CN116080212A - Hydrocarbon resin-based copper-clad plate and preparation method thereof - Google Patents

Hydrocarbon resin-based copper-clad plate and preparation method thereof Download PDF

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Publication number
CN116080212A
CN116080212A CN202211342872.7A CN202211342872A CN116080212A CN 116080212 A CN116080212 A CN 116080212A CN 202211342872 A CN202211342872 A CN 202211342872A CN 116080212 A CN116080212 A CN 116080212A
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clad plate
titanium dioxide
copper
treatment
hydrocarbon resin
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CN116080212B (en
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陈应峰
王小龙
谢谏诤
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Jiangsu Yaohong Electronics Co ltd
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Jiangsu Yaohong Electronics Co 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
    • 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
    • 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
    • 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
    • B32B38/0036—Heat treatment
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/69—Polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • 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
    • B32B2038/0052—Other operations not otherwise provided for
    • B32B2038/0076—Curing, vulcanising, cross-linking
    • 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
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • 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
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • 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
    • B32B2457/00—Electrical equipment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C08J2475/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds

Abstract

The invention discloses a hydrocarbon resin-based copper-clad plate and a preparation method thereof. The copper-clad plate has better wet heat aging resistance, can effectively ensure the stability of dielectric constant and dielectric loss of the copper-clad plate after the wet heat aging treatment, and avoids the damage of the circuit board caused by the abrupt change of the performance of the copper-clad plate; the epoxy resin is used for carrying out supplementary adjustment on the polybutadiene polyurethane material, so that the heat stability of the copper-clad plate can be effectively improved; the titanium dioxide in the modified filler can effectively strengthen the dielectric constant and heat resistance of the copper-clad plate, and the silane coupling agent carries out surface grafting treatment on the titanium dioxide, so that the dispersion uniformity of the titanium dioxide in the copper-clad plate can be effectively enhanced; the modified filler is prepared into the nitrogen-sulfur doped porous carbon material, and the nitrogen-sulfur doped porous carbon material is added into the impregnating compound, so that the dielectric property of the copper-clad plate can be effectively enhanced, the stability of dielectric constant and dielectric loss is ensured, and the circuit board is prevented from being damaged due to rapid change of the property of the copper-clad plate.

Description

Hydrocarbon resin-based copper-clad plate and preparation method thereof
Technical Field
The invention relates to the technical field of copper-clad plates, in particular to a hydrocarbon resin-based copper-clad plate and a preparation method thereof.
Background
The copper-clad plate is a plate-shaped material which is prepared by immersing electronic glass fiber cloth or other reinforcing materials into resin, covering copper foil on one side or both sides and carrying out hot pressing, and is called as a copper-clad laminate, namely the copper-clad plate for short; the copper-clad plate manufacturing industry has wide development prospect along with the development of electronic information and communication industry, and the manufacturing technology is a high and new technology of multidisciplinary mutual penetration, mutual intersection and mutual promotion. The performance of the copper-clad plate determines the quality and performance of the printed circuit board, the preparation performance in manufacturing, the manufacturing level, the manufacturing cost and the long-term reliability and stability to a great extent. Hydrocarbon resins generally refer to petroleum resins (thermoplastic resins) which are not polymers but oligomers having a molecular weight of 300 to 3000.
The existing hydrocarbon resin-based copper-clad plate has poor wet heat aging resistance, and the dielectric constant of the existing hydrocarbon resin-based copper-clad plate is greatly floated and the dielectric loss is increased after the existing hydrocarbon resin-based copper-clad plate is subjected to wet heat aging treatment.
Disclosure of Invention
In order to overcome the defects in the prior art, the embodiment of the invention provides a hydrocarbon resin-based copper-clad plate and a preparation method thereof.
A hydrocarbon resin-based copper-clad plate comprises electronic glass fiber cloth, impregnating compound and copper foil; the impregnating compound comprises the following components in percentage by weight: 9.4 to 10.4 percent of isocyanate, 0.12 to 0.18 percent of dibutyl tin dilaurate, 23 to 27 percent of epoxy resin, 1.3 to 1.7 percent of amine curing agent, 12.6 to 13.6 percent of modified filler and the balance of polybutadiene.
Further, the modified filler comprises the following components in percentage by weight: 28.6 to 29.6 percent of titanium dioxide, 0.9 to 1.1 percent of silane coupling agent KH-570, 7 to 9 percent of chitosan, 25 to 29 percent of sodium lignin sulfonate and the balance of potassium hydroxide.
Further, the impregnating compound comprises the following components in percentage by weight: 9.4% of isocyanate, 0.12% of dibutyltin dilaurate, 23% of epoxy resin, 1.3% of amine curing agent, 12.6% of modified filler and the balance of polybutadiene; the modified filler comprises the following raw materials in percentage by weight: 28.6% of titanium dioxide, 0.9% of silane coupling agent KH-570, 7% of chitosan, 25% of sodium lignin sulfonate and the balance of potassium hydroxide.
Further, the impregnating compound comprises the following components in percentage by weight: 10.4% of isocyanate, 0.18% of dibutyltin dilaurate, 27% of epoxy resin, 1.7% of amine curing agent, 13.6% of modified filler and the balance of polybutadiene; the modified filler comprises the following raw materials in percentage by weight: 29.6% of titanium dioxide, 1.1% of silane coupling agent KH-570, 9% of chitosan, 29% of sodium lignin sulfonate and the balance of potassium hydroxide.
Further, the impregnating compound comprises the following components in percentage by weight: 9.9% of isocyanate, 0.15% of dibutyltin dilaurate, 25% of epoxy resin, 1.5% of amine curing agent, 13.1% of modified filler and the balance of polybutadiene; the modified filler comprises the following raw materials in percentage by weight: 29.1% of titanium dioxide, 1.0% of silane coupling agent KH-570, 8% of chitosan, 27% of sodium lignin sulfonate and the balance of potassium hydroxide.
Further, the amine curing agent: one of ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine and diethylaminopropylamine.
The preparation method of the hydrocarbon resin-based copper-clad plate comprises the following specific preparation steps:
step one: weighing isocyanate, dibutyl tin dilaurate, epoxy resin, amine curing agent, polybutadiene, titanium dioxide in modified filler raw materials, silane coupling agent KH-570, chitosan, sodium lignin sulfonate and potassium hydroxide;
step two: adding titanium dioxide in the first step into the dispersion liquid, performing ultrasonic treatment in a water bath for 12-14 min, then adding a silane coupling agent KH-570, continuing ultrasonic treatment for 30-50 min, standing at room temperature for 15-25 min, and performing suction filtration and drying to obtain modified titanium dioxide;
step three: blending chitosan and sodium lignin sulfonate in the first step, then performing vacuum freeze drying treatment for 3-5 hours to obtain a mixture a, performing carbonization treatment on the mixture a for 1-2 hours to obtain a mixture b, performing blending ball milling treatment on the mixture b and potassium hydroxide in the first step for 20-30 minutes to obtain a mixture c, performing activation treatment on the mixture c for 60-80 minutes, and cooling to obtain a mixture d;
step four: blending the modified titanium dioxide in the second step and the mixture d in the third step to obtain modified filler;
step five: adding the modified filler in the fourth step into the polybutadiene in the first step, carrying out ultrasonic treatment for 30-50 min, adding the isocyanate, the dibutyl tin dilaurate, the epoxy resin and the amine curing agent in the first step, and carrying out high-speed stirring treatment for 50-60 min to obtain an impregnating compound;
step six: dipping the electronic glass fiber cloth in the dipping material prepared in the step five for 30-36 min, solidifying for 5-7 hours at the temperature of 150-158 ℃, and cooling to room temperature after solidification to obtain hydrocarbon resin-based prepreg;
step seven: and symmetrically overlapping the hydrocarbon resin-based prepreg and the copper foil, and then placing the prepreg and the copper foil into a hot press for hot pressing treatment to obtain the hydrocarbon resin-based copper-clad plate.
Further, in the second step, the weight ratio of the titanium dioxide to the dispersion liquid is 1:5-7, the pH value of the dispersion liquid is regulated to be 8.5-9.5 after the dispersion liquid is prepared according to the volume ratio of ethanol to water of 1:1, the water bath temperature is 75-85 ℃, the ultrasonic frequency is 1.3-1.5 MHz, and the ultrasonic power is 300-400W; in the third step, the vacuum freeze-drying temperature is-50 to-40 ℃, the carbonization treatment temperature is 680-720 ℃, a planetary ball mill is adopted for treatment during ball milling, the revolution rotation speed is 400-500 r/min, the rotation speed is 800-1000 r/min, and the activation temperature is 580-620 ℃; in the fifth step, the ultrasonic frequency is 1.6-1.8 MHz, the ultrasonic power is 300-400W, and the stirring rotating speed is 1200-1800 r/min; in the seventh step, the hot press is set to have a hot pressing temperature of 230-250 ℃ and a pressure of 85-95 kg/cm 2 The pressing time is 17-19 h.
Further, in the second step, the weight ratio of the titanium dioxide to the dispersion is 1:5, the pH=8.5 is adjusted after the dispersion is prepared according to the volume ratio of ethanol to water of 1:1, the water bath temperature is 75 ℃, the ultrasonic frequency is 1.3MHz, and the ultrasonic power is 300W; in the third step, the vacuum freeze-drying temperature is-50 ℃, the carbonization treatment temperature is 680 ℃, a planetary ball mill is adopted for treatment during ball milling, the revolution rotation speed is 400r/min, the rotation speed is 800r/min, and the activation temperature is 580 ℃; in the fifth step, the ultrasonic frequency is 1.6MHz, the ultrasonic power is 300W, and the stirring rotating speed is 1200r/min; in the seventh step, the hot press sets a hot press temperature of 230℃and a pressure of 85kg/cm 2 The pressing time is 17h.
Further, in the second step, the weight ratio of the titanium dioxide to the dispersion is 1:6, the pH=9.0 is adjusted after the dispersion is prepared according to the volume ratio of ethanol to water of 1:1, the water bath temperature is 80 ℃, the ultrasonic frequency is 1.4MHz, and the ultrasonic power is 350W; in the third step, the vacuum freeze-drying temperature is-45 ℃, the carbonization treatment temperature is 700 ℃, and the planetary ball mill is adopted for treatment during ball milling, and revolution is carried outThe rotating speed is 450r/min, the autorotation rotating speed is 900r/min, and the activation temperature is 600 ℃; in the fifth step, the ultrasonic frequency is 1.7MHz, the ultrasonic power is 350W, and the stirring rotating speed is 1500r/min; in the seventh step, the hot press sets the hot pressing temperature to 240 ℃ and the pressure to 90kg/cm 2 The pressing time is 18h.
The invention has the technical effects and advantages that:
1. the hydrocarbon resin-based copper-clad plate prepared by adopting the raw material formula disclosed by the invention has better humidity and heat aging resistance, can effectively ensure the stability of dielectric constant and dielectric loss of the copper-clad plate after being subjected to humidity and heat aging treatment, and avoids the damage of a circuit board caused by abrupt change of the performance of the copper-clad plate; polybutadiene and isocyanate in the hydrocarbon resin-based copper-clad plate react and are compounded under the catalysis of dibutyl tin dilaurate to form a polybutadiene polyurethane material, then epoxy resin is added to supplement and regulate the polybutadiene polyurethane material, and a polyurethane chain segment and the epoxy resin form an interpenetrating network, so that a bicontinuous phase structure is gradually formed, the thermal stability of the impregnating material can be effectively improved, and the thermal stability of the copper-clad plate is further improved; the amine curing agent provides curing performance for the epoxy resin, so that the fixation treatment of the epoxy resin can be effectively ensured; the titanium dioxide in the modified filler can effectively strengthen the dielectric constant of the copper-clad plate, and simultaneously can effectively strengthen the heat resistance of the copper-clad plate, the silane coupling agent KH-570 can carry out surface modification treatment on the titanium dioxide, and carry out surface grafting treatment on the titanium dioxide, so that the distribution uniformity of the modified titanium dioxide in an impregnating material can be effectively strengthened, the dispersion uniformity of the titanium dioxide in the copper-clad plate is further strengthened, and the heat resistance of the copper-clad plate, the stability of the dielectric constant and the dielectric loss are further strengthened; the chitosan and sodium lignin sulfonate in the modified filler are respectively used as a nitrogen source and a sulfur source, a carbon precursor is prepared through freeze drying, then a porous carbon material doped with nitrogen and sulfur is prepared through potassium hydroxide activation after carbonization treatment at 700 ℃, and the porous carbon material is added into an impregnating compound, so that the dielectric property of the copper-clad plate can be effectively enhanced, the stability of dielectric constant and dielectric loss is ensured, and the circuit board damage caused by rapid change of the performance of the copper-clad plate is avoided;
2. in the invention, after titanium dioxide is added into dispersion liquid for water bath ultrasonic treatment and silane coupling agent KH-570 is added, ultrasonic treatment is continued, and suction filtration and drying are carried out to obtain modified titanium dioxide, thus effectively ensuring the dispersion uniformity of titanium dioxide in impregnating materials; the chitosan and the sodium lignin sulfonate are compounded and proportioned, a carbon precursor is prepared by freeze drying, and then a layered porous carbon structure with the size of tens of micrometers to tens of micrometers stacked mutually is prepared by simple carbonization and activation; blending the modified titanium dioxide and the mixture d to obtain modified filler; blending modified filler and polybutadiene, and then adding isocyanate, dibutyltin dilaurate, epoxy resin and amine curing agent to perform high-speed stirring to prepare an impregnating compound; carrying out dipping treatment, solidification and cooling treatment on the electronic glass fiber cloth to obtain hydrocarbon resin-based prepreg; and carrying out hot pressing treatment on the hydrocarbon resin-based prepreg and the copper foil to obtain the hydrocarbon resin-based copper-clad plate.
Detailed Description
The following description will clearly and fully describe the technical solutions of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1:
the invention provides a hydrocarbon resin-based copper-clad plate, which comprises electronic glass fiber cloth, impregnating compound and copper foil; the impregnating compound comprises the following components in percentage by weight: 9.4% of isocyanate, 0.12% of dibutyltin dilaurate, 23% of epoxy resin, 1.3% of amine curing agent, 12.6% of modified filler and the balance of polybutadiene; the modified filler comprises the following raw materials in percentage by weight: 28.6% of titanium dioxide, 0.9% of silane coupling agent KH-570, 7% of chitosan, 25% of sodium lignin sulfonate and the balance of potassium hydroxide;
the amine curing agent: ethylenediamine;
the invention also provides a preparation method of the hydrocarbon resin-based copper-clad plate, which comprises the following specific preparation steps:
step one: weighing isocyanate, dibutyl tin dilaurate, epoxy resin, amine curing agent, polybutadiene, titanium dioxide in modified filler raw materials, silane coupling agent KH-570, chitosan, sodium lignin sulfonate and potassium hydroxide;
step two: adding titanium dioxide in the first step into the dispersion liquid, performing ultrasonic treatment in a water bath for 13min, then adding a silane coupling agent KH-570, continuing ultrasonic treatment for 40min, standing at room temperature for 20min, and performing suction filtration and drying to obtain modified titanium dioxide;
step three: blending chitosan and sodium lignin sulfonate in the first step, then performing vacuum freeze drying treatment for 4 hours to obtain a mixture a, performing carbonization treatment on the mixture a for 1.5 hours to obtain a mixture b, performing blending ball milling treatment on the mixture b and potassium hydroxide in the first step for 25 minutes to obtain a mixture c, performing activation treatment on the mixture c for 70 minutes, and cooling to obtain a mixture d;
step four: blending the modified titanium dioxide in the second step and the mixture d in the third step to obtain modified filler;
step five: adding the modified filler in the fourth step into the polybutadiene in the first step, carrying out ultrasonic treatment for 40min, adding the isocyanate, the dibutyl tin dilaurate, the epoxy resin and the amine curing agent in the first step, and carrying out high-speed stirring treatment for 55min to obtain an impregnating compound;
step six: soaking the electronic glass fiber cloth in the soaking material prepared in the step five for 33min, solidifying for 6 hours at the temperature of 154 ℃, and cooling to room temperature after solidification to obtain hydrocarbon resin-based prepreg;
step seven: and symmetrically overlapping the hydrocarbon resin-based prepreg and the copper foil, and then placing the prepreg and the copper foil into a hot press for hot pressing treatment to obtain the hydrocarbon resin-based copper-clad plate.
In the second step, the weight ratio of the titanium dioxide to the dispersion liquid is 1:5, the pH=8.5 is regulated after the dispersion liquid is prepared according to the volume ratio of ethanol to water of 1:1, the water bath temperature is 75 ℃, the ultrasonic frequency is 1.3MHz, and the ultrasonic power is 300W; in the third step, the vacuum freeze-drying temperature is-50 ℃, and carbonization is carried outThe treatment temperature is 680 ℃, a planetary ball mill is adopted for treatment during ball milling, the revolution rotation speed is 400r/min, the rotation speed is 800r/min, and the activation temperature is 580 ℃; in the fifth step, the ultrasonic frequency is 1.6MHz, the ultrasonic power is 300W, and the stirring rotating speed is 1200r/min; in the seventh step, the hot press sets a hot press temperature of 230℃and a pressure of 85kg/cm 2 The pressing time is 17h.
Example 2:
unlike example 1, the impregnating compound comprises, in weight percent: 10.4% of isocyanate, 0.18% of dibutyltin dilaurate, 27% of epoxy resin, 1.7% of amine curing agent, 13.6% of modified filler and the balance of polybutadiene; the modified filler comprises the following raw materials in percentage by weight: 29.6% of titanium dioxide, 1.1% of silane coupling agent KH-570, 9% of chitosan, 29% of sodium lignin sulfonate and the balance of potassium hydroxide.
Example 3:
unlike examples 1-2, the impregnating compound comprises, in weight percent: 9.9% of isocyanate, 0.15% of dibutyltin dilaurate, 25% of epoxy resin, 1.5% of amine curing agent, 13.1% of modified filler and the balance of polybutadiene; the modified filler comprises the following raw materials in percentage by weight: 29.1% of titanium dioxide, 1.0% of silane coupling agent KH-570, 8% of chitosan, 27% of sodium lignin sulfonate and the balance of potassium hydroxide.
Example 4:
unlike example 3, in step two, the weight ratio of titanium dioxide to dispersion was 1:7, the dispersion was formulated with ethanol and water in a volume ratio of 1:1, and then ph=9.5 was adjusted, the water bath temperature was 85 ℃, the ultrasonic frequency was 1.5MHz, and the ultrasonic power was 400W; in the third step, the vacuum freeze-drying temperature is-40 ℃, the carbonization treatment temperature is 720 ℃, a planetary ball mill is adopted for treatment during ball milling, the revolution rotation speed is 500r/min, the rotation speed is 1000r/min, and the activation temperature is 620 ℃; in the fifth step, the ultrasonic frequency is 1.8MHz, the ultrasonic power is 400W, and the stirring rotating speed is 1800r/min; in the seventh step, the hot press sets the hot pressing temperature to 250℃and a pressure of 95kg/cm 2 The pressing time is 19h.
Example 5:
unlike example 3, in step two, the weight ratio of titanium dioxide to dispersion was 1:6, the dispersion was formulated with ethanol and water in a volume ratio of 1:1, and then ph=9.0 was adjusted, the water bath temperature was 80 ℃, the ultrasonic frequency was 1.4MHz, and the ultrasonic power was 350W; in the third step, the vacuum freeze-drying temperature is-45 ℃, the carbonization treatment temperature is 700 ℃, a planetary ball mill is adopted for treatment during ball milling, the revolution rotation speed is 450r/min, the rotation speed is 900r/min, and the activation temperature is 600 ℃; in the fifth step, the ultrasonic frequency is 1.7MHz, the ultrasonic power is 350W, and the stirring rotating speed is 1500r/min; in the seventh step, the hot press sets the hot pressing temperature to 240 ℃ and the pressure to 90kg/cm 2 The pressing time is 18h.
Comparative example 1:
unlike example 3, the following is: the impregnating compound comprises the following components in percentage by weight: 9.9% of isocyanate, 0.15% of dibutyltin dilaurate, 25% of epoxy resin, 1.5% of amine curing agent, 13.1% of modified filler and the balance of polybutadiene; the modified filler comprises the following raw materials in percentage by weight: 1.0% of silane coupling agent KH-570, 8% of chitosan, 27% of sodium lignin sulfonate and the balance of potassium hydroxide.
Comparative example 2:
unlike example 3, the following is: the impregnating compound comprises the following components in percentage by weight: 9.9% of isocyanate, 0.15% of dibutyltin dilaurate, 25% of epoxy resin, 1.5% of amine curing agent, 13.1% of modified filler and the balance of polybutadiene; the modified filler comprises the following raw materials in percentage by weight: 29.1% of titanium dioxide, 8% of chitosan, 27% of sodium lignin sulfonate and the balance of potassium hydroxide.
Comparative example 3:
unlike example 3, the following is: the impregnating compound comprises the following components in percentage by weight: 9.9% of isocyanate, 0.15% of dibutyltin dilaurate, 25% of epoxy resin, 1.5% of amine curing agent, 13.1% of modified filler and the balance of polybutadiene; the modified filler comprises the following raw materials in percentage by weight: 29.1% of titanium dioxide, 1.0% of silane coupling agent KH-570, 27% of sodium lignin sulfonate and the balance of potassium hydroxide.
Comparative example 4:
unlike example 3, the following is: the impregnating compound comprises the following components in percentage by weight: 9.9% of isocyanate, 0.15% of dibutyltin dilaurate, 25% of epoxy resin, 1.5% of amine curing agent, 13.1% of modified filler and the balance of polybutadiene; the modified filler comprises the following raw materials in percentage by weight: 29.1% of titanium dioxide, 1.0% of silane coupling agent KH-570, 8% of chitosan and the balance of potassium hydroxide.
Comparative example 5:
unlike example 5, the following is: without the operation in step two, titanium dioxide, silane coupling agent KH-570 and mixture d were blended.
Comparative example 6:
unlike example 5, the following is: and (3) directly blending chitosan, sodium lignin sulfonate, potassium hydroxide and modified titanium dioxide without operation in the step (III) to obtain the modified filler.
The following steps: isocyanate purchase is from Nantong Runfeng petrochemical Co., ltd., product number: r052; dibutyl tin dilaurate was purchased from sigma aldrich (Shanghai) trade company, cat No.: 29234; epoxy resin E51 purchased from Jinan Zesheng chemical company, inc.; ethylenediamine procurement from Shaanxi's Yuan Shen Biotechnology Co., ltd., quality standard: national standard, grade: a top grade product; polybutadiene was purchased from the hydroxyl-terminated polybutadiene 69102-90-5 purity 99% of the company Wuhan Hua Xiangke Jietection Biotechnology Co., ltd; titanium dioxide is purchased from ataxia nan of chemical industry limited company, titanium dioxide R818 rutile type titanium dioxide; silane coupling agent KH-570 was purchased from Wuhan Kano technology Co., ltd., product number: 8598479; chitosan was purchased from sigma aldrich (Shanghai) trade company, cat No.: c3646; sodium lignin sulfonate was purchased from sigma aldrich (Shanghai) trade limited company, cat No.: 471038; potassium hydroxide was purchased from sigma aldrich (Shanghai) trade company, cat No.: p5958.
The hydrocarbon resin-based copper-clad plate in the comparative example and the embodiment of the invention is subjected to detection treatment, and the humidity resistance and heat aging resistance performance are tested: the hydrocarbon resin-based copper-clad plate in the comparative example and the example is taken out after being kept stand in a humid heat aging box with the temperature of 70 ℃ and the humidity of 95% for 200 hours, the peeling strength, the dielectric constant and the dielectric loss of the copper-clad plate before and after humid heat aging are tested according to GB4722-2017 pairs, and the change rate of the peeling strength, the dielectric constant and the dielectric loss is calculated; the peeling strength before wet heat aging is A1, the dielectric constant before wet heat aging is A2, the dielectric loss A3 before wet heat aging, the peeling strength after wet heat aging is B1, the dielectric constant after wet heat aging is B2, and the dielectric loss B3 after wet heat aging; the change rate of the peel strength is C1, the change rate of the dielectric constant is C2, and the change rate of the dielectric loss is C3; c1 = (B1)/(A1) ×100%; c2 = (B2)/(A2) ×100%; c3 = (B3)/(A3) ×100%; the test results are shown in Table one:
table one:
rate of change in peel strength (%) Dielectric constant change Rate (%) Dielectric loss change Rate (%)
Comparative example 1 71.15 81.23 156.86
Comparative example2 75.46 85.56 143.56
Comparative example 3 76.38 86.35 136.45
Comparative example 4 79.56 89.46 131.38
Comparative example 5 82.61 92.65 137.45
Comparative example 6 74.75 84.56 141.23
Example 1 97.57 98.68 105.68
Example 2 97.45 98.65 105.26
Example 3 97.76 98.85 104.84
Example 4 97.98 98.91 104.71
Example 5 98.24 98.98 103.58
From the above table, it can be seen that: the hydrocarbon resin-based copper-clad plate has better wet heat aging resistance, can effectively ensure the stability of dielectric constant and dielectric loss of the copper-clad plate after being subjected to wet heat aging treatment, and avoids circuit board damage caused by rapid change of the copper-clad plate performance.
According to the invention, polybutadiene and isocyanate in the hydrocarbon resin-based copper-clad plate are subjected to reaction compounding under the catalysis of dibutyl tin dilaurate to form a polybutadiene polyurethane material, then epoxy resin is added to carry out supplementary adjustment on the polybutadiene polyurethane material, and a polyurethane chain segment and the epoxy resin form an interpenetrating network, so that a bicontinuous phase structure is gradually formed, the thermal stability of the impregnating material can be effectively improved, and the thermal stability of the copper-clad plate is further improved; the amine curing agent provides curing performance for the epoxy resin, so that the fixation treatment of the epoxy resin can be effectively ensured; the titanium dioxide in the modified filler can effectively strengthen the dielectric constant of the copper-clad plate, and simultaneously can effectively strengthen the heat resistance of the copper-clad plate, the silane coupling agent KH-570 can carry out surface modification treatment on the titanium dioxide, and carry out surface grafting treatment on the titanium dioxide, so that the distribution uniformity of the modified titanium dioxide in an impregnating material can be effectively strengthened, the dispersion uniformity of the titanium dioxide in the copper-clad plate is further strengthened, and the heat resistance of the copper-clad plate, the stability of the dielectric constant and the dielectric loss are further strengthened; the chitosan and sodium lignin sulfonate in the modified filler are respectively used as a nitrogen source and a sulfur source, a carbon precursor is prepared through freeze drying, then a porous carbon material doped with nitrogen and sulfur is prepared through potassium hydroxide activation after carbonization treatment at 700 ℃, and the porous carbon material is added into an impregnating compound, so that the dielectric property of the copper-clad plate can be effectively enhanced, the stability of dielectric constant and dielectric loss is ensured, and the circuit board damage caused by rapid change of the performance of the copper-clad plate is avoided; in the second step, adding titanium dioxide into the dispersion liquid, carrying out water bath ultrasonic treatment, then adding a silane coupling agent KH-570, continuing ultrasonic treatment, carrying out suction filtration and drying to obtain modified titanium dioxide, and effectively ensuring the dispersion uniformity of the titanium dioxide in the impregnating compound; in the third step, chitosan and sodium lignin sulfonate are subjected to compound proportioning, freeze drying is carried out to prepare a carbon precursor, and then a layered porous carbon structure with the size of tens of micrometers to tens of micrometers stacked with each other is prepared through simple carbonization and activation; in the fourth step, the modified titanium dioxide and the mixture d are blended to obtain modified filler; in the fifth step, modified filler and polybutadiene are blended, and isocyanate, dibutyl tin dilaurate, epoxy resin and amine curing agent are added for high-speed stirring, so as to prepare impregnating compound; in the sixth step, the electronic glass fiber cloth is subjected to dipping treatment, solidification and cooling treatment, and a hydrocarbon resin-based prepreg is obtained; in the seventh step, the hydrocarbon resin-based prepreg and the copper foil are subjected to hot pressing treatment to obtain the hydrocarbon resin-based copper-clad plate.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A hydrocarbon resin-based copper-clad plate is characterized in that: comprises electronic glass fiber cloth, impregnating material and copper foil; the impregnating compound comprises the following components in percentage by weight: 9.4 to 10.4 percent of isocyanate, 0.12 to 0.18 percent of dibutyl tin dilaurate, 23 to 27 percent of epoxy resin, 1.3 to 1.7 percent of amine curing agent, 12.6 to 13.6 percent of modified filler and the balance of polybutadiene.
2. The hydrocarbon resin based copper clad laminate according to claim 1, wherein: the modified filler comprises the following components in percentage by weight: 28.6 to 29.6 percent of titanium dioxide, 0.9 to 1.1 percent of silane coupling agent KH-570, 7 to 9 percent of chitosan, 25 to 29 percent of sodium lignin sulfonate and the balance of potassium hydroxide.
3. The hydrocarbon resin based copper clad laminate according to claim 2, wherein: the impregnating compound comprises the following components in percentage by weight: 9.4% of isocyanate, 0.12% of dibutyltin dilaurate, 23% of epoxy resin, 1.3% of amine curing agent, 12.6% of modified filler and the balance of polybutadiene; the modified filler comprises the following raw materials in percentage by weight: 28.6% of titanium dioxide, 0.9% of silane coupling agent KH-570, 7% of chitosan, 25% of sodium lignin sulfonate and the balance of potassium hydroxide.
4. The hydrocarbon resin based copper clad laminate according to claim 2, wherein: the impregnating compound comprises the following components in percentage by weight: 10.4% of isocyanate, 0.18% of dibutyltin dilaurate, 27% of epoxy resin, 1.7% of amine curing agent, 13.6% of modified filler and the balance of polybutadiene; the modified filler comprises the following raw materials in percentage by weight: 29.6% of titanium dioxide, 1.1% of silane coupling agent KH-570, 9% of chitosan, 29% of sodium lignin sulfonate and the balance of potassium hydroxide.
5. The hydrocarbon resin based copper clad laminate according to claim 2, wherein: the impregnating compound comprises the following components in percentage by weight: 9.9% of isocyanate, 0.15% of dibutyltin dilaurate, 25% of epoxy resin, 1.5% of amine curing agent, 13.1% of modified filler and the balance of polybutadiene; the modified filler comprises the following raw materials in percentage by weight: 29.1% of titanium dioxide, 1.0% of silane coupling agent KH-570, 8% of chitosan, 27% of sodium lignin sulfonate and the balance of potassium hydroxide.
6. The hydrocarbon resin based copper clad laminate according to claim 2, wherein: the amine curing agent: one of ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine and diethylaminopropylamine.
7. A preparation method of a hydrocarbon resin-based copper-clad plate is characterized by comprising the following steps: the preparation method comprises the following specific steps:
step one: weighing isocyanate, dibutyl tin dilaurate, epoxy resin, amine curing agent, polybutadiene, titanium dioxide in modified filler raw materials, silane coupling agent KH-570, chitosan, sodium lignin sulfonate and potassium hydroxide;
step two: adding titanium dioxide in the first step into the dispersion liquid, performing ultrasonic treatment in a water bath for 12-14 min, then adding a silane coupling agent KH-570, continuing ultrasonic treatment for 30-50 min, standing at room temperature for 15-25 min, and performing suction filtration and drying to obtain modified titanium dioxide;
step three: blending chitosan and sodium lignin sulfonate in the first step, then performing vacuum freeze drying treatment for 3-5 hours to obtain a mixture a, performing carbonization treatment on the mixture a for 1-2 hours to obtain a mixture b, performing blending ball milling treatment on the mixture b and potassium hydroxide in the first step for 20-30 minutes to obtain a mixture c, performing activation treatment on the mixture c for 60-80 minutes, and cooling to obtain a mixture d;
step four: blending the modified titanium dioxide in the second step and the mixture d in the third step to obtain modified filler;
step five: adding the modified filler in the fourth step into the polybutadiene in the first step, carrying out ultrasonic treatment for 30-50 min, adding the isocyanate, the dibutyl tin dilaurate, the epoxy resin and the amine curing agent in the first step, and carrying out high-speed stirring treatment for 50-60 min to obtain an impregnating compound;
step six: dipping the electronic glass fiber cloth in the dipping material prepared in the step five for 30-36 min, solidifying for 5-7 hours at the temperature of 150-158 ℃, and cooling to room temperature after solidification to obtain hydrocarbon resin-based prepreg;
step seven: and symmetrically overlapping the hydrocarbon resin-based prepreg and the copper foil, and then placing the prepreg and the copper foil into a hot press for hot pressing treatment to obtain the hydrocarbon resin-based copper-clad plate.
8. The method for preparing the hydrocarbon resin-based copper-clad plate according to claim 7, which is characterized in that: in the second step, the weight ratio of the titanium dioxide to the dispersion liquid is 1:5-7, the pH value of the dispersion liquid is regulated to be 8.5-9.5 after the dispersion liquid is prepared according to the volume ratio of ethanol to water of 1:1, the water bath temperature is 75-85 ℃, the ultrasonic frequency is 1.3-1.5 MHz, and the ultrasonic power is 300-400W; in the third step, the vacuum freeze-drying temperature is-50 to-40 ℃, the carbonization treatment temperature is 680-720 ℃, a planetary ball mill is adopted for treatment during ball milling, the revolution rotation speed is 400-500 r/min, the rotation speed is 800-1000 r/min, and the activation temperature is 580-620 ℃; in the fifth step, the ultrasonic frequency is 1.6-1.8 MHz, the ultrasonic power is 300-400W, and the stirring rotating speed is 1200-1800 r/min; in the seventh step, the hot press is set to have a hot pressing temperature of 230-250 ℃ and a pressure of 85-95 kg/cm 2 The pressing time is 17-19 h.
9. The method for preparing the hydrocarbon resin-based copper-clad plate according to claim 8, which is characterized in that: in the second step, the weight ratio of the titanium dioxide to the dispersion liquid is 1:5, the pH=8.5 is regulated after the dispersion liquid is prepared according to the volume ratio of ethanol to water of 1:1, the water bath temperature is 75 ℃, the ultrasonic frequency is 1.3MHz, and the ultrasonic power is 300W; in the third step, the vacuum freeze-drying temperature is-50 ℃, the carbonization treatment temperature is 680 ℃, a planetary ball mill is adopted for treatment during ball milling, the revolution rotation speed is 400r/min, the rotation speed is 800r/min, and the activation temperature is 580 ℃; in the fifth step, the ultrasonic frequency is 1.6MHz, the ultrasonic power is 300W, and the stirring speed is 1200r/min; in the seventh step, the hot press sets a hot press temperature of 230℃and a pressure of 85kg/cm 2 The pressing time is 17h.
10. The method for preparing the hydrocarbon resin-based copper-clad plate according to claim 8, which is characterized in that: in the second step, the weight ratio of the titanium dioxide to the dispersion liquid is 1:6, the pH=9.0 is regulated after the dispersion liquid is prepared according to the volume ratio of ethanol to water of 1:1, the water bath temperature is 80 ℃, the ultrasonic frequency is 1.4MHz, and the ultrasonic power is 350W; in the third step, the vacuum freeze-drying temperature is-45 ℃, the carbonization treatment temperature is 700 ℃, a planetary ball mill is adopted for treatment during ball milling, the revolution rotation speed is 450r/min, the rotation speed is 900r/min, and the activation temperature is 600 ℃; in the fifth step, the ultrasonic frequency is 1.7MHz, the ultrasonic power is 350W, and the stirring rotating speed is 1500r/min; in the seventh step, the hot press sets the hot pressing temperature to 240 ℃ and the pressure to 90kg/cm 2 The pressing time is 18h.
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