CN101240128B - Method for reducing odor in latex paints - Google Patents
Method for reducing odor in latex paints Download PDFInfo
- Publication number
- CN101240128B CN101240128B CN2008100057786A CN200810005778A CN101240128B CN 101240128 B CN101240128 B CN 101240128B CN 2008100057786 A CN2008100057786 A CN 2008100057786A CN 200810005778 A CN200810005778 A CN 200810005778A CN 101240128 B CN101240128 B CN 101240128B
- Authority
- CN
- China
- Prior art keywords
- butyl
- methyl
- ketone
- isothiazoline
- stablizer
- 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.)
- Active
Links
Abstract
A method for reducing odor arising from surfaces coated with latex paints. The method comprises combining in a latex paint: (i) at least one stabilizer; (ii) at least isothiazolone one biocide comprising 2-methyl-4-isothiazolin-3-one or 2-n-octyl-4-isothiazolin-3-one; and (iii) at least one thickener comprising a polyurethane, hydroxyethyl cellulose, carboxymethyl cellulose, an alkali soluble emulsion polymer, a hydrophobically modified alkali soluble emulsion polymer or a hydrophobically modified hydroxyethyl cellulose.
Description
Technical field
The present invention relates to reduce the method for the smell that produces from the surface that has applied rubber-emulsion paint.
Background technology
Under some envrionment conditionss, comprise under the environment of high heat, humidity and ozone, the basic rubber-emulsion paint of preserving with some 3-isothiazolones (isothiazolone) biocide apply with dry after can emit people and not hope the smell that produces.People once used the sanitas of mantoquita as the isothiazolones biocide, to attempt reducing this smell, were that people are undesirable but be to use copper, because this can cause paint painted.
At USP the 6th, 437, disclosed adding 4-hydroxyl-2,2,6 in No. 020,6-tetramethyl piperidine oxygen base (piperidinoxyl) (4-hydroxyl TEMPO) or diethyl hydroxylamine make the polyurethane thickener stabilization that is used for rubber-emulsion paint.But, the nonmetal stablizer that is used for reducing the smell in the rubber-emulsion paint that comprises the 3-isothiazolones is not described.
The problem that the present invention solved has provided the method for the smell that surface that a kind of minimizing is coated with the rubber-emulsion paint that comprises the 3-isothiazolones produces.
Summary of the invention
The present invention relates to be used for reducing the method for the smell that produces from the surface that is coated with rubber-emulsion paint.This method is included in the rubber-emulsion paint and combines: (i) at least a stablizer, and said stablizer comprises: 4-hydroxyl-2,2,6,6-tetramethyl piperidine oxygen base, sterically hindered phenol, bulky amine, unsaturated fatty acids, vitamin PP, sulfo-dicarboxylicacid or N, N-dialkyl group azanol; (ii) at least a isothiazolones biocide, said biocide comprises: 2-methyl-4-isothiazoline-3-ketone or 2-n-octyl-4-isothiazoline-3-ketone; (iii) at least a thickening material, said thickening material comprises: Natvosol, CMC 99.5, alkali-soluble emulsion polymkeric substance, hydrophobic modified alkali-soluble emulsion polymkeric substance or hydrophobic modified Natvosol.
In an embodiment of the invention, this method is included in the rubber-emulsion paint and combines: (i) at least a stablizer, said stablizer comprise sterically hindered phenol, bulky amine, unsaturated fatty acids, vitamin PP or sulfo-dicarboxylicacid; (ii) at least a isothiazolones biocide, said biocide comprises: 2-methyl-4-isothiazoline-3-ketone or 2-n-octyl-4-isothiazoline-3-ketone; (iii) at least a thickening material, said thickening material comprises: urethane, Natvosol, CMC 99.5, alkali-soluble emulsion polymkeric substance, hydrophobic modified alkali-soluble emulsion polymkeric substance or hydrophobic modified Natvosol.
Detailed Description Of The Invention
" MIT " is 2-methyl-4-isothiazoline-3-ketone, also is called as 2-methyl-3-isothiazolones." CMIT " is 5-chloro-2-methyl-4-isothiazoline-3-ketone, also is called as 5-chloro-2-methyl-3-isothiazolones." OIT " is 2-n-octyl-4-isothiazoline-3-ketone, also is called as 2-n-octyl-3-isothiazolones." BIT " is 1, the 2-benzisothiazole-3-ketone." (methyl) acrylic acid or the like " or " (methyl) propenoate " represented acrylic acid or the like or methacrylic and propenoate or methacrylic ester respectively." alkyl " is the saturated hydrocarbyl that comprises with 1-20 carbon atom of straight chain, side chain or annular form.One preferred embodiment in, alkyl is acyclic.One preferred embodiment in, alkyl comprises 1-8 carbon atom, perhaps comprises 1-4 carbon atom.
Abbreviation below using in this article: ppm=1,000,000/parts by weight (w/w), mL=milliliter, AI=active ingredient, the i.e. total amount of isothiazolones.Unless otherwise indicated, the unit of temperature be degree centigrade (℃), described content or percentage ratio are by weight.
Can use the combination of listed stablizer, can use other stablizer, also can not use.Be applicable to that sterically hindered phenol stablizer of the present invention comprises: 2,6 di tert butyl 4 methyl phenol (BHT) for example, 2,6-di-t-butyl-4-methoxyphenol; 2-tertiary butyl-4-hydroxy methyl-phenoxide (BHA), 3,4, the 5-Propylgallate; 2-(1, the 1-dimethyl ethyl)-1, the 4-dihydroxy-benzene; DBH 2,5 di tert butylhydroquinone, the 4-tert-butyl catechol; Tetramethylolmethane, four (3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic esters) (available from Sheba ltd, commodity eggnog grams by name this 1010 (available from Ciba Corp.as IRGANOX 1010)); Octadecyl-3-(3, the 5-di-tert-butyl-hydroxy phenyl)-propionic ester (available from Sheba ltd, commodity eggnog grams by name this 1076 (available from Ciba Corp.as IRGANOX 1076)); And 2 ', 3-two [[3-[3, the 5-tert-butyl-hydroxy phenyl] propionyl group]] propionyl hydrazine (available from Sheba ltd, commodity eggnog gram by name this MD1024 (available from Ciba Corp.as IRGANOX MD 1024)).Be applicable to that bulky amine of the present invention comprises: 4-hydroxyl-2,2,6 for example, the 6-tetramethyl piperidine is carried and is exerted temperature raising 770 (TINUTVIN 770), diphenylpicrylhydrazyl, methylphenylamine, diphenylamine, tetrabenzyl Ursol D; 1,3,5-triazines-2,4; The 6-triamine, N, N
-[1,2-ethane-two base-two [[[4; 6-two-[butyl (1,2,2,6; 6-pentamethyl--4-piperidyl) amino]-1,3,5-triazines-2-yl] imido]-3,1-propane two bases]] two [N '; N "-dibutyl-N ', N "-two (1,2,2; 6,6-pentamethyl--4-piperidyl)-(available from Sheba ltd, commodity are called Qie Masuobai 119FL (available fromCiba Corp.as CHIMASSORB 119FL)); 1,6-hexanediamine, N, N '-two (2,2; 6,6-tetramethyl--4-piperidyl)-polymkeric substance and 2,4,6-three chloro-1; 3, the 5-triazine is with the reaction product of N-butyl-1-butylamine, N-butyl-2; 2,6, (available from Sheba ltd, commodity are called Qie Masuobai 2020 (availablefrom Ciba Corp.as CHIMASSORB 2020) to 6-tetramethyl--4-piperylhydrazine; And gather [[6-[(1,1,3, the 3-tetramethyl butyl) amino]-1; 3,5-triazine-2,4-two bases] [(2,2; 6,6-tetramethyl--4-piperidyl) imino-]-1,6-hexane two bases [(2,2; 6,6-tetramethyl--4-piperidyl) imines]]) (available from Sheba ltd, commodity are called Qie Masuobai 944 (available from Ciba Corp as CHIMASSORB 944)).Preferred especially N, N-dialkyl group azanol is N, the N-diethyl hydroxylamine.
Lipid acid is the no cycloaliphatic carboxylic acid who comprises 8-24 carbon atom; They comprise 12-22 carbon atom usually.For C-C, lipid acid can be saturated or unsaturated.Undersaturated lipid acid can be monounsaturated or polyunsaturated (having 2 or 3 carbon-to-carbon double bonds usually).Preferred pufas or derivatives thereof is used used as stabilizers.Preferred especially pufas comprises: linolenic acid for example, therapic acid, eicosatetraenoic acid, timnodonic acid, clupanodonic acid; Docosahexenoic acid, linolic acid, eicosadienoic acid, arachidonic acid, two dodecadienoic acids; Adrenic acid, DPA, Melissic Acid (mead acid), cud acid (rumenic acid), punicic acid; 18 carbon are along 8, and are anti-10, trienic acid (jacaric acid), eleostearic acid; Catalpic acid, pik nicotinic acid (pucinic acid) is eaten a meter olefin(e) acid (rumelenicacid), therapic acid and Bai Se pentaene acid (bosseopentaenoic acid).Verivate comprises salt, alkyl ester, triglyceride and triglyceride level.Preferred especially verivate is triglyceride and triglyceride level.
The sulfo-dicarboxylicacid for example comprises 3,3 '-thio-2 acid and 3,3 '-thiodiglycolic acid.
Preferably, the total content of stablizer is 10-2000ppm in the said rubber-emulsion paint.In embodiments more of the present invention, the content of said stablizer is not more than 1500ppm, perhaps is not more than 1000ppm, perhaps is not more than 500ppm, perhaps is not more than 250ppm, perhaps is not more than 200ppm, perhaps is not more than 150ppm.In an embodiment of the invention, the content of said stablizer is at least 20ppm, perhaps is at least 50ppm, perhaps is at least 75ppm.Preferably, the content of said stablizer is the 10-100% of MIT and OIT total amount, more preferably 70-100%.
Rubber-emulsion paint can comprise various polymeric binders, comprises for example acrylic polymers and vinyl acetate polymer, for example ethane-acetic acid ethyenyl ester.In an embodiment of the invention, said paint comprises acrylic polymers, and promptly polymkeric substance comprises at least 75%, more preferably the monomer residue of (methyl) vinylformic acid of at least 90% and (methyl) alkyl acrylate.{ PVC is defined as [(volume of inoganic solids)/(volume of the volume+polymeric binder of inoganic solids)] * 100%} and is preferably 15-70%, more preferably 45-70%, more preferably 55-70% the pigment volume concentration (PVC) of said rubber-emulsion paint.
Preferably, the content of thickening material in the paint (the solid thickening material accounts for the weight percentage of paint gross weight) for 0.1-1.2 weight %, perhaps is 0.1-1.1 weight %, perhaps is 0.1-0.9%, perhaps is 0.15-0.6%.Can comprise one or more other thickening material.In an embodiment of the invention, the thickening material that is used for rubber-emulsion paint comprises Natvosol (HEC).In an embodiment of the invention, rubber-emulsion paint comprises the polyurethane thickener less than 5%, perhaps less than 4%, perhaps less than 3%, perhaps less than 2%, perhaps less than 1%, perhaps less than 0.5%.In an embodiment of the invention, said rubber-emulsion paint does not contain polyurethane thickener.
Preferably, the total content of isothiazolones is 10-2000ppm in the said lacquer.In an embodiment of the invention, the content of said isothiazolones biocide is at least 20ppm, perhaps is at least 50ppm, perhaps is at least 75ppm.In an embodiment of the invention, the content of said isothiazolones is not more than 1500ppm, perhaps is not more than 1000ppm, perhaps is not more than 500ppm, perhaps is not more than 250ppm, perhaps is not more than 200ppm, perhaps is not more than 150ppm.In an embodiment of the invention, said rubber-emulsion paint comprises MIT.In an embodiment of the invention, the MIT that is used for rubber-emulsion paint comprises the CMIT less than 2%, perhaps less than 1%, perhaps less than 0.5%, perhaps less than 0.2%, perhaps less than 0.1%.Preferably, the total amount of MIT and OIT is 10-2000ppm in the said lacquer.In an embodiment of the invention, the total amount of MIT and OIT is at least 20ppm, perhaps is at least 50ppm, perhaps is at least 75ppm.In an embodiment of the invention, the total amount of MIT and OIT is not more than 1500ppm, perhaps is not more than 1000ppm, perhaps is not more than 500ppm, perhaps is not more than 250ppm, perhaps is not more than 200ppm, perhaps is not more than 150ppm.
Said stablizer can add with arbitrary form (for example, as emulsion, dispersion-s, dry powder, thickener or liquid) in any time of paint preparation process.Said stablizer, isothiazolones and thickening material can be in rubber-emulsion paint in any order or form combination arbitrarily.In an embodiment of the invention, said thickening material and stablizer add with the solid ingredient (for example pigment) of lacquer, and biocide adds with liquid polymer latex.In another embodiment, said stablizer adds in the biocide, then this mixture is added in the lacquer.In another embodiment, stablizer and biocide add in the liquid polymer latex.
In an embodiment of the invention, said method is included in and combines following component in the rubber-emulsion paint: (i) at least a stablizer, and said stablizer comprises: bulky amine, unsaturated fatty acids, vitamin PP or sulfo-dicarboxylicacid; (ii) at least a isothiazolones biocide, said biocide comprises: 2-methyl-4-isothiazoline-3-ketone or 2-n-octyl-4-isothiazoline-3-ketone; (iii) at least a thickening material, said thickening material comprises: urethane, Natvosol, CMC 99.5, alkali-soluble emulsion polymkeric substance, hydrophobic modified alkali-soluble emulsion polymkeric substance or hydrophobic modified Natvosol.
Embodiment
The enamel-cover that is used as the basis of this research contains 22% acrylic latex, 22% water, 24% titanium oxide, 14% talcum, 7% clay, 9% lime carbonate, and other minor components that comprises 0.25% Natvosol.Add through MIT and to have prepared a series of lacquer in the basic rubber-emulsion paint 1000ppm.This consumption is ten times of conventional amount used, selects to be used for increasing the smell of generation, so that more easily detect and different samples is distinguished.Be about to add stablizer before adding biocide.The PVC of said lacquer is 63.25%.Then under 40 ℃ or 50 ℃, aging 2 week or 3 weeks in the jar that the paint of stabilization is quickened.After thermal ageing, paint was coated on the glass carrier dry 48 hours.Carry out the sense organ (sense of smell) of sulfur-containing aroma and estimate, the result lists in table 1.
The scavenging agent of selecting is used in combination with the MIT (100ppm) of conventional amount used carries out ideal tracking and test.These results list in Table II.
Table I. comprise the sensory evaluation of the paint film of various free-radical scavengerss.
| Contain the variation (scavenging agent content unit is ppm) of free-radical scavengers in the lacquer of MIT of 1000ppm | In jar after thermal ageing, coating and the dry air from the malodorous intensity of paint film |
| No scavenging agent | Medium to strong |
| 3,3 '-thio-2 acid (1560) | A little less than |
| 4-hydroxyl-2,2,6,6-tetramethyl piperidine oxygen base (4-OH TEMPO) (1000) | Do not have |
| 4-hydroxyl-2,2,6,6-tetramethyl piperidine (1000) | Weak to medium |
| N, N-diethyl hydroxylamine (1000) | A little less than |
| Vitamin PP (1000) | A little less than |
| Carry and exert temperature raising 770 1(1000) | Weak to medium |
| 2,6-di-t-butyl-4-methoxyphenol (1000) | Extremely |
| DBH 2,5 di tert butylhydroquinone (1000) | Do not have |
| 2,6 di tert butyl 4 methyl phenol (BHT) (1000) | Extremely |
| This MD 1024 of eggnog gram 2(1000) | Weak to medium |
| Linolic acid (1000) | Do not have |
1. hindered amine light stabilizer comprises the substituted steric hindrance phenol of benzotriazole (available from Sheba ltd)
2. sterically hindered phenol photostabilizer (available from Sheba ltd)
Table II comprises the sensory evaluation of the paint film of various free-radical scavengerss
| Contain the variation (scavenging agent content is 100ppm) of free-radical scavengers in the paint of MIT of 1000ppm | In jar after thermal ageing, coating and the dry air from the malodorous intensity of paint film |
| 1. there is not scavenging agent | Weak to medium |
| 2.4-hydroxyl-2,2,6,6-tetramethyl piperidine oxygen base (4-OH TEMPO) | Do not have |
| 3.2,6-di-t-butyl-4-methoxyphenol | Extremely |
| 4.2, the 5-di-tert-butyl hydroquinone | Do not have |
| 5.2,6-di-tert-butyl-4-methy phenol (BHT) | Extremely |
| 6. linolic acid | Do not have |
Claims (8)
1. method that is used for reducing the smell that produces from the surface that applies rubber-emulsion paint; This method is included in the rubber-emulsion paint and combines: (i) at least a stablizer, and said stablizer comprises: 2,6 di tert butyl 4 methyl phenol, 2; 6-di-t-butyl-4-methoxyphenol, 2-tertiary butyl-4-hydroxy methyl-phenoxide, 2-(1; The 1-dimethyl ethyl)-1,4-dihydroxy-benzene, DBH 2,5 di tert butylhydroquinone or 4-tert-butyl catechol; (ii) at least a isothiazolones biocide, said biocide comprises: 2-methyl-4-isothiazoline-3-ketone or 2-n-octyl-4-isothiazoline-3-ketone; (iii) at least a thickening material; Said thickening material comprises: Natvosol; CMC 99.5, alkali-soluble emulsion polymkeric substance, hydrophobic modified alkali-soluble emulsion polymkeric substance or hydrophobic modified Natvosol; The total content of biocide described in the wherein said lacquer is 10-2000ppm, and the content of said stablizer is the 70-100% of 2-methyl-4-isothiazoline-3-ketone and 2-n-octyl-4-isothiazoline-3-ketone total amount; Said ppm represents 1,000,000/parts by weight.
2. the method for claim 1 is characterized in that, said isothiazolones biocide is 2-methyl-4-isothiazoline-3-ketone, and said thickening material is a Natvosol.
3. method as claimed in claim 2 is characterized in that said rubber-emulsion paint comprises the polyurethane thickener less than 5%.
4. the method for claim 1 is characterized in that, said rubber-emulsion paint comprises the polyurethane thickener less than 5%.
5. method that is used for reducing the smell that produces from the surface that applies rubber-emulsion paint; This method is included in the rubber-emulsion paint and combines: (i) at least a stablizer, and said stablizer comprises: 2,6 di tert butyl 4 methyl phenol, 2; 6-di-t-butyl-4-methoxyphenol, 2-tertiary butyl-4-hydroxy methyl-phenoxide, 2-(1; The 1-dimethyl ethyl)-1,4-dihydroxy-benzene, DBH 2,5 di tert butylhydroquinone or 4-tert-butyl catechol; (ii) at least a isothiazolones biocide, said biocide comprises: 2-methyl-4-isothiazoline-3-ketone or 2-n-octyl-4-isothiazoline-3-ketone; (iii) at least a thickening material; Said thickening material comprises: urethane, Natvosol, CMC 99.5; The alkali-soluble emulsion polymkeric substance; Hydrophobic modified alkali-soluble emulsion polymkeric substance or hydrophobic modified Natvosol, the total content of biocide described in the wherein said lacquer is 10-2000ppm, the content of said stablizer is the 70-100% of 2-methyl-4-isothiazoline-3-ketone and 2-n-octyl-4-isothiazoline-3-ketone total amount; Said ppm represents 1,000,000/parts by weight.
6. method as claimed in claim 3 is characterized in that, said at least a stablizer comprises 2,6 di tert butyl 4 methyl phenol, 2,6-di-t-butyl-4-methoxyphenol or DBH 2,5 di tert butylhydroquinone.
7. method as claimed in claim 5 is characterized in that, said at least a stablizer comprises 2,6 di tert butyl 4 methyl phenol, 2,6-di-t-butyl-4-methoxyphenol or DBH 2,5 di tert butylhydroquinone.
8. method as claimed in claim 7 is characterized in that, said rubber-emulsion paint comprises 2-methyl-4-isothiazoline-3-ketone and Natvosol.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US90059607P | 2007-02-09 | 2007-02-09 | |
| US60/900,596 | 2007-02-09 | ||
| US92030607P | 2007-03-27 | 2007-03-27 | |
| US60/920,306 | 2007-03-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101240128A CN101240128A (en) | 2008-08-13 |
| CN101240128B true CN101240128B (en) | 2012-06-27 |
Family
ID=39931968
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100057786A Active CN101240128B (en) | 2007-02-09 | 2008-02-01 | Method for reducing odor in latex paints |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN101240128B (en) |
| ZA (1) | ZA200801267B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4079028A (en) * | 1975-10-03 | 1978-03-14 | Rohm And Haas Company | Polyurethane thickeners in latex compositions |
| US4102843A (en) * | 1977-01-07 | 1978-07-25 | Rohm And Haas Company | Dispersing paint pigments |
-
2008
- 2008-02-01 CN CN2008100057786A patent/CN101240128B/en active Active
- 2008-02-06 ZA ZA200801267A patent/ZA200801267B/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4079028A (en) * | 1975-10-03 | 1978-03-14 | Rohm And Haas Company | Polyurethane thickeners in latex compositions |
| US4079028B1 (en) * | 1975-10-03 | 1990-08-21 | Rohm & Haas | |
| US4102843A (en) * | 1977-01-07 | 1978-07-25 | Rohm And Haas Company | Dispersing paint pigments |
Also Published As
| Publication number | Publication date |
|---|---|
| ZA200801267B (en) | 2008-12-31 |
| CN101240128A (en) | 2008-08-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7767729B2 (en) | Method for reducing odor in latex paints | |
| JP2008537700A5 (en) | ||
| NO20060310L (en) | Procedure and coating composition to extend the shelf life of agricultural products after harvesting | |
| KR20100115355A (en) | Efficient coalescing agents | |
| ES2508966T3 (en) | Method for improved production of aluminum hydroxide | |
| CN101240128B (en) | Method for reducing odor in latex paints | |
| CN110284141B (en) | Gas phase rust inhibitor and slow-release gas phase rust-inhibiting capsule containing same | |
| JP2018108099A (en) | Composition containing polyunsaturated fatty acid (lc-pufa) having cells and at least 20 carbon atoms | |
| US3375215A (en) | Cellophane coating compositions comprising vinylidene chloride copolymer, candelillawax and stearate salt | |
| JP7105242B2 (en) | Degradable polymer and manufacturing method | |
| US10099455B1 (en) | Multifaceted coating system | |
| JP2014528969A5 (en) | ||
| JPH02251582A (en) | Temporarily protecting coating composition improved in weather resistance | |
| CN103237851A (en) | Waterborne coating compositions that include 2,2,4-trimethyl-3-oxopentanoate esters as reactive coalescents | |
| US20230068687A1 (en) | Process for preparing a solid form of basic amino acid salts of polyunsaturated fatty acids | |
| JPH0341127B2 (en) | ||
| NL1026390C2 (en) | Germ inhibiting agent for potatoes. | |
| ES2625859T3 (en) | Aqueous polymer dispersion containing an organic acid | |
| JP2021105104A (en) | Hot-melt composition | |
| US3074912A (en) | Stabilization of vinyl acetate | |
| JP7341222B2 (en) | Resin compositions and coatings for water-based paints | |
| JPH04224863A (en) | Copolymer composition containing copolymer and one or more lubricant | |
| JP3556070B2 (en) | Vinyl chloride resin composition for food packaging film | |
| JPH10265634A (en) | Vinyl chloride resin composition | |
| JPS6157340B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210507 Address after: Delaware, USA Patentee after: DDP special electronic materials USA No.8 Co.,Ltd. Address before: Pennsylvania, USA Patentee before: Rohm and Haas Co. Effective date of registration: 20210507 Address after: New York State, USA Patentee after: Nutrition and biotechnology USA second LLC Address before: Delaware, USA Patentee before: DDP special electronic materials USA No.8 Co.,Ltd. |