CN114801348B - Preparation process of high-flame-retardance heat-resistant 22F copper-clad plate - Google Patents

Preparation process of high-flame-retardance heat-resistant 22F copper-clad plate Download PDF

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CN114801348B
CN114801348B CN202210580202.2A CN202210580202A CN114801348B CN 114801348 B CN114801348 B CN 114801348B CN 202210580202 A CN202210580202 A CN 202210580202A CN 114801348 B CN114801348 B CN 114801348B
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phosphorus
epoxy resin
control system
reaction
reaction kettle
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CN114801348A (en
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周培峰
贺卫民
黄丽元
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Jiangmen Kingboard Laminates Holdings Ltd
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Jiangmen Kingboard Laminates Holdings Ltd
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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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/68—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts by incorporating or moulding on preformed parts, e.g. inserts or layers, e.g. foam blocks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/68—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts by incorporating or moulding on preformed parts, e.g. inserts or layers, e.g. foam blocks
    • B29C70/681—Component parts, details or accessories; Auxiliary operations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/88—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised primarily by possessing specific properties, e.g. electrically conductive or locally reinforced
    • B29C70/882—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised primarily by possessing specific properties, e.g. electrically conductive or locally reinforced partly or totally electrically conductive, e.g. for EMI shielding
    • B29C70/885—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised primarily by possessing specific properties, e.g. electrically conductive or locally reinforced partly or totally electrically conductive, e.g. for EMI shielding with incorporated metallic wires, nets, films or plates
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B32B29/02—Layered products comprising a layer of paper or cardboard next to a fibrous or filamentary layer
    • 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
    • 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
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/08—Impregnating
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1488—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
    • 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
    • B32B2260/021—Fibrous or filamentary layer
    • B32B2260/023—Two or more layers
    • 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
    • B32B2260/028—Paper layer
    • 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
    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards

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  • Mechanical Engineering (AREA)
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  • Polymers & Plastics (AREA)
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  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Physics & Mathematics (AREA)
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Abstract

The invention relates to the technical field of material preparation, in particular to a preparation process of a high-flame-retardant heat-resistant 22F copper-clad plate, which comprises the following steps: s1, preparing a base material, namely adding epoxy resin and a phosphorus-containing group compound X into a reaction kettle, and adding a curing agent after the reaction is completed to generate a prepared base material; s2, dipping the base cloth; s3, cutting a base plate; s4, pressing; s5, cutting a finished product; and S6, detecting a finished product. The phosphorus epoxy resin is generated by the reaction of the epoxy resin and the phosphorus-containing group compound and the curing of the curing agent, and the phosphorus epoxy resin generates phosphoric acid, polyphosphoric acid and water vapor in the combustion process, so that the phosphorus epoxy resin is free from a large amount of smoke and toxic gases, is more environment-friendly in use, and does not damage the body health of operators. Meanwhile, in the reaction process, the phosphorus content in the product is strictly controlled through detection in the midway, the precision of the reaction result is enhanced, the state of the generated reactant is stable, and the quality control of the product is enhanced.

Description

Preparation process of high-flame-retardance heat-resistant 22F copper-clad plate
Technical Field
The invention relates to the technical field of material preparation, in particular to a preparation process of a high-flame-retardant heat-resistant 22F copper-clad plate.
Background
A Copper Clad Laminate (CCL), which is a copper clad laminate, is a plate-like material prepared by impregnating electronic glass cloth or other reinforcing materials with resin, coating copper foil on one or both sides, and hot-pressing, and is referred to as a copper clad laminate for short. Various printed circuit boards with different forms and different functions are manufactured into different printed circuits by selectively carrying out the working procedures of processing, etching, drilling, copper plating and the like on a copper-clad plate. The copper clad laminate mainly plays the roles of interconnection conduction, insulation and support for the printed circuit board, and has great influence on the transmission speed, energy loss, characteristic impedance and the like of signals in a circuit, so that the performance, quality, processability in manufacturing, manufacturing level, manufacturing cost, long-term reliability and stability of the printed circuit board are greatly dependent on the copper clad laminate.
Chinese patent publication No.: CN112960914A. Discloses a modified glass fiber and a copper-clad plate, which are obtained by modifying the surface of the glass fiber by using a polyamic acid solution; the polyamic acid solution is synthesized by pyromellitic dianhydride and 4,4' -diaminodiphenyl ether and/or 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane. The fiber adopts PMDA (pyromellitic dianhydride) to respectively synthesize two PAA (polyamide acid) with ODA (4,4' -diaminodiphenyl ether) and 6FAP (2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane); therefore, the current copper-clad plate often contains a halogen chemical structure in raw material selection, and when the copper-clad plate is welded and drilled, the edge of the copper-clad plate is melted and burnt at high temperature, so that harmful gas is very easily generated.
Disclosure of Invention
Therefore, the invention provides a preparation process of a high-flame-retardant heat-resistant 22F copper-clad plate and the copper-clad plate, which are used for overcoming the problem that in the prior art, the current copper-clad plate often contains chemical structures such as benzene rings, amino groups and the like in raw material selection, and harmful gas is easily generated because the edges of the copper-clad plate are melted and combusted at high temperature during welding and drilling of the copper-clad plate.
In order to achieve the purpose, the invention provides a preparation process of a high-flame-retardant heat-resistant 22F copper-clad plate, which comprises the following steps:
s1, preparing a base material, namely adding epoxy resin and a phosphorus-containing group compound X into a reaction kettle, and adding a curing agent after the reaction is completed to generate a prepared base material;
s2, dipping the base cloth, namely putting the base cloth into the prepared base cloth, passing the base cloth through a compression roller device after dipping is finished, and drying the base cloth to prepare a base plate;
s3, cutting a base plate;
and S4, pressing, namely feeding the superposed base plate and the copper foil into a hot press for pressing to complete plate forming, and cooling after forming. Separating the pressed copper-clad plate from the die after cooling;
s5, cutting a finished product, and cutting the pressed copper-clad plate;
and S6, detecting finished products, detecting the performance of the finished copper clad laminate products, and grading.
A control system is arranged in the process of preparing the copper-clad plate for adjusting the working state of each link.
In the step S1, determining the initial ratio of the epoxy resin to the phosphorus-containing group compound X according to the phosphorus content P of the phosphorus-containing group compound X, detecting the phosphorus content of the mixture in the stirring process of the reaction kettle, judging whether to supplement raw materials into the reaction kettle according to the detection result, and adjusting the reaction time length in the reaction kettle according to the raw material supplement amount when the raw materials are required to be supplemented.
Further, in step S1, detecting a phosphorus content P in the phosphorus-containing group compound X, and transmitting a detection result to the control system, wherein a preset addition amount M of the epoxy resin is set in the control system, and the control system calculates an initial addition amount Q of the phosphorus-containing group compound X by the preset addition amount M of the epoxy resin and the phosphorus content P, and Q = gxm ÷ (P × P-G), where G is a target phosphorus content of a compound generated by a reaction of the epoxy resin and the phosphorus-containing group compound X, and P is an initial addition amount of the phosphorus-containing group compound X to calculate a compensation parameter.
Adding the epoxy resin with the addition amount of M and the phosphorus-containing group compound S with the addition amount of Q into a reaction kettle, and starting the reaction kettle to mix the epoxy resin with the phosphorus-containing group compound X.
Further, the control system is provided with a first reaction time T1 of the reaction kettle, when the reaction kettle starts to mix the epoxy resin and the phosphorus-containing group compound X, the control system starts a timing function to time the reaction time in the reaction kettle, when the reaction time reaches T1, a mixture sample is extracted from the reaction kettle, the phosphorus content K in the sample is detected, and the detection result is transmitted to the control system, wherein the control system is internally provided with a standard phosphorus content Kb of the mixture and a deviation range value W of the phosphorus content.
The control system calculates the absolute value delta K of the difference between the phosphorus content K of the mixture and the phosphorus content standard value Kb of the mixture, wherein delta K = | K-Kb |, and the control system compares the absolute value delta K of the difference with the phosphorus content deviation range value W:
when delta K is less than or equal to W, the control system judges that the phosphorus content deviation is within a reasonable range;
when the delta K is larger than W, the control system judges that the phosphorus content deviation is not in a reasonable range, and the control system judges the supplementary added materials and the supplementary added amount to the reaction kettle according to the relation between the K and the Kb and the value of the delta K.
Further, when K is more than Kb, the control system judges that the phosphorus content of the mixture is too high, and the epoxy resin is added into the reaction kettle in a supplementing way, wherein the supplementing adding quantity M' of the epoxy resin is determined by the absolute value delta K of the difference and the initial adding quantity Q of the epoxy resin M and the phosphorus-containing group compound X.
Solving the equation system of M' as follows:
Figure BDA0003662721230000031
where α is the calculated compensation value for M'.
Further, when K is less than Kb, the control system judges that the phosphorus content of the mixture is insufficient, and a phosphorus-containing group compound X needs to be additionally added into the reaction kettle, wherein the additional adding amount Q' of the phosphorus-containing group compound X is determined by the absolute value delta K of the difference and the initial adding amount Q of the epoxy resin M and the phosphorus-containing group compound X.
Solving the equation system of Q' as:
Figure BDA0003662721230000032
further, a second preset reaction time period T2 of the reaction kettle is arranged in the control system, and the control system determines whether to adjust the second preset reaction time period T2 according to the phosphorus content deviation.
Further, when the control system judges that the phosphorus content deviation is within a reasonable range, the control system does not adjust the preset time length of the second reaction, the reaction kettle is continuously started to stir the epoxy resin and the phosphorus-containing group compound S, the control system times the stirring time length, and when the stirring time length of the reaction kettle reaches T2, the control system judges that the reaction of the epoxy resin and the phosphorus-containing group compound X is completed.
Further, when the control system judges that the phosphorus content deviation is not in the reasonable range, the control system adjusts the second reaction preset time length T2 according to the supplemented and added material quantity A, and the adjusted second reaction time length is T2'.
And continuously starting the reaction kettle to stir the epoxy resin and the phosphorus-containing group compound X, timing the stirring time by the control system, and judging that the reaction of the epoxy resin and the phosphorus-containing group compound X is finished by the control system when the stirring time of the reaction kettle reaches T2'.
T2' = T2+ A x b, wherein b is a parameter for adjusting the stirring time of the reaction kettle.
A first preset supplementary material adding value A1, a second preset supplementary material adding value A2, a first preset reaction kettle stirring time length adjusting parameter value b1, a second preset reaction kettle stirring time length adjusting parameter value b2 and a third preset reaction kettle stirring time length adjusting parameter value b3 are arranged in the control system;
the control system compares the material quantity A added in the supplement with a first preset supplement material adding value A1 and a second preset supplement material adding value A2:
when A is less than or equal to A1, selecting the numerical value of a first preset reaction kettle stirring time length adjusting parameter value b1 as a reaction kettle stirring time length adjusting parameter b;
when A1 is larger than A and is smaller than or equal to A2, selecting the numerical value of a second preset reaction kettle stirring time length adjusting parameter b2 as a reaction kettle stirring time length adjusting parameter b;
and when A is larger than A2, selecting the numerical value of a third preset reaction kettle stirring time length adjusting parameter value b3 as a reaction kettle stirring time length adjusting parameter b.
The material quantity A is the supplementary adding quantity Q 'of the phosphorus-containing group compound X or the supplementary adding quantity M' of the epoxy resin.
Further, the type of the epoxy resin is bisphenol a epoxy resin, the phosphorus group-containing compound X is DOPO, the curing agent is DDS, the phosphorus content standard value Kb is 2%, the phosphorus content deviation range value W is 0.1%, the first reaction duration T1 of the reaction kettle is 1 hour, and the second reaction preset duration T2 is 7 hours;
stirring bisphenol A type epoxy resin and DOPO in a reaction kettle at the stirring temperature of 130 ℃;
the DDS added into the phosphorus-containing epoxy resin obtained by the reaction of the bisphenol A epoxy resin and DOPO is 20 percent of the phosphorus-containing epoxy resin contained in the reaction kettle.
DOPO is 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, DDS is amine curing agent 4,4-diaminodiphenyl sulfone.
The base cloth is composed of two adhesive tapes, and adhesive paper is arranged between the adhesive tapes.
The invention also discloses a high flame-retardant heat-resistant 22F copper-clad plate which is prepared according to the preparation process of the high flame-retardant heat-resistant 22F copper-clad plate and is characterized in that the glass transition temperature of the copper-clad plate is higher than 125 ℃, the soldering-resistant time is 50s, and the dielectric constant range is 3.8-4.0.
Compared with the prior art, the phosphorus-containing epoxy resin has the beneficial effects that the epoxy resin reacts with the phosphorus-containing group compound, the curing agent is used for curing to generate the phosphorus-containing epoxy resin, the phosphorus-containing epoxy resin generates phosphoric acid, polyphosphoric acid and water vapor in the combustion process, a large amount of smoke and toxic gas are not generated, the environment is protected during use, and the health of operators is not damaged. Meanwhile, in the reaction process, the phosphorus content in the product is strictly controlled through midway detection, the precision of the reaction result is enhanced, the state of the generated reactant is stable, and the quality control of the product is enhanced.
Furthermore, the phosphorus content of the same raw material, different production batches and different processing manufacturers can be different, the phosphorus content standard of the DOPO in the embodiment of the invention is more than or equal to 14 percent, the phosphorus content of the phosphorus-based compound is accurately detected, the phosphorus element content of the product is strictly controlled, the precision of the reaction result is enhanced, the state of the generated reactant is stable, and the quality control of the product is enhanced.
Furthermore, in the reaction process, the phosphorus content of the mixture is accurately detected, the phenomenon of unreasonable proportion of the raw materials of the finished product caused by non-uniform phosphorus content of the raw material phosphorus group compound is prevented, the range of the phosphorus content of the finished product is strictly controlled, the precision of the reaction result is enhanced, the state of the generated reactant is stable, and the quality control of the product is enhanced.
Furthermore, when raw material supplement is required to be carried out in the reaction kettle, and K is more than Kb, the phosphorus content of a part of the phosphorus group compound which is randomly inspected is lower than that of the added phosphorus group compound, so that in order to ensure that the phosphorus content of the finally generated finished product is in a reasonable range, supplementary epoxy resin is added into the reaction kettle, the range of the phosphorus content of the finished product is strictly controlled, the precision of a reaction result is enhanced, the state of the generated reactant is stable, and the quality control of the product is enhanced. Meanwhile, the addition amount of the epoxy resin is determined by the absolute value delta K of the difference value and the initial addition amount Q of the epoxy resin M and the phosphorus-containing group compound X, so that the adjustment accuracy is ensured.
Furthermore, when raw material supplement is required to be carried out in the reaction kettle, and K is less than Kb, the phosphorus content of a part of the phosphorus group compound which is randomly inspected is higher than that of the added phosphorus group compound, in order to ensure that the phosphorus content of the finally generated finished product is in a reasonable range, the phosphorus group compound is supplemented into the reaction kettle, the range of the phosphorus content of the finished product is strictly controlled, the precision of a reaction result is enhanced, the state of the generated reactant is stable, and the quality control of the product is enhanced. Meanwhile, the addition amount of the phosphorus group compound is determined by the absolute value delta K of the difference and the initial addition amount Q of the initial epoxy resin M and the phosphorus group compound X, so that the adjustment accuracy is ensured.
Furthermore, after the raw materials are supplemented and added into the reaction kettle, the newly supplemented raw materials and the original raw materials are not mixed sufficiently, so that the stirring time of the reaction kettle is prolonged, and the reactants in the reaction kettle are ensured to react sufficiently.
Further, when more raw materials are supplemented and added, the value of the second reaction time after adjustment is larger than the value of T2', and meanwhile, in order to ensure that reactants in the reaction kettle react fully, the stirring time adjusting parameter of the reaction kettle is set, and the value of the stirring time adjusting parameter of the reaction kettle is larger when more raw materials are supplemented and added.
Drawings
Fig. 1 is a flow chart of a preparation process of a high flame-retardant heat-resistant 22F copper-clad plate in the embodiment of the invention.
Detailed Description
In order that the objects and advantages of the invention will be more clearly understood, the invention is further described below with reference to examples; it should be understood that the specific embodiments described herein are merely illustrative of the invention and do not delimit the invention.
Preferred embodiments of the present invention are described below with reference to the accompanying drawings. It should be understood by those skilled in the art that these embodiments are only for explaining the technical principles of the present invention, and do not limit the scope of the present invention.
It should be noted that in the description of the present invention, the terms of direction or positional relationship indicated by the terms "upper", "lower", "left", "right", "inner", "outer", etc. are based on the directions or positional relationships shown in the drawings, which are only for convenience of description, and do not indicate or imply that the device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention.
Furthermore, it should be noted that, in the description of the present invention, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
Referring to fig. 1, fig. 1 is a flow chart of a process for manufacturing a high flame retardant and heat resistant 22F copper clad laminate according to an embodiment of the present invention.
The invention provides a preparation process of a high-flame-retardance heat-resistant 22F copper-clad plate, which comprises the following steps:
s1, preparing a base material, namely adding epoxy resin and a phosphorus-containing group compound X into a reaction kettle, and adding a curing agent after the reaction is completed to generate a prepared base material;
s2, dipping the base cloth, namely putting the base cloth into the prepared base cloth, passing the base cloth through a compression roller device after dipping is finished, and drying the base cloth to prepare a base plate;
s3, cutting a base plate;
and S4, pressing, namely feeding the overlapped base plate and the copper foil into a hot press for pressing to complete plate forming, and cooling after forming. Separating the pressed copper-clad plate from the die after cooling;
s5, cutting a finished product, and cutting the pressed copper-clad plate;
and S6, detecting finished products, detecting the performance of the finished copper clad laminate products, and grading.
A control system is arranged in the process of preparing the copper-clad plate for adjusting the working state of each link.
In the step S1, determining the initial ratio of the epoxy resin to the phosphorus-containing group compound X according to the phosphorus content P of the phosphorus-containing group compound X, detecting the phosphorus content of the mixture in the stirring process of the reaction kettle, judging whether to supplement raw materials into the reaction kettle according to the detection result, and adjusting the reaction time length in the reaction kettle according to the raw material supplement amount when the raw materials are required to be supplemented.
In the first embodiment, the epoxy resin type is bisphenol a type epoxy resin, the phosphorus group-containing compound X is DOPO, and the curing agent is DDS.
The molecular formula of DOPO is:
Figure BDA0003662721230000071
the molecular formula of the bisphenol A epoxy resin is as follows:
Figure BDA0003662721230000072
this application is through epoxy and phosphorus group containing compound reaction to solidify through the curing agent and generate phosphorus epoxy, phosphorus epoxy generates phosphoric acid, polyphosphoric acid and vapor in the combustion process, does not have a large amount of smog and toxic gas and produces, and is more environmental protection when using, does not harm operating personnel's healthy simultaneously. Meanwhile, in the reaction process, the phosphorus content in the product is strictly controlled through midway detection, the precision of the reaction result is enhanced, the state of the generated reactant is stable, and the quality control of the product is enhanced.
Specifically, in step S1, the phosphorus content P in the phosphorus-containing group compound X is detected, and the detection result is transmitted to the control system, wherein a preset epoxy resin addition amount M is set in the control system, and the control system calculates an initial addition amount Q of the phosphorus-containing group compound X by the preset epoxy resin addition amount M and the phosphorus content P, wherein Q = G × M ÷ (P × P-G), where G is a target phosphorus content of a compound generated by the reaction of the epoxy resin and the phosphorus-containing group compound X, and P is an initial addition amount of the phosphorus-containing group compound X to calculate a compensation parameter.
As for the DOPO in the embodiment of the invention, the phosphorus content standard is more than or equal to 14 percent, the phosphorus content in the product is strictly controlled by accurately detecting the phosphorus content in the phosphorus group compound, the precision of the reaction result is enhanced, the state of the generated reactant is stable, and the quality control of the product is enhanced.
Adding the epoxy resin with the addition amount of M and the phosphorus-containing group compound X with the addition amount of Q into a reaction kettle, and starting the reaction kettle to mix the epoxy resin and the phosphorus-containing group compound X.
Specifically, the control system is provided with a first reaction time T1 of the reaction kettle, when the reaction kettle starts to mix epoxy resin and a phosphorus-containing group compound S, the control system starts a timing function to time the reaction time in the reaction kettle, when the reaction time reaches T1, a mixture sample is extracted from the reaction kettle, the phosphorus content K in the sample is detected, and a detection result is transmitted to the control system, wherein a mixture phosphorus content standard value Kb and a phosphorus content deviation range value W are arranged in the control system.
The control system calculates the absolute value delta K of the difference between the phosphorus content K of the mixture and the phosphorus content standard value Kb of the mixture, wherein delta K = | K-Kb |, and the control system compares the absolute value delta K of the difference with the phosphorus content deviation range value W:
when delta K is less than or equal to W, the control system judges that the phosphorus content deviation is within a reasonable range;
when the delta K is larger than W, the control system judges that the phosphorus content deviation is not in a reasonable range, and the control system judges the material and the additive amount which are supplemented and added into the reaction kettle according to the size relation between the K and the Kb and the value of the delta K.
In the reaction process, the phosphorus content of the mixture is accurately detected, the phenomenon of unreasonable proportion of the raw materials of the finished product caused by non-uniform phosphorus content of the raw material phosphorus group compound is prevented, the range of the phosphorus content of the finished product is strictly controlled, the precision of the reaction result is enhanced, the state of the generated reactant is stable, and the quality control of the product is enhanced.
Specifically, when K > Kb, the control system judges that the phosphorus content of the mixture is too high, and replenishes the epoxy resin into the reaction kettle, wherein the replenishment amount M' of the epoxy resin is determined by the absolute value delta K of the difference and the initial addition amount Q of the epoxy resin M and the phosphorus-containing group compound X.
The system of equations for M' is found to be:
Figure BDA0003662721230000081
where α is the calculated compensation value for M'.
When the raw materials are required to be supplemented in the reaction kettle and K is more than Kb, the phosphorus content of part of the phosphorus group compound which is randomly inspected is lower than that of the added phosphorus group compound, in order to ensure that the phosphorus content of the finally generated finished product is in a reasonable range, the supplementary epoxy resin is supplemented in the reaction kettle, the range of the phosphorus content of the finished product is strictly controlled, the precision of the reaction result is enhanced, the state of the generated reactant is stable, and the product control is enhanced. Meanwhile, the addition amount of the epoxy resin is determined by the absolute value delta K of the difference and the initial addition amount Q of the epoxy resin M and the phosphorus-containing group compound X, so that the adjustment accuracy is ensured.
Specifically, when K is less than Kb, the control system judges that the phosphorus content of the mixture is insufficient, and a phosphorus-containing group compound X needs to be added into the reaction kettle in a supplementing mode, wherein the supplementing adding amount Q' of the phosphorus-containing group compound X is determined by the absolute value delta K of the difference and the initial adding amount Q of the epoxy resin M and the phosphorus-containing group compound X.
Solving the equation system of Q' as:
Figure BDA0003662721230000091
specifically, a reaction kettle second reaction preset time length T2 is arranged in the control system, and the control system determines whether to adjust the second reaction preset time length T2 according to the phosphorus content deviation.
When raw material supplement is required to be carried out in the reaction kettle and K is less than Kb, the phosphorus content of a part of the phosphorus group compound which is randomly inspected is higher than that of the added phosphorus group compound, in order to ensure that the phosphorus content of the finally generated finished product is in a reasonable range, the phosphorus group supplement compound is supplemented into the reaction kettle, the range of the phosphorus content of the finished product is strictly controlled, the precision of a reaction result is enhanced, the state of the generated reactant is stable, and the quality control of the product is enhanced. Meanwhile, the addition amount of the phosphorus group compound is determined by the absolute value delta K of the difference and the initial addition amount Q of the initial epoxy resin M and the phosphorus group compound X, so that the adjustment accuracy is ensured.
Specifically, when the control system judges that the phosphorus content deviation is within a reasonable range, the control system does not adjust the preset time length of the second reaction, the reaction kettle is continuously started to stir the epoxy resin and the phosphorus-containing group compound X, the control system times the stirring time length, and when the stirring time length of the reaction kettle reaches T2, the control system judges that the reaction of the epoxy resin and the phosphorus-containing group compound X is completed.
Specifically, when the control system judges that the phosphorus content deviation is not in a reasonable range, the control system adjusts the preset second reaction time length T2 according to the supplemented and added material quantity A, and the adjusted second reaction time length is T2'.
After the raw materials are supplemented and added into the reaction kettle, the newly supplemented raw materials and the original raw materials are not mixed sufficiently, so that the stirring time of the reaction kettle is prolonged, and the reactants in the reaction kettle are ensured to react sufficiently.
And continuously starting the reaction kettle to stir the epoxy resin and the phosphorus-containing group compound X, timing the stirring time by the control system, and judging that the reaction of the epoxy resin and the phosphorus-containing group compound X is completed by the control system when the stirring time of the reaction kettle reaches T2'.
T2' = T2+ A x b, wherein b is a parameter for adjusting the stirring time of the reaction kettle.
A first preset supplementary material adding value A1, a second preset supplementary material adding value A2, a first preset reaction kettle stirring time length adjusting parameter value b1, a second preset reaction kettle stirring time length adjusting parameter value b2 and a third preset reaction kettle stirring time length adjusting parameter value b3 are arranged in the control system; b1 is more than b2 and less than b3.
The control system compares the material quantity A added in the supplement with a first preset supplement material adding value A1 and a second preset supplement material adding value A2:
when A is less than or equal to A1, selecting the numerical value of a first preset reaction kettle stirring time length adjusting parameter value b1 as a reaction kettle stirring time length adjusting parameter b;
when A1 is larger than A and is smaller than or equal to A2, selecting the numerical value of a second preset reaction kettle stirring time length adjusting parameter value b2 as a reaction kettle stirring time length adjusting parameter b;
and when A is larger than A2, selecting the numerical value of a third preset reaction kettle stirring time length adjusting parameter value b3 as a reaction kettle stirring time length adjusting parameter b.
When the number of the supplementary added raw materials is more, the adjusted second reaction time is larger for the value T2', and meanwhile, in order to ensure that reactants in the reaction kettle react fully, the stirring time adjusting parameter of the reaction kettle is set, and the stirring time adjusting parameter value of the reaction kettle is larger when the number of the supplementary added raw materials is more.
The material quantity A is the supplementary adding quantity Q 'of the phosphorus-containing group compound X or the supplementary adding quantity M' of the epoxy resin.
Specifically, the phosphorus content standard value Kb is 2%, the phosphorus content deviation range value W is 0.1%, the first reaction time T1 of the reaction kettle is 1h, and the second reaction preset time T2 is 7h;
stirring bisphenol A type epoxy resin and DOPO in a reaction kettle at the stirring temperature of 130 ℃;
the DDS added into the phosphorus-containing epoxy resin obtained by the reaction of the bisphenol A epoxy resin and DOPO is 20 percent of the phosphorus-containing epoxy resin contained in the reaction kettle.
DOPO is 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, DDS is amine curing agent 4,4-diaminodiphenyl sulfone.
The DOPO and the epoxy resin directly react to synthesize the phosphorus-containing epoxy resin with the molecular formula of
It is contemplated that the epoxy resin type in this embodiment is bisphenol a epoxy resin, and other epoxy resins that can react with the phosphorus-containing compound can also be used in the present invention to prepare phosphorus-containing epoxy resins, including but not limited to cycloaliphatic epoxy resins;
in the present embodiment, the phosphorus-containing compound X is DOPO, and it is contemplated that other phosphorus-containing compounds capable of reacting with an epoxy resin to form a phosphorus-containing epoxy resin may also be used in the preparation process of the present invention, including but not limited to derivatives of DOPO.
The invention also discloses a high flame-retardant heat-resistant 22F copper-clad plate which is prepared according to the preparation process of the high flame-retardant heat-resistant 22F copper-clad plate and is characterized in that the glass transition temperature of the copper-clad plate is higher than 125 ℃, the soldering-resistant time is 50s, and the dielectric constant range is 3.8-4.0.
The copper-clad plate generates phosphoric acid, polyphosphoric acid and water vapor in the welding and drilling process, does not generate a large amount of smog and toxic gases, is more environment-friendly when in use, and does not damage the health of operators.
Example two: selecting trifunctional epoxy resin (1- [ alpha-methyl-alpha- (4-hydroxy) ethyl ] -4- [ alpha, alpha-di- (4-hydroxyphenyl) ethyl ] benzene ring epoxy resin) to react with phosphorus-containing hydroquinone, wherein a catalyst is triphenylphosphine, heating to 150 ℃, the phosphorus content standard value Kb is 3.3%, the phosphorus content deviation range value W is 0.12%, the first reaction duration T1 of the reaction kettle is 1h, and the second reaction preset duration T2 is 8h, so as to generate the phosphorus-containing epoxy resin with the epoxy equivalent of 241 g/eq.
In the third embodiment, the naphthol novolac epoxy resin and the novolac epoxy resin are used for replacing the trifunctional epoxy resin in the second embodiment, and are reacted with phosphorus-containing hydroquinone, the catalyst is triphenylphosphine, the temperature is raised to 150 ℃, the phosphorus content standard value Kb is 3%, the phosphorus content deviation range value W is 0.1%, the first reaction time length T1 of the reaction kettle is 1h, the preset second reaction time length T2 is 8h, and phosphorus-containing epoxy resin with the epoxy equivalent weight of 235g/eq is generated.
In the fourth embodiment, a bisphenol epoxy resin is reacted with phosphorus-containing hydroquinone in place of the trifunctional epoxy resin in the second embodiment, the catalyst is triphenylphosphine, the temperature is raised to 150 ℃, the phosphorus content standard value Kb is 3.5%, the phosphorus content deviation range value W is 0.15%, the first reaction time length T1 of the reaction kettle is 1h, the preset second reaction time length T2 is 8h, and phosphorus-containing epoxy resin with an epoxy equivalent weight of 235g/eq is produced.
Examples two-four use a diamine as a curing agent.
So far, the technical solutions of the present invention have been described in connection with the preferred embodiments shown in the drawings, but it is easily understood by those skilled in the art that the scope of the present invention is obviously not limited to these specific embodiments. Equivalent changes or substitutions of related technical features can be made by those skilled in the art without departing from the principle of the invention, and the technical scheme after the changes or substitutions can fall into the protection scope of the invention.

Claims (6)

1. A preparation process of a high flame-retardant heat-resistant 22F copper-clad plate is characterized by comprising the following steps of,
s1, preparing a base material, namely adding epoxy resin and a phosphorus-containing group compound X into a reaction kettle, and adding a curing agent after the reaction is completed to generate a prepared base material;
s2, impregnating the base cloth, namely putting the base cloth into the prepared base material, passing the base cloth through a compression roller device after the impregnation is finished, and drying the base cloth to prepare a base plate;
s3, cutting a base plate;
s4, pressing, namely feeding the base plate and the copper foil after the overlapping into a hot press for pressing, completing the forming of the plate, cooling after the forming, and separating the pressed copper-clad plate from the die after the cooling is completed;
s5, cutting a finished product, and cutting the pressed copper-clad plate;
s6, detecting finished products, detecting the performance of the finished copper clad laminate products, and grading;
a control system is arranged in the process of preparing the copper-clad plate for adjusting the working state of each link; in the step S1, determining the initial ratio of the epoxy resin to the phosphorus-containing group compound X according to the phosphorus content P of the phosphorus-containing group compound X, detecting the phosphorus content of the mixture in the stirring process of the reaction kettle, judging whether to supplement raw materials into the reaction kettle according to the detection result, and adjusting the reaction time length in the reaction kettle according to the raw material supplement amount when the raw materials are required to be supplemented; detecting the phosphorus content P in the phosphorus-containing group compound X, transmitting a detection result to the control system, wherein a preset epoxy resin addition amount M is arranged in the control system, the control system calculates an initial addition amount Q of the phosphorus-containing group compound X through the preset epoxy resin addition amount M and the phosphorus content P, the epoxy resin with the addition amount M and the phosphorus-containing group compound X with the addition amount Q are added into a reaction kettle, and the reaction kettle is started to mix the epoxy resin and the phosphorus-containing group compound X;
the control system is provided with a first reaction time T1 of the reaction kettle, when the reaction kettle starts to mix the epoxy resin and the phosphorus-containing group compound X, the control system starts a timing function to time the reaction time in the reaction kettle, when the reaction time reaches T1, a mixture sample is extracted from the reaction kettle, the phosphorus content K in the sample is detected, and a detection result is transmitted to the control system, wherein a mixture phosphorus content standard value Kb and a phosphorus content deviation range value W are arranged in the control system; the control system calculates the absolute value delta K of the difference between the phosphorus content K of the mixture and the phosphorus content standard value Kb of the mixture,
delta K = | -K-Kb |, the control system compares the absolute value of the difference delta K with a phosphorus content deviation range value W, and when the delta K is less than or equal to W, the control system judges that the phosphorus content deviation is within a reasonable range; when the delta K is larger than W, the control system judges that the phosphorus content deviation is not in a reasonable range, and the control system judges the material and the additive amount which are supplemented and added into the reaction kettle according to the relation between the K and the Kb and the value of the delta K;
when K is larger than Kb, the control system judges that the phosphorus content of the mixture is too high, and the epoxy resin is added into the reaction kettle in a supplementing manner, wherein the adding amount M' of the epoxy resin is determined by the absolute value delta K of the difference and the initial adding amount Q of the initial epoxy resin M and the phosphorus-containing group compound X; solving the equation system of M' as follows:
Figure DEST_PATH_IMAGE001
wherein, alpha is a calculated compensation value of M';
when K is less than Kb, the control system judges that the phosphorus content of the mixture is insufficient, a phosphorus-containing group compound X needs to be added into the reaction kettle in a supplementing mode, the supplementing adding amount Q 'of the phosphorus-containing group compound X is determined by the absolute value delta K of the difference and the initial adding amount Q of the epoxy resin M and the phosphorus-containing group compound X, and the equation set of Q' is obtained as follows:
Figure 527089DEST_PATH_IMAGE002
。
2. the preparation process of the high flame retardant and heat resistant 22F copper-clad plate according to claim 1, wherein a reaction kettle second reaction preset time period T2 is arranged in the control system, and the control system determines whether to adjust the second reaction preset time period T2 according to the phosphorus content deviation.
3. The preparation process of the high flame-retardant heat-resistant 22F copper-clad plate according to claim 2, wherein when the control system determines that the phosphorus content deviation is within a reasonable range, the control system does not adjust the preset time of the second reaction, the reaction kettle is continuously started to stir the epoxy resin and the phosphorus-containing group compound X, the control system times the stirring time, and when the stirring time of the reaction kettle reaches T2, the control system determines that the reaction of the epoxy resin and the phosphorus-containing group compound X is completed.
4. The preparation process of the high flame retardant and heat resistant 22F copper-clad plate according to claim 3, wherein when the control system determines that the phosphorus content deviation is not within a reasonable range, the control system adjusts a second reaction preset time period T2 according to the amount A of the supplementary added material, and the adjusted second reaction time period is T2';
the reaction kettle is continuously started to stir the epoxy resin and the phosphorus-containing group compound X, the control system times the stirring time, and when the stirring time of the reaction kettle reaches T2', the control system judges that the reaction of the epoxy resin and the phosphorus-containing group compound X is completed;
the material quantity A is the supplementary adding quantity Q 'of the phosphorus-containing group compound X or the supplementary adding quantity M' of the epoxy resin.
5. The process for preparing the high flame retardant and heat resistant 22F copper-clad plate according to claim 4, wherein the epoxy resin type is bisphenol A epoxy resin, the phosphorus group-containing compound X is DOPO, the curing agent is DDS, the phosphorus content standard value Kb is 2%, the phosphorus content deviation range value W is 0.1%, the first reaction duration T1 of the reaction kettle is 1h, and the second preset reaction duration T2 is 7h;
stirring bisphenol A type epoxy resin and DOPO in a reaction kettle at the stirring temperature of 130 ℃;
the DDS added into the phosphorus-containing epoxy resin obtained by the reaction of the bisphenol A epoxy resin and DOPO is 20 percent of the phosphorus-containing epoxy resin contained in the reaction kettle.
6. A high flame-retardant heat-resistant 22F copper-clad plate is prepared by the preparation process of the high flame-retardant heat-resistant 22F copper-clad plate according to any one of claims 1 to 5, and is characterized in that the glass transition temperature of the copper-clad plate is higher than 125 ℃, the soldering time is 50s, and the dielectric constant is within the range of 3.8-4.0.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1721475A (en) * 2004-07-16 2006-01-18 无锡阿科力化工有限公司 Halogen-free epoxy resin and process for preparing same
CN103333464A (en) * 2013-06-28 2013-10-02 青岛富斯林化工科技有限公司 Phosphorus-containing halogen-free flame-retardant epoxy resin composition and applications
CN103627146A (en) * 2013-11-08 2014-03-12 建滔（江苏）化工有限公司 Preparation and application of high-flexibility phosphorus-containing halogen-free epoxy resin
CN113694804A (en) * 2021-08-24 2021-11-26 广东摩尔物联技术有限公司 Method for automatically controlling feeding ratio of materials

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1721475A (en) * 2004-07-16 2006-01-18 无锡阿科力化工有限公司 Halogen-free epoxy resin and process for preparing same
CN103333464A (en) * 2013-06-28 2013-10-02 青岛富斯林化工科技有限公司 Phosphorus-containing halogen-free flame-retardant epoxy resin composition and applications
CN103627146A (en) * 2013-11-08 2014-03-12 建滔（江苏）化工有限公司 Preparation and application of high-flexibility phosphorus-containing halogen-free epoxy resin
CN113694804A (en) * 2021-08-24 2021-11-26 广东摩尔物联技术有限公司 Method for automatically controlling feeding ratio of materials

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