CN105315930A - Styrene-type thermoplastic elastomer laminating adhesive emulsion and preparation method thereof - Google Patents
Styrene-type thermoplastic elastomer laminating adhesive emulsion and preparation method thereof Download PDFInfo
- Publication number
- CN105315930A CN105315930A CN201410256184.8A CN201410256184A CN105315930A CN 105315930 A CN105315930 A CN 105315930A CN 201410256184 A CN201410256184 A CN 201410256184A CN 105315930 A CN105315930 A CN 105315930A
- Authority
- CN
- China
- Prior art keywords
- thermoplastic elastomer
- emulsion
- analog thermoplastic
- styrene analog
- multiple film
- 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.)
- Granted
Links
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a styrene-type thermoplastic elastomer laminating adhesive emulsion and a preparation method thereof. The laminating adhesive emulsion is a composite emulsion composed of a styrene-type thermoplastic elastomer, tackifying resin, an organic solvent, water, an emulsifier and an emulsion additive agent in a compounding manner. The preparation method includes the steps of mixing and dissolving the styrene-type thermoplastic elastomer, the tackifying resin and the organic solvent, adding the emulsifier and water with shear treatment until a homogeneous emulsion is formed, and adding the emulsion additive agent to the emulsion with uniform stirring to obtain the adhesive emulsion. The preparation method is simple and convenient to use. The styrene-type thermoplastic elastomer laminating adhesive emulsion has good stability and laminating effect, is low in cost and is safe and toxic-free.
Description
Technical field
The present invention relates to multiple film latex solution of a kind of styrene analog thermoplastic elastomer and preparation method thereof, belong to multiple film glue modification field.
Background technology
Insider knows: multiple film glue refers to a kind of glue of BOPP Film laminated on paper, comprises oiliness and aqueous laminating adhesive.Solvent-type film-covered adhesive uses comparatively early, general by styrene analog thermoplastic elastomer as SBS, SIS, tackifying resin and organic solvent type by a certain percentage mixed dissolution are made, have that multiple film is effective, technical maturity, the feature that efficiency is high, its disadvantage be inflammable, explosive, poisonous, infringement workers ' health, contaminate environment, there is disaster hidden-trouble, cost is high.The appearance of aqueous laminating adhesive, successfully overcomes above shortcoming.The aqueous laminating adhesive applied the earliest and popularize is the multiple film glue of VAE class, but its bonding force is not good enough, and resistance to low temperature is poor.Acrylate polymer emulsion and polyaminoester emulsion obtained successful Application in multiple film glue afterwards, improve the force of cohesion of multiple film glue, solve the equilibrium relationship of force of cohesion and initial bonding strength, bonding strength, and overcome the product after compound and carry out embossing, cross cutting, play drum, to the operation problem such as mounting.Many patents are had in aqueous laminating adhesive.As " aqueous laminating adhesive and preparation method thereof ", the patent No.: 200510026475 etc., aqueous laminating adhesive mostly adopts the technology of letex polymerization to produce.
Summary of the invention
The object of the invention is to be to provide a kind of good stability and multiple film is effective, cost is low, the multiple film latex solution of the oil mixing with water type styrene analog thermoplastic elastomer of safety non-toxic.
Another object of the present invention is to provide a kind of technique simply, and the method for the multiple film latex solution of described styrene analog thermoplastic elastomer is prepared in simple operation.
The invention provides the multiple film latex solution of a kind of styrene analog thermoplastic elastomer, the composite gum emulsion that the multiple film latex solution of this styrene analog thermoplastic elastomer is made up of styrene analog thermoplastic elastomer, tackifying resin, organic solvent, water, emulsifying agent and emulsion additive compound; Wherein, mass ratio 1:2 ~ 4:3.5 ~ 4.5:10 ~ 12 of styrene analog thermoplastic elastomer, tackifying resin, organic solvent and water; The quality of emulsifying agent is 0.3 ~ 0.8% of quality; Emulsion additive accounts for 12 ~ 18% of composite gum emulsion total mass.
Present invention also offers the preparation method of the multiple film latex solution of a kind of described styrene analog thermoplastic elastomer, this preparation method is by styrene analog thermoplastic elastomer, tackifying resin and organic solvent mixed dissolution, obtains sizing agent; Add emulsifying agent in described sizing agent after, then add water, shear simultaneously, until form uniform emulsion; In gained emulsion, add emulsion additive, stir, to obtain final product.
The multiple film latex solution of styrene analog thermoplastic elastomer of the present invention and preparation method also comprise following optimal technical scheme:
Described tackifying resin is preferably 3 times of styrene analog thermoplastic elastomer quality.
Described organic solvent is preferably 4 times of styrene analog thermoplastic elastomer quality.
Described water is preferably 11 times of styrene analog thermoplastic elastomer quality; Described water is preferably distilled water or redistilled water.
Described emulsifier is preferably 0.5% of quality.
Described emulsion additive is preferably 15% of quality of the emulsion.
The mass ratio 1:3:3:11 of styrene analog thermoplastic elastomer, tackifying resin, organic solvent and water in the multiple film latex solution of most preferred styrene analog thermoplastic elastomer; The quality of emulsifying agent is 0.5% of quality; Emulsion additive accounts for 15% of composite gum emulsion total mass.
Described styrene analog thermoplastic elastomer is one or more in SBS, SIS, Hydrogenated SBS, hydrogenation SIS.
Described tackifying resin is terpenes, rosin, C
5petroleum resin, C
9one or more in petroleum resin; Be preferably terpenes, rosin, C
5petroleum resin, C
9any combination of any two or three in petroleum resin; Described tackifying resin is conventional commercial resins.
Described emulsion additive is one or more in benzene emulsion, aqueous polyvinyl acetate emulsion, VAE emulsion; Be preferably VAE emulsion.
Described organic solvent is one or more in 6# solvent oil, 120# solvent oil, toluene, dimethylbenzene, ethyl acetate, methyl acetate, butylacetate, ethyl formate, methylene dichloride, ethylene dichloride; Be preferably the combination of one or more the 3 ~ 5:1 in mass ratio in 6# solvent oil and/or 120# solvent oil and toluene, dimethylbenzene, ethyl acetate, methyl acetate, butylacetate, ethyl formate, methylene dichloride, ethylene dichloride; Most preferably be the combination of one or more 4:1 in mass ratio in 6# solvent oil and/or 120# solvent oil and toluene, dimethylbenzene, ethyl acetate, methyl acetate, butylacetate, ethyl formate, methylene dichloride, ethylene dichloride.
Described emulsifying agent is all selected from conventional emulsifying agent, can be that one or more the combination in anionic emulsifier, cationic emulsifier, nonionic emulsifier can; Be preferably cationic emulsifier and nonionic emulsifier to combine 1:0.5 ~ 1.5 in mass ratio, or anionic emulsifier and nonionic emulsifier combine 1:3 ~ 7 in mass ratio.Described cationic emulsifier is preferably conventional doped quaternary ammonium salt class, and described anionic emulsifier is preferably conventional Sulfonates, and described nonionic emulsifying agent is preferably conventional polyethers.
The needs that the solution of the present invention can use according to difference, also can add water-based defoamer, emulsion stabilizer uses, not affect result of use.
When adding water in the preparation method of the multiple film latex solution of described styrene analog thermoplastic elastomer with many after first few, first slow rear fast mode add water.
In the preparation method of the multiple film latex solution of described styrene analog thermoplastic elastomer, velocity of shear is 8000 ~ 12000r/min.
The preparation method of the multiple film latex solution of the preferred styrene analog thermoplastic elastomer of the present invention is: by styrene analog thermoplastic elastomer, tackifying resin and organic solvent mixed dissolution, obtain sizing agent; Add emulsifying agent in described sizing agent after, more slowly add water, shear with 8000 ~ 12000r/min speed simultaneously, and the speed added water slowly is accelerated along with the carrying out of shearing, and strengthens add-on continuously, until form uniform emulsion simultaneously; In gained emulsion, add emulsion additive, stir, to obtain final product.
The present invention has outstanding effect: the present invention first with styrene analog thermoplastic elastomer, tackifying resin and organic solvent for composite adhesive, be dispersed in water by auxiliary agent again, obtain a kind of good stability and multiple film is effective, cost is low, the multiple film latex solution of the oil mixing with water type styrene analog thermoplastic elastomer of safety non-toxic.The further preferred version of the present invention obtains multiple film latex solution emulsion viscosity between 150 ~ 250mPaS, and stability of emulsion is greater than 3 months; Be applied to paper/mould multiple film, there is good initial bonding strength and stripping strength; Adopt bonding to BOPP film of kraft paper, during stripping, kraft paper destroys; Ox-hide is 25 ~ 45N/25mm to stripping strength during ox-hide bonding.
Embodiment
Following examples are intended to further illustrate the present invention, instead of limit the scope of the invention.
Embodiment 1
By following formula, first by styrene analog thermoplastic elastomer, tackifying resin, organic solvent mixing, stirring and dissolving at normal temperatures, make full-bodied solvent-based adhesive, then emulsifying agent is added wherein, deionized water is added under high-shear (rotating speed 10000r/min) mulser, water feeding method is first few rear many, first slow rear fast, styrene analog thermoplastic elastomer sizing agent emulsion can be obtained, after reduction rotating speed, add VAE emulsion, stir certain hour and namely obtain the multiple film latex solution of stable styrene analog thermoplastic elastomer.
Formula: SBS100 part; Terpine resin 150 parts; Rosin 60 parts; C
9petroleum resin 90 parts; 6
#solvent oil 320 parts; Methylene dichloride 80 parts; Deionized water 1100 parts; Cationic emulsifier: octadecyl trimethyl ammonium chloride 2 parts; Nonionic emulsifying agent: NP-103.5 part; VAE emulsion (56% solid content) 15wt%;
The emulsion viscosity of this formula is 220mPaS, and stability of emulsion is greater than 90 days, and when peeling off after multiple film, kraft paper destroys; The bonding stripping strength of ox-hide to ox-hide is 40N/25mm.
Embodiment 2
Preparation method is as embodiment 1
Formula: SBS50 part; SIS50 part; Terpenes 210 parts; C
9petroleum resin 90 parts; 6
#solvent oil 320 parts; Methylene dichloride 80 parts; Deionized water 1100 parts; Anionic emulsifier: Sodium dodecylbenzene sulfonate 1 part; Nonionic emulsifying agent NP-105 part; VAE emulsion (56% solid content) 15wt%;
The emulsion viscosity of this formula is 150mPaS, and stability of emulsion is greater than 90 days, and when peeling off after multiple film, kraft paper destroys.Ox-hide is 36N/25mm to the stripping strength of ox-hide.
Embodiment 3
Preparation method is as embodiment 1
SIS100 part; Terpine resin 200 parts; Rosin 100 parts; 6
#solvent oil 300 parts; Toluene 50 parts; Deionized water 1000 parts; Cationic emulsifier: palmityl trimethyl ammonium chloride 2 parts; Nonionic emulsifying agent OP-102 part; VAE emulsion (56% solid content) 15wt%.
The emulsion viscosity of this formula is 200mPaS, and stability of emulsion is greater than 90 days, and when peeling off after multiple film, kraft paper destroys.The bonding stripping strength of ox-hide to ox-hide is 26N/25mm.
Embodiment 4
Preparation method is as embodiment 1
SBS100 part; C
5petroleum resin 200 parts; Terpenes 150 parts; C
9petroleum resin 50 parts; 120
#solvent oil 340 parts; Methylene dichloride 50 parts; Toluene 50 parts; Deionized water 1200 parts; Anionic emulsifier: Sodium dodecylbenzene sulfonate 1.5 parts; Nonionic emulsifying agent: NP-105 part; VAE emulsion (56% solid content) 16wt%.
The emulsion viscosity of this formula is 210mPaS, and stability of emulsion is greater than 90 days, and when peeling off after multiple film, kraft paper destroys.The bonding stripping strength of ox-hide to ox-hide is 45N/25mm.
Embodiment 5
Preparation method is as embodiment 1
SBS100 part; Rosin 300 parts; C
9petroleum resin 80 parts; 6
#solvent oil 340 parts; Ethyl acetate 40 parts; Toluene 40 parts; Deionized water 1100 parts; Anionic emulsifier: Sodium dodecylbenzene sulfonate 1.5 parts; Nonionic emulsifying agent: OP-104.5 part; VAE emulsion (56% solid content) 15wt%.
The emulsion viscosity of this formula is 160mPaS, and stability of emulsion is greater than 90 days, and when peeling off after multiple film, kraft paper destroys.The bonding stripping strength of ox-hide to ox-hide is 25N/25mm.
Claims (17)
1. the multiple film latex solution of styrene analog thermoplastic elastomer, is characterized in that, the composite gum emulsion be made up of styrene analog thermoplastic elastomer, tackifying resin, organic solvent, water, emulsifying agent and emulsion additive compound; Wherein, mass ratio 1:2 ~ 4:3.5 ~ 4.5:10 ~ 12 of styrene analog thermoplastic elastomer, tackifying resin, organic solvent and water; The quality of emulsifying agent is 0.3 ~ 0.8% of quality; Emulsion additive accounts for 12 ~ 18% of composite gum emulsion total mass.
2. the multiple film latex solution of styrene analog thermoplastic elastomer as claimed in claim 1, it is characterized in that, described tackifying resin is 3 times of styrene analog thermoplastic elastomer quality.
3. the multiple film latex solution of styrene analog thermoplastic elastomer as claimed in claim 1, it is characterized in that, described organic solvent is 4 times of styrene analog thermoplastic elastomer quality.
4. the multiple film latex solution of styrene analog thermoplastic elastomer as claimed in claim 1, it is characterized in that, described water is 11 times of styrene analog thermoplastic elastomer quality.
5. the multiple film latex solution of styrene analog thermoplastic elastomer as claimed in claim 1, it is characterized in that, described emulsifier is 0.5% of quality.
6. the multiple film latex solution of styrene analog thermoplastic elastomer as claimed in claim 1, it is characterized in that, described emulsion additive is 15% of quality of the emulsion.
7. the multiple film latex solution of the styrene analog thermoplastic elastomer as described in any one of claim 1 ~ 6, is characterized in that, the mass ratio 1:3:3:11 of styrene analog thermoplastic elastomer, tackifying resin, organic solvent and water; The quality of emulsifying agent is 0.5% of quality; Emulsion additive accounts for 15% of composite gum emulsion total mass.
8. the multiple film latex solution of styrene analog thermoplastic elastomer as claimed in claim 1, it is characterized in that, described styrene analog thermoplastic elastomer is one or more in SBS, SIS, Hydrogenated SBS, hydrogenation SIS.
9. the multiple film latex solution of styrene analog thermoplastic elastomer as claimed in claim 1, it is characterized in that, described tackifying resin is terpenes, rosin, C
5petroleum resin, C
9one or more in petroleum resin.
10. the multiple film latex solution of styrene analog thermoplastic elastomer as claimed in claim 9, it is characterized in that, described tackifying resin is terpenes, rosin, C
5petroleum resin, C
9any combination of any two or three in petroleum resin.
The multiple film latex solution of 11. styrene analog thermoplastic elastomers as claimed in claim 1, it is characterized in that, described emulsion additive is one or more in benzene emulsion, aqueous polyvinyl acetate emulsion, VAE emulsion.
The multiple film latex solution of 12. styrene analog thermoplastic elastomers as claimed in claim 11, it is characterized in that, described emulsion additive is VAE emulsion.
The multiple film latex solution of 13. styrene analog thermoplastic elastomers as claimed in claim 1, it is characterized in that, described organic solvent is one or more in 6# solvent oil, 120# solvent oil, toluene, dimethylbenzene, ethyl acetate, methyl acetate, butylacetate, ethyl formate, methylene dichloride, ethylene dichloride.
The multiple film latex solution of 14. styrene analog thermoplastic elastomers as claimed in claim 13, it is characterized in that, described organic solvent is the combination of one or more the 3 ~ 5:1 in mass ratio in 6# solvent oil and/or 120# solvent oil and toluene, dimethylbenzene, ethyl acetate, methyl acetate, butylacetate, ethyl formate, methylene dichloride, ethylene dichloride.
The preparation method of 15. 1 kinds of multiple film latex solutions of the styrene analog thermoplastic elastomer as described in any one of claim 1 ~ 6, is characterized in that, by styrene analog thermoplastic elastomer, tackifying resin and organic solvent mixed dissolution, obtain sizing agent; Add emulsifying agent in described sizing agent after, then add water, shear simultaneously, until form uniform emulsion; In gained emulsion, add emulsion additive, stir, to obtain final product.
The preparation method of the multiple film latex solution of 16. styrene analog thermoplastic elastomers as claimed in claim 15, is characterized in that, when adding water with many after first few, first slow rear fast mode add water.
The preparation method of the multiple film latex solution of 17. styrene analog thermoplastic elastomers as claimed in claim 15, it is characterized in that, velocity of shear is 8000 ~ 12000r/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410256184.8A CN105315930B (en) | 2014-06-11 | 2014-06-11 | A kind of styrene analog thermoplastic elastomer laminating adhesive latex solution and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410256184.8A CN105315930B (en) | 2014-06-11 | 2014-06-11 | A kind of styrene analog thermoplastic elastomer laminating adhesive latex solution and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105315930A true CN105315930A (en) | 2016-02-10 |
| CN105315930B CN105315930B (en) | 2018-08-24 |
Family
ID=55244271
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410256184.8A Active CN105315930B (en) | 2014-06-11 | 2014-06-11 | A kind of styrene analog thermoplastic elastomer laminating adhesive latex solution and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105315930B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105623563A (en) * | 2016-03-30 | 2016-06-01 | 光山县博正树脂有限公司 | Environment-friendly film mulching glue and preparation method thereof |
| CN107619647A (en) * | 2017-09-07 | 2018-01-23 | 武汉市华林粘合剂有限公司 | A kind of environment-friendly type aqueous paste box adhesive and preparation method thereof |
| CN108441149A (en) * | 2018-04-17 | 2018-08-24 | 李阳 | A kind of porous breathable coating heat-seal adhesive and preparation method thereof and coating process |
| CN109504323A (en) * | 2018-11-27 | 2019-03-22 | 深圳市顾康力化工有限公司 | Novel aqueous epoxy-modified SBS all-purpose adhesive of one kind and preparation method thereof |
| CN109897579A (en) * | 2019-01-07 | 2019-06-18 | 佛山市东方树新材料科技有限公司 | A kind of SBS aqua type glue spraying and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1102198A (en) * | 1993-10-26 | 1995-05-03 | 郑州市合成化工技术有限公司 | Method for producing adhesion agent capable of adhering polypropylene film to paper printed matter |
| CN1664043A (en) * | 2005-02-25 | 2005-09-07 | 苏州市丛岭胶粘剂有限公司 | Sealing adhesive |
| CN101338175A (en) * | 2008-08-28 | 2009-01-07 | 华南师范大学 | Water-emulsion type paper-plastic composite adhesive and method for preparing same |
-
2014
- 2014-06-11 CN CN201410256184.8A patent/CN105315930B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1102198A (en) * | 1993-10-26 | 1995-05-03 | 郑州市合成化工技术有限公司 | Method for producing adhesion agent capable of adhering polypropylene film to paper printed matter |
| CN1664043A (en) * | 2005-02-25 | 2005-09-07 | 苏州市丛岭胶粘剂有限公司 | Sealing adhesive |
| CN101338175A (en) * | 2008-08-28 | 2009-01-07 | 华南师范大学 | Water-emulsion type paper-plastic composite adhesive and method for preparing same |
Non-Patent Citations (3)
| Title |
|---|
| 周文华等: "水性纸塑复膜胶的研究进展及发展动向", 《粘接》 * |
| 林畅等: "新型SBS水乳型纸塑复膜胶粘剂制备及其稳定性", 《现代化工》 * |
| 靳包平等: "纸塑复合胶粘剂研究进展", 《北京联合大学学报》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105623563A (en) * | 2016-03-30 | 2016-06-01 | 光山县博正树脂有限公司 | Environment-friendly film mulching glue and preparation method thereof |
| CN107619647A (en) * | 2017-09-07 | 2018-01-23 | 武汉市华林粘合剂有限公司 | A kind of environment-friendly type aqueous paste box adhesive and preparation method thereof |
| CN108441149A (en) * | 2018-04-17 | 2018-08-24 | 李阳 | A kind of porous breathable coating heat-seal adhesive and preparation method thereof and coating process |
| CN109504323A (en) * | 2018-11-27 | 2019-03-22 | 深圳市顾康力化工有限公司 | Novel aqueous epoxy-modified SBS all-purpose adhesive of one kind and preparation method thereof |
| CN109897579A (en) * | 2019-01-07 | 2019-06-18 | 佛山市东方树新材料科技有限公司 | A kind of SBS aqua type glue spraying and preparation method thereof |
| CN109897579B (en) * | 2019-01-07 | 2020-11-17 | 佛山市东方树新材料科技有限公司 | SBS water-based spray adhesive and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105315930B (en) | 2018-08-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105315930A (en) | Styrene-type thermoplastic elastomer laminating adhesive emulsion and preparation method thereof | |
| JP4676945B2 (en) | Aqueous adhesive composition, adhesive tape and wire harness | |
| CN103305143B (en) | Double-faced adhesive tape | |
| CN105199638B (en) | A kind of SBS adhesive for polar substrates bonding and preparation method thereof | |
| CN105637055B (en) | Hot-melt adhesive | |
| TW200736359A (en) | Adhesive composition | |
| CN103773293A (en) | Low temperature coated styrene thermoplastic elastomer-based hot-melt pressure-sensitive adhesive | |
| CN106634716B (en) | A kind of Aqueous Adhesives, preparation method and its application | |
| CN103834332A (en) | SBS (styrene-butadiene-styrene)-neoprene graft polymerization composite adhesive and preparation method thereof | |
| CN103484040A (en) | Environment-friendly nail-free glue for construction and preparation method thereof | |
| JP2019508535A5 (en) | ||
| CN105153980A (en) | Salt spray resistant SBS adhesive and preparation method thereof | |
| CN104610888B (en) | A kind of adhesive and the adhesive tape for including it | |
| CN105623556A (en) | Formula of hot melt adhesive for furniture edge sealing | |
| CN103396746B (en) | A kind of high-performance water-based pressure sensitive adhesive and preparation method thereof | |
| US9163165B2 (en) | Primerless removable adhesive systems | |
| CN103045137A (en) | Modified SBS (Styrene Butadiene Styrene) adhesive substance for furniture | |
| JP2011231258A (en) | Adhesive tape for self-adhesion | |
| JP2011084615A (en) | Emulsion self-adhesive and self-adhesive tape using the same | |
| KR102191813B1 (en) | Solvent type adhesive composition improved heat resistance, manufacturing method of the same and adhesive film including the same | |
| CN103865438A (en) | Composite glue solution, preparation method thereof, and composite paper applying the same | |
| CN104194639B (en) | The preparation method of the brilliant nilox resin of resistive connection | |
| CN109233706A (en) | A kind of overlay film cardboard box glue | |
| JPS6147185B2 (en) | ||
| CN102234362A (en) | Styrene-isoprene hyperbranched copolymer and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |