CN105969001A - Oxidation-resistant woodenware coating and preparation method thereof - Google Patents
Oxidation-resistant woodenware coating and preparation method thereof Download PDFInfo
- Publication number
- CN105969001A CN105969001A CN201610113847.XA CN201610113847A CN105969001A CN 105969001 A CN105969001 A CN 105969001A CN 201610113847 A CN201610113847 A CN 201610113847A CN 105969001 A CN105969001 A CN 105969001A
- Authority
- CN
- China
- Prior art keywords
- add
- joined
- minute
- antioxidation
- stirred
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Plant Pathology (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses an oxidation-resistant woodenware coating, which comprises from the following raw materials, by weight part, 0.6-1 of chlorthal-dimethyl, 2-3 of sodium pyrophosphate, 0.1-0.13 of potassium periodate, 1-2 of sodium acetate, 7-10 of chitosan, 24-30 of polyvinyl alcohol, 0.1-0.2 of nanometer alpha-Fe2O3, 1.3-2 of polyglyceryl fatty acid ester, 2-3 of sericin, 5-7 of beeswax, 70-100 of natural latex, 560-600 of an acrylic acid emulsion, 140-160 of titanium dioxide, 1-2 of tris(nonylphenyl) phosphite, 20-30 of urea, 3-5 of an antioxidant DLTP, 1-2 of phthalic anhydride, 2-3 of manganese iso-octoate and 0.8-1 of sodium alkyl benzene sulfonate. Through addition of an oxidation-resistant emulsion, the oxidation-resistant performance of a coating film is effectively improved, the weather resistance is improved, and the protection time to the woodenware is prolonged.
Description
Technical field
The present invention relates to woodwork coating technical field, particularly relate to a kind of antioxidation woodwork coating and preparation method thereof.
Background technology
Acrylic emulsion class woodwork coating in the market there is also following shortcoming: 1. film is the softest, grinability is poor
；2. the coating poor permeability to ground so that the adhesive force between film and the ground after film forming is not enough；3. acrylic emulsion
Poor mainly by physical film deposition, the resistance to water of film and solvent resistance, and the phenomenon of film " hot sticky cold crisp " is serious；4. film
Glossiness is low, and richness is poor.Therefore to improve disadvantages mentioned above, it is modified acrylic emulsion coating just seeming the heaviest
Want.
Summary of the invention
The object of the invention is contemplated to make up the defect of prior art, it is provided that a kind of antioxidation woodwork coating and preparation side thereof
Method.
The present invention is achieved by the following technical solutions:
A kind of antioxidation woodwork coating, it is made up of the raw material of following weight parts:
Chlorine dimethyl phthalate 0.6-1, sodium pyrophosphate 2-3, Potassium metaperiodate. 0.1-0.13, sodium acetate 1-2, chitosan 7-10, poly-second
Enol 24-30, nanosized α-Fe_2O_3 0.1-0.2, polyglyceryl fatty acid ester 1.3-2, sericin 2-3, Cera Flava 5-7, natural emulsion 70-
100, acrylic emulsion 560-600, titanium dioxide 140-160, trisnonyl phenyl phosphite 1-2, carbamide 20-30, antioxidant
DLTP3-5, phthalic anhydride 1-2, manganese iso-octoate 2-3, sodium alkyl benzene sulfonate 0.8-1.
The preparation method of a kind of described antioxidation woodwork coating, comprises the following steps:
(1) sodium pyrophosphate is joined in 20-30 times of water, stir, add Potassium metaperiodate., for buffer；
(2) abovementioned alkyl benzene sulfonic acid sodium salt is joined in 14-16 times of water, stir, add anti-oxidant DLTP, at 80-90 DEG C
Insulated and stirred 2-3 minute, obtains antioxidation emulsion；
(3) being joined by sodium acetate in 20-30 times of water, the hydrochloric acid of dropping 10-15mol/l, regulation PH is 4-5, adds chitosan,
Stirring, drip above-mentioned buffer, be passed through argon after dropping, lucifuge is reacted 46-50 hour, adds mixed system weight
The ethylene glycol of 2-5%, stirs, sucking filtration, lyophilization, obtains oxidation chitosan；
(4) above-mentioned polyglyceryl fatty acid ester is joined in 3-5 times of dehydrated alcohol, stir, add chlorine dimethyl phthalate, stir
Mix uniformly, for mixed ester alcohol liquid；
(5) above-mentioned Cera Flava is joined in 2-3 times of dehydrated alcohol, insulated and stirred 7-10 minute at 80-90 DEG C, add phosphorous acid
Three nonyl phenyl esters, stirring, to room temperature, mixes with above-mentioned mixed ester alcohol liquid, stirs, and adds sericin, 100-200 rev/min of stirring
30-40 minute, add antioxidation emulsion, send in the water-bath of 70-90 DEG C, insulated and stirred 7-9 minute, obtain antioxidation colloidal sol；
(6) nanosized α-Fe_2O_3 is joined in 200-250 times of dehydrated alcohol, ultrasonic disperse 2-3 minute；
(7) above-mentioned polyvinyl alcohol is joined in 3-4 times of water, stir, add the alcohol dispersion liquid of nanosized α-Fe_2O_3, super
Sound 10-15 minute, rises high-temperature and is 85-90 DEG C, add above-mentioned antioxidation colloidal sol, insulated and stirred 90-100 minute, add natural
Latex, 200-300 rev/min is stirred 1-2 hour, obtains modified natural emulsion；
(8) above-mentioned oxidation chitosan is joined in 6-10 times of water, be 9-11 with ammonia regulation PH, mix with modified natural emulsion
Closing, magnetic agitation 20-30 minute, add and remain each raw material, 200-300 rev/min is stirred 2-3 hour, to obtain final product.
The invention have the advantage that
The coating of the present invention has a good solvent resistance:
After adding due to oxidation chitosan, the aldehyde radical in its strand crosslinks with albumen in natural emulsion, this crosslinking points
Existence can increase the rising of the fracture strength of latex film, and the oxidation chitosan Middle molecule chain on the other hand added divides with natural emulsion
The effect such as protein molecular chain generation oxygen key in subchain and latex, intermolecular Van der Waals force strengthens, and shows on material macro property
For the increase of mechanical strength, simultaneously during latex film-forming, hydroaropic substance is assembled to film surface migration, at latex film
Surface forms a kind of grease resistance protecting film, so that the solvent resistance of modified milk glued membrane increases；
The film coated surface of the coating of the present invention has good water-resistance:
In sericin grafted-organosilicon, siloxanes segment is hydrophobic chain segment, and during film forming, these segments are toward film surface
Migrate, assemble, so that modified latex film has hydrophobicity；
The coating of the present invention has a good anti-microbial property:
The nanosized α-Fe_2O_3 that the present invention uses reacts generation OH free radical under the catalysis of visible ray and has the strongest energy of oxidation
Power, can react with most of Organic substances and make it degrade until being converted into CO2 and H2O, have good fungistatic effect；
The coating of the present invention has a good surface resistive:
Occur dehydration anti-between the hydroxyl on the nanosized α-Fe_2O_3 surface that the present invention adds and with the hydroxyl on polyvinyl alcohol molecule
Should, form the crosslinking tangled structure of chemical, form stable Si-O-C covalent bond, destroying this covalent bond needs to provide extra
Power, therefore film coated surface resistance has obtained corresponding lifting；
Present invention adds antioxidation emulsion, can effectively improve the antioxygenic property of film, improve weatherability, postpone wood
The guard time of device.
Detailed description of the invention
A kind of antioxidation woodwork coating, it is made up of the raw material of following weight parts:
Chlorine dimethyl phthalate 0.6, sodium pyrophosphate 2, Potassium metaperiodate. 0.1, sodium acetate 1, chitosan 7, polyvinyl alcohol 24, nanometer α
Fe2O30.1, polyglyceryl fatty acid ester 1.3, sericin 2, Cera Flava 5, natural emulsion 70, acrylic emulsion 560, titanium dioxide 140, Asia
Tricresyl phosphate nonyl phenyl ester 1, carbamide 20, anti-oxidant DLTP 3, phthalic anhydride 1, manganese iso-octoate 2, sodium alkyl benzene sulfonate 0.8.
The preparation method of a kind of described antioxidation woodwork coating, comprises the following steps:
(1) sodium pyrophosphate is joined in 20 times of water, stir, add Potassium metaperiodate., for buffer；
(2) being joined in 14 times of water by abovementioned alkyl benzene sulfonic acid sodium salt, stir, add anti-oxidant DLTP, at 80 DEG C, insulation is stirred
Mix 2 minutes, obtain antioxidation emulsion；
(3) being joined by sodium acetate in 20 times of water, the hydrochloric acid of dropping 10mol/l, regulation PH is 4, adds chitosan, and stirring is all
Even, drip above-mentioned buffer, after dropping, be passed through argon, lucifuge is reacted 46 hours, adds the second two of mixed system weight 2%
Alcohol, stirs, sucking filtration, lyophilization, obtains oxidation chitosan；
(4) above-mentioned polyglyceryl fatty acid ester is joined in 3 times of dehydrated alcohol, stir, add chlorine dimethyl phthalate, stirring
Uniformly, for mixed ester alcohol liquid；
(5) above-mentioned Cera Flava is joined in 2 times of dehydrated alcohol, insulated and stirred 7 minutes at 80 DEG C, add tricresyl phosphite nonyl benzene
Ester, stirring, to room temperature, mixes with above-mentioned mixed ester alcohol liquid, stirs, and adds sericin, and 100 revs/min are stirred 30 minutes, add
Antioxidation emulsion, sends in the water-bath of 70 DEG C, and insulated and stirred 7 minutes obtains antioxidation colloidal sol；
(6) nanometer α Fe2O3 is joined in 200 times of dehydrated alcohol, ultrasonic disperse 2 minutes；
(7) above-mentioned polyvinyl alcohol is joined in 3 times of water, stir, the alcohol dispersion liquid of addition nanometer α Fe2O3, ultrasonic 10
Minute, rising high-temperature is 85 DEG C, adds above-mentioned antioxidation colloidal sol, insulated and stirred 90 minutes, adds natural emulsion, and 200 revs/min are stirred
Mix 1 hour, obtain modified natural emulsion；
(8) above-mentioned oxidation chitosan is joined in 6 times of water, be 9 with ammonia regulation PH, mix with modified natural emulsion, magnetic force
Stirring 20 minutes, add and remain each raw material, 200 revs/min are stirred 2 hours, to obtain final product.
State in a reservoir: stir without lump；
Fineness :≤35 μm；
Bin stability: 50 DEG C/7d, without exception；
Hardness: >=B；
Resistance to water: 24h, without exception；
Alkali resistance: 50g/l sodium bicarbonate, 1h, without exception；
Alcohol resistance: 50% ethanol, 1h, without exception.
Claims (2)
1. an antioxidation woodwork coating, it is characterised in that it is made up of the raw material of following weight parts:
Chlorine dimethyl phthalate 0.6-1, sodium pyrophosphate 2-3, Potassium metaperiodate. 0.1-0.13, sodium acetate 1-2, chitosan 7-10, poly-second
Enol 24-30, nanosized α-Fe_2O_3 0.1-0.2, polyglyceryl fatty acid ester 1.3-2, sericin 2-3, Cera Flava 5-7, natural emulsion 70-
100, acrylic emulsion 560-600, titanium dioxide 140-160, trisnonyl phenyl phosphite 1-2, carbamide 20-30, antioxidant
DLTP3-5, phthalic anhydride 1-2, manganese iso-octoate 2-3, sodium alkyl benzene sulfonate 0.8-1.
2. the preparation method of an antioxidation woodwork coating as claimed in claim 1, it is characterised in that comprise the following steps:
(1) sodium pyrophosphate is joined in 20-30 times of water, stir, add Potassium metaperiodate., for buffer；
(2) abovementioned alkyl benzene sulfonic acid sodium salt is joined in 14-16 times of water, stir, add anti-oxidant DLTP, at 80-90 DEG C
Insulated and stirred 2-3 minute, obtains antioxidation emulsion；
(3) being joined by sodium acetate in 20-30 times of water, the hydrochloric acid of dropping 10-15mol/l, regulation PH is 4-5, adds chitosan,
Stirring, drip above-mentioned buffer, be passed through argon after dropping, lucifuge is reacted 46-50 hour, adds mixed system weight
The ethylene glycol of 2-5%, stirs, sucking filtration, lyophilization, obtains oxidation chitosan；
(4) above-mentioned polyglyceryl fatty acid ester is joined in 3-5 times of dehydrated alcohol, stir, add chlorine dimethyl phthalate, stir
Mix uniformly, for mixed ester alcohol liquid；
(5) above-mentioned Cera Flava is joined in 2-3 times of dehydrated alcohol, insulated and stirred 7-10 minute at 80-90 DEG C, add phosphorous acid
Three nonyl phenyl esters, stirring, to room temperature, mixes with above-mentioned mixed ester alcohol liquid, stirs, and adds sericin, 100-200 rev/min of stirring
30-40 minute, add antioxidation emulsion, send in the water-bath of 70-90 DEG C, insulated and stirred 7-9 minute, obtain antioxidation colloidal sol；
(6) nanosized α-Fe_2O_3 is joined in 200-250 times of dehydrated alcohol, ultrasonic disperse 2-3 minute；
(7) above-mentioned polyvinyl alcohol is joined in 3-4 times of water, stir, add the alcohol dispersion liquid of nanosized α-Fe_2O_3, super
Sound 10-15 minute, rises high-temperature and is 85-90 DEG C, add above-mentioned antioxidation colloidal sol, insulated and stirred 90-100 minute, add natural
Latex, 200-300 rev/min is stirred 1-2 hour, obtains modified natural emulsion；
(8) above-mentioned oxidation chitosan is joined in 6-10 times of water, be 9-11 with ammonia regulation PH, mix with modified natural emulsion
Closing, magnetic agitation 20-30 minute, add and remain each raw material, 200-300 rev/min is stirred 2-3 hour, to obtain final product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610113847.XA CN105969001A (en) | 2016-03-01 | 2016-03-01 | Oxidation-resistant woodenware coating and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610113847.XA CN105969001A (en) | 2016-03-01 | 2016-03-01 | Oxidation-resistant woodenware coating and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105969001A true CN105969001A (en) | 2016-09-28 |
Family
ID=56988542
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610113847.XA Pending CN105969001A (en) | 2016-03-01 | 2016-03-01 | Oxidation-resistant woodenware coating and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105969001A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101148561A (en) * | 2006-09-23 | 2008-03-26 | 拜尔材料科学股份公司 | Polyurethane paint powder |
| CN101245219A (en) * | 2008-02-29 | 2008-08-20 | 浙江天女集团制漆有限公司 | Alkyd paint with low content of VOC and manufacture method thereof |
| CN103694815A (en) * | 2013-12-06 | 2014-04-02 | 华阳新兴科技（天津）集团有限公司 | Scrapable formaldehyde closed film and preparation method thereof |
| CN105176340A (en) * | 2015-09-07 | 2015-12-23 | 王璐 | Furniture antibiosis, mildew prevention and flame retardation coating |
| CN105238182A (en) * | 2015-11-02 | 2016-01-13 | 阜阳市金木工艺品有限公司 | Compact imporous wood coating and preparation method therefor |
-
2016
- 2016-03-01 CN CN201610113847.XA patent/CN105969001A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101148561A (en) * | 2006-09-23 | 2008-03-26 | 拜尔材料科学股份公司 | Polyurethane paint powder |
| CN101245219A (en) * | 2008-02-29 | 2008-08-20 | 浙江天女集团制漆有限公司 | Alkyd paint with low content of VOC and manufacture method thereof |
| CN103694815A (en) * | 2013-12-06 | 2014-04-02 | 华阳新兴科技（天津）集团有限公司 | Scrapable formaldehyde closed film and preparation method thereof |
| CN105176340A (en) * | 2015-09-07 | 2015-12-23 | 王璐 | Furniture antibiosis, mildew prevention and flame retardation coating |
| CN105238182A (en) * | 2015-11-02 | 2016-01-13 | 阜阳市金木工艺品有限公司 | Compact imporous wood coating and preparation method therefor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105238182A (en) | Compact imporous wood coating and preparation method therefor | |
| CN103351675B (en) | A kind of washability exterior coating and preparation method thereof | |
| CN105969000A (en) | Matte woodenware coating and manufacturing method thereof | |
| CN107722870B (en) | Plate production environmentally friendly glutinous rice glue and preparation method thereof | |
| CN103540175A (en) | Colloidal silica waterproof paint | |
| CN102925074A (en) | Solid glue and preparation process thereof | |
| CN105238185A (en) | Anti-stripping wood coating and preparation method therefor | |
| CN104448268B (en) | Modified alkyd resin and preparation method thereof, two component light top coat top coats and preparation method thereof | |
| CN105969001A (en) | Oxidation-resistant woodenware coating and preparation method thereof | |
| CN105969005A (en) | Alpha-Fe2O3 modified woodenware coating and preparation method thereof | |
| CN105968995A (en) | Sericin-modified woodenware coating and manufacturing method thereof | |
| CN105969002A (en) | High-molecular woodenware coating and preparation method thereof | |
| CN105936755A (en) | Moisture-proof latex paint | |
| CN105968999A (en) | Woodenware emulsion coating and manufacturing method thereof | |
| CN105968998A (en) | Woodenware coating and manufacturing method thereof | |
| CN105968993A (en) | Flat woodenware coating and manufacturing method thereof | |
| CN105238187A (en) | Decorative wood coating and preparation method therefor | |
| CN101864235B (en) | Method for preparing exterior wall coating | |
| CN105968994A (en) | Cellulose woodenware coating and manufacturing method thereof | |
| CN105969004A (en) | Modified sericin woodenware coating and preparation method thereof | |
| CN104761740B (en) | The preparation method of hollow silica/polyacrylate laminated film | |
| CN105968997A (en) | Woodenware coating with faint fragrance and manufacturing method of woodenware coating | |
| CN105969003A (en) | Highly-dispersed woodenware coating and preparation method thereof | |
| CN105238186A (en) | Environmental-friendly non-toxic wood coating and preparation method therefor | |
| CN105968996A (en) | Flexible woodenware coating and manufacturing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160928 |
|
| RJ01 | Rejection of invention patent application after publication |