CN103113546B - Self-lubricating multi-element copolymerized thermosetting resin and preparation method and application thereof - Google Patents
Self-lubricating multi-element copolymerized thermosetting resin and preparation method and application thereof Download PDFInfo
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- CN103113546B CN103113546B CN201310030406.XA CN201310030406A CN103113546B CN 103113546 B CN103113546 B CN 103113546B CN 201310030406 A CN201310030406 A CN 201310030406A CN 103113546 B CN103113546 B CN 103113546B
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- 0 *c1ccccc1 Chemical compound *c1ccccc1 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N Cc(cc1)ccc1O Chemical compound Cc(cc1)ccc1O IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- QWVGKYWNOKOFNN-UHFFFAOYSA-N Cc(cccc1)c1O Chemical compound Cc(cccc1)c1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Oc1ccccc1 Chemical compound Oc1ccccc1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses self-lubricating multi-element copolymerized thermosetting resin and a preparation method and application thereof. The preparation method comprises the following steps of: reacting phenol, anacardol, an acid catalyst and a nylon-6 under a temperature-raising action to obtain a bisphenol copolymer of phenol and anacardol; adding formaldehyde water solution into the bisphenol copolymer; adding tripolycyanamide after the temperature is raised and preserved; and finally adding polyviny alcohol to react to obtain the self-lubricating multi-element copolymerized thermosetting resin. A drill hole cover plate subjected to hot pressing by using the resin is high in flexibility, and can internally lubricate a rotating head and has high heat conduction and electric conduction coefficients; and a drill bit can be instantly deformed when rotating downwards, so that the accuracy of the drill hole is guaranteed, needle breakage and abrasion of the drill bit are easily avoided, and heat generated during working can be rapidly taken away to prevent high-temperature annealing and static aggregation of the drill bit.
Description
Technical field
The present invention relates to the production process of resin of the boring thermosetting resin dipping lamination cover plate of widely used electronic circuit board (PCB) on market and backing plate.
Technical background
Electronic circuit board boring cover plate and backing plate are that a kind of important electronic circuit board (PCB) processes auxiliary material, high-quality cover plate effectively can improve precision and the quality of boring, reduce surface when holing and produce burr, lubricate and assist rotating the needle to dispel the heat, preventing broken needle phenomenon.Current electronic product is progressively to the development of miniaturization high integration, and electronic component packing density progressively improves, and the boring demand of small-bore increases rapidly, and the density in hole constantly promotes, more than meeting, require that boring cover plate and backing plate must be accomplished:
1, smooth, without prying, surperficial zero defect cut.
2, hardness is moderate, can not too hard worn drill bit.
3, resin can not pollute hole wall.
4, thermal conductivity is large can take away rapidly the heat of boring generation and drill bit can be assisted to lubricate,
Can be recessed rapidly when 5, having certain toughness rotating the needle to contact, make drill bit exactitude position.
Conventional PCB boring cover plate and backing plate can be divided into aluminium foil plastic cement composition board by material, aluminium sheet, resin impregnating laminated board, aluminium foil resol plate.
Summary of the invention
For resin impregnating laminated board, aluminium foil resol plate is generally utilize converted paper (insulation paper) to be immersed in resol, forms via thermocompressor pressing.Object of the present invention is just to provide a kind of electronic circuit board boring cover plate and backing plate drill bit self-lubricating multi-component copolymer thermosetting resin substitutes the resol produced for cover plate, it can overcome the resol plate produced at present and easily occur prying, poor heat conduction, cannot self-lubricating drilling bit, hole the problems such as easy broken needle in small-bore.Production technique is simple, with low cost.The burr hole cover using the impregnated paper of this resin to make after hot pressing, backing plate have splendid snappiness and surface hardness, have good heat radiation and the ability of lubricates drill bit, greatly reduce the wearing and tearing of drill bit and the probability of broken needle, ensure borehole accuracy.Extensively can substitute the tung oil phenolic resin of current used costliness.
Implementation method of the present invention is as follows: a kind of self-lubricating multi-component copolymer thermosetting resin and preparation method thereof, comprises the following steps:
A () adds phenol 60-80 part, cardanol 30-40 part, an acidic catalyst 1-2 part, nylon-6 3-5 part, starts stirring and is warming up to 50-60 DEG C, is warming up to 90-95 DEG C after fully dissolving, react after 120-140 minute and lower the temperature, obtain the bisphenol copolymer of phenol-cardanol;
In this step, phenol and cardanol react the chemical equation generating two points of multipolymers and are:
Formalin 100-120 part that concentration is 37% is added in (b) bisphenol copolymer in step (a)., adjustment ph value to 8.0, be warming up to 95 DEG C, insulation reaction adds trimeric cyanamide 5-8 part after 60 minutes, react 30 minutes, finally add polyvinyl alcohol 1-4 part, react after 30-50 minute and stop heating, be cooled to 70 DEG C and maintain the temperature at 70 DEG C and start to vacuumize, decompression dehydration, remove vacuum after no longer extracting moisture out, add alcohol dilution to required viscosity, obtain self-lubricating multi-component copolymer thermosetting resin;
Chemical equation involved in this step is as follows:
The bisphenol copolymer of phenol-cardanol and formaldehyde reaction:
With the reaction of trimeric cyanamide:
With the reaction of polyvinyl acetal:
The mutual crosslinking reaction of above compound can form the net macromolecular structure of multi-component copolymer.
In step (b) products therefrom, Graphite Powder 99 4-7 part is added before infusion product.
What adjust ph adopted in step (b) is 30% aqueous sodium hydroxide solution, ammoniacal liquor or triethylamine.
Adding alcohol dilution to required viscosity is that to measure the glue elution time be between 15-18 second in painting four glasss.
The resin that the method for the invention obtains, and preparing the application in hot-forming electronic circuit board boring cover plate or backing plate by this resin impregnated paper.
Described an acidic catalyst is tosic acid or 2% dilute sulphuric acid.
Phenol and cardanol first react and generate bis-phenol by the present invention, in the structure of resol, introduce long chain alkane structure, improve the snappiness of resin, plate surface energy moment concave deformation when turning under ensureing drill bit, ensure borehole accuracy, not easily broken needle and worn drill bit.The introducing of trimeric cyanamide can improve the moisture resistance of cured article, improves sheet material and deposits in process the problem producing prying.Nylon-6 adds resin as internal lubricant, can lubricates drill bit and can improve impact and the flexural strength of sheet material.Graphite Powder 99 can increase heat conduction and the electroconductibility of resin, and the heat produced when taking away rapidly work prevents drill bit high temperature annealing and static focus.
As the resol plate that PCB drilling liner plate uses, too low hardness can make boring surface produce peak, and too high hardness can accelerate bit wear, is best through life-time service experience shore hardness between 90-94.After modified phenolic resins impregnation paper after heat present method obtained is pressed into the thick sheet material of 1.5mm by the surface hardness that shore hardness instrument is measured be: more than 91-93(result is the mean value of multiple sample, and probe temperature is normal temperature 25 DEG C).
Graphite Powder 99 not only can also increase heat conduction and the electroconductibility of resin as solid lubricant, the heat produced when taking away rapidly work, prevents drill bit high temperature annealing and static focus.25 DEG C time, test the surface resistivity of the sheet material that modified phenolic resins is produced, the mean value of 10 groups of samples is ρ=1.36x105 Ω cm.Possess certain specific conductivity, effectively can prevent static focus.
The reaction of cardanol and phenol, the hydrocarbon chain of long-chain is introduced in the resol finally obtained, not only increase the snappiness of resin, reduce internal stress during resin solidification, also impart the hydrophobic nature that resin is very strong, finally made sheet material not easily because internal stress and the moisture absorption produce prying distortion, has splendid dimensional stability in long-term storage.
The modified phenolic resins obtained for present method respectively impregnation paper is pressed into the sheet material of 1.5mm think gauge 1145mmx1250mm, sheet material lies on marble countertop by envrionment temperature 10-35 DEG C, tests the bow value of every 1000mm as following table according to the method for GB GB/T4722-92:
| Storage period | Bow value |
| Produce | 0.064 |
| Place 10 days | 0.11 |
| Place 30 days | 0.13 |
| Place 60 days | 0.14 |
| Place 90 days | 0.14 |
Embodiment:
Following embodiment is used for further illustrating the present invention, but is not limited to content of the present invention.
Embodiment 1
A () adds phenol 60 parts, cardanol 30 parts, an acidic catalyst tosic acid 1 part, nylon-6 3 parts starts stirring and is warming up to 50 DEG C, is warming up to 90 DEG C after fully dissolving, and reacts after 120 minutes and lowers the temperature, obtain the bisphenol copolymer of phenol-cardanol;
The formalin 100 parts that concentration is 37% is added in (b) bisphenol copolymer in step (a)., then ph value to 8.0 is adjusted with the aqueous sodium hydroxide solution of 30%, be warming up to 95 DEG C, insulation reaction adds trimeric cyanamide 5 parts after 60 minutes, react 30 minutes, finally add polyvinyl alcohol 1 part, react after 30 minutes and stop heating, be cooled to 70 DEG C and maintain the temperature at 70 DEG C and start to vacuumize, decompression dehydration.No longer extract out after moisture and remove vacuum, add alcohol dilution to required viscosity (being coated with four glasss of measurement glue elution times is between 15-18 second);
C () adds Graphite Powder 99 5 parts before infusion product in step (b) products therefrom, the loose evenly rear use of point high-speed stirring.
Embodiment 2
A () adds phenol 80 parts, cardanol 40 parts, an acidic catalyst 2% dilute sulphuric acid 2 parts, nylon-6 4 parts starts stirring and is warming up to 60 DEG C, is warming up to 95 DEG C after fully dissolving, and reacts after 140 minutes and lowers the temperature, obtain the bisphenol copolymer of phenol-cardanol;
The formalin 120 parts that concentration is 37% is added in (b) bisphenol copolymer in step (a)., then by ammoniacal liquor adjustment ph value to 8.0, be warming up to 95 DEG C, insulation reaction adds trimeric cyanamide 8 parts after 60 minutes, react 30 minutes, finally add polyvinyl alcohol 4 parts, continue reaction and after 50 minutes, stop heating, be cooled to 70 DEG C and maintain the temperature at 70 DEG C and start to vacuumize, decompression dehydration.No longer extract out after moisture and remove vacuum, add alcohol dilution to required viscosity (being coated with four glasss of measurement glue elution times is between 15-18 second);
C () adds Graphite Powder 99 5 parts before infusion product in step (b) products therefrom, use after high-speed stirring is uniformly dispersed.
Embodiment 3
A () adds phenol 70 parts, cardanol 35 parts, an acidic catalyst 2% dilute sulphuric acid 1.5 parts, nylon-6 4 parts starts stirring and is warming up to 55 DEG C, is warming up to 92 DEG C after fully dissolving, and reacts after 130 minutes and lowers the temperature, obtain the bisphenol copolymer of phenol-cardanol;
The formalin 110 parts that concentration is 37% is added in (b) bisphenol copolymer in step (a)., then by triethylamine adjustment ph value to 8.0, be warming up to 95 DEG C, insulation reaction adds trimeric cyanamide 6 parts after 60 minutes, react 30 minutes, finally add polyvinyl alcohol 4 parts, continue reaction and after 40 minutes, stop heating, be cooled to 70 DEG C and maintain the temperature at 70 DEG C and start to vacuumize, decompression dehydration.No longer extract out after moisture and remove vacuum, add alcohol dilution to required viscosity (being coated with four glasss of measurement glue elution times is between 15-18 second);
C () adds Graphite Powder 99 5 parts before infusion product in step (b) products therefrom, use after high-speed stirring is uniformly dispersed.
The resin that above-described embodiment obtains, and by this resin impregnated paper for the preparation of hot-forming electronic circuit board boring cover plate or backing plate.
Claims (5)
1. a preparation method for self-lubricating multi-component copolymer thermosetting resin, comprises the following steps:
A () adds phenol 60-80 part, cardanol 30-40 part, an acidic catalyst 1-2 part, nylon-6 3-5 part, starts stirring and is warming up to 50-60 DEG C, is warming up to 90-95 DEG C after fully dissolving, react after 120-140 minute and lower the temperature, obtain the bisphenol copolymer of phenol-cardanol;
In this step, phenol and cardanol react the chemical equation generating two points of multipolymers and are:
Formalin 100-120 part that concentration is 37% is added in (b) bisphenol copolymer in step (a), adjusted to ph to 8.0, be warming up to 95 DEG C, insulation reaction adds trimeric cyanamide 5-8 part after 60 minutes, react 30 minutes, finally add polyvinyl alcohol 1-4 part, react after 30-50 minute and stop heating, be cooled to 70 DEG C and maintain the temperature at 70 DEG C and start to vacuumize, decompression dehydration, vacuum is removed after no longer extracting moisture out, add alcohol dilution to required viscosity, required viscosity is that to measure the glue elution time be between 15-18 second in painting four glasss, obtain self-lubricating multi-component copolymer thermosetting resin,
Chemical equation involved in this step is as follows:
The bisphenol copolymer of phenol-cardanol and formaldehyde reaction:
With the reaction of trimeric cyanamide:
With the reaction of polyvinyl acetal:
The mutual crosslinking reaction of above compound can form the net macromolecular structure of multi-component copolymer.
2. the preparation method of self-lubricating multi-component copolymer thermosetting resin according to claim 1, is characterized in that: before infusion product, add Graphite Powder 99 4-7 part in step (b) products therefrom.
3. the preparation method of self-lubricating multi-component copolymer thermosetting resin according to claim 1, is characterized in that: what adjust ph adopted in the step (b) is 30% aqueous sodium hydroxide solution, ammoniacal liquor or triethylamine.
4. the application in hot-forming electronic circuit board boring cover plate or backing plate prepared by the paper of self-lubricating multi-component copolymer thermosetting resin dipping according to claim 1.
5. the preparation method of self-lubricating multi-component copolymer thermosetting resin according to claim 1, is characterized in that: described an acidic catalyst is tosic acid or 2% dilute sulphuric acid.
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| CN103449979A (en) * | 2013-08-19 | 2013-12-18 | 上海美东生物材料有限公司 | Bisphenol epoxy resin and preparation method thereof |
| CN105500738A (en) * | 2016-01-19 | 2016-04-20 | 烟台柳鑫新材料科技有限公司 | Backing board for drilling and production method thereof |
| CN109334179A (en) * | 2018-08-14 | 2019-02-15 | 烟台柳鑫新材料科技有限公司 | A kind of antistatic self-lubricating type PCB cover plate for drilling hole and preparation method thereof |
| CN110202902A (en) * | 2019-05-24 | 2019-09-06 | 烟台柳鑫新材料科技有限公司 | A kind of PCB back drill cover board and preparation method thereof |
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| US9782947B2 (en) * | 2007-05-25 | 2017-10-10 | W. L. Gore & Associates, Inc. | Fire resistant laminates and articles made therefrom |
| CN101353405B (en) * | 2008-08-12 | 2011-06-29 | 中国西电集团公司 | Method for modifying tung oil modified phenolic resin with melamine |
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Address after: North Gate Industrial Park of Hubei city in Yichang Province town of Ming 444200 Yuan'an County Applicant after: YICHANG WUXING MATERIAL SCIENCE & TECHNOLOGY Co.,Ltd. Address before: North Gate Industrial Park of Hubei city in Yichang Province town of Ming 444200 Yuan'an County Applicant before: YICHANG WUXING MATERIAL SCIENCE & TECHNOLOGY Co.,Ltd. |
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Denomination of invention: A self-lubricating multicomponent copolymer thermosetting resin and its preparation method and application Effective date of registration: 20220930 Granted publication date: 20150128 Pledgee: Hubei Yuan'an Rural Commercial Bank Co.,Ltd. Pledgor: YICHANG WUXING MATERIAL SCIENCE & TECHNOLOGY Co.,Ltd. Registration number: Y2022980017401 |
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