CN102533183A - Solvent type organosilicon modified acrylate pressure sensitive adhesive, preparation method and application thereof - Google Patents
Solvent type organosilicon modified acrylate pressure sensitive adhesive, preparation method and application thereof Download PDFInfo
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- CN102533183A CN102533183A CN2010105924116A CN201010592411A CN102533183A CN 102533183 A CN102533183 A CN 102533183A CN 2010105924116 A CN2010105924116 A CN 2010105924116A CN 201010592411 A CN201010592411 A CN 201010592411A CN 102533183 A CN102533183 A CN 102533183A
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Abstract
The invention relates to a solvent type organosilicon modified acrylate pressure sensitive adhesive, a preparation method and an application thereof. The adhesive is prepared by polymerization of the following raw material components in a reaction kettle, wherein the components comprise, by weight, 1-10 parts of a component A, 10-30 parts of 2-ethyl hexyl acrylate, 10-30 parts of butyl acrylate, 2-5 parts of styrene, 2-4 parts of methyl methacrylate, 1-4 parts of hydroxypropyl acrylate, 1-2 parts of acrylic acid, 0.1-0.8 parts of dibenzoyl peroxide, and 45-55 parts of acetic ether, wherein the component A is prepared by polymerization of 50-75 parts by weight of octamethylcyclotetrasiloxane, 5-15 parts by weight of gamma-methacryloxy propyl trimethoxyl silane, 15-40 parts by weight of hexamethyldisiloxane, and 0.05-0.24 parts by weight of tetramethylammonium hydroxide. With the prepared pressure sensitive adhesive for the protective film, the increase of the stripping strength of the protective film can be inhibited, the bonding strength for the low surface energy surface can be increased, and the disadvantages of large increase amplitude of the stripping strength and small bonding strength for the low surface energy surface in the existing pressure sensitive adhesive can be overcome.
Description
Technical field
The present invention relates to a kind of pressure sensitive adhesive, refer in particular to a kind of two-pack crosslinking structure type acrylate pressure-sensitive adhesive and preparation method thereof.
Background technology
Pressure sensitive adhesive is to presser sensor, need not heat, not need solvent, do not need bigger pressure, only need pressurization a little or with pointing once by realizing bonding a kind of tackiness agent.Be characterized in gluing that easily that takes off is not difficult, stripping and not decreasing can not dried up at long time inner glue layer, so pressure sensitive adhesive is also referred to as non-setting adhesive.Pressure-sensitive adhesive is processed pressure-sensitive adhesive article sale such as various sealing tapes, glued membrane mostly and is applied.8 big functions of use such as that the pressure-sensitive adhesive goods have is bonding, tie up, decorate, strengthen, fix, protection, insulation and identification obtain application more and more widely in packing, printing, building decoration, production, household electrical appliances industry, health care even daily life.
Surface protection film is a most important aspect in the pressure sensitive adhesive goods; It is a kind of film material that the other materials surface is had defencive function; It mainly is base material with the Vilaterm, is pressure-sensitive adhesive with rubber or propenoate, processes through methods such as coating dryings.Be mainly used in the protective packing of the demanding product surface of various surface appearances, preventing its surface tear, pollution and wearing and tearing etc. in carrying, storage, installation, secondary processing process, thereby make article keep good surface appearance.Range of application mainly contains: stainless steel plate, mirror steel plate and copper coin, aluminium sheet, composited aluminum and plastic decking, color steel sheet, organic board, plastic-steel section bar, aluminium section bar, door and window processing, instrument equipment, household electrical appliances, mechanical component processing, colour picture tube, automobile processing industry etc.
The surface protection film main technical requirements is:
1. utilize pressure sensitive adhesive moment property followed and releasable characteristic;
2. pressure-sensitive adhesive does not allow to come off and remains in by the protecting materials surface;
3. by the prolonged constant or slow increase of adhesion on protecting materials surface, can be smoothly from being peeled by the protecting materials surface;
4. pressure-sensitive adhesive layer and plastic-based film have excellent physicals to satisfy various secondary processing requirements.
Protective membrane generally is divided into rubber-type, organosilicon type and acrylate type with pressure sensitive adhesive by its composition, and the above two generally only limit to the very high occasion of ask for something and use because production and use cost are higher.And plurality of advantages such as that the pure acrylic acid ester pressure-sensitive has is cheap, easy to use, good weatherability, in recent years, development is very fast, is widely used in the industrial production.But protective membrane has following shortcoming with pure acrylic acid ester class pressure sensitive adhesive:
A. protective membrane and increased greatlyyer by the peeling force between the protective surface, protective membrane is difficult for tearing and is prone to leave over cull and contaminated surface;
B. surface tension is bigger, and is poor to the cementability on low surface energy substrates surface.
Summary of the invention
The objective of the invention is to existing acrylate pressure-sensitive adhesive peeling force be prone to increase, to the deficiency of low surface energy substrates bonding strength difference; And a kind of solvent type organic silicone modified acrylate pressure sensitive adhesive is provided, it can suppress growth, raising bonding strength and the high-temp resisting high-humidity resisting aging resistance surperficial to low surface energy of peeling force.
The present invention also aims to provide the preparation method and the application of above-mentioned solvent type organic silicone modified acrylate pressure sensitive adhesive.
The technical scheme that the present invention adopts is:
The solvent type organic silicone modified acrylate pressure sensitive adhesive comprises following each component raw material polymerization and prepares that it is formed proportioning and counts by weight as follows: composition A 1～10, ethyl acrylate 10～30, Bing Xisuandingzhi 10～30, vinylbenzene 2～5, TEB 3K 2～4, Propylene glycol monoacrylate 1～4, vinylformic acid 1～2, BPO 0.1～0.8, ETHYLE ACETATE 45～55;
Described composition A comprises octamethylcyclotetrasiloxane 50～75 weight parts, γ monomethyl acryloxy propyl trimethoxy silicane 5～15 weight parts, SWS-F 221 15～40 weight parts, TMAH 0.05～0.24 weight part polymerization and prepares.
The preparation method of solvent type organic silicone modified acrylate pressure sensitive adhesive comprises 1. producing of composition A:
A adds octamethylcyclotetrasiloxane, TMAH in the reaction vessel, stirs;
B under 88～92 ℃, nitrogen protection, reaction 1h;
C adds the γ monomethyl acryloxy propyl trimethoxy silicane that mixes, SWS-F 221 in the reaction vessel, at 88～92 ℃ of following insulation reaction 3h again;
D vacuumizes under the 0.01MPa condition and removed the small molecules that dereaction produced in 1 hour;
E cools to 40 ℃ and obtains composition A with bottom discharge.
2. producing of solvent type organic silicone modified acrylate pressure sensitive adhesive:
A takes by weighing composition A, ethyl acrylate, Bing Xisuandingzhi, vinylbenzene, TEB 3K, Propylene glycol monoacrylate, vinylformic acid, BPO in proportion, adds to mix single still, stirs while feeding in raw material, and promptly gets mixture;
The ETHYLE ACETATE that b takes by weighing charging capacity 1/4th adds reaction kettle, stirs simultaneously and is warming up to 80～85 ℃;
C reacts 1.5h to the said mixture of reaction kettle adding 1/4th down at 80～85 ℃;
D drips remaining said mixture in reaction kettle, 4h drips off;
E drips off the back at 80～85 ℃ of following isothermal reaction 2h;
F reduces to 40 ℃ with temperature of reaction kettle, adds the residual acetic acid ethyl ester, stirs discharging after 5 minutes, promptly gets the solvent type organic silicone modified acrylate pressure sensitive adhesive.
Said solvent type organic silicone modified acrylate pressure sensitive adhesive mixes the back with a certain proportion of linking agent as required and on basement membrane, is coated with the application of processing Pressuresensitive Tape.
Said Pressuresensitive Tape is affixed on by the protection surface.
Said Pressuresensitive Tape is attached to by the surperficial the preceding paragraph of protection and need tears from being protected the surface after the time, and tears the back and do not stayed cull by the protection surface.
Because acrylate pressure-sensitive adhesive is hard and surface tension is bigger; Influence the adhesiveproperties of pressure sensitive adhesive: (1) is to slower by the wetting contact of sticking base material; When beginning to contact by maxxaedium to final balance, peeling force amplification is bigger, is prone to stay cull; (2) relatively poor to low surface energy wetting of surfaces ability, cause bonding strength not enough.And the pressure sensitive adhesive that the present invention makes, utilize the organosilicon low surface tension, than characteristics such as softness suppress peeling force growth, improve bonding strength, to remedy the deficiency of pure acrylic acid ester pressure-sensitive to the low surface energy surface.
Embodiment
Embodiment 1
(1) composition A's is synthetic
Composition A is made up of following materials of weight proportions:
Octamethylcyclotetrasiloxane 66.13, γ monomethyl acryloxy propyl trimethoxy silicane 11.25, SWS-F 221 22.5, TMAH 0.12.
The preparation of composition A comprises the steps:
A adds octamethylcyclotetrasiloxane, TMAH in the there-necked flask of the 500mL that has reflux exchanger, whisking appliance, TM and nitrogen conduit;
B under 88～92 ℃, nitrogen protection, reaction 1h;
C adds the γ monomethyl acryloxy propyl trimethoxy silicane that mixes, SWS-F 221 in the there-necked flask again, insulation reaction 3h;
D vacuumizes under the 0.01MPa condition and removed the small molecules that dereaction produced in 1 hour;
E cools to and obtains being used for the composition A that modification acrylate is a resin below 40 ℃.
(2) pressure sensitive adhesive according to the invention is made up of following materials of weight proportions:
Composition A 2.0, ethyl acrylate 20, Bing Xisuandingzhi 20, vinylbenzene 3.5, TEB 3K 2, Propylene glycol monoacrylate 1.5, vinylformic acid 1, BPO 0.2, ETHYLE ACETATE 49.8.
The preparation of pressure sensitive adhesive according to the invention comprises the steps:
A takes by weighing composition A, ethyl acrylate, Bing Xisuandingzhi, vinylbenzene, TEB 3K, Propylene glycol monoacrylate, vinylformic acid, BPO in proportion, adds to mix single still, stirs while feeding in raw material, and promptly gets mixture;
B takes by weighing 1/4th ETHYLE ACETATE adding reaction kettle, stirs simultaneously and is warming up to 80～85 ℃;
C reacts 1.5h to the mixture of reaction kettle adding 1/4th;
D drips remaining mixture in reaction kettle, 4h drips off;
E drips off the back at 80～85 ℃ of following isothermal reaction 2h;
F reduces to 40 ℃ with temperature of reaction kettle, adds the residual acetic acid ethyl ester, stirs discharging after 5 minutes, promptly gets the solvent type organic silicone modified acrylate pressure sensitive adhesive.
Embodiment 2
(1) composition A's is synthetic
Composition A is made up of following materials of weight proportions:
Octamethylcyclotetrasiloxane 50, γ monomethyl acryloxy propyl trimethoxy silicane 15, SWS-F 221 34.76, TMAH 0.24.
The preparation of composition A comprises the steps:
A adds octamethylcyclotetrasiloxane, TMAH in the there-necked flask of the 500mL that has reflux exchanger, whisking appliance, TM and nitrogen conduit;
B under 88～92 ℃, nitrogen protection, reaction 1h;
C adds the γ monomethyl acryloxy propyl trimethoxy silicane that mixes, SWS-F 221 in the there-necked flask again, insulation reaction 3h;
D vacuumizes under the 0.01MPa condition and removed the small molecules that dereaction produced in 1 hour;
E cools to and obtains being used for the composition A that modification acrylate is a resin below 40 ℃.
(2) pressure sensitive adhesive according to the invention is made up of following materials of weight proportions:
Composition A 6.0, ethyl acrylate 18, Bing Xisuandingzhi 20, vinylbenzene 3.5, TEB 3K 2, Propylene glycol monoacrylate 2.5, vinylformic acid 2, BPO 0.2, ETHYLE ACETATE 49.8.
The preparation of pressure sensitive adhesive according to the invention comprises the steps:
A takes by weighing composition A, ethyl acrylate, Bing Xisuandingzhi, vinylbenzene, TEB 3K, Propylene glycol monoacrylate, vinylformic acid, BPO in proportion, adds to mix single still, stirs while feeding in raw material, and promptly gets mixture;
B takes by weighing 1/4th ETHYLE ACETATE adding reaction kettle, stirs simultaneously and is warming up to 80～85 ℃;
C reacts 1.5h to the mixture of reaction kettle adding 1/4th;
D drips remaining mixture in reaction kettle, 4h drips off;
E drips off the back at 80～85 ℃ of following isothermal reaction 2h;
F reduces to 40 ℃ with temperature of reaction kettle, adds the residual acetic acid ethyl ester, stirs discharging after 5 minutes, promptly gets the solvent type organic silicone modified acrylate pressure sensitive adhesive.
Embodiment 3
(1) composition A's is synthetic
Composition A is made up of following materials of weight proportions:
Octamethylcyclotetrasiloxane 50, γ monomethyl acryloxy propyl trimethoxy silicane 15, SWS-F 221 34.76, TMAH 0.24.
The preparation of composition A comprises the steps:
A adds octamethylcyclotetrasiloxane, TMAH in the there-necked flask of the 500mL that has reflux exchanger, whisking appliance, TM and nitrogen conduit;
B under 88～92 ℃, nitrogen protection, reaction 1h;
C adds the γ monomethyl acryloxy propyl trimethoxy silicane that mixes, SWS-F 221 in the there-necked flask again, insulation reaction 3h;
D vacuumizes under the 0.01MPa condition and removed the small molecules that dereaction produced in 1 hour;
E cools to and obtains being used for the composition A that modification acrylate is a resin below 40 ℃.
(2) pressure sensitive adhesive according to the invention is made up of following materials of weight proportions:
Composition A 10, ethyl acrylate 18, Bing Xisuandingzhi 16, vinylbenzene 3.5, TEB 3K 2, Propylene glycol monoacrylate 2.5, vinylformic acid 2, BPO 0.2, ETHYLE ACETATE 49.8.
The preparation of pressure sensitive adhesive according to the invention comprises the steps:
A takes by weighing composition A, ethyl acrylate, Bing Xisuandingzhi, vinylbenzene, TEB 3K, Propylene glycol monoacrylate, vinylformic acid, BPO in proportion, adds to mix single still, stirs while feeding in raw material, and promptly gets mixture;
B takes by weighing 1/4th ETHYLE ACETATE adding reaction kettle, stirs simultaneously and is warming up to 80～85 ℃;
C reacts 1.5h to the mixture of reaction kettle adding 1/4th;
D drips remaining mixture in reaction kettle, 4h drips off;
E drips off the back at 80～85 ℃ of following isothermal reaction 2h;
F reduces to 40 ℃ with temperature of reaction kettle, adds the residual acetic acid ethyl ester, stirs discharging after 5 minutes, promptly gets the solvent type organic silicone modified acrylate pressure sensitive adhesive.
Claims (3)
1. solvent type organic silicone modified acrylate pressure sensitive adhesive; It is characterized in that: comprise following each component raw material polymerization and prepare that it is formed proportioning and counts by weight as follows: composition A 1～10, ethyl acrylate 10～30, Bing Xisuandingzhi 10～30, vinylbenzene 2～5, TEB 3K 2～4, Propylene glycol monoacrylate 1～4, vinylformic acid 1～2, BPO 0.1～0.8, ETHYLE ACETATE 45～55;
Described composition A comprises octamethylcyclotetrasiloxane 50～75 weight parts, γ monomethyl acryloxy propyl trimethoxy silicane 5～15 weight parts, SWS-F 221 15～40 weight parts, TMAH 0.05～0.24 weight part polymerization and prepares.
2. the preparation method of the said solvent type organic silicone modified acrylate pressure sensitive adhesive of claim 1 is characterized in that:
Comprise 1. producing of composition A:
A adds octamethylcyclotetrasiloxane, TMAH in the reaction vessel, stirs;
B under 88～92 ℃, nitrogen protection, reaction 1h;
C adds the γ monomethyl acryloxy propyl trimethoxy silicane that mixes, SWS-F 221 in the reaction vessel again, insulation reaction 3h;
D vacuumized under the 0.01MPa condition 1 hour;
E cools to 40 ℃ and obtains composition A with bottom discharge.
2. producing of solvent type organic silicone modified acrylate pressure sensitive adhesive:
A takes by weighing composition A, ethyl acrylate, Bing Xisuandingzhi, vinylbenzene, TEB 3K, Propylene glycol monoacrylate, vinylformic acid, BPO in proportion, adds to mix single still, stirs while feeding in raw material, and promptly gets mixture;
The ETHYLE ACETATE that b takes by weighing charging capacity 1/4th adds reaction kettle, stirs simultaneously and is warming up to 80～85 ℃;
C reacts 1.5h to the said mixture of reaction kettle adding 1/4th;
D drips remaining said mixture in reaction kettle, 4h drips off;
E drips off the back at 80～85 ℃ of following isothermal reaction 2h;
F reduces to 40 ℃ with temperature of reaction kettle, adds the residual acetic acid ethyl ester, stirs discharging after 5 minutes, promptly gets the solvent type organic silicone modified acrylate pressure sensitive adhesive.
3. the said solvent type organic silicone modified acrylate pressure sensitive adhesive of claim 1 is coated with the application of processing Pressuresensitive Tape on basement membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105924116A CN102533183A (en) | 2010-12-09 | 2010-12-09 | Solvent type organosilicon modified acrylate pressure sensitive adhesive, preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010105924116A CN102533183A (en) | 2010-12-09 | 2010-12-09 | Solvent type organosilicon modified acrylate pressure sensitive adhesive, preparation method and application thereof |
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| CN102533183A true CN102533183A (en) | 2012-07-04 |
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| CN2010105924116A Pending CN102533183A (en) | 2010-12-09 | 2010-12-09 | Solvent type organosilicon modified acrylate pressure sensitive adhesive, preparation method and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103724521A (en) * | 2014-01-13 | 2014-04-16 | 张家港保税区康得菲尔实业有限公司 | Preparation method of single-component polyacrylate pressure-sensitive adhesive for optical protective film |
| CN105176450A (en) * | 2015-09-10 | 2015-12-23 | 上海晶华胶粘新材料股份有限公司 | Blending polymer with function of silica gel and acrylate glue and preparation method of blending polymer |
| CN105273667A (en) * | 2014-06-06 | 2016-01-27 | 上海晶华胶粘新材料股份有限公司 | High-temperature-resistant silicone-acrylate pressure-sensitive adhesive and preparation method thereof |
| CN111944435A (en) * | 2020-08-19 | 2020-11-17 | 常州百佳年代薄膜科技股份有限公司 | Hot melt adhesive film, preparation method and application thereof, and organic silicon polymer |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1461017A (en) * | 2003-07-02 | 2003-12-10 | 清华大学 | TiO2 non-linear pressure-sensitive ceramic resistor and its preparation method |
-
2010
- 2010-12-09 CN CN2010105924116A patent/CN102533183A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1461017A (en) * | 2003-07-02 | 2003-12-10 | 清华大学 | TiO2 non-linear pressure-sensitive ceramic resistor and its preparation method |
Non-Patent Citations (3)
| Title |
|---|
| 尹朝辉等: "新型硅改性丙烯酸酯压敏胶的研究", 《中国胶粘剂》 * |
| 武鹏等: "保护膜用压敏胶剥离强度增幅研究", 《中国胶粘剂》 * |
| 毛胜华等: "保护膜用有机硅改性丙烯酸酯乳液压敏胶的研究", 《粘接》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103724521A (en) * | 2014-01-13 | 2014-04-16 | 张家港保税区康得菲尔实业有限公司 | Preparation method of single-component polyacrylate pressure-sensitive adhesive for optical protective film |
| CN105273667A (en) * | 2014-06-06 | 2016-01-27 | 上海晶华胶粘新材料股份有限公司 | High-temperature-resistant silicone-acrylate pressure-sensitive adhesive and preparation method thereof |
| CN105273667B (en) * | 2014-06-06 | 2019-02-12 | 上海晶华胶粘新材料股份有限公司 | High temperature resistant silicon-acrylic pressure-sensitive adhesive and preparation method thereof |
| CN105176450A (en) * | 2015-09-10 | 2015-12-23 | 上海晶华胶粘新材料股份有限公司 | Blending polymer with function of silica gel and acrylate glue and preparation method of blending polymer |
| CN111944435A (en) * | 2020-08-19 | 2020-11-17 | 常州百佳年代薄膜科技股份有限公司 | Hot melt adhesive film, preparation method and application thereof, and organic silicon polymer |
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