CN1044128C - Surface thickening agent for organic silicon adhesive - Google Patents
Surface thickening agent for organic silicon adhesive Download PDFInfo
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- CN1044128C CN1044128C CN93112608A CN93112608A CN1044128C CN 1044128 C CN1044128 C CN 1044128C CN 93112608 A CN93112608 A CN 93112608A CN 93112608 A CN93112608 A CN 93112608A CN 1044128 C CN1044128 C CN 1044128C
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- organic silicon
- thickening agent
- silicon adhesive
- surface thickening
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Abstract
The present invention relates to a surface thickening agent for organic silicon adhesive, which comprises titanium ester, organic silicon resin, organic silicon ester and organic solvent. The preparation method of the present invention comprises the steps: reaction is carried out under an ordinary temperature; the organic silicon resin is firstly dissolved in the organic solvent under continuous agitation, and then the titanium ester and the organic silicon ester are added in the solution. The surface thickening agent gas the advantages of good storage stability, wide application scope, good heat resistance, etc.
Description
The present invention relates to the surface thickening agent that a kind of organic silicon adhesive is used.
With silicone resin and room temperature vulcanized silicone rubber is that the many components of main raw composition and the organic silicon adhesive and the sealing agent of single-component are widely used in various fields.The organic silicon adhesive great majority of this many components and single-component must be handled bonded material surface by means of suitable surface thickening agent, just can make solid material surface have certain bond strength.
In prior art, surface thickening agent for organic silicon adhesive generally is made up of silane coupling agent and organic solvent, as described in USP3481815 and the Fr.1509762.Silane coupling agent has RSiX
3General structure, wherein R is-CH=CH
2,-CH
2CH
2CH
3Deng group, X is the group of facile hydrolysis, as-OCH
3,-OC
2H
3Comprise aliphatic hydrocarbon, aromatic hydrocarbon, halogenated aliphatic hydrocarbon or aromatic hydrocarbon, ketone and alcohol etc. with organic solvents such as Cl.Domestic silane coupling agent commonly used has vinyltriethoxysilane, γ-An Bingjisanyiyangjiguiwan, γ-sulfydryl for propyl trimethoxy silicane and γ-glycidyl ethers propyl trimethoxy silicane or the like.
Adopt the above-mentioned surface thickening agent of forming by silane coupling agent and organic solvent that solid material surface is carried out tackified finish,, have following some shortcomings part though can solve the adhesion problem of some organic silicon adhesives; One, above-mentioned thickening agent has almost been thrown the tackify effect to metallic surface and many frostings of low surface energies such as gold and silver and nickel.Two, it is not good enough to contain the thickening agent resistance toheat that the organo-silicon coupling agent of amino and epoxide group and organic solvent form, and the tolerant temperature of institute is below 175 ℃ during long term operation; Adopt R to be-CH=CH
2Or-CH
2CH
2CH
3During the silane coupling agent of group, though resistance toheat can increase, its tackify effect is relatively poor.Three, the thickening agent period of storage of silane coupling agent and organic solvent composition is short, and phenomenons such as precipitation and gel easily take place, and influences the tackify effect.
The wide area surface thickening agent that the purpose of this invention is to provide the bonding usefulness of multiple material such as a kind of organic silicon adhesive and metal, plastics.It is not only applicable to the tackified finish of common metal materials such as steel, aluminium and copper, but also is applicable to the tackified finish of the metallic surface of many low surface energies such as gold and silver, nickel and chromium.This thickening agent has good resistance toheat, good storage stability and to the adaptability of construction technology and environment.
The present invention is achieved in that the composition of the surface thickening agent that this organic silicon adhesive is used comprises:
A. titanic acid ester, 3～20% (weight)
B. silicone resin: 2～30% (weight)
C. organosilicon acid esters: 10～25% (weight)
D. organic solvent: 45～85% (weight)
The chemical molecular formula general formula of the titanic acid ester described in the said components is: Ti (OR)
4, R is that carbonatoms is 2～4 alkyl in the formula.These titanic acid ester comprise; Titanium ethanolate, metatitanic acid n-propyl, isopropyl titanate, tetrabutyl titanate, iso-butyl titanate etc.Titanic acid ester is the main component of thickening agent of the present invention, and it is very easily hydrolysis in air, and and then condensation.It is bonded solid material surface and the coupling agent between the organosilicon polymer in the tackiness agent.
Silicone resin described in the said components is the reaction product of water glass and hexamethyldisiloxane, and this is reflected under the hydrochloric acid existence and carries out.This silicone resin is a kind of film forming material, and it has different molecular structures along with the difference of synthesis condition.Organosilicon acid esters described in the said components is ortho-silicate or its hydrolysis condensation product.Hydrolysis-condensation reaction carries out under acidic conditions.This class ortho-silicate comprises: methyl orthosilicate, ethyl orthosilicate, orthosilicic acid n-propyl, orthosilicic acid isopropyl ester, the positive butyl ester of orthosilicic acid, orthosilicic acid isobutyl ester etc.Hydrolysis condensation product can be dimer, tripolymer, the tetramer, pentamer and six aggressiveness etc.Organic solvent described in the said components can be selected from alkane, halogenation alkane, aromatic hydrocarbons, halogenated aromatic or their mixture.These organic solvents have suitable evaporation rate.The alkane and the halogenation alkane that are suitable for have normal hexane, hexanaphthene, isohexane, heptane, octane-iso, methylcyclohexane, sherwood oil, non-leaded gasoline, trieline, zellon, ethylene dichloride and tetrachloroethane etc.The aromatic hydrocarbon and the halogenated aromatic that are suitable for have: benzene,toluene,xylene, monochloro-benzene, dichlorobenzene, monochlorotoluene and toluene dichloride etc.
Organic solvent the best in the component of the present invention is the non-halogenated alkane with moderate volatility, as normal hexane, normal heptane, hexanaphthene, octane-iso and sherwood oil etc.
During the present invention formed, titanic acid ester content the best was 5～10% (weight).
The preparation method of surface thickening agent for organic silicon adhesive of the present invention is that reaction is carried out at normal temperatures, under constantly stirring, earlier silicone resin is dissolved in the organic solvent fully, then, adds titanic acid ester and organosilicon acid esters in the solution that makes.
Surface thickening agent for organic silicon adhesive of the present invention compared with prior art has following advantage: 1. the present invention is a kind of wide area surface thickening agent, it not only has good tackify effect to metal material surfaces such as steel, aluminium and copper, and it is also fine to the metallic surface tackify effect of low surface energies such as gold and silver and nickel, in addition, the many frostings of tackify comprise polyester plastics, unplasticizied polyolefin plastics, polyamide plastics and Acrylite or the like effectively.2. the present invention has splendid heat-resistant air aging property, can long term operation under 200 ℃ temperature, and can short-term job under 250 ℃ temperature.3. the present invention has splendid package stability, deposit 2 years after, the outward appearance of product, viscosity and the equal no change of tackify effect.4. construction technology of the present invention is simple, and is good to the adaptability of environment, and dew is put in air more stable behind the coated.
Now the invention will be further described in conjunction with the embodiments.
Below each embodiment, except that indicating especially, " part " is " weight part "; The organic silicon adhesive that uses in order to the effect that shows the present invention is composed as follows: component numbering component title consumption (weight part)
1. room temperature vulcanized silicone rubber (kinetic viscosity 40～50Pas) 100
2. the hydrophobicity gas phase white 35 crossed of silane treatment
Carbon black (the about 200m of specific surface area
2/ g)
3. titanium dioxide (rutile-type) 3
4. the ultrafine particle light calcium carbonate 3
5. titanium dioxide (Y type) 0.8
6. the silicane linking agent 3
7. ethyl orthosilicate 3
8. the silicane linking agent 3
9. organotin 0.5
Wherein 1. to 5. component is with the mixing body of paste of making of opening rubber mixing machine, as the first component, 6. extremely 8. component mixes even back as component B.Use preceding first, second two components are mixed to be solidified into cross-linked rubber, play the function of tackiness agent.The performance of solidifying the back tackiness agent is as follows:
Under the room temperature after 200 ℃ * 200h hot air aging two components mix the back tackiness agent＜2h serviceable time 5.7 4.5 tensile strengths, 500 400 tensile yield, % hardness, Shao Shi A type 43 37 tear strengths, kN/m 16 15 temperature limit of brittleness-70 ℃ are constantly--and embodiment one
With water glass and hexamethyldisiloxane in the presence of hydrochloric acid, react and silicone resin be dissolved in 75 parts of heptane for 2 parts.When organic silicone resin all after the dissolving, add 11 parts of the tetraethyl silicate of contracting, this tetraethyl silicate that contracts is to compile the poly-macromole products that form by four to five ethyl orthosilicate molecules.Then under agitation in solution, add 3.5 parts of tetrabutyl titanates.Just obtain a transparent liquid constituent after stirring, be called treatment agent A.
With the thickening agent of treatment agent A, with the surface thickening agent of R-15 (Shanghai Rubber Products Insitute produce be the surface thickening agent of material of main part) as silicon rubber vulcanization glue with the borosilicate compound as the metallic surface.Above-mentioned two kinds of treatment agents coated respectively all dried under room temperature 1 hour behind two kinds of material surfaces, applied organic silicon adhesive then, fitted, and solidified six days under room temperature, and the test result that obtains aging front and back is as shown in table 1.
Table 1.
| Test event and condition | Before aging | The aging back of 200 ℃ * 200h (embodiment one) | ||
| Controlled trial * | Embodiment one | |||
| Silicon rubber vulcanization glue and surface are bonding through anodized LY12CZ alloy aluminum, stripping strength, kN/m silicon rubber vulcanization glue with | The normal temperature test | 0.5 | 6.0 | 3.6 |
| -60 ℃ of tests | 1.3 | 7.2 | 8.4 | |
| The test of 200 ℃ of test normal temperature | 0 0.5 | Silicon rubber vulcanization glue fracture 6.0 | Silicon rubber vulcanization glue fracture 3.6 | |
| 1Cr18NiTi steel alloy bonding, stripping strength, kN/m | -60 ℃ of tests | 1.5 | 7.2 | 6.0 |
| 200 ℃ of tests | 0 | The fracture of silicon rubber vulcanization glue | The fracture of silicon rubber vulcanization glue |
* adhesive face was not handled with thickening agent of the present invention, below each the example with.Embodiment two
With the thickening agent of the treatment agent A among the embodiment one as various metals and lacquer painting material, the gold and silver, red copper and the polyurethane paint interview sheet that adopt the bonding treated dose of A of above-mentioned silicone adhesive to handle, after the self-vulcanizing six days, test result (normal temperature test) as shown in table 2.
Table 2
Embodiment three
| The test piece red copper test piece polyurethane paint interview sheet of the test piece electroplate of test piece kind surface gold-plating | The adherent shearing resistance, MPa | |
| Controlled trial 0 0.1 0.3 0.2 | Embodiment two＞1.6 (gold-plated part is peeled off) 4.5 4.0 2.1 | |
With water glass and hexamethyldisiloxane in the presence of hydrochloric acid, react and silicone resin be dissolved in 80 parts of sherwood oils for 5 parts, after the silicone resin of waiting dissolves fully, add contract 11 parts of 12 parts of tetraethyl silicate and different third enzymes of metatitanic acid described in the example one, obtain transparent liquid constituent after stirring and be referred to as treatment agent B.
Treatment agent B coated is in stainless steel (1Cr18Ni9Ti) test piece, and bonding with above-mentioned silicone adhesive, measure normal temperature behind the treatment agent coated and reveal and put the time (under the condition of relative humidity 85 ± 5%) to the influence of bond strength, the result is as shown in table 3.
Table 3.
Embodiment four
| Dew behind the coated treatment agent B is put the time, h | 0.5 | 1 | 2 | 4 | 6 | 24 |
| The pull strength of stainless steel test piece, MPa | 4.5 | 4.4 | 4.4 | 4.2 | 4.3 | 4.5 |
With water glass and hexamethyldisiloxane in the presence of hydrochloric acid, react and have the tree silicone resin be dissolved in 70 parts of trichloroethane for 25 parts, after organic silicone resin all dissolves, add 30 parts of ethyl orthosilicates, 7 parts of metatitanic acid n-propyls, after stirring, obtain transparent liquid constituent, be referred to as treatment agent C.
Carry out Anodising aluminium alloy (LY12CZ) test piece that surface thickening is handled so that above-mentioned organic silicon adhesive is bonding with treatment agent C, after six days, record shearing resistance is 4.2MPa to bonding sample through self-vulcanizing, and the analog value of controlled trial is 0.4MPa.Embodiment five
Consisting of of treatment agent: 27 parts of silicone resins, 45 parts of dimethylbenzene, 10 parts of ethyl orthosilicates, 18 parts of titanium ethanolates; Preparation technology is identical with embodiment four, and bond test and test piece are also identical with embodiment four, and the bonding shearing resistance that records is 3.7MPa, and the controlled trial analog value is 0.3MPa.
Claims (5)
1, the surface thickening agent used of a kind of organic silicon adhesive is characterized in that forming and comprises:
A. titanic acid ester: 3～20% (weight),
B. silicone resin: 2～30% (weight),
C. organosilicon acid esters: 10～25% (weight),
D. organic solvent: 45-85% (weight),
Described silicone resin is the reaction product of water glass and hexamethyldisiloxane.
2, the surface thickening agent used of organic silicon adhesive as claimed in claim 1 is characterized in that described titanic acid ester chemical molecular general formula is Ti (OR)
4, R is that carbonatoms is 2～4 alkyl in the formula.
3, the surface thickening agent used of organic silicon adhesive as claimed in claim 1 or 2, it is characterized in that described organosilicon acid esters is ortho-silicate or its hydrolysis condensation product, described organic solvent can be selected from alkane, halogenation alkane, aromatic hydrocarbons, halogenated aromatic or their mixture.
4, the surface thickening agent used of organic silicon adhesive as claimed in claim 1 or 2 is characterized in that wherein content the best of titanic acid ester is 5～10% (weight).
5, the preparation method of the surface thickening agent used of organic silicon adhesive as claimed in claim 1 or 2, it is characterized in that, reaction is carried out at normal temperatures, under constantly stirring, earlier be dissolved in silicone resin in the organic solvent fully, then, in the solution that makes, add titanic acid ester and organosilicon acid esters.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93112608A CN1044128C (en) | 1993-11-17 | 1993-11-17 | Surface thickening agent for organic silicon adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93112608A CN1044128C (en) | 1993-11-17 | 1993-11-17 | Surface thickening agent for organic silicon adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1105052A CN1105052A (en) | 1995-07-12 |
| CN1044128C true CN1044128C (en) | 1999-07-14 |
Family
ID=4990202
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93112608A Expired - Fee Related CN1044128C (en) | 1993-11-17 | 1993-11-17 | Surface thickening agent for organic silicon adhesive |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1044128C (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005097719A (en) * | 2003-08-15 | 2005-04-14 | Hoden Seimitsu Kako Kenkyusho Ltd | Non-chromium surface treatment agent for galvanized product |
| DE602004002633T2 (en) * | 2003-08-15 | 2007-08-16 | Hoden Seimitsu Kako Kenkyusho Co., Ltd., Atsugi | Chromium-free agent for the treatment of metal surfaces |
| ATE554917T1 (en) | 2006-05-26 | 2012-05-15 | Borealis Tech Oy | COATED TUBE WITH A POLYOLEFIN LAYER WITH IMPROVED ADHESION |
| CN103214946B (en) * | 2013-04-28 | 2016-01-27 | 深圳市新亚新材料有限公司 | A kind of single-component room-temperature-vulsilicone silicone rubber silane coupling agent and preparation method thereof |
| JP2016522968A (en) * | 2013-05-13 | 2016-08-04 | ヒソン ケミカル リミテッド | Aluminum pouch film for secondary battery, packaging material including the same, secondary battery including the same, and manufacturing method thereof |
| CN104774587B (en) * | 2014-03-18 | 2017-04-12 | 深圳市康利邦科技有限公司 | High-viscosity high-heat resistance modified organic silicone resin binder and preparation method thereof |
| CN105505294B (en) * | 2015-12-22 | 2018-08-07 | 广东标美硅氟新材料有限公司 | A kind of silane coupling agent Nian Jie with dry-type transformer material for addition-type silicon rubber |
| CN109096956A (en) * | 2018-07-11 | 2018-12-28 | 合肥德济新材料科技有限公司 | Addition-type silicon rubber single-coating-type Heat vulcanization adhesive |
| CN108948961A (en) * | 2018-07-12 | 2018-12-07 | 广西德本仕密封材料有限公司 | It is a kind of to improve silicone adhesive the aqueous basecoat agent and preparation method Nian Jie with wood substrate |
| CN109897571B (en) * | 2019-03-07 | 2020-10-02 | 广东天剑新材料科技有限公司 | Preparation method of anti-aging waterproof glass cement |
| CN114536651A (en) * | 2022-02-16 | 2022-05-27 | 深圳市乐目通讯有限公司 | Processing method of silica gel flexible circuit board |
| CN114507490A (en) * | 2022-03-02 | 2022-05-17 | 张道高 | Surface tackifying treatment agent for organic silicon adhesive |
| CN117143343B (en) * | 2023-10-27 | 2023-12-26 | 上海奇克氟硅材料有限公司 | Method for preparing ethyl silicone oil by sodium condensation method and ethyl silicone oil |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0347049A2 (en) * | 1988-06-15 | 1989-12-20 | Dow Corning Corporation | Improved primer compositions |
-
1993
- 1993-11-17 CN CN93112608A patent/CN1044128C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0347049A2 (en) * | 1988-06-15 | 1989-12-20 | Dow Corning Corporation | Improved primer compositions |
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| Publication number | Publication date |
|---|---|
| CN1105052A (en) | 1995-07-12 |
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Granted publication date: 19990714 Termination date: 20101117 |