CN106626615A - Manufacturing method of insulation tabula rasa and insulation tabula rasa - Google Patents
Manufacturing method of insulation tabula rasa and insulation tabula rasa Download PDFInfo
- Publication number
- CN106626615A CN106626615A CN201611185028.2A CN201611185028A CN106626615A CN 106626615 A CN106626615 A CN 106626615A CN 201611185028 A CN201611185028 A CN 201611185028A CN 106626615 A CN106626615 A CN 106626615A
- Authority
- CN
- China
- Prior art keywords
- tabula rasa
- insulation
- spacer
- preparation
- insulation tabula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- B32B15/18—Layered products comprising a layer of metal comprising iron or steel
-
- 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
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- 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
- B32B37/10—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
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
-
- 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
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
-
- 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
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/206—Insulating
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Laminated Bodies (AREA)
Abstract
The invention relates to the field of printed circuit board (PCB), and especially relates to a manufacturing method of an insulation tabula rasa and an insulation tabula rasa. The manufacturing method comprises the following steps: at first, mixing a thermosetting mixture, a powdery filling material, a flame retardant, and a solid initiator, diluting the mixture by a solvent, stirring to evenly mix the mixture so as to uniformly disperse the filling material in the resin to obtain a glue solution, dipping glass fiber cloth into the glue solution, controlling the thickness to reach a preset value, removing the solvent to form an adhesive sheet; pressing one isolation sheet on the upper surface and lower surface of the adhesive sheet, wherein the isolation sheets are rough and incompatible with the adhesive sheet; then pressing a layer of steel plate on both isolation sheets, placing the plate in a pressing machine to carry out pressing and curing, after pressing, curing, and moulding, removing the steel plates, peeling off the isolation sheets, and finally obtaining the insulation tabula rasa, whose upper surface and lower surface both have certain roughness. The upper surface and lower surface of the produced insulation tabula rasa are both rough, so multiple insulation tabula rasa can be pressed together to produce a PCB multilayer plate, and a double-face copper-clad plate erosion technology or a polishing technology is not needed.
Description
Technical field
The present invention relates to printed-board technology field, more particularly to a kind of preparation method and insulation light of insulation tabula rasa
Plate.
Background technology
Printed circuit board (PCB) (Printed Circuit Board, PCB) is almost the basis of any electronic product, occurs in
Almost in each electronic equipment, if it is, in general, that having electronic devices and components in some equipment, then they are also all to be collected
Into on the printed circuit board (PCB) of different sizes.Insulation tabula rasa is the important base material for making printed circuit board (PCB).
The mode of existing production insulation tabula rasa is to separate the material that bonding sheet is combined with steel plate by adding mould release membrance to be used as,
The insulation tabula rasa of so production cannot be used directly for PCB pressing multi-layer sheet, such as directly use, and insulation board interface and PP easily occurs
The problem of layering, current PCB is mainly the following two kinds mode and realizes as used insulation tabula rasa pressing PCB multilayer board：1) purchase
The CCL dual platens of deposited copper are bought, is etched and PCB multilayer board pressing is used further to after two-sided Copper Foil, but the method, waste Copper Foil, production
Cost is also very high；2) mechanical grinding is carried out to the tabula rasa that insulate, after the roughness for increasing insulation plate surface PCB multilayer board pressure is used further to
Close, but the method has following limitation：Nog plate operation is increased, production cost is high；The specification that can be used for nog plate is limited, it is impossible to real
The now application of whole specifications；There is erratic behavior in the physics mode of nog plate, the quality that surface roughness is realized differs, and affects pressing
Local adhesion；Different resins system sheet material, need to be inconvenient using different nog plate parameters, mode of operation.
In sum, this is accomplished by proposing a kind of preparation method of new insulation tabula rasa to overcome the problem with present on.
The content of the invention
It is an object of the invention to provide a kind of preparation method of insulation tabula rasa, overcomes insulation tabula rasa and cannot be used directly for
PCB presses multiple-plate problem.
Another object of the present invention is to provide a kind of insulation tabula rasa being made using the preparation method.
It is that, up to this purpose, the present invention is employed the following technical solutions：
A kind of preparation method of insulation tabula rasa, comprises the steps：
By the mixing of Thermosetting mixtures, powder filler, fire retardant and solid initiator, diluted with solvent, and stir mixing
Uniformly, make that filler is homogeneous to be dispersed in resin, glue is obtained, with glass fabric the glue is impregnated, and control to predetermined
Thickness, then remove solvent formed bonding sheet；
Respectively cover one layer of spacer in the upper and lower surface of bonding sheet, the spacer itself has a roughness, and with it is described
Bonding sheet is incompatible, then one layer of steel plate is covered on every layer of spacer, then puts press pressing solidification into；
After pressing curing molding, steel plate, then spacer of tearing are removed, that is, obtain the insulation that upper and lower surface is respectively provided with roughness
Tabula rasa.
Preferably, the spacer is mixed by non-stick material and the carrier with matsurface.
Preferably, the non-stick material is rosin, silicone oil, mould release or resistant to elevated temperatures and incompatible with FR-4 resins
Macromolecule chemical industry material.
Preferably, the carrier with matsurface is glass cloth, the Copper Foil with roughness or surface irregularity
Carrier in kind.
Preferably, the roughness of the spacer is more than or equal to 6 μm.
Preferably, the upper and lower surface in individual bonding sheet covers spacer, or multiple being molded in heat baking semi-solid preparation are glued
The upper and lower surface of sheeting covers spacer.
One kind insulation tabula rasa, it adopts above-mentioned preparation method to be made.
Beneficial effects of the present invention：
The invention provides the preparation method and insulation tabula rasa of a kind of insulation tabula rasa, it is covered in the upper and lower surface of bonding sheet
Substituting original mould release membrance, first, spacer itself has certain roughness, spacer and bonding sheet pressure to one layer of spacer
After conjunction, bonding sheet surface is set to form certain roughness, without the need for by etching double face copper or additionally increasing technique for grinding, solving
Insulation tabula rasa of having determined cannot directly apply to the problem of PCB multilayer board pressing；Secondly, spacer can play the work of protection bonding sheet
With；Finally, spacer itself is incompatible with bonding sheet, when in use, it is easy to which spacer is torn.
Specific embodiment
Technical scheme is further illustrated below by specific embodiment.
The invention provides a kind of preparation method of insulation tabula rasa, comprises the steps：
Step one：By the mixing of Thermosetting mixtures, powder filler, fire retardant and solid initiator, diluted with solvent, and stirred
Mix and be well mixed, make that filler is homogeneous to be dispersed in resin, glue is obtained, with glass fabric the glue is impregnated, and control
To predetermined thickness, then remove solvent and form bonding sheet；
Step 2：The upper and lower surface of multiple bonding sheets for drying semi-solid preparation in individual bonding sheet upper and lower surface or heat respectively covers one
Layer spacer, spacer has roughness, and incompatible with bonding sheet, then one layer of steel plate is covered on every layer of spacer, then
Put press pressing solidification into；
Step 3：Pressing curing molding after, remove steel plate, then spacer of tearing, that is, obtain upper and lower surface be respectively provided with it is coarse
The insulation tabula rasa of degree.
Wherein, spacer is mixed by non-stick material and the carrier with matsurface, and non-stick material is rosin, silicon
Oil, mould release or resistant to elevated temperatures and incompatible with FR-4 resins macromolecule chemical industry material, the carrier with matsurface is glass
The carrier in kind of cloth, the Copper Foil with roughness or surface irregularity.Spacer itself has roughness, and roughness is big
In equal to 6 μm, after solidifying with bonding sheet pressing, the insulation light plate surface for making curing molding is deformed upon, and generation meets the requirements
Concavo-convex matsurface staggeredly.In insulation tabula rasa using front, spacer can play a part of protection insulation tabula rasa, in insulation tabula rasa
When using, spacer is torn, because of spacer and the incompatible characteristic of insulation tabula rasa, make spacer be highly susceptible to tearing.
In addition, Thermosetting mixtures include a kind of molecular weight be less than 11000 by carbon hydrogen element constitute containing 60% with
The solid allyl resin of the liquid resin of upper vinyl and a kind of low-molecular-weight；Powder filler is powdered quartz, nothing
The silica of sizing, spherical silica, titanium dioxide, strontium titanates, barium titanate, boron nitride, aluminium nitride, carborundum, oxidation
One or more in aluminium, glass fibre, polytetrafluoroethylene (PTFE), polyphenylene sulfide, polyether sulfone, wherein, optimal filler is silica,
Angle value is 1-15 μm in the particle diameter of filler, and angle value is 1-10 μm in the particle diameter of preferred filler, and the filler positioned at the particle diameter section is in tree
There is good dispersiveness in fat liquid；The fire retardant for being adopted is preferred with not reducing dielectric properties, can be brominated or phosphorous resistance
Combustion agent；Curing initiator has cumyl peroxide, peroxide selected from the material that can produce free radical, preferably curing initiator
Change t-butyl perbenzoate, 2,5- bis- (2- ethyihexanoylperoxies) -2,5- dimethylhexanes etc.；Glass fabric plays raising substrate
Dimensional stability, reduce the effect shunk in the curing process of laminate resin, required according to substrate it is different, using different
Glass fabric.
Present invention also offers a kind of insulation tabula rasa, it adopts above-mentioned preparation method to be made, and its upper and lower surface is
Matsurface, may be directly applied to PCB multilayer board pressing, without the need for by etching double face copper or additionally increasing technique for grinding.
Obviously, the above embodiment of the present invention illustrates example of the present invention just for the sake of clear, and is not right
The restriction of embodiments of the present invention.For those of ordinary skill in the field, may be used also on the basis of the above description
To make other changes in different forms.There is no need to be exhaustive to all of embodiment.It is all this
Any modification, equivalent and improvement made within the spirit and principle of invention etc., should be included in the claims in the present invention
Protection domain within.
Claims (7)
1. a kind of preparation method of insulation tabula rasa, comprises the steps：
By the mixing of Thermosetting mixtures, powder filler, fire retardant and solid initiator, diluted with solvent, and be uniformly mixed,
Make that filler is homogeneous to be dispersed in resin, glue is obtained, with glass fabric the glue is impregnated, and control to predetermined thickness
Degree, then removes solvent and forms bonding sheet；
It is characterized in that：
Respectively cover one layer of spacer in the upper and lower surface of bonding sheet, the spacer itself has a roughness, and with the bonding
Piece is incompatible, then one layer of steel plate is covered on every layer of spacer, then puts press pressing solidification into；
After pressing curing molding, steel plate, then spacer of tearing are removed, that is, obtain the insulation light that upper and lower surface is respectively provided with roughness
Plate.
2. it is according to claim 1 insulation tabula rasa preparation method, it is characterised in that the spacer is by non-stick material
It is mixed with the carrier with matsurface.
3. it is according to claim 2 insulation tabula rasa preparation method, it is characterised in that the non-stick material be rosin,
Silicone oil, mould release or resistant to elevated temperatures and incompatible with FR-4 resins macromolecule chemical industry material.
4. the preparation method of insulation tabula rasa according to claim 2, it is characterised in that the carrier with matsurface is
The carrier in kind of glass cloth, the Copper Foil with roughness or surface irregularity.
5. according to claim 1 or 4 insulation tabula rasa preparation method, it is characterised in that the roughness of the spacer
More than or equal to 6 μm.
6. it is according to claim 1 insulation tabula rasa preparation method, it is characterised in that in the upper and lower surface of individual bonding sheet
Spacer is covered, or the upper and lower surface for drying multiple bonding sheets that semi-solid preparation is molded in heat covers spacer.
7. a kind of insulation tabula rasa, it is characterised in that it adopts preparation method as claimed in claim 1 to be made.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611185028.2A CN106626615A (en) | 2016-12-20 | 2016-12-20 | Manufacturing method of insulation tabula rasa and insulation tabula rasa |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611185028.2A CN106626615A (en) | 2016-12-20 | 2016-12-20 | Manufacturing method of insulation tabula rasa and insulation tabula rasa |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106626615A true CN106626615A (en) | 2017-05-10 |
Family
ID=58834793
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611185028.2A Pending CN106626615A (en) | 2016-12-20 | 2016-12-20 | Manufacturing method of insulation tabula rasa and insulation tabula rasa |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106626615A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114179400A (en) * | 2021-12-15 | 2022-03-15 | 苏州市华研富士新材料有限公司 | Production device and process of high-strength high-temperature-resistant glass fiber composite board |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101643565A (en) * | 2009-08-24 | 2010-02-10 | 广东生益科技股份有限公司 | Composite material, high frequency circuit board prepared from same and preparation method thereof |
| CN102014590A (en) * | 2010-12-18 | 2011-04-13 | 广东生益科技股份有限公司 | Production method of multi-layer printed circuit board and multi-layer printed circuit board |
| CN104191794A (en) * | 2014-09-18 | 2014-12-10 | 苏州生益科技有限公司 | Method for manufacturing laminated board |
| CN105657963A (en) * | 2014-11-14 | 2016-06-08 | 三星电机株式会社 | Insulation laminate board for printed circuit board, printed circuit board utilizing insulation laminate board and manufacturing method thereof |
-
2016
- 2016-12-20 CN CN201611185028.2A patent/CN106626615A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101643565A (en) * | 2009-08-24 | 2010-02-10 | 广东生益科技股份有限公司 | Composite material, high frequency circuit board prepared from same and preparation method thereof |
| CN102014590A (en) * | 2010-12-18 | 2011-04-13 | 广东生益科技股份有限公司 | Production method of multi-layer printed circuit board and multi-layer printed circuit board |
| CN104191794A (en) * | 2014-09-18 | 2014-12-10 | 苏州生益科技有限公司 | Method for manufacturing laminated board |
| CN105657963A (en) * | 2014-11-14 | 2016-06-08 | 三星电机株式会社 | Insulation laminate board for printed circuit board, printed circuit board utilizing insulation laminate board and manufacturing method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114179400A (en) * | 2021-12-15 | 2022-03-15 | 苏州市华研富士新材料有限公司 | Production device and process of high-strength high-temperature-resistant glass fiber composite board |
| CN114179400B (en) * | 2021-12-15 | 2024-03-29 | 苏州市华研富士新材料有限公司 | High-strength high-temperature-resistant glass fiber composite board production device and technology |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101585955B (en) | Resin composition, resin-coated copper foil produced by same and copper-clad plate produced by utilizing resin-coated copper foil | |
| CN107964203A (en) | A kind of low dielectric prepreg composition, copper-clad plate and preparation method thereof | |
| CN101583489A (en) | Insulating resin sheet multilayer body, multilayer printed wiring board obtained by laminating the insulating resin sheet multilayer bodies | |
| AU2010345325A1 (en) | Composite material, high-frequency circuit substrate made therefrom and making method thereof | |
| EP1338624A4 (en) | Liquid thermosetting resin composition, printed wiring boards and process for their production | |
| CN106633785B (en) | For the pre-preg material of circuit substrate, laminate, preparation method and include its printed circuit board | |
| JP6981634B2 (en) | A resin composition, a prepreg containing the resin composition, a laminated board containing the resin composition, and a resin-attached metal foil containing the resin composition. | |
| CN105348732A (en) | Circuit substrate and preparation method therefor | |
| CN110982202A (en) | Thermosetting resin composition, prepreg prepared from thermosetting resin composition and copper-clad plate | |
| CN106189083B (en) | A kind of copper-clad plate of glass fabric enhancing | |
| CN106188998A (en) | A kind of PTFE medium substrate high-frequency copper-clad plate | |
| CN106626615A (en) | Manufacturing method of insulation tabula rasa and insulation tabula rasa | |
| JP3011867B2 (en) | Manufacturing method of laminated board | |
| WO2010147083A1 (en) | Prepreg comprising high-dielectric-constant resin composition, and copper-clad laminate sheet | |
| CN111038031A (en) | Method for preparing prepreg, prepreg prepared by method and copper-clad plate | |
| CN105451472B (en) | A kind of processing method and stacked wiring board of stacked wiring board | |
| CN202941039U (en) | Composite substrate high-frequency copper-clad plate | |
| CN103192577A (en) | High-thermal-conductivity copper-clad plate manufacturing method | |
| CN206446210U (en) | A kind of multilager base plate for being used to make insulation tabula rasa | |
| JPS6369106A (en) | Laminate plate for electricity and printed wiring board using the same | |
| CN110467798A (en) | Resin combination, insulating film and the product using the insulating film | |
| JP2011001400A (en) | Resin composition with high dielectric constant, and resin sheet with high dielectric constant and copper foil with resin with high dielectric constant obtained by using the same | |
| JP2004083718A (en) | Resin composition, resin cured product, prepreg, laminate, printed wiring board, and multilayer printed wiring board | |
| CN1224567A (en) | Resin-carrying metal foil for multilayered wiring board, process for mfg. same, multilayered wiring board, and electronic device | |
| JPH02133437A (en) | Production of electrical laminate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information |
Inventor after: Zeng Meiyan Inventor after: Wang Shuijuan Inventor before: Zhuo Xiufen Inventor before: Hu Lanqing |
|
| CB03 | Change of inventor or designer information | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170510 |
|
| RJ01 | Rejection of invention patent application after publication |