CN103881304B - There is the volatile composition epoxy resin of low organism - Google Patents
There is the volatile composition epoxy resin of low organism Download PDFInfo
- Publication number
- CN103881304B CN103881304B CN201410075184.8A CN201410075184A CN103881304B CN 103881304 B CN103881304 B CN 103881304B CN 201410075184 A CN201410075184 A CN 201410075184A CN 103881304 B CN103881304 B CN 103881304B
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- weight
- composition
- composition epoxy
- resin
- 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.)
- Expired - Fee Related
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
One has 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 the auxiliary agent of d) 0-40 % by weight.Described composition epoxy resin has the mechanical propertys such as low organism volatility, high heat resistance and toughness, can be used for the industries such as printing, electronics, coating.
Description
Technical field
The present invention relates to a kind of composition epoxy resin, particularly relate 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 electrical insulating material, 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 containing a large amount of organic solvents, in use easily cause organic solvent to volatilize, and these organic solvents comprise the material to environment and human hazard such as toluene.
Therefore, need the solid content improving epoxy resin, reduce organic volatile wherein, make the finished product have 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 composition epoxy resin that a class is brand-new, 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, provides a kind of new composition epoxy resin, 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 of the epoxy resin with following structural (I) and (II):
（II）；
Wherein, R is H or CH
3, R1 is the residue after cardanol removes phenol structure.
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 the present compositions, the amount of described epoxy resin can be 20-90 % by weight, preferred 20-70 % by weight, 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 commercially have been bought.As the present invention one preferred embodiment, described resol can be prepared by following methods: 1., by phenol and aldehyde 1: 0.5 ~ 0.9 add reactor in molar ratio, then add an acidic catalyst, stir, be warming up to 70 ~ 100 DEG C simultaneously, and maintain 1 ~ 8 hour, obtained resol; 2., to the resol that 1. step obtains carry out distillation process, be less than 0.5wt% to phenol content; Step 1. described in an acidic catalyst be selected from hydrochloric acid, oxalic acid, phosphoric acid, sulfuric acid, ethyl sulfate, halogenosulfonic acid and Phenylsulfonic acid and alkyl substituents thereof one or more.
In the present compositions, the amount of described resol can be 1-40 % by weight, preferred 2-30 % by weight, 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, such as amine, anhydrides and phenols or phenolic.Such as, described amine curing agent is mphenylenediamine, Ursol D, m-xylene diamine, 4, and 4 '-diaminodiphenyl-methane or DDS; Described acid anhydride type curing agent is styrene-grafted maleic anhydride etc.
In the present compositions, the amount of described solidifying agent can be 1-25 % by weight, and preferred 1-20 % by weight, based on the gross weight of composition.
Described auxiliary agent can be any suitable material, such as, improve the glass fibre of composition epoxy resin mechanical property, granulated glass sphere, calcium carbonate, carbon black, carbon nanotube, talcum, titanium dioxide, nano silicon etc.Auxiliary agent can also comprise curing catalyst, compatilizer, softening agent, silane coupling agent, releasing agent etc.
In the present compositions, the amount of described auxiliary agent can be 0-50 % by weight, and preferred 0-40 % by weight, based on the gross weight of composition.
The beneficial effect of the invention
The present inventor studies through hard, being surprisingly found out that by combining specific epoxy resin, resol, solidifying agent and auxiliary agent, composition can be made to have the mechanical propertys such as low organism volatility, high heat resistance and toughness.
Present invention uses special epoxy resin, it contains formula (I) and formula (II) structure, is liquid at normal temperatures, and directly can mix with other components, and not need to add solvent, it has low organism volatility; Meanwhile, owing to introducing resol in composition, enhance thermotolerance and the physical strength of composition epoxy resin significantly.
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 only for illustration of the present invention, and should not be considered as limiting scope of the present invention.Unreceipted actual conditions person in embodiment, conveniently condition is carried out.
Preparation example 1
Mixed under nitrogen atmosphere with 20 parts by weight of cardanol by the diglycidylether of 80 parts by weight of bisphenol A, then heated mixt is to 90 DEG C, adds 400ppm ethyl triphenyl PA as catalyzer.Heated mixt keeps 3 hours to 170 DEG C subsequently, and obtain epoxy resin A subsequently, it contains the epoxy resin of 55 % by weight formula (I) structures and the epoxy resin of 45 % by weight formula (II) structures.
Preparation example 2
Mixed under nitrogen atmosphere with 8 parts by weight of cardanol by the diglycidylether of 92 parts by weight of bisphenol A, then heated mixt is to 90 DEG C, adds 200ppm ethyl triphenyl PA as catalyzer.Heated mixt keeps 2 hours to 180 DEG C subsequently, and obtain epoxy resin B subsequently, it contains the epoxy resin of 81 % by weight formula (I) structures and the epoxy resin of 19 % by weight formula (II) structures.
Preparation example 3
Mixed under nitrogen atmosphere with 35 parts by weight of cardanol by the diglycidylether of 65 parts by weight of bisphenol A, then heated mixt is to 90 DEG C, adds 300ppm ethyl triphenyl PA as catalyzer.Heated mixt keeps 3 hours to 180 DEG C subsequently, and obtain epoxy resin C subsequently, it contains the epoxy resin of 20 % by weight formula (I) structures and the epoxy resin of 80 % by weight formula (II) structures.
Preparation example 4
Mixed under nitrogen atmosphere with 15 parts by weight of cardanol by the diglycidylether of 85 parts by weight of bisphenol F, then heated mixt is to 90 DEG C, adds 350ppm ethyl triphenyl PA as catalyzer.Heated mixt keeps 4 hours to 170 DEG C subsequently, and obtain epoxy resin D subsequently, it contains the epoxy resin of 65 % by weight formula (I) structures and the epoxy resin of 35 % by weight formula (II) structures.
Epoxy resin prepared by above-mentioned preparation example 1-4 is liquid state, can not solubilizing agent or only add a small amount of solvent when mixing with other components, such as, in the above-mentioned epoxy resin of 90 weight part, add 10 parts by weight solvent, such as toluene.Now, soltion viscosity is about 10000 ~ 12000cps 25 DEG C time, and conventional bisphenol A diglycidyl ether, the D.E.R. that such as Tao Shi produces
tM671-X75 is solid 25 DEG C time, 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 25 DEG C time.
Embodiment
In the four-hole bottle having magnetic stirring apparatus, prolong, constant pressure funnel and thermometer, epoxy resin is added under nitrogen protection.Then optional auxiliary agent is added wherein, stir.Add resol and solidifying agent subsequently, after stirring, namely obtain composition epoxy resin.If need solidifying product, heat temperature raising solidifies.
According to the formula of table 1, a series of composition of the present invention can be obtained.
Table 1
Owing to not using volatilizable organism, particularly solvent in embodiment 1-4, therefore it has low organism volatility; And comprise toluene in comparative example 1, it is residual in the final product, so the organic volatile object height that the finished product contain, to environment and the mankind unfavorable.
With thermogravimetic analysis (TGA) (TGA) and dynamic mechanically mechanical property (DMA) analysis, the resistance toheat of the composition that embodiment 1-4 and comparative example 1-2 obtains is evaluated: adopt 5% weightless temperature of TGA and the residual heavy sign resistance toheat of 900 DEG C, adopt Tan (δ) peak value of DMA to characterize the second-order transition temperature of cured resin.The composition obtained by embodiment 1-4 and comparative example 1-2 by after 130 DEG C of+150 DEG C of+200 DEG C of solidifications in 6 hours in 2 hours in 2 hours, obtains fine and close casting matrix in electric heating convection oven.
The composition obtained by embodiment 1-4 and comparative example 1-2 by mould pressing process and quartz fabric make 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 DEG C/2h+150 DEG C/6h+200 DEG C/6h.Table 2 listed in by matrix material at room temperature tensile strength and elongation at break, and resin composite materials has excellent mechanical property as can be seen here.
Table 2
As can be seen from Table 2, the composition of the embodiment 1-4 containing epoxy resin and resol has better thermotolerance and more excellent toughness, and the thermotolerance of the composition of comparative example 2 not containing resol and poor toughness; In addition, the thermotolerance of the composition of the embodiment 3 and 4 containing 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 in right.
Claims (7)
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,
Described epoxy resin is the mixture of the epoxy resin with following structural (I) and (II):
Wherein, R is H or CH
3, R1 is the residue after cardanol removes phenol structure.
2. composition epoxy resin as claimed in claim 1, it is characterized in that: the epoxy resin of formula (I) accounts for the 20-80% of epoxy resin gross weight, the epoxy resin of formula (II) accounts for the 20-80% of epoxy resin gross weight.
3. composition epoxy resin as claimed in claim 1, is characterized in that: resol b) be selected from phenol formaldehyde resin, phenol acetaldehyde resin, resorcinol formaldehyde resin, Resorcinol formaldehyde resin.
4. composition epoxy resin as claimed in claim 1, is characterized in that: described solidifying agent is mphenylenediamine.
5. composition epoxy resin as claimed in claim 1, is characterized in that: described auxiliary agent is nano silicon.
6. the composition epoxy resin as described in any one of claim 1-5 is used for the purposes of coating.
7. the composition epoxy resin as described in any one of claim 1-5 is used 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 CN103881304A (en) | 2014-06-25 |
| CN103881304B true 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) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10246607B2 (en) * | 2017-07-20 | 2019-04-02 | Chang Chun Plastics Co., Ltd. | Resin composition, coating composition and article by using the same |
| 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 |
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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103881304A (en) | 2014-06-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI540146B (en) | Insulation formulations | |
| JP2012052096A (en) | Curable composition | |
| WO2016039486A1 (en) | Thermosetting resin composition | |
| KR20160140586A (en) | Aromatic amine resin, maleimide resin, and curable resin composition and cured product thereof | |
| TW201410768A (en) | Toughening masterblends | |
| CN103881305B (en) | Composition epoxy resin | |
| CN103881304B (en) | There is the volatile composition epoxy resin of low organism | |
| TWI548690B (en) | High performance thermoset useful for electrical laminate, high density interconnect and interconnect substrate applications | |
| JP6968018B2 (en) | Epoxy resin powder paint | |
| JP5028844B2 (en) | Epoxy resin composition, cured product thereof, novel epoxy compound and production method thereof | |
| CN103194040B (en) | Phenolic resin composition | |
| JP6331500B2 (en) | Epoxy resin composition and cured product | |
| JP2008195907A (en) | Thermosetting benzoxazine resin composition | |
| JP6423316B2 (en) | New aldehyde-containing resin | |
| TWI724229B (en) | Maleimide resin molded body, method for producing maleimide resin molded body, maleimide resin composition and cured product thereof | |
| JP2011057908A (en) | Epoxy resin cured product | |
| US20190002685A1 (en) | Flame-retardant, high temperature resistant thermosets on the basis of naphthalene-based epoxy resins and cyanate esters | |
| JP6482511B2 (en) | Maleimide resin molded body, method for producing maleimide resin molded body, maleimide resin composition and cured product thereof | |
| WO2014055305A2 (en) | Curable epoxy resin compositions | |
| JP2014080494A (en) | Curable imide compound, method for producing the same, curable resin composition, and cured material | |
| WO2016033079A1 (en) | Synthesis of naphthol novolac | |
| JP6942550B2 (en) | Method for producing resin composition, resin varnish, laminated board, thermosetting molding material, encapsulant, and method for producing propenyl group-containing resin. | |
| JP2018104609A (en) | One-pack thermosetting resin composition and cured article thereof | |
| JP4244626B2 (en) | Epoxy resin composition and electrically insulating material | |
| JP2004339381A (en) | Epoxy resin, method for producing the same, epoxy resin composition and cured product thereof |
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 |
Inventor after: Wang Yushi Inventor after: Xu Weining Inventor before: Fu You Inventor before: Fu Yu Sheng |
|
| CB03 | Change of inventor or designer information | ||
| 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. |
|
| TR01 | Transfer of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160302 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |