CN103113546A - 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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- CN103113546A CN103113546A CN201310030406XA CN201310030406A CN103113546A CN 103113546 A CN103113546 A CN 103113546A CN 201310030406X A CN201310030406X A CN 201310030406XA CN 201310030406 A CN201310030406 A CN 201310030406A CN 103113546 A CN103113546 A CN 103113546A
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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 a kind of important electronic circuit board (PCB) processing auxiliary materials, high-quality cover plate can effectively improve precision and the quality of boring, when reducing boring, the surface produces burr, and lubricated and auxiliary rotating the needle heat radiation prevents the broken needle phenomenon.Progressively to the development of miniaturization high integration, the electronic component packing density progressively improves electronic product at present, and the boring demand of small-bore increases rapidly, and the density in hole constantly promotes, and must accomplish for satisfying above boring cover plate and the backing plate of requiring:
1, smooth, without prying, surperficial zero defect cut.
2, hardness is moderate, and too drill bit is damaged in hard grind.
3, resin can not pollute hole wall.
4, thermal conductivity is large can take away rapidly the heat of boring generation and can assist drill bit lubricated,
Can be recessed rapidly when 5, certain toughness rotating the needle contact being arranged, make the drill bit exactitude position.
PCB boring cover plate and backing plate commonly used 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
Be used for the resin impregnating laminated board, aluminium foil resol plate is generally to utilize converted paper (insulation paper) to be immersed in resol, forms via the thermocompressor pressing.Purpose of the present invention just is to provide a kind of electronic circuit board boring cover plate and backing plate substitutes with drill bit self-lubricating multi-component copolymer thermosetting resin the resol that is used for cover plate production, prying easily appears in the resol plate that it can overcome present production, poor heat conduction, can't self-lubricating drilling bit, the problems such as the easy broken needle of small-bore boring.Production technique is simple, and is with low cost.Use burr hole cover, the backing plate that the impregnated paper of this resin is made after hot pressing to have splendid snappiness and surface hardness, good heat radiation and the ability of lubricated drill bit are arranged, reduced greatly the wearing and tearing of drill bit and the probability of broken needle, guarantee borehole accuracy.Can extensively substitute the tung oil phenolic resin of the present costliness of using.
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) add phenol 60-80 part, cardanol 30-40 part, an acidic catalyst 1-2 part, nylon-6 3-5 part begins stirring and is warming up to 50-60 ℃, fully is warming up to 90-95 ℃ after dissolving, react cooling after 120-140 minute, obtain the bis-phenol multipolymer of phenol-cardanol;
In this step, the chemical equation of two minutes multipolymers of phenol and cardanol reaction generation are:
(b) adding concentration in the bis-phenol multipolymer in step (a) is formalin 100-120 part of 37%, adjust ph value to 8.0, be warming up to 95 ℃, insulation reaction adds trimeric cyanamide 5-8 part after 60 minutes, reacted 30 minutes, add at last polyvinyl alcohol 1-4 part, react stopped heating after 30-50 minute, be cooled to 70 ℃ and maintain the temperature at 70 ℃ and begin 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 related in this step is as follows:
Bis-phenol multipolymer and the formaldehyde reaction of phenol-cardanol:
Reaction with trimeric cyanamide:
Reaction with polyvinyl acetal:
The mutual crosslinking reaction of above compound can form the net macromolecular structure of multi-component copolymer.
Add Graphite Powder 99 4-7 part in step (b) products therefrom before infusion product.
What regulate the employing of pH value in step (b) is 30% aqueous sodium hydroxide solution, ammoniacal liquor or triethylamine.
Adding alcohol dilution to required viscosity is that 15-18 is between second for being coated with four glasss of measurement glue elution times.
The resin that the method for the invention obtains, and preparing hot-forming electronic circuit board boring cover plate or the application in backing plate with this resin impregnated paper.
Described an acidic catalyst is tosic acid or 2% dilute sulphuric acid.
The present invention first generates bis-phenol with phenol and cardanol reaction, introduced the long chain alkane structure in the structure of resol, improved the snappiness of resin, plate surface energy moment concave deformation when guaranteeing to turn under drill bit, guarantee borehole accuracy, be difficult for broken needle and wearing and tearing drill bit.The introducing of trimeric cyanamide can improve the moisture resistance of cured article, improves sheet material and deposits the problem that produces prying in process.Nylon-6 adds resin as internal lubricant, can lubricate 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 that produces when taking away work rapidly prevents drill bit high temperature annealing and static focus.
As the resol plate that the PCB drilling liner plate uses, too low hardness can make boring surface produce peak, and too high hardness can be accelerated bit wear, is best between 90-94 through life-time service experience shore hardness.The modified phenolic resins impregnation paper after heat that present method is obtained is pressed into the surface hardness of measuring with the shore hardness instrument after the thick sheet material of 1.5mm: the above result of 91-93(is the mean value of a plurality of samples, and probe temperature is 25 ℃ of normal temperature).
Graphite Powder 99 not only can be used as heat conduction and the electroconductibility that solid lubricant can also increase resin, and the heat that produces when taking away work rapidly prevents drill bit high temperature annealing and static focus.The surface resistivity of the sheet material that the test modified phenolic resins is produced in the time of 25 ℃, the mean value of 10 groups of samples is ρ=1.36x105 Ω cm.Possessed certain specific conductivity, can effectively prevent static focus.
The reaction of cardanol and phenol, introduced the hydrocarbon chain of long-chain in the resol that finally obtains, not only increased the snappiness of resin, internal stress when having reduced resin solidification, also given resin very strong hydrophobic nature, final made sheet material is difficult for due to internal stress and the distortion of moisture absorption generation prying, splendid dimensional stability being arranged in long-term storage.
The modified phenolic resins that obtains for present method impregnation paper respectively is pressed into the sheet material of the thick specification 1145mmx1250mm of 1.5mm, envrionment temperature 10-35 ℃ lies in sheet material on marble countertop, tests bow value such as the following table of every 1000mm according to the method for GB GB/T4722-92:
| Storage period | The bow value |
| Produce | 0.064 |
| Placed 10 days | 0.11 |
| Placed 30 days | 0.13 |
| Placed 60 days | 0.14 |
| Placed 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) add 60 parts of phenol, 30 parts of cardanols, 1 part of an acidic catalyst tosic acid, 3 parts of nylon-6s begin stirring and are warming up to 50 ℃, fully are warming up to 90 ℃ after dissolving, react cooling after 120 minutes, obtain the bis-phenol multipolymer of phenol-cardanol;
(b) adding concentration in the bis-phenol multipolymer in step (a) is 100 parts of 37% formalins, then adjust ph value to 8.0 with 30% aqueous sodium hydroxide solution, be warming up to 95 ℃, insulation reaction adds 5 parts of trimeric cyanamides after 60 minutes, reacted 30 minutes, and added at last 1 part of polyvinyl alcohol, react stopped heating after 30 minutes, be cooled to 70 ℃ and maintain the temperature at 70 ℃ and begin to vacuumize, decompression dehydration.Remove vacuum after no longer extracting moisture out, add alcohol dilution to required viscosity (being coated with four glasss of measurement glue elution times is that 15-18 is between second);
(c) add 5 parts of Graphite Powder 99s in step (b) products therefrom before infusion product, loose evenly rear use of minute high-speed stirring.
Embodiment 2
(a) add 80 parts of phenol, 40 parts of cardanols, 2 parts of an acidic catalyst 2% dilute sulphuric acids, 4 parts of nylon-6s begin stirring and are warming up to 60 ℃, fully are warming up to 95 ℃ after dissolving, react cooling after 140 minutes, obtain the bis-phenol multipolymer of phenol-cardanol;
(b) adding concentration in the bis-phenol multipolymer in step (a) is 120 parts of 37% formalins, then adjust ph value to 8.0 with ammoniacal liquor, be warming up to 95 ℃, insulation reaction adds 8 parts of trimeric cyanamides after 60 minutes, reacted 30 minutes, and added at last 4 parts of polyvinyl alcohol, continue to react stopped heating after 50 minutes, be cooled to 70 ℃ and maintain the temperature at 70 ℃ and begin to vacuumize, decompression dehydration.Remove vacuum after no longer extracting moisture out, add alcohol dilution to required viscosity (being coated with four glasss of measurement glue elution times is that 15-18 is between second);
(c) add 5 parts of Graphite Powder 99s in step (b) products therefrom before infusion product, the high-speed stirring rear use that is uniformly dispersed.
Embodiment 3
(a) add 70 parts of phenol, 35 parts of cardanols, 1.5 parts of an acidic catalyst 2% dilute sulphuric acids, 4 parts of nylon-6s begin stirring and are warming up to 55 ℃, fully are warming up to 92 ℃ after dissolving, react cooling after 130 minutes, obtain the bis-phenol multipolymer of phenol-cardanol;
(b) adding concentration in the bis-phenol multipolymer in step (a) is 110 parts of 37% formalins, then adjust ph value to 8.0 with triethylamine, be warming up to 95 ℃, insulation reaction adds 6 parts of trimeric cyanamides after 60 minutes, reacted 30 minutes, and added at last 4 parts of polyvinyl alcohol, continue to react stopped heating after 40 minutes, be cooled to 70 ℃ and maintain the temperature at 70 ℃ and begin to vacuumize, decompression dehydration.Remove vacuum after no longer extracting moisture out, add alcohol dilution to required viscosity (being coated with four glasss of measurement glue elution times is that 15-18 is between second);
(c) add 5 parts of Graphite Powder 99s in step (b) products therefrom before infusion product, the high-speed stirring rear use that is uniformly dispersed.
The resin that above-described embodiment obtains, and with this resin impregnated paper for the preparation of hot-forming electronic circuit board boring cover plate or backing plate.
Claims (6)
1. self-lubricating multi-component copolymer thermosetting resin and preparation method thereof comprises the following steps:
(a) add phenol 60-80 part, cardanol 30-40 part, an acidic catalyst 1-2 part, nylon-6 3-5 part begins stirring and is warming up to 50-60 ℃, fully is warming up to 90-95 ℃ after dissolving, react cooling after 120-140 minute, obtain the bis-phenol multipolymer of phenol-cardanol;
In this step, the chemical equation of two minutes multipolymers of phenol and cardanol reaction generation are:
(b) adding concentration in the bis-phenol multipolymer in step (a) is formalin 100-120 part of 37%, adjust ph value to 8.0, be warming up to 95 ℃, insulation reaction adds trimeric cyanamide 5-8 part after 60 minutes, reacted 30 minutes, add at last polyvinyl alcohol 1-4 part, react stopped heating after 30-50 minute, be cooled to 70 ℃ and maintain the temperature at 70 ℃ and begin 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 related in this step is as follows:
Bis-phenol multipolymer and the formaldehyde reaction of phenol-cardanol:
Reaction with trimeric cyanamide:
Reaction with polyvinyl acetal:
The mutual crosslinking reaction of above compound can form the net macromolecular structure of multi-component copolymer.
2. self-lubricating multi-component copolymer thermosetting resin according to claim 1 and preparation method thereof, is characterized in that: add Graphite Powder 99 4-7 part in step (b) products therefrom before infusion product.
3. self-lubricating multi-component copolymer thermosetting resin according to claim 1 and preparation method thereof is characterized in that: what regulate the employing of pH value in step (b) is 30% aqueous sodium hydroxide solution, ammoniacal liquor or triethylamine.
4. self-lubricating multi-component copolymer thermosetting resin according to claim 1 and preparation method thereof is characterized in that: adding alcohol dilution to required viscosity is that 15-18 is between second for being coated with four glasss of measurement glue elution times.
5. the resin that obtains as method as described in arbitrary in claim 1-4, and with the application of this resin impregnated paper in the hot-forming electronic circuit board of preparation is holed cover plate or backing plate.
6. according to according to self-lubricating multi-component copolymer thermosetting resin claimed in claim 1 and preparation method thereof, it is characterized in that: described an acidic catalyst is tosic acid or 2% dilute sulphuric acid.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05320298A (en) * | 1992-05-20 | 1993-12-03 | Shin Kobe Electric Mach Co Ltd | Production of oil-modified phenolic resin for use in laminate |
| CN101353405A (en) * | 2008-08-12 | 2009-01-28 | 西安电力机械制造公司 | Method for modifying tung oil modified phenolic resin with melamine |
| CN101687396A (en) * | 2007-05-25 | 2010-03-31 | 戈尔企业控股股份有限公司 | Fire resistant laminates and articles made therefrom |
-
2013
- 2013-01-28 CN CN201310030406.XA patent/CN103113546B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05320298A (en) * | 1992-05-20 | 1993-12-03 | Shin Kobe Electric Mach Co Ltd | Production of oil-modified phenolic resin for use in laminate |
| CN101687396A (en) * | 2007-05-25 | 2010-03-31 | 戈尔企业控股股份有限公司 | Fire resistant laminates and articles made therefrom |
| CN101353405A (en) * | 2008-08-12 | 2009-01-28 | 西安电力机械制造公司 | Method for modifying tung oil modified phenolic resin with melamine |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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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 |