CN108162558A - A kind of manufacturing method of heat-resistant tearing mode paper-based copper-coated board - Google Patents
A kind of manufacturing method of heat-resistant tearing mode paper-based copper-coated board Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
- C08G8/32—Chemically modified polycondensates by organic acids or derivatives thereof, e.g. fatty oils
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- B32—LAYERED PRODUCTS
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/098—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
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- B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
- B32B21/02—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board the layer being formed of fibres, chips, or particles, e.g. MDF, HDF, OSB, chipboard, particle board, hardboard
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/026—Wood layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/06—Vegetal fibres
- B32B2262/062—Cellulose fibres, e.g. cotton
- B32B2262/067—Wood fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2305/00—Condition, form or state of the layers or laminate
- B32B2305/07—Parts immersed or impregnated in a matrix
- B32B2305/076—Prepregs
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/582—Tearability
- B32B2307/5825—Tear resistant
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2361/00—Phenoplast, aminoplast
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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Abstract
The present invention discloses a kind of manufacturing method of heat-resistant tearing mode paper-based copper-coated board, includes the following steps：Step 1: preparing cardanol-aldehyde resin, small-molecular-weight phenolic resin is prepared；By cardanol-aldehyde resin and small-molecular-weight phenolic resin mixing preparation into resin solution；Cardanol-aldehyde resin and small-molecular-weight phenolic resin allotment dosage are respectively 780 820 parts by weight and 60 80 parts by weight, are deployed into the resin solution of solid content 50 55%；Step 2: in being soaked in the resin solution with wood pulp paper, prepreg is made in drying, and hot pressing is to get paper-based copper-coated board of the present invention together with adhesive coated foil.The present invention is prepared with intrinsic toughening phenol-formaldehyde resin modified, there is preferable toughness and heat resistance, substantially improves the heat resistance of copper-clad plate, and plank is made to have good tear resistance.
Description
The application be to be 2015.12.17 application No. is " 201510952365.9 ", the applying date application theme be " waist
The manufacturing method of the preparation method of fruit phenolic resin, application and paper-based copper-coated board " proposes divisional application.
Technical field
The present invention relates to copper-clad plate manufacturing field, in particular to a kind of manufacturers of heat-resistant tearing mode paper-based copper-coated board
Method.
Background technology
Paper-based copper-coated board has extensive purposes in electronic product.In paper-based copper-coated board manufacture, mainly obtain product
Preferable punching is obtained, with the technology of tung oil modified phenolic resin, epoxy soybean oil modified phenolic resin production paper-based copper-coated board
It reaches its maturity, and has been widely used.Anacardol is a kind of new material for starting application in copper-clad plate production in recent years,
Due in its molecule on phenyl ring there are one long chain hydrocarbon groups, by its novolak resin mixed with phenol, it is possible to provide resin it is flexible
Property, currently as tung oil modified phenolic resin or the response type auxiliary toughener of epoxy soybean oil modified phenolic resin, covering copper
Commonly used in plate manufacture, it can reduce the dosage of tung oil or epoxidized soybean oil, reduce the material cost in production.But directly
It is mixed with anacardol and a certain amount of phenol, formaldehyde is added to react novolak resin, although resin can be improved largely
Flexibility, but the copper-clad plate punching produced is still bad, and bow warping is big, resistance to dip solderability undesirable.The reason is that in phenol
In the forming process of urea formaldehyde, the alkyl on anacardol phenyl ring cannot participate in the formation of macromolecular main chain, in the form of cantilever chain
In the presence of toughening effect is limited.If anacardol proportion is excessive, since the degree of functionality of anacardol is low compared with phenol, in addition long-chain
Steric effect, the solidfied material crosslink density for making generation is small, therefore influences the heat resistance of copper-clad plate, tear resistance.
Invention content
The purpose of the present invention is to provide a kind of manufacturing methods of heat-resistant tearing mode paper-based copper-coated board, prepare with interior
Toughening modifying phenolic resin has preferable toughness and heat resistance, substantially improves the heat resistance of copper-clad plate, and it is good to have plank
Tear resistance.
In order to achieve the above objectives, solution of the invention is：
A kind of manufacturing method of heat-resistant tearing mode paper-based copper-coated board, includes the following steps：
Step 1: preparing cardanol-aldehyde resin, small-molecular-weight phenolic resin is prepared；By cardanol-aldehyde resin and small-molecular-weight
Phenolic resin mixing preparation is into resin solution；Cardanol-aldehyde resin and small-molecular-weight phenolic resin allotment dosage are respectively 780-
820 parts by weight and 60-80 parts by weight are deployed into the resin solution of solid content 50-55%；
Step 2: in being soaked in the resin solution with wood pulp paper, prepreg is made in drying, hot together with adhesive coated foil
Pressure is to get paper-based copper-coated board of the present invention；
Wherein, in step 1 cardanol-aldehyde resin preparation method, include the following steps：
1) in reaction kettle, based on 2200-2700 parts of anacardol, coordinate 300-350 parts of bisphenol-A and 350-450
The epoxidized soybean oil of part, first carries out pyroreaction under 15-18 parts of catalyst action；It is first that bisphenol-A and epoxy is big in operation
Soya-bean oil is added in reaction kettle and is stirred, and adds anacardol in the case of stirring；It starts to warm up later when reaching 100 DEG C,
Add in catalyst；And continue to heat up, reactor temperature is made to reach 173 DEG C, starts timing, keeps 170-182 DEG C of reaction temperature
120 minutes；
2) in the reaction product obtained by 1) step, add 550-650 parts phenol, 2000-2200 parts of formaldehyde and
30-95 parts of basic catalyst is reacted；
3) 2) reaction product obtained by step is subjected to vacuum dehydration, obtains cardanol-aldehyde resin of the present invention；
Described part is parts by weight；
The preparation method of the small-molecular-weight phenolic resin is：At reflux, by the formaldehyde of 900-1000 parts by weight,
The phenol of 900-1000 parts by weight and the ammonium hydroxide of 40-45 parts by weight are pumped into reaction kettle and start stirring；Later in 30 ± 10min
95-100 DEG C is inside warming up to, insulation reaction；60 ± 10min is reacted under the conditions of maintaining the temperature at 95-100 DEG C, when gelatinization is surveyed in sampling
Between, when gel time is at range (100-120 seconds/160 DEG C), start vacuum dehydration；When dehydration temperaturre is raised to 75 DEG C, sampling
Gel time is surveyed, gel time reaches at 60-90 seconds/160 DEG C, adds in 650-700 parts of methanol；It cools, that is, makes later
Obtain small-molecular-weight phenolic resin.
The catalyst is methylimidazole.
2) in the step operation, first cool down after 1) step reaction, sampling viscosimetric is in 350-500CPS/120
In the range of DEG C, and when temperature is down to 140 DEG C, phenol and formaldehyde are added in the case of stirring, when continuing to be cooled to less than 60 DEG C
It adds in basic catalyst and stirs；It heats up later, starts to remember the reaction time when temperature rises to 90 DEG C；Keep the temperature at 90-
95 DEG C, sampling survey gel time, when gel time reaches 160-210 seconds, it is true to proceed by 3) step after reaction 30-40 minutes
Sky dehydration.
The triethylamine and 45-55 parts of ammonium hydroxide that the basic catalyst is 30-40 parts.
3) in the step operation, after vacuum dehydration to 5-10 DEG C of resin transparent temperature nature rise, 160-3460 is added in
The solvent of part, and cool down；It at least stirs 30 minutes later, and rear stopping stirring below 40 DEG C of temperature, obtains cashew nut of the present invention
Phenolic resin.
The solvent is 2900-3100 parts of methanol, the acetone of 160-180 parts of toluene and 160-180 part or acetic acid second
Ester.
After using the above scheme, a kind of preparation method of heat-resistant tearing mode paper-based copper-coated board of the present invention, employed in
Cardanol-aldehyde resin based on anacardol, coordinate a certain amount of bisphenol-A and epoxidized soybean oil, first carried out under catalyst action
Pyroreaction, the first step pyroreaction is while bisphenol-A and epoxidized soybean oil, anacardol carry out etherification reaction, anacardol
Long chain hydrocarbon groups carry out a degree of self-polymeric reaction chain extension, reactant is synthesized in phenolic resin due to there is double bond structure on phenyl ring
In the process, long-chain participates in the formation of macromolecular main chain, prepares with intrinsic toughening phenol-formaldehyde resin modified, there is preferable toughness and resistance to
It is hot.By the cardanol-aldehyde resin of synthesis and small-molecular-weight thermosetting phenolic resin (with ammonia-catalyzed) cooperation, it is deployed into tree
Lipoprotein solution (solid content 50-55%) is soaked with wood pulp paper, and prepreg is made in drying, together with adhesive coated foil hot pressing can obtain
Copper-clad plate.The use of small-molecular-weight phenolic resin can improve the crosslink density of resin cured matter, improve the heat resistance of copper-clad plate, and
Make plank that there is good tear resistance.
Specific embodiment
This case is described in further detail With reference to embodiment.
The present invention relates to a kind of preparation methods of cardanol-aldehyde resin, include the following steps：
1) in reaction kettle, based on 2200-2700 parts of anacardol, coordinate 300-350 parts of bisphenol-A and 350-450
The epoxidized soybean oil of part, first carries out pyroreaction under 15-18 parts of catalyst action；
Concrete operations embodiment is first to sequentially add 300-350 parts of bisphenol-A and 350-450 parts of epoxidized soybean oil
(about 5 minutes) are stirred in reaction kettle, add 2200-2700 parts of anacardol in the case of stirring；It covers and adds later
Expect port lid, start logical steam heating；When temperature reaches 100 DEG C, 15-18 parts of catalyst is added in, which is preferably implemented
Example is methylimidazole (methylimidazole is preferably dissolved with the methanol of same parts by weight)；And continue to heat up, make warm in reaction kettle
Degree reaches 173 DEG C, starts timing, 170-182 DEG C of holding reaction temperature 120 minutes.
2) in the reaction product obtained by 1) step, add 550-650 parts phenol, 2000-2200 parts of formaldehyde and
30-95 parts of basic catalyst is reacted, and is specifically reacted under the conditions of 90-100 DEG C；
Concrete operations embodiment is first to lead to cold water cooling after 1) step reaction, and sample viscosimetric；Sampling is surveyed viscous
Degree sequentially adds 550-650 parts in the case of stirring in the range of 350-500CPS/120 DEG C, and when temperature is down to 140 DEG C
Phenol and 2000-2200 parts of formaldehyde；When continuing to be cooled to less than 60 DEG C, 30-95 parts of basic catalyst and stirring are added in；
Stir about 5 minutes later lead to steam heating；Start to remember the reaction time when temperature rises to 90 DEG C, keep the temperature at 90-95
DEG C, sampling survey gel time, when gel time reaches 160-210 seconds, proceeds by 3) step vacuum after reaction 30-40 minutes
Dehydration.
The basic catalyst preferred embodiment, the triethylamine for being 30-40 parts and 45-55 parts of ammonium hydroxide.
3) 2) reaction product obtained by step is subjected to vacuum dehydration, obtains cardanol-aldehyde resin of the present invention；Specific behaviour
It is after vacuum dehydration to 5-10 DEG C of resin transparent temperature nature rise, to add in 160-3460 parts of solvent, and logical cold as embodiment
Water cooling；It at least stirs 30 minutes later, and rear stopping stirring below 40 DEG C of temperature, obtains cardanol-aldehyde resin of the present invention.
The solvent preferred embodiment, is 2900-3100 parts of methanol, 160-180 parts of toluene and 160-180 part
Acetone or ethyl acetate.
Above-described part is parts by weight, and specific each material mixture ratio is as shown in table below.
| Serial number | Raw material title | Specification | Inventory (kg) | Remarks |
| 1 | Epoxidized soybean oil | It is qualified | 350-450 | |
| 2 | Bisphenol-A | It is qualified | 300-350 | |
| 3 | Anacardol | Technical grade | 2200-2700 | |
| 4 | Methylimidazole/methanol | 15-18/18 | ||
| 5 | Phenol | 99 | 550-650 | |
| 6 | Formaldehyde | 37% | 2000-2200 | |
| 7 | Triethylamine | 98% | 30-40 | |
| 8 | Ammonium hydroxide | 22-25% | 45-55 | * |
| 9 | Methanol | Technical grade | 2900-3100 | |
| 10 | Toluene | Technical grade | 160-180 | |
| 11 | Acetone or ethyl acetate | Technical grade | 160-180 |
Each one preferred embodiment of material mixture ratio is as shown in table below.
Quality index in preparation process is with reference to as follows：
| Detection project | Testing conditions | Examination criteria |
| Appearance | Room temperature | Brownish red transparency liquid |
| Gel time | 160±2℃ | 90-180 seconds |
| Solid content | 150℃1H | 52-62% |
Anacardol improves the flexible of phenolic resin due to having Long carbon chain structure on phenyl ring, with Cardanol Modified PF Resin
Property, early there are application, such as friction material in other industry, the history for having decades mainly directly mixes anacardol with phenol
It closes, is reacted with formaldehyde and phenolic resin is made with regard to that can meet the requirements.But application of the anacardol in paper-based copper-coated board is away from the present only seven
The history of 8 years, copper-clad plate have the performance requirement feature of its own, and anacardol is visited at present in copper-clad plate using reference is also in
The rope stage.As disclosed in background technology, in traditional technology, it is that epoxidized soybean oil is completed to reach toughening effect, and anacardol is only
It is to help out.Epoxidized soybean oil dosage is big, and after one of phenyl ring etherification reaction with bisphenol-A, another is not joined
Generation phenolic resin is reacted with formaldehyde again with the phenyl ring of etherification reaction, realize not only toughening but also ensures the purpose of other performances.Tradition
In preparation process, since anacardol proportion is smaller, anacardol molecule is dispersed in epoxidized soybean oil and bisphenol-A simultaneously after mixing
It is surrounded, the probability that self-polymeric reaction occurs is relatively low.
And resins synthesis of the present invention, it is originally leading using anacardol, toughening is that anacardol carries out certain journey at high temperature
The autohemagglutination of degree, forms the oligomer such as dimerization or trimer, these oligomer contain two or more phenyl ring, then and formaldehyde
Reaction forms phenolic resin, and resin is made to have flexibility.The main ingredient of resin of the present invention is anacardol, epoxidized soybean oil, double
Phenol A and phenol proportion are greatly decreased, since the market price of anacardol is more much lower than above-mentioned three kinds of substances, so can be big
The big material cost for reducing product, this is also one of main object of the present invention.
The invention further relates to a kind of applications of cardanol-aldehyde resin, and the above-mentioned cardanol-aldehyde resin being prepared into is applied to paper
The manufacture of base copper-clad plate.
The invention further relates to a kind of manufacturing methods of paper-based copper-coated board, include the following steps：
Step 1: preparing above-mentioned cardanol-aldehyde resin, small-molecular-weight phenolic resin is prepared；By cardanol-aldehyde resin and small point
Son measures phenolic resin mixing preparation into resin solution；
Cardanol-aldehyde resin and small-molecular-weight phenolic resin allotment dosage, respectively specific embodiment, 780-820 parts by weight
With 60-80 parts by weight, it is deployed into the resin solution of solid content 50-55%；One preferred embodiment, the anacardol of 800 parts by weight
Urea formaldehyde and the small-molecular-weight phenolic resin of 80 parts by weight are thoroughly mixed for use in mixing device；
Above-mentioned cardanol-aldehyde resin is prepared, it is no longer tired in detail herein to state with reference to described above；
The small-molecular-weight phenolic resin preferred embodiment is with the small-molecular-weight phenolic resin of ammonia-catalyzed, preparation side
Method is：The ammonium hydroxide of the formaldehyde of 900-1000 parts by weight, the phenol of 900-1000 parts by weight and 40-45 parts by weight is pumped into reaction kettle
In, after reacting carry out vacuum dehydration can be prepared by small-molecular-weight phenolic resin；
Operation preferred embodiment is, at reflux, by the formaldehyde of 900-1000 parts by weight, 900-1000 parts by weight
Phenol and the ammonium hydroxide of 40-45 parts by weight be pumped into reaction kettle and start stirring；Open steam valve later, make material 30 ±
95-100 DEG C is warming up in 10min, insulation reaction；60 ± 10min is reacted under the conditions of maintaining the temperature at 95-100 DEG C, glue is surveyed in sampling
Change the time, when gel time is in (100-120 seconds/160 DEG C) range, start vacuum dehydration；When dehydration temperaturre goes back up to 75 DEG C
When, gel time is surveyed in sampling, and gel time reaches at 60-90 seconds/160 DEG C, adds in 650-700 parts of methanol；Postcooling drop
Temperature obtains small-molecular-weight phenolic resin.
Specific each material mixture ratio is as shown in table below.
Each one preferred embodiment of material mixture ratio is as shown in table below.
| Serial number | Raw material title | Specification % | Inventory (kg) |
| 1 | Formaldehyde | 37 | 950 |
| 2 | Phenol | 100 | 950 |
| 3 | Ammonium hydroxide | 22-25 | 42 |
| 4 | Methanol | Industry | 685 |
Quality index in preparation process is with reference to as follows：
| Serial number | Project name | Standard |
| 1 | Appearance | Light yellow clear liquid |
| 2 | Solid content (150 DEG C, 1 hour) | 50-55% |
| 3 | Gel time | 60-100 seconds/160 DEG C |
Step 2: in being soaked in the resin solution with wood pulp paper, prepreg is made in drying, hot together with adhesive coated foil
Pressure is to get paper-based copper-coated board of the present invention；
A specific mode of operation is, with indicated weight 130g/m2Wood pulp paper, the resin liquid to be prepared by step 1 is soaked, through dry
It is dry that the impregnation material that resin content is 44%-46% is made.8 impregnation material and 1 25um adhesive coated foils overlapping are taken, in 100Kg/
cm2, the copper-clad laminate that thickness is 1.6mm is made in hot pressing 100-120 minutes under the conditions of 160 DEG C -165 DEG C.The resistance to leaching of plank
Weldering property (260 DEG C) 15 seconds or more, punching are 40-80 DEG C, other performances reach CPFCP-04 technologies in GB 4723-92 standards and refer to
Mark requirement.
The foregoing is merely the preferred embodiment of the present invention, all equivalent changes done with scope of the invention as claimed and
Modification should all belong to the range of the claims in the present invention.
Claims (4)
1. a kind of manufacturing method of heat-resistant tearing mode paper-based copper-coated board, which is characterized in that include the following steps：
Step 1: preparing cardanol-aldehyde resin, small-molecular-weight phenolic resin is prepared；By cardanol-aldehyde resin and small-molecular-weight phenolic aldehyde
Resin mixing preparation is into resin solution；Cardanol-aldehyde resin and small-molecular-weight phenolic resin allotment dosage are respectively 780-820 weights
Part and 60-80 parts by weight are measured, are deployed into the resin solution of solid content 50-55%；
Step 2: in being soaked in the resin solution with wood pulp paper, prepreg is made in drying, the hot pressing together with adhesive coated foil, i.e.,
Obtain paper-based copper-coated board；
Wherein, in step 1 cardanol-aldehyde resin preparation method, include the following steps：
1) in reaction kettle, based on 2200-2700 parts of anacardol, the bisphenol-A of 300-350 parts of cooperation and 350-450 parts
Epoxidized soybean oil first carries out pyroreaction under 15-18 parts of catalyst action；In operation, first by bisphenol-A and epoxidized soybean oil
It adds in reaction kettle and is stirred, add anacardol in the case of stirring；It starts to warm up when reaching 100 DEG C, adds in later
Catalyst；And continue to heat up, reactor temperature is made to reach 173 DEG C, starts timing, 170-182 DEG C of reaction temperature 120 is kept to divide
Clock；
2) in the reaction product obtained by 1) step, 550-650 parts of phenol, 2000-2200 parts of formaldehyde and 30-95 are added
The basic catalyst of part is reacted；
3) 2) reaction product obtained by step is subjected to vacuum dehydration, obtains cardanol-aldehyde resin；
Described part is parts by weight；
The preparation method of the small-molecular-weight phenolic resin is：At reflux, by the formaldehyde of 900-1000 parts by weight, 900-
The phenol of 1000 parts by weight and the ammonium hydroxide of 40-45 parts by weight are pumped into reaction kettle and start stirring；It is risen in 30 ± 10min later
Temperature is to 95-100 DEG C, insulation reaction；60 ± 10min is reacted under the conditions of maintaining the temperature at 95-100 DEG C, gel time is surveyed in sampling, when
Gel time starts vacuum dehydration at range (100-120 seconds/160 DEG C)；When dehydration temperaturre is raised to 75 DEG C, glue is surveyed in sampling
Change the time, gel time reaches at 60-90 seconds/160 DEG C, adds in 650-700 parts of methanol；It cools, obtains small later
Molecular weight phenolic resin.
2. a kind of manufacturing method of heat-resistant tearing mode paper-based copper-coated board as described in claim 1, which is characterized in that it is described 2)
In step operation, first cool down after 1) step reaction, sampling viscosimetric is in the range of 350-500CPS/120 DEG C, and temperature
When being down to 140 DEG C, phenol and formaldehyde are added in the case of stirring, and basic catalyst is added in simultaneously when continuing to be cooled to less than 60 DEG C
Stirring；It heats up later, starts to remember the reaction time when temperature rises to 90 DEG C；90-95 DEG C is kept the temperature at, 30-40 points of reaction
Gel time is surveyed in sampling after clock, when gel time reaches 160-210 seconds, proceeds by 3) step vacuum dehydration.
3. a kind of manufacturing method of heat-resistant tearing mode paper-based copper-coated board as described in claim 1, which is characterized in that it is described 3)
In step operation, after vacuum dehydration to 5-10 DEG C of resin transparent temperature nature rise, 160-3460 parts of solvent is added in, and cold
But；It at least stirs 30 minutes later, and rear stopping stirring below 40 DEG C of temperature, obtains cardanol-aldehyde resin.
4. a kind of manufacturing method of heat-resistant tearing mode paper-based copper-coated board as claimed in claim 3, which is characterized in that described molten
Agent is 2900-3100 parts of methanol, the acetone or ethyl acetate of 160-180 parts of toluene and 160-180 part.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711323444.9A CN108162558B (en) | 2015-12-17 | 2015-12-17 | Manufacturing method of heat-resistant tear-resistant paper-based copper-clad plate |
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| CN114000372A (en) * | 2021-12-08 | 2022-02-01 | 福建利豪电子科技股份有限公司 | Preparation process of wastewater-free cardanol modified phenolic resin and application of cardanol modified phenolic resin in copper-clad plate |
| CN115874489A (en) * | 2022-12-07 | 2023-03-31 | 山东仁丰特种材料股份有限公司 | Composite carbon paper, preparation method and battery |
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| CN111732519B (en) * | 2020-07-13 | 2023-04-25 | 杭州至华新材料科技有限公司 | Vegetable oil-based flexible amine curing agent, preparation method thereof and vegetable oil-based flexible epoxy resin |
| CN114716633A (en) * | 2022-03-11 | 2022-07-08 | 建滔(佛冈)积层板有限公司 | Polyethylene glycol modified melamine resin and preparation method and application thereof |
| CN116693471B (en) * | 2023-06-07 | 2023-11-03 | 北京工商大学 | Bio-based epoxy chain extender, and preparation method and application thereof |
| CN117382265B (en) * | 2023-12-12 | 2024-02-20 | 福建利豪电子科技股份有限公司 | Manufacturing method of one-time rubberizing flame-retardant paper-based copper-clad plate |
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| CN115874489A (en) * | 2022-12-07 | 2023-03-31 | 山东仁丰特种材料股份有限公司 | Composite carbon paper, preparation method and battery |
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Also Published As
| Publication number | Publication date |
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| CN108297519B (en) | 2020-08-18 |
| CN108297519A (en) | 2018-07-20 |
| CN108162558B (en) | 2020-01-07 |
| CN105461871A (en) | 2016-04-06 |
| CN105461871B (en) | 2017-12-29 |
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