CN103881304A - Epoxy resin composition with low organic matter volatility - Google Patents
Epoxy resin composition with low organic matter volatility Download PDFInfo
- Publication number
- CN103881304A CN103881304A CN201410075184.8A CN201410075184A CN103881304A CN 103881304 A CN103881304 A CN 103881304A CN 201410075184 A CN201410075184 A CN 201410075184A CN 103881304 A CN103881304 A CN 103881304A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- weight
- composition
- resin
- resol
- 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
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses an epoxy resin composition with low organic matter volatility. The epoxy resin composition comprises the following components in percentage by weight: (a), 20-90% of epoxy resin, (b), 1-40% of phenolic resin, (c), 1-20% of curing agent, and (d), 0-40wt% of auxiliaries. The epoxy resin composition disclosed by the invention has the mechanical performances of low organic matter volatility, high heat resistance, high toughness, and the like, and can be applied to industries such as printing, electronics, paint, and the like.
Description
Technical field
The present invention relates to a kind of composition epoxy resin, relate in particular to a kind of composition epoxy resin with mechanical propertys such as low organism volatility, high heat resistance and toughness.
Background technology
Epoxy resin has been widely used in various electronic isolation materials, mainly because it has good thermotolerance, chemical resistant properties and good insulating property and dielectric properties, Common Curing Agents has amine, anhydrides and phenols or phenolic, particularly in the application of copper-clad plate, conventional Dyhard RU 100 (amine) and resol (phenolic), as the solidifying agent of epoxy resin, have good processibility, thermotolerance, chemical resistant properties and insulating property.But conventional epoxy resin has low solid content, wherein contain a large amount of organic solvents, in use easily cause organic solvent volatilization, and these organic solvents comprise that toluene etc. is to environment and the harmful material of the mankind.
Therefore, need to improve the solid content of epoxy resin, reduce organic volatile wherein, make the finished product there is good mechanical property, such as thermotolerance and toughness etc. simultaneously.
Summary of the invention
In view of above-mentioned prior art situation, the present inventor has conducted intensive studies ordinary epoxy resin, develops the brand-new composition epoxy resin of a class, and it comprises epoxy resin, resol, solidifying agent and optional auxiliary agent.
The technical problem to be solved in the present invention is for above-mentioned deficiency of the prior art, and a kind of new composition epoxy resin is provided, and it has the mechanical propertys such as low organism volatility, high heat resistance and toughness, can be used for the industries such as electronics, printing, coating.
Composition epoxy resin provided by the invention, comprising:
A) epoxy resin of 20-90 % by weight;
B) resol of 1-40 % by weight;
C) solidifying agent of 1-20 % by weight; And
D) auxiliary agent of 0-40 % by weight.
Described epoxy resin is the mixture with following structural (I) and epoxy resin (II):
（II）；
Wherein, R is H or CH
3, R1 is that cardanol removes phenol structure residue afterwards.
Wherein, the epoxy resin of formula (I) accounts for the 20-80% of epoxy resin gross weight, and the epoxy resin of formula (II) accounts for the 20-80% of epoxy resin gross weight.
In composition of the present invention, the amount of described epoxy resin can be 20-90 % by weight, preferably 20-70 % by weight, and particularly preferably 25-60 % by weight, even preferably 30-50 % by weight, based on the gross weight of composition.
Described resol can be any suitable resol, is preferably selected from phenol formaldehyde resin, phenol acetaldehyde resin, resorcinol formaldehyde resin, Resorcinol formaldehyde resin.Particularly preferably phenol formaldehyde resin.
Conventional resol is more commercial resol, and it can buy on market.As one of the present invention preferred embodiment, described resol can be prepared by following methods: 1., phenol and aldehyde 1: 0.5 in molar ratio～0.9 are added to reactor, then add an acidic catalyst, stir, be warming up to 70～100 ℃ simultaneously, and maintain 1～8 hour, make resol; 2., resol that 1. step is obtained distills processing, is less than 0.5wt% to phenol content; Step 1. described in an acidic catalyst be selected from one or more in hydrochloric acid, oxalic acid, phosphoric acid, sulfuric acid, ethyl sulfate, halogenosulfonic acid and Phenylsulfonic acid and alkyl substituent thereof.
In composition of the present invention, the amount of described resol can be 1-40 % by weight, preferably 2-30 % by weight, and particularly preferably 5-30 % by weight, even preferably 10-20 % by weight, based on the gross weight of composition.
Described solidifying agent can be the solidifying agent of any epoxy resin, for example amine, anhydrides and phenols or phenolic.For example, described amine curing agent is mphenylenediamine, Ursol D, m-xylene diamine, 4,4 '-diaminodiphenyl-methane or DDS; Described acid anhydride type curing agent is styrene-grafted maleic anhydride etc.
In composition of the present invention, the amount of described solidifying agent can be 1-25 % by weight, and preferably 1-20 % by weight, based on the gross weight of composition.
Described auxiliary agent can be any suitable material, for example, improve glass fibre, granulated glass sphere, calcium carbonate, carbon black, carbon nanotube, talcum, titanium dioxide, nano silicon of composition epoxy resin mechanical property etc.Auxiliary agent can also comprise curing catalyst, compatilizer, softening agent, silane coupling agent, releasing agent etc.
In composition of the present invention, the amount of described auxiliary agent can be 0-50 % by weight, and preferably 0-40 % by weight, based on the gross weight of composition.
The beneficial effect of the invention
The inventor through study hardly, is surprisingly found out that by combining specific epoxy resin, resol, solidifying agent and auxiliary agent, can makes composition have the mechanical propertys such as low organism volatility, high heat resistance and toughness.
The present invention has used special epoxy resin, and it contains formula (I) and formula (II) structure, is liquid at normal temperatures, can directly mix with other components, and not need to add solvent, and it has low organism volatility; Meanwhile, owing to having introduced resol in composition, strengthened significantly thermotolerance and the physical strength of composition epoxy resin.
Embodiment
Below in conjunction with embodiment, embodiment of the present invention are described in detail, but it will be appreciated by those skilled in the art that the following example is only for the present invention is described, and should not be considered as limiting scope of the present invention.In embodiment, unreceipted actual conditions person, carries out according to normal condition.
Preparation example 1
The diglycidylether of 80 weight part dihydroxyphenyl propanes is mixed under nitrogen atmosphere with 20 parts by weight of cardanol, and then heated mixt to 90 ℃, adds 400ppm ethyl triphenyl PA as catalyzer.Heated mixt to 170 ℃ keeping 3 hours subsequently, obtains epoxy resin A, the epoxy resin of the epoxy resin that it contains 55 % by weight formula (I) structures and 45 % by weight formula (II) structures subsequently.
Preparation example 2
The diglycidylether of 92 weight part dihydroxyphenyl propanes is mixed under nitrogen atmosphere with 8 parts by weight of cardanol, and then heated mixt to 90 ℃, adds 200ppm ethyl triphenyl PA as catalyzer.Heated mixt to 180 ℃ keeping 2 hours subsequently, obtains epoxy resin B, the epoxy resin of the epoxy resin that it contains 81 % by weight formula (I) structures and 19 % by weight formula (II) structures subsequently.
Preparation example 3
The diglycidylether of 65 weight part dihydroxyphenyl propanes is mixed under nitrogen atmosphere with 35 parts by weight of cardanol, and then heated mixt to 90 ℃, adds 300ppm ethyl triphenyl PA as catalyzer.Heated mixt to 180 ℃ keeping 3 hours subsequently, obtains epoxy resin C, the epoxy resin of the epoxy resin that it contains 20 % by weight formula (I) structures and 80 % by weight formula (II) structures subsequently.
Preparation example 4
The diglycidylether of 85 weight part Bisphenol F is mixed under nitrogen atmosphere with 15 parts by weight of cardanol, and then heated mixt to 90 ℃, adds 350ppm ethyl triphenyl PA as catalyzer.Heated mixt to 170 ℃ keeping 4 hours subsequently, obtains epoxy resin D, the epoxy resin of the epoxy resin that it contains 65 % by weight formula (I) structures and 35 % by weight formula (II) structures subsequently.
Epoxy resin prepared by above-mentioned preparation example 1-4 is liquid state, and solubilizing agent or only add a small amount of solvent not while mixing with other components, for example, add 10 parts by weight solvent, for example toluene in the above-mentioned epoxy resin of 90 weight part.Now, soltion viscosity is about 10000～12000cps in the time of 25 ℃, and conventional bisphenol A diglycidyl ether, the D.E.R. that for example Tao Shi produces
tM671-X75 is solid in the time of 25 ℃, 75 weight part D.E.R.
tM671-X75 is dissolved in the solution of 25 parts by weight of toluene, and its viscosity is about 14300cps in the time of 25 ℃.
Embodiment
Under nitrogen protection, in the four-hole bottle that has magnetic stirring apparatus, prolong, constant pressure funnel and thermometer, add epoxy resin.Then optional auxiliary agent is added wherein, stir.Add subsequently resol and solidifying agent, after stirring, obtain composition epoxy resin.If need solidifying product, heat temperature raising solidifies.
According to the formula of table 1, can obtain a series of compositions of the present invention.
Table 1
Owing to not using volatilizable organism, particularly solvent in embodiment 1-4, therefore it has low organism volatility; And in comparative example 1, comprising toluene, it remains in the finished product, so the organic volatile object height that the finished product contain is unfavorable to environment and the mankind.
Analyze the resistance toheat of the composition that embodiment 1-4 and comparative example 1-2 are obtained evaluates with thermogravimetic analysis (TGA) (TGA) and dynamic mechanically mechanical property (DMA): adopt 5% weightless temperature of TGA and the residual heavy sign resistance toheat of 900 ℃, adopt Tan (δ) peak value of DMA to characterize the second-order transition temperature of cured resin.The composition that embodiment 1-4 and comparative example 1-2 are obtained obtains fine and close casting matrix after within 6 hours, solidifying by 130 ℃ 2 hours+150 ℃ 2 hours+200 ℃ in electric heating convection oven.
The composition and the quartz fabric that embodiment 1-4 and comparative example 1-2 are obtained by mould pressing process are made matrix material, gained matrix material specification is 200mm × 200mm × 2mm, wherein the quartz fabric number of plies is 15 layers, resin content is about 30%, and condition of cure is 130 ℃/2h+150 ℃/6h+200 ℃/6h.Matrix material at room temperature tensile strength and elongation at break is listed in table 2, and resin composite materials has good mechanical property as can be seen here.
Table 2
As can be seen from Table 2, the composition of the embodiment 1-4 that contains epoxy resin and resol has better thermotolerance and better toughness, and does not contain thermotolerance and the poor toughness of the comparative example's 2 of resol composition; The thermotolerance of the composition of the embodiment 3 and 4 that in addition, contains auxiliary agent nano silicon is better.
Above-mentioned explanation only provides as illustrative embodiment of the present invention, and it is only example, should restrictively not explain.The art personnel understand that variation of the present invention is also included within the scope of claim.
Claims (8)
1. there is the volatile composition epoxy resin of low organism, comprising:
A) epoxy resin of 20-90 % by weight;
B) resol of 1-40 % by weight;
C) solidifying agent of 1-20 % by weight; And
D) auxiliary agent of 0-40 % by weight.
2. composition epoxy resin as claimed in claim 1, is characterized in that: described epoxy resin is the mixture with following structural (I) and epoxy resin (II):
（II）；
Wherein, R is H or CH
3, R1 is that cardanol removes phenol structure residue afterwards.
3. composition epoxy resin as claimed in claim 2, is characterized in that: the epoxy resin of formula (I) accounts for the 20-80% of epoxy resin gross weight, and the epoxy resin of formula (II) accounts for the 20-80% of epoxy resin gross weight.
4. composition epoxy resin as claimed in claim 1, is characterized in that: resol a) is selected from phenol formaldehyde resin, phenol acetaldehyde resin, resorcinol formaldehyde resin, Resorcinol formaldehyde resin.
5. the composition epoxy resin as described in claim 1-4 any one, is characterized in that: described solidifying agent is mphenylenediamine.
6. the composition epoxy resin as described in claim 1-5 any one, is characterized in that: described auxiliary agent is nano silicon.
7. the composition epoxy resin as described in claim 1-6 any one is for the purposes of coating.
8. the composition epoxy resin as described in claim 1-6 any one is for the purposes of printed wiring.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410075184.8A CN103881304B (en) | 2014-03-04 | 2014-03-04 | There is the volatile composition epoxy resin of low organism |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410075184.8A CN103881304B (en) | 2014-03-04 | 2014-03-04 | There is the volatile composition epoxy resin of low organism |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103881304A true CN103881304A (en) | 2014-06-25 |
| CN103881304B CN103881304B (en) | 2016-03-02 |
Family
ID=50950452
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410075184.8A Expired - Fee Related CN103881304B (en) | 2014-03-04 | 2014-03-04 | There is the volatile composition epoxy resin of low organism |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103881304B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107974161A (en) * | 2017-12-22 | 2018-05-01 | 江苏波迩德特种材料科技有限公司 | A kind of coating and preparation method thereof that blocks water of carbon nanotubes |
| CN109280331A (en) * | 2017-07-20 | 2019-01-29 | 长春人造树脂厂股份有限公司 | Resin combination, coating composition and its product |
| CN112250645A (en) * | 2020-10-28 | 2021-01-22 | 浙江万盛股份有限公司 | Preparation method of novel cardanol modified epoxy resin |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731966A (en) * | 2012-07-09 | 2012-10-17 | 广东生益科技股份有限公司 | Thermosetting epoxy resin composition as well as prepreg and copper-foil-plated laminated board manufactured by using same |
| CN102942892A (en) * | 2012-11-28 | 2013-02-27 | 九江福莱克斯有限公司 | Epoxy phenolic resin adhesive and epoxy phenolic adhesive tape and laminated board manufactured by adhesive |
| CN103173175A (en) * | 2013-03-23 | 2013-06-26 | 广东新展化工新材料有限公司 | Organic silicone modified epoxy resin sealant and preparation method thereof |
| CN103194040A (en) * | 2013-04-18 | 2013-07-10 | 天津虹炎科技有限公司 | Phenolic resin composition |
-
2014
- 2014-03-04 CN CN201410075184.8A patent/CN103881304B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731966A (en) * | 2012-07-09 | 2012-10-17 | 广东生益科技股份有限公司 | Thermosetting epoxy resin composition as well as prepreg and copper-foil-plated laminated board manufactured by using same |
| CN102942892A (en) * | 2012-11-28 | 2013-02-27 | 九江福莱克斯有限公司 | Epoxy phenolic resin adhesive and epoxy phenolic adhesive tape and laminated board manufactured by adhesive |
| CN103173175A (en) * | 2013-03-23 | 2013-06-26 | 广东新展化工新材料有限公司 | Organic silicone modified epoxy resin sealant and preparation method thereof |
| CN103194040A (en) * | 2013-04-18 | 2013-07-10 | 天津虹炎科技有限公司 | Phenolic resin composition |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109280331A (en) * | 2017-07-20 | 2019-01-29 | 长春人造树脂厂股份有限公司 | Resin combination, coating composition and its product |
| CN109280331B (en) * | 2017-07-20 | 2019-11-26 | 长春人造树脂厂股份有限公司 | Resin combination, coating composition and its product |
| CN107974161A (en) * | 2017-12-22 | 2018-05-01 | 江苏波迩德特种材料科技有限公司 | A kind of coating and preparation method thereof that blocks water of carbon nanotubes |
| CN112250645A (en) * | 2020-10-28 | 2021-01-22 | 浙江万盛股份有限公司 | Preparation method of novel cardanol modified epoxy resin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103881304B (en) | 2016-03-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104024337B (en) | Silane-containing compositions, hardening resin composition and sealing material | |
| TWI667281B (en) | Thermosetting resin composition | |
| JP2012052096A (en) | Curable composition | |
| KR20160140586A (en) | Aromatic amine resin, maleimide resin, and curable resin composition and cured product thereof | |
| CN103881305B (en) | Composition epoxy resin | |
| TW201410768A (en) | Toughening masterblends | |
| CN103881304B (en) | There is the volatile composition epoxy resin of low organism | |
| JP2017501265A (en) | Curable composition | |
| JP6968018B2 (en) | Epoxy resin powder paint | |
| CN103194040B (en) | Phenolic resin composition | |
| WO2016145661A1 (en) | Epoxy molding compound, its manufacturing process and use, and transistor outline package product containing molded product thereof | |
| JP5983590B2 (en) | Curable resin composition, sealing material, and electronic device product using the same | |
| CN105400476B (en) | A kind of modified lignin resin polyamic acid/epoxy resin composite adhesive and preparation method thereof | |
| JP6249996B2 (en) | Polyimide resin composition and method for producing the same | |
| JP6331500B2 (en) | Epoxy resin composition and cured product | |
| JP2008195907A (en) | Thermosetting benzoxazine resin composition | |
| JP6423316B2 (en) | New aldehyde-containing resin | |
| US20190002685A1 (en) | Flame-retardant, high temperature resistant thermosets on the basis of naphthalene-based epoxy resins and cyanate esters | |
| TW201434950A (en) | Curable epoxy resin compositions | |
| JP6482511B2 (en) | Maleimide resin molded body, method for producing maleimide resin molded body, maleimide resin composition and cured product thereof | |
| JPWO2020080158A1 (en) | Thermally conductive resin composition | |
| WO2020080158A1 (en) | Thermally conductive resin composition | |
| CN104877133A (en) | Benzoxazine ring-containing aryl nitrile special resin and benzoxazine resin copolymer resin and industrial preparation method thereof | |
| EP3628671A1 (en) | High heat epoxy coating powders, processes of making, and uses thereof | |
| US20150166825A1 (en) | Toughened epoxy resin formulations |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Wang Yushi Inventor after: Xu Weining Inventor before: Fu You Inventor before: Fu Yu Sheng |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170330 Address after: 518106 District, Shenzhen, Gongming, Guangming Street, Li Songlang community, the first industrial district, Fort Road, No. 1, floor, floor two, A District Patentee after: SHENZHEN TIANNINGDA ADHESIVES TECHNOLOGY CO.,LTD. Address before: 300112 Tianjin City, North Industrial Park Xiqing District Jin Xia Lu No. 18 C District No. 6 Patentee before: TIANJIN HONGYAN TECHNOLOGY Co.,Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160302 |