CN108162558B - Manufacturing method of heat-resistant tear-resistant paper-based copper-clad plate - Google Patents
Manufacturing method of heat-resistant tear-resistant paper-based copper-clad plate Download PDFInfo
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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
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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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- B32—LAYERED PRODUCTS
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- 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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- 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
- 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
- B32B2307/50—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 invention discloses a manufacturing method of a heat-resistant tear-resistant paper-based copper-clad plate, which comprises the following steps: step one, preparing cashew phenolic resin, and preparing low-molecular-weight phenolic resin; mixing cashew phenolic resin and low-molecular-weight phenolic resin to prepare a resin solution; the blending amount of the cashew phenolic resin and the low molecular weight phenolic resin is 780-820 parts by weight and 60-80 parts by weight respectively, and the cashew phenolic resin and the low molecular weight phenolic resin are blended into a resin solution with the solid content of 50-55%; and secondly, impregnating wood pulp paper in the resin solution, drying to prepare a prepreg, and hot-pressing the prepreg and the glued copper foil together to obtain the paper-based copper-clad plate. The modified phenolic resin with internal toughening prepared by the invention has better toughness and heat resistance, greatly improves the heat resistance of the copper-clad plate and ensures that the plate has good tear resistance.
Description
The subject of the present application is the waist of application No. 201510952365.9, application No. 2015.12.17
A preparation method and application of the fruit phenolic resin and a manufacturing method of the paper-based copper-clad plate are provided.
Technical Field
The invention relates to the field of copper-clad plate manufacturing, in particular to a manufacturing method of a heat-resistant tear-resistant paper-based copper-clad plate.
Background
The paper-based copper-clad plate has wide application in electronic products. In the manufacturing of the paper-based copper-clad plate, the product mainly obtains better punching property, and the technology for producing the paper-based copper-clad plate by using the tung oil modified phenolic resin and the epoxy soybean oil modified phenolic resin is mature day by day and is widely applied. The cardanol is a new material which begins to be applied in the production of copper clad plates in recent years, and because a long-chain alkyl group is arranged on a benzene ring in the molecule of the cardanol, the cardanol and phenol are mixed to synthesize phenolic resin, so that the flexibility of the resin can be provided, the cardanol is generally applied in the production of the copper clad plates as a reactive auxiliary toughening agent of tung oil modified phenolic resin or epoxy soybean oil modified phenolic resin, the consumption of tung oil or epoxy soybean oil can be reduced, and the material cost in production can be reduced. However, cardanol is directly mixed with a certain amount of phenol, formaldehyde is added to react to synthesize the phenolic resin, although the flexibility of the resin can be improved to a great extent, the manufactured copper-clad plate still has poor punching performance, large plate warping and poor dip soldering resistance. The reason is that in the forming process of the phenolic resin, the hydrocarbon group on the benzene ring of the cardanol cannot participate in the formation of a macromolecular main chain, exists in the form of a cantilever chain, and has limited toughening effect. If the proportion of cardanol is too large, the functionality of cardanol is lower than that of phenol, and the generated condensate has low crosslinking density due to the long-chain steric effect, so that the heat resistance and the tear resistance of the copper-clad plate are affected.
Disclosure of Invention
The invention aims to provide a method for manufacturing a heat-resistant tear-resistant paper-based copper-clad plate, which is used for preparing a modified phenolic resin with internal toughening, has better toughness and heat resistance, greatly improves the heat resistance of the copper-clad plate and enables the plate to have good tear resistance.
In order to achieve the above purpose, the solution of the invention is:
a manufacturing method of a heat-resistant tear-resistant paper-based copper-clad plate comprises the following steps:
step one, preparing cashew phenolic resin, and preparing low-molecular-weight phenolic resin; mixing cashew phenolic resin and low-molecular-weight phenolic resin to prepare a resin solution; the blending amount of the cashew phenolic resin and the low molecular weight phenolic resin is 780-820 parts by weight and 60-80 parts by weight respectively, and the cashew phenolic resin and the low molecular weight phenolic resin are blended into a resin solution with the solid content of 50-55%;
step two, soaking wood pulp paper in the resin solution, drying to prepare a prepreg, and hot-pressing the prepreg and the glued copper foil together to obtain the paper-based copper-clad plate;
the preparation method of the cashew nut phenolic resin in the first step comprises the following steps:
1) taking 2200-2700 parts of cardanol as a main component in a reaction kettle, matching with 300-350 parts of bisphenol A and 350-450 parts of epoxidized soybean oil, and carrying out high-temperature reaction under the action of 15-18 parts of a catalyst; in the operation, firstly adding bisphenol A and epoxy soybean oil into a reaction kettle, stirring and mixing, and adding cardanol under the stirring condition; then, when the temperature rises to 100 ℃, adding a catalyst; continuously heating to enable the temperature in the reaction kettle to reach 173 ℃, starting timing, and keeping the reaction temperature of 170-182 ℃ for 120 minutes;
2) adding 650 parts of phenol, 2000-2200 parts of formaldehyde and 30-95 parts of alkaline catalyst into the reaction product obtained in the step 1) for reaction;
3) vacuum dehydrating the reaction product obtained in the step 2) to obtain the cashew phenolic resin;
the parts are all parts by weight;
the preparation method of the low molecular weight phenolic resin comprises the following steps: under the reflux state, pumping 1000 parts by weight of 900-plus-one formaldehyde, 1000 parts by weight of 900-plus-one phenol and 40-45 parts by weight of ammonia water into a reaction kettle and starting stirring; then heating to 95-100 ℃ within 30 +/-10 min, and carrying out heat preservation reaction; keeping the temperature at 95-100 ℃ for reaction for 60 +/-10 min, sampling and measuring the gel time, and starting vacuum dehydration when the gel time is in the range (100-; when the dehydration temperature is raised to 75 ℃, sampling and measuring the gelling time, wherein the gelling time reaches 60-90 seconds/160 ℃, and adding 650-700 parts of methanol; and cooling to obtain the low molecular weight phenolic resin.
The catalyst is dimethyl imidazole.
In the operation of the step 2), after the reaction in the step 1) is finished, firstly cooling, sampling and measuring the viscosity within the range of 350-CPS/120 ℃, adding phenol and formaldehyde under the stirring condition when the temperature is reduced to 140 ℃, and continuously cooling to below 60 ℃, adding an alkaline catalyst and stirring; then heating, and starting recording the reaction time when the temperature is increased to 90 ℃; keeping the temperature at 90-95 ℃, sampling and measuring the gel time after reacting for 30-40 minutes, and starting to perform the step 3) of vacuum dehydration when the gel time reaches 160-210 seconds.
The basic catalyst comprises 30-40 parts of triethylamine and 45-55 parts of ammonia water.
In the step 3), after vacuum dehydration is carried out until the transparent temperature of the resin naturally rises to 5-10 ℃, 160-3460 parts of solvent is added and the mixture is cooled; and then stirring for at least 30 minutes, and stopping stirring after the temperature is below 40 ℃, thus obtaining the cashew phenolic resin.
The solvent is 2900-3100 parts of methanol, 160-180 parts of toluene and 160-180 parts of acetone or ethyl acetate.
After the scheme is adopted, the heat-resistant tear-resistant paper-based copper-clad plate is prepared by the method that the adopted cashew phenol formaldehyde resin mainly takes cardanol, a certain amount of bisphenol A and epoxidized soybean oil are matched, high-temperature reaction is carried out under the action of a catalyst, the first-step high-temperature reaction is carried out, long-chain alkyl on a cardanol benzene ring carries out a certain degree of self-polymerization chain extension due to the double-bond structure while the bisphenol A, the epoxidized soybean oil and the cardanol are subjected to etherification reaction, and long chains participate in the formation of a macromolecular main chain in the synthesis process of the cardanol resin, so that the modified phenolic resin with internal toughening is prepared, and the modified phenolic resin has better toughness and heat resistance. The synthesized cashew phenolic resin is matched with small molecular thermosetting phenolic resin (catalyzed by ammonia water) to be prepared into resin solution (solid content is 50-55%), wood pulp paper is soaked in the resin solution, a prepreg is prepared by drying the resin solution, and the prepreg and the glued copper foil are hot-pressed together to obtain the copper-clad plate. The use of the low molecular weight phenolic resin can improve the crosslinking density of the resin condensate, improve the heat resistance of the copper-clad plate and ensure that the plate has good tear resistance.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments.
The invention relates to a preparation method of cashew phenolic resin, which comprises the following steps:
1) taking 2200-2700 parts of cardanol as a main component in a reaction kettle, matching with 300-350 parts of bisphenol A and 350-450 parts of epoxidized soybean oil, and carrying out high-temperature reaction under the action of 15-18 parts of a catalyst;
the specific operation example is that 300-350 parts of bisphenol A and 350-450 parts of epoxidized soybean oil are sequentially added into a reaction kettle to be stirred and mixed (about 5 minutes), and 2200-2700 parts of cardanol is added under the stirring condition; then covering a feeding hole cover, and starting introducing steam to heat; when the temperature reaches 100 ℃, 15 to 18 parts of a catalyst, which is a preferred example of a dimethylimidazole (dimethylimidazole is preferably dissolved with the same weight part of methanol), is added; and continuously heating to make the temperature in the reaction kettle reach 173 ℃, starting timing, and keeping the reaction temperature of 170-182 ℃ for 120 minutes.
2) Adding 650 parts of phenol, 2000-2200 parts of formaldehyde and 30-95 parts of alkaline catalyst into the reaction product obtained in the step 1), and reacting at 90-100 ℃;
the specific operation embodiment is that cold water is firstly introduced for cooling after the reaction in the step 1) is finished, and a sample is taken for measuring the viscosity; when the sampling viscosity is in the range of 350-; continuously cooling to below 60 ℃, adding 30-95 parts of alkaline catalyst and stirring; then stirring for about 5 minutes, and introducing steam to raise the temperature; starting to record the reaction time when the temperature is increased to 90 ℃, keeping the temperature at 90-95 ℃, sampling and measuring the gel time after reacting for 30-40 minutes, and starting to perform the step 3) of vacuum dehydration when the gel time reaches 160-210 seconds.
The basic catalyst is preferably 30-40 parts of triethylamine and 45-55 parts of ammonia water.
3) Vacuum dehydrating the reaction product obtained in the step 2) to obtain the cashew phenolic resin; the specific operation example is that after the resin is dehydrated in vacuum until the transparent temperature of the resin naturally rises to 5-10 ℃, 160-3460 parts of solvent is added, and cold water is introduced for cooling; and then stirring for at least 30 minutes, and stopping stirring after the temperature is below 40 ℃, thus obtaining the cashew phenolic resin.
Preferred examples of the solvent are 2900-.
The parts are weight parts, and the specific material ratio is shown in the following table.
| Serial number | Name of raw material | Specification of | Batch (kg) | Remarks for note |
| 1 | Epoxidized soybean oil | Qualified | 350-450 | |
| 2 | Bisphenol A | Qualified | 300-350 | |
| 3 | Cardanol | Industrial grade | 2200-2700 | |
| 4 | Dimethyl imidazole/methanol | 15-18/18 | ||
| 5 | Phenol and its preparation | 99 | 550-650 | |
| 6 | Formaldehyde (I) | 37％ | 2000-2200 | |
| 7 | Triethylamine | 98％ | 30-40 | |
| 8 | Aqueous ammonia | 22-25％ | 45-55 | * |
| 9 | Methanol | Industrial grade | 2900-3100 | |
| 10 | Toluene | Industrial grade | 160-180 | |
| 11 | Acetone or ethyl acetate | Industrial grade | 160-180 |
A preferred embodiment of the formulation of each material is shown in the following table.
The quality indexes in the preparation process are referred as follows:
| detecting items | Detection conditions | Detection standard |
| Appearance of the product | At room temperature | Brownish red transparent liquid |
| Gel time | 160±2℃ | 90180 seconds |
| Solids content | 150℃1H | 52-62％ |
The cardanol has a long carbon chain structure on a benzene ring, so that the flexibility of the phenolic resin is improved by using the cardanol modified phenolic resin, the cardanol modified phenolic resin has been applied to other industries such as friction materials and the like for decades, and the cardanol is mainly directly mixed with phenol and reacts with formaldehyde to prepare the phenolic resin which can meet the requirements. However, the application of cardanol in paper-based copper-clad plates only has seven-eight years of history, the copper-clad plates have the characteristics of performance requirements, and the application of cardanol in the copper-clad plates is still in a reference and exploration stage at present. As disclosed in the background art, in the conventional art, the toughening effect is achieved by using epoxidized soybean oil, and cardanol only plays an auxiliary role. The epoxy soybean oil has large consumption, and after etherification reaction with one benzene ring of bisphenol A, the other benzene ring which does not participate in the etherification reaction is reacted with formaldehyde to generate phenolic resin, thereby achieving the purposes of toughening and ensuring other properties. In the traditional preparation process, because the proportion of cardanol is small, cardanol molecules are dispersed and enclosed in epoxidized soybean oil and bisphenol A after mixing, and the probability of occurrence of self-polymerization reaction is low.
The synthesis of the resin of the invention originally takes cardanol as the main material, the toughening is that cardanol carries out certain degree of self-polymerization at high temperature to form oligomers such as dipolymer or tripolymer, and the oligomers contain two or more than two benzene rings and then react with formaldehyde to form phenolic resin, so that the resin has flexibility. The main components of the resin are cardanol, epoxidized soybean oil, bisphenol A and phenol, the proportion of the cardanol is greatly reduced, and the market price of the cardanol is much lower than that of the cardanol, so that the material cost of the cardanol resin can be greatly reduced, and the cardanol resin is also one of the main purposes of the invention.
The invention also relates to an application of the cashew phenolic resin, and the prepared cashew phenolic resin is applied to the manufacturing of the paper-based copper-clad plate.
The invention also relates to a manufacturing method of the paper-based copper-clad plate, which comprises the following steps:
step one, preparing the cashew phenolic resin, and preparing a low-molecular-weight phenolic resin; mixing cashew phenolic resin and low-molecular-weight phenolic resin to prepare a resin solution;
the dosage of cashew phenolic resin and low molecular weight phenolic resin is 780-820 weight parts and 60-80 weight parts respectively in the specific embodiment, and the cashew phenolic resin and the low molecular weight phenolic resin are prepared into resin solution with the solid content of 50-55%; in a preferred embodiment, 800 parts by weight of cashew phenolic resin and 80 parts by weight of low molecular weight phenolic resin are fully stirred and mixed in a rubber mixer for standby;
preparing the cashew nut phenolic resin, referred to above, and not described in detail herein;
the preferred embodiment of the low molecular weight phenolic resin is the low molecular weight phenolic resin catalyzed by ammonia water, and the preparation method comprises the following steps: pumping 1000 parts by weight of 900-containing formaldehyde, 1000 parts by weight of 900-containing phenol and 40-45 parts by weight of ammonia water into a reaction kettle, and after reaction, performing vacuum dehydration to obtain the low molecular weight phenolic resin;
the operation preferred embodiment is that under the reflux state, 1000 weight portions of formaldehyde 900-; then opening a steam valve to heat the materials to 95-100 ℃ within 30 +/-10 min, and carrying out heat preservation reaction; keeping the temperature at 95-100 ℃ for reaction for 60 +/-10 min, sampling and measuring the gel time, and starting vacuum dehydration when the gel time is in the range of (100-; when the dehydration temperature is raised to 75 ℃, sampling and measuring the gelling time, wherein the gelling time reaches 60-90 seconds/160 ℃, and adding 650 plus 700 parts of methanol; and cooling to obtain the low molecular weight phenolic resin.
The specific material ratios are shown in the following table.
A preferred embodiment of the formulation of each material is shown in the following table.
| Serial number | Name of raw material | Specification% | Batch (kg) |
| 1 | Formaldehyde (I) | 37 | 950 |
| 2 | Phenol and its preparation | 100 | 950 |
| 3 | Aqueous ammonia | 22-25 | 42 |
| 4 | Methanol | Industrial process | 685 |
The quality indexes in the preparation process are referred as follows:
| serial number | Name of item | Standard of merit |
| 1 | Appearance of the product | Light yellow transparent liquid |
| 2 | Solids content (150 ℃,1 hour) | 50-55％ |
| 3 | Gel time | 60-100 seconds/160 DEG C |
Step two, soaking wood pulp paper in the resin solution, drying to prepare a prepreg, and hot-pressing the prepreg and the glued copper foil together to obtain the paper-based copper-clad plate;
in a specific operation mode, the standard weight is 130g/m2The wood pulp paper is soaked with the resin liquid prepared according to the step one, and is dried to prepare the soaking glue stock with the resin content of 44-46 percent. Taking 8 sheets of the dipped sizing material and 1 sheet of 25um coated copper foil to be overlapped at 100Kg/cm2And hot pressing at 160-165 ℃ for 100-120 minutes to obtain the copper clad laminate with the thickness of 1.6 mm. The dip-soldering resistance (260 ℃) of the plate is more than 15 seconds, the punching time is 40-80 ℃, and other properties meet the technical index requirements of CPFCP-04 in GB 4723-92 standard.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made within the scope of the claims of the present invention should fall within the scope of the claims of the present invention.
Claims (4)
1. The manufacturing method of the heat-resistant tear-resistant paper-based copper-clad plate is characterized by comprising the following steps of:
step one, preparing cashew phenolic resin, and preparing low-molecular-weight phenolic resin; mixing cashew phenolic resin and low-molecular-weight phenolic resin to prepare a resin solution; the blending amount of the cashew phenolic resin and the low molecular weight phenolic resin is 780-820 parts by weight and 60-80 parts by weight respectively, and the cashew phenolic resin and the low molecular weight phenolic resin are blended into a resin solution with the solid content of 50-55%;
step two, soaking wood pulp paper in the resin solution, drying to prepare a prepreg, and hot-pressing the prepreg and the glued copper foil together to obtain the paper-based copper-clad plate;
the preparation method of the cashew nut phenolic resin in the first step comprises the following steps:
1) taking 2200-2700 parts of cardanol as a main component in a reaction kettle, matching with 300-350 parts of bisphenol A and 350-450 parts of epoxidized soybean oil, and carrying out high-temperature reaction under the action of 15-18 parts of a catalyst; in the operation, firstly adding bisphenol A and epoxy soybean oil into a reaction kettle, stirring and mixing, and adding cardanol under the stirring condition; then, when the temperature rises to 100 ℃, adding a catalyst; continuously heating to enable the temperature in the reaction kettle to reach 173 ℃, starting timing, and keeping the reaction temperature of 170-182 ℃ for 120 minutes;
2) adding 650 parts of phenol, 2000-2200 parts of formaldehyde and 30-95 parts of alkaline catalyst into the reaction product obtained in the step 1) for reaction;
3) carrying out vacuum dehydration on the reaction product obtained in the step 2) to obtain the cashew phenolic resin;
the parts are all parts by weight;
the preparation method of the low molecular weight phenolic resin comprises the following steps: under the reflux state, pumping 1000 parts by weight of 900-plus-one formaldehyde, 1000 parts by weight of 900-plus-one phenol and 40-45 parts by weight of ammonia water into a reaction kettle and starting stirring; then heating to 95-100 ℃ within 30 +/-10 min, and carrying out heat preservation reaction; keeping the temperature at 95-100 ℃ for reaction for 60 +/-10 min, sampling and measuring the gel time, and starting vacuum dehydration when the gel time is within the range of 100-; when the dehydration temperature is raised to 75 ℃, sampling and measuring the gelling time, wherein the gelling time reaches 60-90 seconds/160 ℃, and adding 650-700 parts of methanol; and cooling to obtain the low molecular weight phenolic resin.
2. The method for manufacturing the heat-resistant tear-resistant paper-based copper-clad plate according to claim 1, wherein in the operation of the step 2), the temperature is reduced after the reaction of the step 1), the sampled viscosity is within the range of 350-500CPS/120 ℃, when the temperature is reduced to 140 ℃, phenol and formaldehyde are added under the condition of stirring, and when the temperature is continuously reduced to below 60 ℃, an alkaline catalyst is added and stirred; then heating, and starting recording the reaction time when the temperature is increased to 90 ℃; keeping the temperature at 90-95 ℃, sampling and measuring the gel time after reacting for 30-40 minutes, and starting to perform the step 3) of vacuum dehydration when the gel time reaches 160-210 seconds.
3. The method for manufacturing the heat-resistant tear-resistant paper-based copper-clad plate according to claim 1, wherein in the operation of step 3), after vacuum dehydration is performed until the resin transparency temperature naturally rises to 5-10 ℃, 3460 parts of solvent are added and cooled; and then stirring for at least 30 minutes, and stopping stirring after the temperature is below 40 ℃, thus obtaining the cashew phenolic resin.
4. The method for manufacturing the heat-resistant tear-resistant paper-based copper-clad plate according to claim 3, wherein the solvent comprises 2900-.
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 |
Applications Claiming Priority (2)
| 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 |
| CN201510952365.9A CN105461871B (en) | 2015-12-17 | 2015-12-17 | The manufacture method of the preparation method of cardanol-aldehyde resin, application and paper-based copper-coated board |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510952365.9A Division CN105461871B (en) | 2015-12-17 | 2015-12-17 | The manufacture method of the preparation method of cardanol-aldehyde resin, application and paper-based copper-coated board |
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| Publication Number | Publication Date |
|---|---|
| CN108162558A CN108162558A (en) | 2018-06-15 |
| CN108162558B true CN108162558B (en) | 2020-01-07 |
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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 |
| CN114000372B (en) * | 2021-12-08 | 2023-01-03 | 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 |
| 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 |
| CN115874489B (en) * | 2022-12-07 | 2024-02-13 | 山东仁丰特种材料股份有限公司 | Composite carbon paper, preparation method and battery |
| 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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| CN108162558A (en) | 2018-06-15 |
| CN105461871A (en) | 2016-04-06 |
| CN105461871B (en) | 2017-12-29 |
| CN108297519A (en) | 2018-07-20 |
| CN108297519B (en) | 2020-08-18 |
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