モノマーである後記一般式（Ｉ）及び（肩）
で表わされるビシクロオルトエステル類及びスピロオル
トエステル類が多孔性剛性物体の含浸剤として優れた特
性を有すること、更に当該非収縮性モノマーと（メタ）
アクリル酸エステルを組合せると優れた含浸剤が得られ
ることを見出し、本発明を完成した。[Means for Solving the Problems] Under such circumstances, the present inventors have conducted intensive research and found that the following general formulas (I) and (shoulder), which are non-shrinkable monomers, are non-shrinkable monomers.
Bicycloorthoesters and spiroorthoesters represented by the above have excellent properties as an impregnating agent for porous rigid objects, and furthermore, the non-shrinkable monomer and (meth)
It was discovered that an excellent impregnating agent can be obtained by combining acrylic acid esters, and the present invention was completed.
従って、本発明は、次の一般式（Ｉ）
（式中％ Ｒ１は水素原子又は低級アルキル基を示す）
で表わされるビンクロオルトエステル類又は次の一般式
（Ｉ）
（式中、ｎは１〜３の整数、ｍは１〜８の整数を示す）
で表わされるスピロオルトエステル類を含有することを
特徴とする多孔性剛性物体用含浸剤を提供するものであ
る。Therefore, the present invention provides vinyl orthoesters represented by the following general formula (I) (in which % R1 represents a hydrogen atom or a lower alkyl group) or the following general formula (I) (in which n is The present invention provides an impregnating agent for porous rigid objects, which is characterized by containing a spiro-orthoester represented by the following (integer of 1 to 3, m is an integer of 1 to 8).
更に本発明は、上記ビシクロオルトエステル類（Ｉ）又
はスピロオルトエステル類（璽）及び（メタ）アクリル
酸エステルを含有する多孔性剛性物体用含浸剤を提供す
るものである。Furthermore, the present invention provides an impregnating agent for porous rigid objects containing the above-mentioned bicycloorthoester (I) or spiroorthoester (seal) and (meth)acrylic acid ester.
本発明におりて、（Ｉ）式のビシクロオルトエステル類
としては、例えば１−ビニル−４−二ｆｋ−２，６，７
−）リオキサピシクロ（２，２，２）オクタン、１−ｆ
ロペニルー４−メチル−２，６，７−）リオキサピシク
ロ（２，２，２）オクタン、１−ブテニル−４−メチル
−２，６，７−）リオキサピシクロ（２，２，２）オク
タン等が、また（璽）式のスピロオルトエステル類とし
ては、例えば２−）ｆレン−１，４，６−）＋Ｊオキサ
スピロ（４，６）ウンデカン、２−メチレン−１゜４．
６−）リオキサスピロ（４，６）ドデカン、２−メチレ
ン−１，４，６−ドリオキサスビロ（４，６）デカン等
が挙げられる。In the present invention, the bicycloorthoesters of formula (I) include, for example, 1-vinyl-4-2fk-2,6,7
-) rioxapicyclo(2,2,2)octane, 1-f
Lopenyl-4-methyl-2,6,7-)lioxapicyclo(2,2,2)octane, 1-butenyl-4-methyl-2,6,7-)lioxapicyclo(2,2,2)octane, etc. Examples of spiro-orthoesters of the formula (seal) include 2-)f-lene-1,4,6-)+Joxaspiro(4,6)undecane, 2-methylene-1°4.
6-)rioxaspiro(4,6)dodecane, 2-methylene-1,4,6-dorioxaspiro(4,6)decane, and the like.
本発明の含浸剤は、重合性モノマーとして（Ｉ）又は（
Ｉ）式の化合物を単独で使用することもできるが、これ
に他の重合性モノマーを併用することもできる。他の重
合性モノマーとしては、従来含浸剤として使用されてい
るものは何れも使用することができるが、その中でも（
メタ）アクリル酸エステル類が特に好ましい。The impregnating agent of the present invention contains (I) or (
Although the compound of formula I) can be used alone, it can also be used in combination with other polymerizable monomers. As other polymerizable monomers, any of those conventionally used as impregnating agents can be used, but among them (
Particularly preferred are meth)acrylic acid esters.
（メタ）アクリル酸エステル類と併用する場合、（Ｉ）
又は（Ｉ）式の化合物が全重合性モノマーの１０％ｗ
／ ｖ以上になるようにするのが好ましく％（Ｉ）又は
（Ｉ）式の化合物がこれよシ少ないと体積収縮率が大き
くなシ本発明の目的は達成されない。When used in combination with (meth)acrylic esters, (I)
or the compound of formula (I) is 10%w of the total polymerizable monomers
It is preferable that the amount of % (I) or the compound of formula (I) is less than this because the volumetric shrinkage rate will be large and the object of the present invention will not be achieved.
本発明の含浸剤は、前記重合性モノマーに１従来一般に
使用されている重合触媒、重合抑制剤、可塑剤等を適宜
配合することによシ製造される。The impregnating agent of the present invention is produced by suitably blending the polymerizable monomer with a polymerization catalyst, a polymerization inhibitor, a plasticizer, etc. that have been commonly used in the past.
重合触媒としては、例えばベンゾイル、Ｑ−オキサイド
、メチルエチルケトンノｑ−オキサイド、各種アルキル
／Ｑ−エステル、アゾビスイソブチロニトリル、レドッ
クス触媒、有機金属過酸化物等のラジカル重合触媒；
ＢＦ、、ｈｔｃｔ、等のハロダン化金属、Ｃ１，ＣＣ０
ＯＨ、Ｆ、ＣＣｏｏｎ等のＨ供与物質、ペンシルスルホ
ニウム塩、ムｔｃｔ、ｃ、ｍ、等のカチオン重合触媒が
挙げられる。ラジカル重合触媒及びカチオン重合触媒は
、それぞれ含浸剤全組成のＯ，ＯＳ〜５％ｗ ／ ｗ及
び０．０１〜５％ｗ ／ ｙ配合するのが好ましい。Examples of polymerization catalysts include radical polymerization catalysts such as benzoyl, Q-oxide, methyl ethyl ketone q-oxide, various alkyl/Q-esters, azobisisobutyronitrile, redox catalysts, and organometallic peroxides;
Metal halides such as BF, htct, C1, CC0
Examples include H donor substances such as OH, F, and CCoon, cationic polymerization catalysts such as pencil sulfonium salts, mu-tct, c, m, and the like. The radical polymerization catalyst and the cationic polymerization catalyst are preferably blended in an amount of O, OS ~5% w/w and 0.01~5% w/y of the total impregnating agent composition, respectively.
重合抑制剤としては、例えばヒドロキノン、メトキシヒ
ドロキノン等の置換ヒドロキノン類、各種アルキル化フ
ェノール類等が挙げられ、これらは含浸剤全組成の０．
００１〜２％Ｗ ／ ｗ配合するのが好ましい。Examples of the polymerization inhibitor include substituted hydroquinones such as hydroquinone and methoxyhydroquinone, various alkylated phenols, and the like.
It is preferable to mix 0.001 to 2% W/w.
可塑剤としては、例えばフタル酸エステル、リン酸エス
テル、工？キシ系脂肪酸エステル、脂肪族二塩基酸エス
テル等が挙げられ、これらは含浸剤全組成の０．５〜２
０％Ｗ ／ ’ＩＦ配合、するのが好ましい。Examples of plasticizers include phthalate esters, phosphate esters, and plasticizers. Examples include xyl fatty acid esters, aliphatic dibasic acid esters, etc., and these account for 0.5 to 2 of the total composition of the impregnating agent.
It is preferable to mix 0% W/'IF.
本発明の含浸剤を用いて多孔性剛性物体の細孔をシール
するＫは、自体公知の方法が採用される。すなわち、多
孔性剛性物体を減圧下含浸剤に浸漬して、孔中に含浸剤
を吸引し、これを９０℃で約１０分間処理して重合性モ
ノマーを重合させて孔をシールする。To seal the pores of a porous rigid object using the impregnating agent of the present invention, a method known per se is employed. That is, a porous rigid object is immersed in an impregnating agent under reduced pressure to draw the impregnating agent into the pores, and then treated at 90° C. for about 10 minutes to polymerize the polymerizable monomer and seal the pores.
本発明含浸剤の重合性モノマーは重合による体積収縮が
ないと共に、その重合物は剛性物体との密着性がよいの
で、当該孔を気密にシールし、漏れを完全に防止するこ
とができる０
〔実施例〕
次に実施例を挙げて説明する。The polymerizable monomer of the impregnating agent of the present invention has no volume shrinkage due to polymerization, and the polymer has good adhesion to rigid objects, so the pores can be airtightly sealed and leakage can be completely prevented. Examples] Next, examples will be described.
実施例１
含浸剤の調製：
ｌ−ビニル−４−エチル−２，６，７−）リオキサビシ
クロ（２，２，２）オクタン（式（ｒ）の重合性モノマ
ー）５０ｆ、 メタクリル酸２−ヒドロキシプロピル
５０Ｆ及びトリメタクリル酸トリメチロールゾロノ９ン
１０Ｆを混合、攪拌し、この混合溶液ＫＰ−メトキシフ
ェノール０．１ｆ、ペンシルスルホニウム塩１ｒ、次論
でアゾビスイソブチロニトリル０、２５ ｔを加え、十
分攪拌、溶解して含浸剤を得る。このように得られた含
浸剤は９０℃に加熱すると、およそ４分２０秒で硬化し
、樹脂化する。Example 1 Preparation of impregnation agent: l-vinyl-4-ethyl-2,6,7-)lioxabicyclo(2,2,2)octane (polymerizable monomer of formula (r)) 50f, methacrylic acid 2- Hydroxypropyl 50F and trimethylolzolononine 9-trimethacrylate 10F were mixed and stirred, and this mixed solution was added with 0.1f of KP-methoxyphenol, 1r of pencilsulfonium salt, and 0.25t of azobisisobutyronitrile. Add, stir thoroughly, and dissolve to obtain an impregnating agent. When the impregnating agent thus obtained is heated to 90° C., it hardens and becomes a resin in approximately 4 minutes and 20 seconds.
実施例２
含浸剤の調製：
２−メチレン−１，４，６−）リオキサスビロ（４，６
）クンデカン（式（Ｉ）の重合性モノマー）ｓｏｐ、メ
タクリル酸２−ヒドロキシゾロぎル５０Ｆ及びトリメタ
クリル酸トリメチロールゾロノ９ン１０ｆを混合、攪拌
シ、この混合溶液４Ｃｐ−メトキシフェノール０．１２
１ペンゾルスルホニクム塩ｌＦ、次いでアゾビスイソブ
チロニトリル０．２５ Ｆを加え、十分攪拌、溶解して
含浸剤を得る。このように得られた含浸剤は９０℃に加
熱するとおよそ３分３０秒で硬化し、樹脂化する。Example 2 Preparation of impregnating agent: 2-methylene-1,4,6-)rioxasubilo(4,6
) Kundecane (polymerizable monomer of formula (I)) sop, 2-hydroxyzorogyl methacrylate 50F and trimethylolzolonon trimethacrylate 10f were mixed, stirred, and this mixed solution 4Cp-methoxyphenol 0.12
1 F of pensol sulfonicum salt and then 0.25 F of azobisisobutyronitrile are added and thoroughly stirred and dissolved to obtain an impregnating agent. When the impregnating agent thus obtained is heated to 90° C., it hardens and becomes a resin in approximately 3 minutes and 30 seconds.
実施例３
多孔性剛性物体の含浸処理：
（Ｉ） あらかじめ溶剤洗浄し、十分乾燥した巣を有
する圧漏れダイカスト製品・ギヤーケース９個を含浸タ
ンク（オートクレーブ）内に入れ、密閉後タンク内を真
空？ンゾで１〜３ ｍｍＨｆＩ／ｃ：１Ｇ空引きして、
１５分間保持したのち、実施例１で調製した含浸剤（本
発明品）を、タンク内の真空の吸引力によって、中の鋳
物が完全に浸漬されるまで注入する。次いで、含浸タン
クを大気圧に戻したのち、コンプレッサーによる圧搾空
気を用いて、６Ｈ／ｃｘ”の加圧状態にして、１５分間
保持する。その後、再び大気圧に戻し、含浸タンクから
含浸液を抜いて、中の鋳物を取シ出し、付着している含
浸液を液切シし、更に表面に残る含浸液は洗浄水あるい
は溶剤を用いて洗浄する。洗浄後ただちに９０℃の熱水
中Ｋ１０分間浸漬し、巣孔中に充填した含浸液を硬化さ
せる。硬化後、圧搾空気（Ｉに＃、／ＩＩ”）を用いて
、水没による正副試験を行った。また、従来品としては
、メタクリル酸−２−ヒドロキシ７Ｏｒ：１ピル（８５
Ｆ）、）リメタクリル酸トリメチロールゾロノｑン（ｔ
５Ｆ）、ｐ−メトキシフエ／−ル（０，ＩＦ）及びアゾ
ビスイソブチロニトリル（０，２５Ｆ）からなる含浸液
を使用し、本発明品と同様に操作した。Example 3 Impregnation treatment of a porous rigid object: (I) Nine pressure-leak die-cast products/gear cases with cavities that have been previously washed with a solvent and sufficiently dried are placed in an impregnation tank (autoclave), and after sealing, the tank is evacuated. ? 1 to 3 mmHfI/c: 1G empty with Nzo,
After holding for 15 minutes, the impregnating agent prepared in Example 1 (product of the present invention) is injected into the tank by the suction force of the vacuum in the tank until the casting inside is completely immersed. Next, after returning the impregnating tank to atmospheric pressure, it is pressurized to 6H/cx'' using compressed air from a compressor and held for 15 minutes.Then, the pressure is returned to atmospheric pressure again, and the impregnating liquid is drained from the impregnating tank. Remove the casting inside, drain the impregnating liquid that has adhered to it, and wash the impregnating liquid remaining on the surface using cleaning water or a solvent. Immediately after washing, wash it in K10 hot water at 90°C. The impregnating liquid filled into the pores was immersed for a minute to harden. After curing, a positive and negative test by submersion in water was conducted using compressed air (# for I, /II''). In addition, as a conventional product, methacrylic acid-2-hydroxy 7Or:1 pill (85
F),) trimethylolzolonone methacrylate (t
Using an impregnating solution consisting of p-methoxyphenol (0, IF) and azobisisobutyronitrile (0,25F), the same procedure as in the product of the present invention was performed.
表１ 正副試験結果
試験圧（空気） ＠ １ ’Ｊ ／ ｔ＊ ”合格：圧
漏れを認めず
（２） 自動車用アルミホイールは低圧鋳造品である
が、引は巣による圧漏れ不良品が発生する。鋳造工場で
は漏れ量について特大、大火、大、中、小、微量と定性
的に表示しているが、このうち特に漏れ量の大きな特大
、大火、大の不要ホイールを選び、この３段階について
、本発明品と従来品の含浸効果を（Ｉ）と同様にして比
較した。結果を表２に示すが、明らかに本発明による含
浸剤を適用した場合は、顕著な効果を示している。Table 1 Original and sub-test results Test pressure (air) @ 1 'J/t* "Passed: No pressure leak observed (2) Aluminum wheels for automobiles are low-pressure cast products, but some defective products with pressure leaks due to shrinkage cavities occurred. In foundries, the amount of leakage is qualitatively displayed as extra-large, large-scale, large, medium, small, and trace amounts, and among these, unnecessary wheels with especially large leakage amounts of extra-large, large-scale, and large are selected and classified into three levels. The impregnating effects of the inventive product and the conventional product were compared in the same way as in (I).The results are shown in Table 2, and it is clear that the impregnating agent of the present invention has a remarkable effect. .
以下余白・
表２ 正副試験結果
（３） 実施例１及び実施例２によシ調製した含浸剤
の性能を、耐熱性と耐作動油性について、従来品と比較
した。この試験にはドリルで０．６ ｍｍｇの貫通孔を
あけたアルミ板（材質ＡＣ４Ｃアルぐ合金、板厚Ｉ Ｑ
ｍｍ ）の孔部分に含浸剤を注入・硬化させたものを
テストピースとして使用した。Margins below: Table 2 Original and Sub Test Results (3) The performance of the impregnating agents prepared in Examples 1 and 2 was compared with conventional products in terms of heat resistance and hydraulic oil resistance. For this test, an aluminum plate (material: AC4C aluminum alloy, plate thickness: IQ) with a through hole of 0.6 mm in diameter was used.
A test piece in which an impregnating agent was injected into the hole (mm) and cured was used as a test piece.
耐熱性試験にはテストピースを１５０℃の恒温槽（熱風
循環式）の中に置き、２４時間毎に正副試験を実施した
。各含浸液のテストピースの圧漏れを生じるまでの時間
を比較した。試験結果ｔ−第１図に示す。For the heat resistance test, the test piece was placed in a constant temperature bath (hot air circulation type) at 150° C., and a positive and negative test was conducted every 24 hours. The time required for pressure leakage of test pieces for each impregnating solution was compared. The test results are shown in FIG.
耐作動油性試験にはテストぎ−スを恒温槽に張込んだ１
２５℃のエンジンオイル中に浸漬し、３日目毎に正副試
験を実施した。各含浸液のテストピースの圧漏れを生じ
るまでの日数を比較した。試験結果を第２図に示す。For the hydraulic oil resistance test, a test gear was placed in a constant temperature bath1.
It was immersed in engine oil at 25° C., and a positive and negative test was conducted every third day. The number of days until pressure leakage occurred for the test pieces of each impregnation solution was compared. The test results are shown in Figure 2.
第１図及び第２図から、本発明品が従来品に比べて、耐
熱性、耐作動油性ともに優れていることが証明される。From FIG. 1 and FIG. 2, it is proven that the product of the present invention is superior to conventional products in both heat resistance and hydraulic oil resistance.
実施例４
１−ビニル−４−エチル−２，６，７−）リオキサピシ
クロ（２、２、２）オクタン又は２−メチレン−１，４
，６−）リオキサスビ０（４，６）ウンデカンとメタア
クリル酸２−ヒドロキシｆＱピルの混合割合を変えた含
浸剤を実施例１又は２と同様にして調製した。この含浸
剤の比重を測定し、次いでビーカー中に含浸剤を少量採
取して、９０℃熱水中で１０分間加熱して硬化物を得、
この硬化物を一定寸法に切断してその容積と重量を測定
して、比重を求める。含浸剤と硬化物の比重から重合に
よる体積収縮率を算出する。この結果を表３に示す。Example 4 1-vinyl-4-ethyl-2,6,7-)lioxapicyclo(2,2,2)octane or 2-methylene-1,4
, 6-)Impregnating agents were prepared in the same manner as in Example 1 or 2, with different mixing ratios of rioxasubio(4,6)undecane and 2-hydroxy fQ pill methacrylate. The specific gravity of this impregnating agent was measured, and then a small amount of the impregnating agent was collected in a beaker and heated in 90°C hot water for 10 minutes to obtain a cured product.
This cured product is cut to a certain size, its volume and weight are measured, and the specific gravity is determined. The volume shrinkage rate due to polymerization is calculated from the specific gravity of the impregnating agent and the cured product. The results are shown in Table 3.
以下余白 表３ 体積収縮率Margin below Table 3 Volumetric shrinkage rate
第１図は本発明含浸剤で細孔を封入・密閉したテストピ
ースの耐熱性試験結果を、第２図は同テストピースの耐
作動油性試験結果を示す。
以上FIG. 1 shows the results of a heat resistance test of a test piece whose pores were sealed and sealed with the impregnating agent of the present invention, and FIG. 2 shows the results of a hydraulic oil resistance test of the same test piece. that's all
Claims (1)
（II） ▲数式、化学式、表等があります▼（II） （式中、ｎは１〜３の整数、ｍは１〜８の整数を示す） で表わされるスピロオルトエステル類を含有することを
特徴とする多孔性剛性物体用含浸剤。 ２、（メタ）アクリル酸エステル、並びに次の一般式（
I ） ▲数式、化学式、表等があります▼（ I ） （式中、Ｒ＿１は水素原子又は低級アルキル基を示す） で表わされるビシクロオルトエステル類又は次の一般式
（II） ▲数式、化学式、表等があります▼（II） （式中、ｎは１〜３の整数、ｍは１〜８の整数を示す） で表わされるスピロオルトエステル類を含有することを
特徴とする多孔性剛性物体用含浸剤。[Scope of Claims] 1. Bicycloorthoesters represented by the following general formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1 represents a hydrogen atom or a lower alkyl group) Or spiroorthoesters represented by the following general formula (II) ▲Mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, n is an integer of 1 to 3, m is an integer of 1 to 8) An impregnating agent for porous rigid objects characterized by containing. 2, (meth)acrylic acid ester, and the following general formula (
I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1 represents a hydrogen atom or a lower alkyl group) Bicycloorthoesters or the following general formula (II) ▲Mathematical formulas, chemical formulas, There are tables, etc. ▼ (II) For porous rigid objects characterized by containing spiroorthoesters represented by (where n is an integer of 1 to 3 and m is an integer of 1 to 8) Impregnating agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1339387A JPS63182391A (en) | 1987-01-23 | 1987-01-23 | Impregnating agent for porous rigid material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1339387A JPS63182391A (en) | 1987-01-23 | 1987-01-23 | Impregnating agent for porous rigid material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63182391A true JPS63182391A (en) | 1988-07-27 |
Family
ID=11831863
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1339387A Pending JPS63182391A (en) | 1987-01-23 | 1987-01-23 | Impregnating agent for porous rigid material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63182391A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2724044A1 (en) * | 1994-08-30 | 1996-03-01 | Thomson Csf | PROCESS FOR THE PROTECTION OF POROUS COMPONENTS SUBJECT TO HIGH POTENTIAL DIFFERENCES AND COMPONENTS THUS PRODUCED |
| JP2008128386A (en) * | 2006-11-21 | 2008-06-05 | Cosmo Koki Co Ltd | Pipe fitting |
| JP2008138787A (en) * | 2006-12-01 | 2008-06-19 | Cosmo Koki Co Ltd | Pipe fitting for branch member |
| JP2008296257A (en) * | 2007-05-31 | 2008-12-11 | Nippon Giken:Kk | Method for removing residual washing liquid in organic impregnation sealing method |
| CN105921725A (en) * | 2016-05-30 | 2016-09-07 | 初丽萍 | Method for magnetic nanoparticle modified methacrylate magnetic impregnant for metal castings |
| CN109227030A (en) * | 2018-10-24 | 2019-01-18 | 汉江弘源襄阳碳化硅特种陶瓷有限责任公司 | A kind of crack forming mechanism and reinforcement of silicon carbide ceramics pump flow passage components |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5365360A (en) * | 1976-11-25 | 1978-06-10 | Toagosei Chem Ind Co Ltd | Pore-sealing of multiporous article |
| JPS543645A (en) * | 1977-06-08 | 1979-01-11 | Riken Piston Ring Ind Co Ltd | Method for inscribing pistonring |
| JPS59164335A (en) * | 1983-03-10 | 1984-09-17 | Toagosei Chem Ind Co Ltd | Curable resin composition for sealing or casting |
-
1987
- 1987-01-23 JP JP1339387A patent/JPS63182391A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5365360A (en) * | 1976-11-25 | 1978-06-10 | Toagosei Chem Ind Co Ltd | Pore-sealing of multiporous article |
| JPS543645A (en) * | 1977-06-08 | 1979-01-11 | Riken Piston Ring Ind Co Ltd | Method for inscribing pistonring |
| JPS59164335A (en) * | 1983-03-10 | 1984-09-17 | Toagosei Chem Ind Co Ltd | Curable resin composition for sealing or casting |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2724044A1 (en) * | 1994-08-30 | 1996-03-01 | Thomson Csf | PROCESS FOR THE PROTECTION OF POROUS COMPONENTS SUBJECT TO HIGH POTENTIAL DIFFERENCES AND COMPONENTS THUS PRODUCED |
| EP0700058A1 (en) * | 1994-08-30 | 1996-03-06 | Thomson-Csf | Process for protection of porous components submitted to high potential differences and components manufactured by this process |
| WO2004075215A1 (en) * | 1994-08-30 | 2004-09-02 | Jean-Pierre Delvinquier | Method for protection of porous components subject to high potential differences and components produced thus |
| JP2008128386A (en) * | 2006-11-21 | 2008-06-05 | Cosmo Koki Co Ltd | Pipe fitting |
| JP2008138787A (en) * | 2006-12-01 | 2008-06-19 | Cosmo Koki Co Ltd | Pipe fitting for branch member |
| JP2008296257A (en) * | 2007-05-31 | 2008-12-11 | Nippon Giken:Kk | Method for removing residual washing liquid in organic impregnation sealing method |
| CN105921725A (en) * | 2016-05-30 | 2016-09-07 | 初丽萍 | Method for magnetic nanoparticle modified methacrylate magnetic impregnant for metal castings |
| CN109227030A (en) * | 2018-10-24 | 2019-01-18 | 汉江弘源襄阳碳化硅特种陶瓷有限责任公司 | A kind of crack forming mechanism and reinforcement of silicon carbide ceramics pump flow passage components |
| CN109227030B (en) * | 2018-10-24 | 2019-08-27 | 汉江弘源襄阳碳化硅特种陶瓷有限责任公司 | A kind of crack forming mechanism and reinforcement of silicon carbide ceramics pump flow passage components |
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