CN110183593A - A kind of hud typed surface sizing strengthening agent and preparation method thereof - Google Patents
A kind of hud typed surface sizing strengthening agent and preparation method thereof Download PDFInfo
- Publication number
- CN110183593A CN110183593A CN201910408945.XA CN201910408945A CN110183593A CN 110183593 A CN110183593 A CN 110183593A CN 201910408945 A CN201910408945 A CN 201910408945A CN 110183593 A CN110183593 A CN 110183593A
- Authority
- CN
- China
- Prior art keywords
- parts
- alkyd resin
- added
- vinyl monomer
- hud typed
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/16—Sizing or water-repelling agents
Abstract
The invention discloses a kind of hud typed surface sizing strengthening agents and preparation method thereof, first in the diethylene glycol dimethyl ether solution of alkyd resin, isocyanates is added, the vinyl monomer containing hydroxyl is added after reaction, then obtain the polymerizable type alkyd resin component containing vinyl segment after reacting；Then polymerizable type alkyd resin component is subjected to distribution polymerization；Organic acid and drier are finally added in system, sufficiently after reaction plus water dispersion obtains hud typed surface sizing strengthening agent.Product of the present invention multicomponent, more active sites self-crosslinked interpenetrating net chemical structure can realize the unification of hydrophobic performance, bond properties and filming performance, solve the problems, such as the industries common technologies such as poor, the hair and powder dropping phenomenon of paper poor water resistance, surface strength, for paper for surface sizing, surface strength, water resistance and folding strength of paper etc. can be greatly improved.
Description
Technical field
The present invention relates to paper surface sizing agent field, especially a kind of hud typed surface sizing strengthening agent and its preparation side
Method.
Background technique
Alkyd resin has superior adhesion strength and film forming, is used for paint field for a long time, but is seldom answered
For paper surface sizing agent.Acrylic resin is used for paper due to its good waterproof performance, weather resistance, mechanical strength for a long time
Open the development and application of Cypres.There is part research to be prepared for the modification of cationic by the method for chemical modification at present
Alkyd/acrylic resin, but there is also lotion solid content is low, cross-linked network is insufficient, and alkyd resin and acrylic resin do not have shape
Lead to problems such as it be easy split-phase at good chemical crosslinking, vinyl monomer will be introduced on alkyd molecule segment, and pass through
The research that step-by-step polymerization obtains core-shell emulsion has not been reported substantially.
Compared with plasm-glue-blending, top sizing it have following advantages: (1) can purify production system, mitigate plain boiled water circulation
Burden, improves the flexibility of sizing and wet end chemistry management, has fabulous runnability, easy to operate；(2) improve ink
Printability guarantees running at high speed for paper machine；(3) Cypres replace plasm-glue-blending, significantly reduce cost.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of hud typed surface sizing strengthening agent, this method prepares nucleocapsid
Type surface sizing strengthening agent can greatly improve the water resistance and physical strength of paper, especially improve the folding strength of paper.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of preparation method of hud typed surface sizing strengthening agent, includes the following steps:
First in the diethylene glycol dimethyl ether solution of alkyd resin, isocyanates is added, is added after reaction and contains hydroxyl
Vinyl monomer, then the polymerizable type alkyd resin component containing vinyl segment is obtained after reacting；
Then polymerizable type alkyd resin component is subjected to distribution polymerization:
Take polymerizable type alkyd resin component and vinyl monomer, self-cross linking monomer and other types containing long side-chain radical
Vinyl monomer prepare core component reaction liquid by free-radical polymerized under the action of initiator；
Take polymerizable type alkyd resin component and anionic monomer, the vinyl monomer containing long side-chain radical, selfing receipts or other documents in duplicate
Body and other kinds of vinyl monomer, which are added after mixing into core component reaction liquid, to carry out free-radical polymerized, obtains nucleocapsid
Component mixing systems；
Organic acid and drier are finally added in system, sufficiently after reaction plus water dispersion obtains hud typed top sizing and increases
Strong agent.
Preferably, alkyd resin diethylene glycol dimethyl ether solution is by alkyd resin and diethylene glycol dimethyl ether by 1:
The mass ratio of (0.3-1), which is uniformly mixed, to be obtained.
Preferably, the polymerizable type alkyd resin component containing vinyl segment is that alkyd resin diethylene glycol dimethyl ether is molten
Liquid is warming up to 50~75 DEG C, and isocyanate-monomer is added, is reacted, and the vinyl monomer that hydroxyl is then added reacts
It arrives；
Wherein, in parts by weight, every 100 parts of alkyd resins, are added 15~30 parts of isocyanate-monomers and 1-3 parts contain
The vinyl monomer of hydroxyl.
Preferably, the isocyanates is one of MDI tripolymer, TDI tripolymer, HDI and IPDI tripolymer or more
The mixture of any proportion of kind；
The hydroxyl vinyl monomer be hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and
One of hydroxy propyl methacrylate or a variety of mixtures arbitrarily matched.
Preferably, in parts by weight, polymerizable type alkyd resin component carries out the specific steps of distribution polymerization are as follows:
1~5 part of vinyl monomer containing long side-chain radical, 3~5 parts of vinyl monomers containing hydroxyl, 0.5-2 parts are contained
There are vinyl monomer, 1-3 parts of epoxy resin, 10~20 parts of other kinds of vinyl monomers and the 1-3 parts of oil-solubles of epoxy group
Initiator mixing, obtains mixed liquid B；
The polymerizable type alkyd resin component of 1/2 mass, 2~10 parts of anionic monomers, 1~3 part are contained into long side-chain radical
Vinyl monomer, 1~3 part of vinyl monomer containing hydroxyl, the 0.5-2 parts of vinyl monomers containing epoxy group, 1-3 parts of rings
Oxygen resin, 0.5-2 parts of organo-silicon coupling agents containing vinyl, 12~25 parts of other kinds of vinyl monomers and 1-3 parts of oil are molten
Property initiator mixing, obtain mixed liquor C；
The polymerizable type alkyd resin component of 1/2 mass is warming up to 120-150 DEG C, then starts that mixed liquid B, drop is added dropwise
Complete subsequent continuous insulation reaction, obtains core component reaction liquid；
Continue to be kept for 120-150 DEG C of system temperature, then starts to be added dropwise mixed liquor C into core component reaction liquid, after dripping off
Continue insulation reaction, obtains nucleocapsid component mixing systems.
Preferably, the vinyl monomer containing long side-chain radical is butyl acrylate, butyl methacrylate, acrylic acid
Own ester, hexyl methacrylate, 2-EHA, 2-Ethylhexyl Methacrylate, n-octyl, methyl-prop
One of olefin(e) acid n-octyl and Isooctyl acrylate monomer or a variety of mixtures arbitrarily matched；
The vinyl monomer containing epoxy group is glycidyl methacrylate or glycidyl acrylate
One or both of the mixture that arbitrarily matches；
The epoxy resin is one of first epoxy resin E20, E44, E51 or a variety of mixtures arbitrarily matched；
The other kinds of vinyl monomer is methyl acrylate, methyl methacrylate, ethyl acrylate, methyl-prop
One of olefin(e) acid ethyl ester, styrene and α-methylstyrene or a variety of mixtures arbitrarily matched；
The anionic monomer is the mixture that one or both of methacrylic acid or acrylic acid arbitrarily match.
Preferably, the oil-soluble initiator is azodiisobutyronitrile, azobisisoheptonitrile, two isobutyric acid diformazan of azo
One of ester, benzoyl peroxide and tert-butyl hydroperoxide or a variety of mixtures arbitrarily matched；
The organo-silicon coupling agent containing vinyl be vinyltrimethoxysilane, vinyltriethoxysilane and
One of vinyl tripropoxy silane or a variety of mixtures arbitrarily matched.
Preferably, in parts by weight, nucleocapsid component mixing systems temperature is down to 80-90 DEG C, 1-3 is added into system
The drier and 3-12 parts of organic base of part, being then dispersed to system effective mass score with 80-90 DEG C of deionized water is 45-
50%, obtain hud typed surface sizing strengthening agent.
Preferably, the organic base is ethylenediamine, triethylamine, dimethylethanolamine, triethanolamine, diethanol amine and second
One of hydramine or a variety of mixtures arbitrarily matched；
The drier is one of cobalt naphthenate, manganese naphthenate, cobalt iso-octoate and manganese iso-octoate or a variety of any
The mixture of proportion.
A kind of hud typed surface sizing strengthening agent, is made by the preparation method.
Compared with prior art, the present invention has following technical effect that
Vinyl modified alkyd is used for multiple cross-linked core-shell emulsion by the present invention, the advantage is that products made thereby for paper
When opening top sizing, alkyd can quickly crosslink reaction by high temperature drying under drier effect；And band on molecule segment
Some epoxy groups can also crosslink in paper drying process with anionic group-COOH reacts；Organosilicon coupling simultaneously
Agent can with the hydroxyl of hydroxyl or polymer molecule segment on paper fibre, carboxyl between polymer molecule, intramolecular and point
Son is reacted with crosslinking between paper fibre.So that polymer can be in intermolecular, intramolecular in paper drying process
And a kind of multiple cross-linked system is formed between molecule and fiber, the adhesive strength between fiber is enhanced, to greatly improve
The water resistance and physical strength of paper.The introducing of vinyl monomer and alkyd resin containing long side-chain radical, can improve polymer
The flexibility of glue film improves its filming performance, to improve the folding strength of paper.Product of the present invention multicomponent, more active sites
Self-crosslinked interpenetrating net chemical structure can realize the unification of hydrophobic performance, bond properties and filming performance, and it is water-fast to solve paper
Property the industries common technology problem such as poor, surface strength is poor, folding strength is poor, hair and powder dropping phenomenon, be used for paper for surface sizing, can be big
Surface strength, water resistance and the folding strength of width raising paper.
Specific embodiment
To keep the features and advantages of the present invention more obvious and easy to understand, the present invention is made With reference to embodiment
Further details of explanation.
A kind of preparation method of hud typed surface sizing strengthening agent of the present invention, comprising the following steps:
1) alkyd resin and diethylene glycol dimethyl ether are uniformly mixed by the mass ratio of 1:0.3-1 and obtain alkyd resin diethyl
Glycol dimethyl ether solution；
2) alkyd resin diethylene glycol dimethyl ether solution (wherein 100 parts of alkyd resin) is warming up to 50~75 DEG C, be added
15~30 parts of isocyanate-monomers react 1-2 hours.Then the vinyl monomer of 1-3 parts of hydroxyls is added in reaction solution again,
The reaction was continued 1 hour obtains component A.
3) vinyl monomer by 1~5 part containing long side-chain radical, 3~5 parts of vinyl monomers containing hydroxyl, 0.5-2 parts
Vinyl monomer, 1-3 part epoxy resin, 10~20 parts of other kinds of vinyl monomers containing epoxy group and 1-3 parts of oil are molten
Property initiator mixing, obtain mixed liquid B.
4) vinyl monomer by 1/2 component A, 2~10 parts of anionic monomers, 1~3 part containing long side-chain radical, 1~3
Part vinyl monomer containing hydroxyl, the 0.5-2 parts of vinyl monomers containing epoxy group, 1-3 parts of epoxy resin, 0.5-2 parts contain
The organo-silicon coupling agent of vinyl, 12~25 parts of other kinds of vinyl monomers and 1-3 parts of oil-soluble initiator mixing, obtain
Mixed liquor C.
5) 1/2 component A is added into three-necked flask, system is warming up to 120-150 DEG C.Then start that mixed liquor is added dropwise
B, about 2-3h are dripped off, and are dripped off subsequent continuation of insurance temperature 1.5-2h, are obtained core component D.
6) continue to be kept for 120-150 DEG C of system temperature, then start to be added dropwise in mixed liquor C to core component D, about 2-3h drop
It is complete, subsequent continuation of insurance temperature 1.5-2h is dripped off, nucleocapsid component mixing systems E is obtained.
7) nucleocapsid component mixing systems temperature is down to 80-90 DEG C, into system plus 1-3 parts drier and 3-12 parts
Organic base, being then dispersed to system effective mass score with 80-90 DEG C of deionized water is 45-50%, obtains hud typed surface
Gluing reinforcing agent.
It is between 150-190 based on oleic acid that the alkyd resin acid value, which is by iodine number, and acid value is in 15-20, Gu be containing value
One of alkyd resin of 97.5%-99.7% or a variety of mixtures arbitrarily matched.
The isocyanates is one of MDI tripolymer, TDI tripolymer, HDI and IPDI tripolymer or a variety of arbitrarily matches
The mixture of ratio.
The hydroxyl vinyl monomer is one of (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate
Or a variety of mixtures arbitrarily matched.
The vinyl monomer containing long side-chain radical is (methyl) butyl acrylate, (methyl) Hexyl 2-propenoate, (first
Base) 2-EHA, (methyl) n-octyl, one of (methyl) Isooctyl acrylate monomer or a variety of arbitrarily match
The mixture of ratio.
The vinyl monomer containing epoxy group is glycidyl methacrylate or glycidyl acrylate
One or both of the mixture that arbitrarily matches.
The epoxy resin is one of first epoxy resin E20, E44, E51 or a variety of mixtures arbitrarily matched.
The other kinds of vinyl monomer is methyl acrylate, methyl methacrylate, ethyl acrylate, methyl-prop
One of olefin(e) acid ethyl ester, styrene, α-methylstyrene or a variety of mixtures arbitrarily matched.
The oil-soluble initiator is azodiisobutyronitrile, azobisisoheptonitrile, azo-bis-iso-dimethyl, peroxidating
Benzoyl, one of tert-butyl hydroperoxide or a variety of mixtures arbitrarily matched.
The anionic monomer is the mixture that one or both of methacrylic acid or acrylic acid arbitrarily match.
The coupling agent containing vinyl organosilicon is vinyltrimethoxysilane, vinyltriethoxysilane, second
One of alkenyl tripropoxy silane or a variety of mixtures arbitrarily matched.
The organic base are as follows: ethylenediamine, triethylamine, dimethylethanolamine, triethanolamine, diethanol amine, in ethanol amine
One or more mixtures arbitrarily matched.
The drier is one of cobalt naphthenate, manganese naphthenate, cobalt iso-octoate, manganese iso-octoate or a variety of arbitrarily matches
The mixture of ratio.
Preparation process of the invention is described in detail below in conjunction with specific embodiment:
Embodiment 1:
1) alkyd resin (oleic acid iodine number 155, acid value 18, mass fraction 98%) and diethylene glycol dimethyl ether are pressed into 1:0.5
Mass ratio be uniformly mixed obtain alkyd resin diethylene glycol dimethyl ether solution；
2) alkyd resin diethylene glycol dimethyl ether solution (wherein 100 parts of alkyd resin) is warming up to 60 DEG C, is added 17.5
Part MDI tripolymer, reacts 1 hour.Then 1.5 parts of hydroxyethyl methacrylates are added in reaction solution again, the reaction was continued 1 hour
Obtain component A.
3) vinyl monomer of 2 parts of isooctyl methacrylate, 3 parts of hydroxy propyl methacrylates, 1 part of acrylic acid are shunk
Glyceride, 1.5 parts of epoxy resin E44,12 parts of styrene and 2 parts of benzoyl peroxide mixing, obtain mixed liquid B.
4) by 1/2 component A, 4 parts of acrylic acid, 2 parts of isooctyl methacrylate, 2 parts of hydroxy propyl methacrylates, 1.5
Part glycidyl acrylate, 2 parts of epoxy resin E44,1.2 parts of vinyl tripropoxy silane, 13 parts of styrene and 2 parts of peroxides
Change benzoyl mixing, obtains mixed liquor C.
5) 1/2 component A is added into three-necked flask, system is warming up to 120 DEG C.Then start that mixed liquid B is added dropwise, about
2h is dripped off, and is dripped off subsequent continuation of insurance temperature 1.5h, is obtained core component D.
6) continue to be kept for 120 DEG C of system temperature, then start to be added dropwise in mixed liquor C to core component D, about 2h is dripped off, and is dripped off
Subsequent continuation of insurance temperature 1.5h, obtains nucleocapsid component mixing systems E.
7) nucleocapsid component mixing systems temperature is down to 80 DEG C, 1 part of cobalt naphthenate and 6 parts of three second is added into system
Amine, being then dispersed to system effective mass score with 80 DEG C of deionized water is 47%, obtains hud typed surface sizing strengthening agent.
Embodiment 2:
1) alkyd resin (oleic acid iodine number 180, acid value 20, mass fraction 99%) and diethylene glycol dimethyl ether are pressed into 1:0.7
Mass ratio be uniformly mixed obtain alkyd resin diethylene glycol dimethyl ether solution；
2) alkyd resin diethylene glycol dimethyl ether solution (wherein 100 parts of alkyd resin) is warming up to 70 DEG C, is added 20 parts
HDI trimer reacts 1.5 hours.Then 3 parts of hydroxypropyl acrylates are added in reaction solution again, the reaction was continued 1 hour obtains group
Divide A.
3) by 4 parts of hexyl methacrylates, 5 parts of hydroxy-ethyl acrylates, 1.6 parts of glycidyl methacrylate, 2 parts of rings
Oxygen resin E51,15 parts of methyl methacrylates and 2 parts of azodiisobutyronitrile mixing, obtain mixed liquid B.
4) by 1/2 component A, 5 parts of methacrylic acids, 3 parts of butyl methacrylates, 3 parts of hydroxy-ethyl acrylates, 1.5 parts
Glycidyl acrylate, 2 parts of epoxy resin E44,2 parts of vinyltrimethoxysilanes, 18 parts of styrene and 3 parts of azos two are different
Butyronitrile mixing, obtains mixed liquor C.
5) 1/2 component A is added into three-necked flask, system is warming up to 130 DEG C.Then start that mixed liquid B is added dropwise, about
2.5h is dripped off, and is dripped off subsequent continuation of insurance temperature 2h, is obtained core component D.
6) continue to be kept for 130 DEG C of system temperature, then start to be added dropwise in mixed liquor C to core component D, about 3h is dripped off, and is dripped off
Subsequent continuation of insurance temperature 2h, obtains nucleocapsid component mixing systems E.
7) nucleocapsid component mixing systems temperature is down to 85 DEG C, 2 parts of manganese naphthenate and 8 parts of second two is added into system
Amine, being then dispersed to system effective mass score with 85 DEG C of deionized water is 50%, obtains hud typed surface sizing strengthening agent.
Embodiment 3:
1) alkyd resin (oleic acid iodine number 190, acid value 15, mass fraction 99.5%) and diethylene glycol dimethyl ether are pressed 1:
0.65 mass ratio is uniformly mixed and obtains alkyd resin diethylene glycol dimethyl ether solution；
2) alkyd resin diethylene glycol dimethyl ether solution (wherein 100 parts of alkyd resin) is warming up to 55 DEG C, is added 25 parts
HDI trimer reacts 2 hours.Then 3 parts of hydroxypropyl acrylates are added in reaction solution again, the reaction was continued 1 hour obtains component
A。
3) by 4 parts of n-octyls, 4 parts of hydroxyethyl methacrylates, 1.25 parts of glycidyl methacrylate,
1.6 parts of epoxy resin E51,15 parts of ethyl methacrylate and 3 parts of azobisisoheptonitrile mixing, obtain mixed liquid B.
4) by 1/2 component A, 5 parts of acrylic acid, 2.8 parts of Isooctyl acrylate monomers, 2 parts of hydroxy propyl methacrylates, 1.6 parts
Glycidyl acrylate, 2.5 parts of epoxy resin (E44:E51=1:1), 1.5 parts of vinyltriethoxysilane, 17 parts other
The vinyl monomer (styrene: methyl methacrylate=2:1) of type and 3 parts of benzoyl peroxide mixing, obtain mixed liquor
C。
5) 1/2 component A is added into three-necked flask, system is warming up to 140 DEG C.Then start that mixed liquid B is added dropwise, about
2.5h is dripped off, and is dripped off subsequent continuation of insurance temperature 1.5h, is obtained core component D.
6) continue to be kept for 140 DEG C of system temperature, then start to be added dropwise in mixed liquor C to core component D, about 3h is dripped off, and is dripped off
Subsequent continuation of insurance temperature 1.5h, obtains nucleocapsid component mixing systems E.
7) nucleocapsid component mixing systems temperature is down to 80 DEG C, 2 parts of cobalt iso-octoate and 7 parts of dimethyl is added into system
Ethanol amine, being then dispersed to system effective mass score with 90 DEG C of deionized water is 48%, obtains hud typed top sizing and increases
Strong agent.
Embodiment 4:
1) alkyd resin (oleic acid iodine number 150, acid value 19, mass fraction 99.5%) and diethylene glycol dimethyl ether are pressed into 1:1
Mass ratio be uniformly mixed obtain alkyd resin diethylene glycol dimethyl ether solution；
2) alkyd resin diethylene glycol dimethyl ether solution (wherein 100 parts of alkyd resin) is warming up to 75 DEG C, is added 22 parts
HDI trimer reacts 1.5 hours.Then again by the vinyl monomer (hydroxy-ethyl acrylate: methacrylic acid of 2.6 parts of hydroxyls
Hydroxypropyl acrylate=1:2) it is added in reaction solution, the reaction was continued 1 hour obtains component A.
3) by 3 parts of isooctyl methacrylate, 3.5 parts of hydroxy propyl methacrylates, 1.6 parts of methyl propenoic acid glycidyls
Ester, 2.5 parts of epoxy resin (E44:E51=2:1), 18.5 parts of styrene and 1-3 parts of benzoyl peroxide mixing, obtain mixed liquor
B。
4) by 1/2 component A, 3 parts of acrylic acid, 3 parts of butyl acrylates, 2.6 parts of hydroxy propyl methacrylates, 1.9 parts of first
Base glycidyl acrylate, 2.5 parts of epoxy resin E20,1.7 parts of vinyltriethoxysilane, 22 parts of methyl methacrylates
Ester and azo-bis-iso-dimethyl mixing, obtain mixed liquor C.
5) 1/2 component A is added into three-necked flask, system is warming up to 130 DEG C.Then start that mixed liquid B is added dropwise, about
3h is dripped off, and is dripped off subsequent continuation of insurance temperature 2h, is obtained core component D.
6) continue to be kept for 130 DEG C of system temperature, then start to be added dropwise in mixed liquor C to core component D, about 3h is dripped off, and is dripped off
Subsequent continuation of insurance temperature 1.8h, obtains nucleocapsid component mixing systems E.
7) nucleocapsid component mixing systems temperature is down to 85 DEG C, into system plus 2 parts cobalt naphthenate and 8 parts of dimethyl second
Hydramine, being then dispersed to system effective mass score with 90 DEG C of deionized water is 45%, obtains hud typed top sizing enhancing
Agent.
Embodiment 5:
1) alkyd resin (oleic acid iodine number 150, acid value 19, mass fraction 99.5%) and diethylene glycol dimethyl ether are pressed 1:
0.9 mass ratio is uniformly mixed and obtains alkyd resin diethylene glycol dimethyl ether solution；
2) alkyd resin diethylene glycol dimethyl ether solution (wherein 100 parts of alkyd resin) is warming up to 65 DEG C, is added 25.5
Part MDI tripolymer, reacts 2 hours.Then 3 parts of hydroxypropyl acrylates are added in reaction solution again, the reaction was continued 1 hour obtains group
Divide A.
3) by 4 parts of butyl acrylates, 4.5 parts of hydroxypropyl acrylates, 1.8 parts of glycidyl methacrylate, 2.5 parts of rings
Oxygen resin E20,20 parts of styrene and 3 parts of azodiisobutyronitrile mixing, obtain mixed liquid B.
4) by 1/2 component A, 8 parts of acrylic acid, 3 parts of butyl acrylates, 3 parts of hydroxyethyl methacrylates, 1.5 parts of propylene
Acid glycidyl ester, 3 parts of epoxy resin E20,2 parts of vinyltriethoxysilane, 17 parts of methyl acrylates and 3 parts of benzoyl peroxides
Formyl mixing, obtains mixed liquor C.
5) 1/2 component A is added into three-necked flask, system is warming up to 150 DEG C.Then start that mixed liquid B is added dropwise, about
3h is dripped off, and is dripped off subsequent continuation of insurance temperature 2h, is obtained core component D.
6) continue to be kept for 150 DEG C of system temperature, then start to be added dropwise in mixed liquor C to core component D, about 3h is dripped off, and is dripped off
Subsequent continuation of insurance temperature 2h, obtains nucleocapsid component mixing systems E.
7) nucleocapsid component mixing systems temperature is down to 90 DEG C, 2 parts of manganese naphthenate and 12 parts of three second is added into system
Amine, being then dispersed to system effective mass score with 90 DEG C of deionized water is 48%, obtains hud typed surface sizing strengthening agent.
Application experiment of the Cypres being prepared under the conditions of different embodiments on paper:
| Embodiment | Tensile strength (kN/m) | Surface strength (m/s) | Degree of sizing (s) | Folding strength (double times) |
| Body paper | 2.2 | 0.3 | 0.0 | 8.0 |
| Embodiment 1 | 3.1 | 2.1 | 40 | 130 |
| Embodiment 2 | 3.8 | 2.7 | 55 | 169 |
| Embodiment 3 | 4.2 | 3.1 | 59 | 176 |
| Embodiment 4 | 3.6 | 2.4 | 36 | 145 |
| Embodiment 5 | 3.2 | 1.9 | 21 | 135 |
Note: experiment paper is cotton fiber paper, Substance 90g/m2, resin added 2.5g/m2.
Embodiment 7:
1) alkyd resin and diethylene glycol dimethyl ether are uniformly mixed by the mass ratio of 1:0.3 and obtain alkyd resin diethyl two
Diethylene glycol dimethyl ether solution；
2) alkyd resin diethylene glycol dimethyl ether solution (wherein 100 parts of alkyd resin) is warming up to 50 DEG C, is added 15 parts
Isocyanate-monomer reacts 1 hour.Then the vinyl monomer of 1 part of hydroxyl is added in reaction solution again, it is 1 small that the reaction was continued
When obtain component A.
3) vinyl monomer by 1 part containing long side-chain radical, 3 parts of vinyl monomers containing hydroxyl, 0.5 part contain epoxy
The vinyl monomer of base, 1 part of epoxy resin, 10 parts of other kinds of vinyl monomers and 1 part of oil-soluble initiator mixing, obtain
Mixed liquid B.
4) vinyl monomer by 1/2 component A, 2 parts of anionic monomers, 1 part containing long side-chain radical, 1 part contain hydroxyl
Vinyl monomer, 0.5 part of vinyl monomer containing epoxy group, 1 part of epoxy resin, 0.5 part of organosilicon containing vinyl it is even
Join agent, 12 parts of other kinds of vinyl monomers and 1 part of oil-soluble initiator mixing, obtains mixed liquor C.
5) 1/2 component A is added into three-necked flask, system is warming up to 120 DEG C.Then start that mixed liquid B is added dropwise, about
2h is dripped off, and is dripped off subsequent continuation of insurance temperature 1.5h, is obtained core component D.
6) continue to be kept for 120 DEG C of system temperature, then start to be added dropwise in mixed liquor C to core component D, about 2-3h is dripped off, drop
Complete subsequent continuation of insurance temperature 1.5h, obtains nucleocapsid component mixing systems E.
7) nucleocapsid component mixing systems temperature is down to 80 DEG C, into system plus 1-3 parts of drier and 3 parts organic
Alkali, being then dispersed to system effective mass score with 80 DEG C of deionized water is 45%, obtains hud typed surface sizing strengthening agent.
Wherein raw material selection is as follows:
Embodiment 8:
1) alkyd resin and diethylene glycol dimethyl ether are uniformly mixed by the mass ratio of 1:1 and obtain alkyd resin diethylene glycol
Dimethyl ether solution；
2) alkyd resin diethylene glycol dimethyl ether solution (wherein 100 parts of alkyd resin) is warming up to 75 DEG C, is added 30 parts
Isocyanate-monomer reacts 2 hours.Then the vinyl monomer of 3 parts of hydroxyls is added in reaction solution again, it is 1 small that the reaction was continued
When obtain component A.
3) vinyl monomer by 5 parts containing long side-chain radical, 5 parts of vinyl monomers containing hydroxyl, 2 parts contain epoxy group
Vinyl monomer, 3 parts of epoxy resin, 20 parts of other kinds of vinyl monomers and the mixing of 3 parts of oil-soluble initiators, mixed
Close liquid B.
4) vinyl monomer by 1/2 component A, 10 parts of anionic monomers, 3 parts containing long side-chain radical, 3 parts contain hydroxyl
Vinyl monomer, 2 parts of vinyl monomers containing epoxy group, 3 parts of epoxy resin, 2 parts of organo-silicon coupling agents containing vinyl,
25 parts of other kinds of vinyl monomers and 3 parts of oil-soluble initiator mixing, obtain mixed liquor C.
5) 1/2 component A is added into three-necked flask, system is warming up to 150 DEG C.Then start that mixed liquid B is added dropwise, about
3h is dripped off, and is dripped off subsequent continuation of insurance temperature 2h, is obtained core component D.
6) continue to be kept for 150 DEG C of system temperature, then start to be added dropwise in mixed liquor C to core component D, about 3h is dripped off, and is dripped off
Subsequent continuation of insurance temperature 2h, obtains nucleocapsid component mixing systems E.
7) nucleocapsid component mixing systems temperature is down to 90 DEG C, 3 parts of drier and 12 parts of organic base is added into system,
Then being dispersed to system effective mass score with 90 DEG C of deionized water is 50%, obtains hud typed surface sizing strengthening agent.
Embodiment 9:
1) alkyd resin and diethylene glycol dimethyl ether are uniformly mixed by the mass ratio of 1:108 and obtain alkyd resin diethyl two
Diethylene glycol dimethyl ether solution；
2) alkyd resin diethylene glycol dimethyl ether solution (wherein 100 parts of alkyd resin) is warming up to 70 DEG C, is added 20 parts
Isocyanate-monomer reacts 1.5 hours.Then the vinyl monomer of 2 parts of hydroxyls is added in reaction solution again, the reaction was continued 1
Hour obtains component A.
3) vinyl monomer by 3 parts containing long side-chain radical, 4 parts of vinyl monomers containing hydroxyl, 1 part contain epoxy group
Vinyl monomer, 1.5 parts of epoxy resin, 10 parts of other kinds of vinyl monomers and the mixing of 2 parts of oil-soluble initiators, obtain
Mixed liquid B.
4) vinyl monomer by 1/2 component A, 8 parts of anionic monomers, 2 parts containing long side-chain radical, 1.2 parts contain hydroxyl
The vinyl monomer of base, 1 part of vinyl monomer containing epoxy group, 1.3 parts of epoxy resin, 1 part of organosilicon containing vinyl are even
Join agent, 16 parts of other kinds of vinyl monomers and 2 parts of oil-soluble initiator mixing, obtains mixed liquor C.
5) 1/2 component A is added into three-necked flask, system is warming up to 130 DEG C.Then start that mixed liquid B is added dropwise, about
2.5h is dripped off, and is dripped off subsequent continuation of insurance temperature 1.8h, is obtained core component D.
6) continue to be kept for 130 DEG C of system temperature, then start to be added dropwise in mixed liquor C to core component D, about 2.0h is dripped off, drop
Complete subsequent continuation of insurance temperature 1.8h, obtains nucleocapsid component mixing systems E.
7) nucleocapsid component mixing systems temperature is down to 88 DEG C, 2 parts of drier and 10 parts of organic base is added into system,
Then being dispersed to system effective mass score with 85 DEG C of deionized water is 46%, obtains hud typed surface sizing strengthening agent.Its
Middle raw material selection is as follows:
In conclusion a kind of preparation method of hud typed surface sizing strengthening agent of the present invention, the first diethyl of alkyd resin
In glycol dimethyl ether solution, isocyanates is added, the vinyl monomer containing hydroxyl is added after reacting a period of time, after reaction
To the polymerizable type alkyd resin containing vinyl segment.Then modified alkyd resin is mixed with other monomers in two steps into
Row polymerization.Step 1: taking modified alkyd resin and vinyl monomer, self-cross linking monomer and other types containing long side-chain radical
Vinyl monomer prepare core component by free-radical polymerized under the action of initiator.Step 2: taking modified alkyd tree
Rouge is mixed with anionic monomer, the vinyl monomer containing long side-chain radical, self-cross linking monomer and other kinds of vinyl monomer
Addition carries out free-radical polymerized into first step reaction solution after uniformly, obtains shell component.Then being added in system a certain amount of has
Machine acid and drier, add water dispersion to obtain a kind of hud typed surface sizing strengthening agent of multi-curing.
Vinyl modified alkyd of the invention is used for multiple cross-linked core-shell emulsion, and products made thereby is used for paper for surface sizing
When, under drier effect cross-linking reaction occurs for alkyd, other reactive groups are also in paper drying process on molecule segment
Reaction is crosslinked, a kind of multiple cross-linked system is formd, highly cross-linked system can be formed in paper surface.Product of the present invention is more
Component, the self-crosslinked interpenetrating net chemical structure of more active sites can realize the unification of hydrophobic performance, bond properties and filming performance,
It solves the problems, such as the industries common technologies such as poor, the hair and powder dropping phenomenon of paper poor water resistance, surface strength, is applied for paper surface
Glue can greatly improve surface strength, water resistance and folding strength of paper etc..
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
A specific embodiment of the invention is only limitted to this, for those of ordinary skill in the art to which the present invention belongs, is not taking off
Under the premise of from present inventive concept, several simple deduction or replace can also be made, the present invention is all shall be regarded as belonging to and is mentioned
The scope of patent protection that claims of friendship determine.
Claims (10)
1. a kind of preparation method of hud typed surface sizing strengthening agent, which comprises the steps of:
First in the diethylene glycol dimethyl ether solution of alkyd resin, isocyanates is added, the ethylene containing hydroxyl is added after reaction
Base monomer, then the polymerizable type alkyd resin component containing vinyl segment is obtained after reacting；
Then polymerizable type alkyd resin component is subjected to distribution polymerization:
Take polymerizable type alkyd resin component and vinyl monomer, self-cross linking monomer and other kinds of second containing long side-chain radical
Alkenyl monomer prepares core component reaction liquid by free-radical polymerized under the action of initiator；
Take polymerizable type alkyd resin component and anionic monomer, the vinyl monomer containing long side-chain radical, self-cross linking monomer and
Other kinds of vinyl monomer, which is added after mixing into core component reaction liquid, to carry out free-radical polymerized, obtains nucleocapsid component
Mixed system；
Organic acid and drier are finally added in system, sufficiently after reaction plus water dispersion obtains hud typed top sizing enhancing
Agent.
2. a kind of preparation method of hud typed surface sizing strengthening agent according to claim 1, it is characterised in that: alkyd tree
Rouge diethylene glycol dimethyl ether solution is by alkyd resin and diethylene glycol dimethyl ether by 1:(0.3-1) mass ratio be uniformly mixed
It arrives.
3. a kind of preparation method of hud typed surface sizing strengthening agent according to claim 1, it is characterised in that: contain second
The polymerizable type alkyd resin component of alkenyl segment is that alkyd resin diethylene glycol dimethyl ether solution is warming up to 50~75 DEG C, is added
Isocyanate-monomer is reacted, and the vinyl monomer that hydroxyl is then added reacts to obtain；
Wherein, in parts by weight, 15~30 parts of isocyanate-monomers and 1-3 parts of hydroxyls are added in every 100 parts of alkyd resins
Vinyl monomer.
4. a kind of preparation method of hud typed surface sizing strengthening agent according to claim 1 or 3, it is characterised in that: institute
Stating isocyanates is one of MDI tripolymer, TDI tripolymer, HDI and IPDI tripolymer or a variety of mixing arbitrarily matched
Object；
The hydroxyl vinyl monomer is hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and methyl
One of hydroxypropyl acrylate or a variety of mixtures arbitrarily matched.
5. a kind of preparation method of hud typed surface sizing strengthening agent according to claim 1, it is characterised in that: according to weight
Number meter is measured, polymerizable type alkyd resin component carries out the specific steps of distribution polymerization are as follows:
1~5 part of vinyl monomer containing long side-chain radical, 3~5 parts of vinyl monomers containing hydroxyl, 0.5-2 parts are contained into ring
The vinyl monomer of oxygroup, 1-3 parts of epoxy resin, 10~20 parts of other kinds of vinyl monomers and 1-3 parts of oil-solubles cause
Agent mixing, obtains mixed liquid B；
By the polymerizable type alkyd resin component of 1/2 mass, 2~10 parts of anionic monomers, 1~3 part of second containing long side-chain radical
Alkenyl monomer, 1~3 part of vinyl monomer containing hydroxyl, the 0.5-2 parts of vinyl monomers containing epoxy group, 1-3 parts of asphalt mixtures modified by epoxy resin
Rouge, 0.5-2 parts of organo-silicon coupling agent, 12~25 parts of other kinds of vinyl monomers and 1-3 parts of oil-solubles containing vinyl draw
Agent mixing is sent out, mixed liquor C is obtained；
The polymerizable type alkyd resin component of 1/2 mass is warming up to 120-150 DEG C, then starts that mixed liquid B is added dropwise, after dripping off
Continue insulation reaction, obtains core component reaction liquid；
Continue to be kept for 120-150 DEG C of system temperature, then starts to be added dropwise mixed liquor C into core component reaction liquid, continue after dripping off
Insulation reaction obtains nucleocapsid component mixing systems.
6. a kind of preparation method of hud typed surface sizing strengthening agent according to claim 1 or 5, it is characterised in that: institute
State the vinyl monomer containing long side-chain radical be butyl acrylate, butyl methacrylate, Hexyl 2-propenoate, methacrylic acid oneself
Ester, 2-EHA, 2-Ethylhexyl Methacrylate, n-octyl, n octyl methacrylate and propylene
One of different monooctyl ester of acid or a variety of mixtures arbitrarily matched；
The vinyl monomer containing epoxy group is in glycidyl methacrylate or glycidyl acrylate
The mixture that one or two arbitrarily match；
The epoxy resin is one of first epoxy resin E20, E44, E51 or a variety of mixtures arbitrarily matched；
The other kinds of vinyl monomer is methyl acrylate, methyl methacrylate, ethyl acrylate, methacrylic acid
One of ethyl ester, styrene and α-methylstyrene or a variety of mixtures arbitrarily matched；
The anionic monomer is the mixture that one or both of methacrylic acid or acrylic acid arbitrarily match.
7. a kind of preparation method of hud typed surface sizing strengthening agent according to claim 6, it is characterised in that: the oil
Soluble initiator is azodiisobutyronitrile, azobisisoheptonitrile, azo-bis-iso-dimethyl, benzoyl peroxide and tert-butyl
One of hydrogen peroxide or a variety of mixtures arbitrarily matched；
The organo-silicon coupling agent containing vinyl is vinyltrimethoxysilane, vinyltriethoxysilane and ethylene
One of base tripropoxy silane or a variety of mixtures arbitrarily matched.
8. a kind of preparation method of hud typed surface sizing strengthening agent according to claim 1, it is characterised in that: according to weight
Measure number meter, nucleocapsid component mixing systems temperature be down to 80-90 DEG C, into system plus 1-3 parts drier and 3-12 parts
Organic base, being then dispersed to system effective mass score with 80-90 DEG C of deionized water is 45-50%, obtains hud typed surface
Gluing reinforcing agent.
9. a kind of preparation method of hud typed surface sizing strengthening agent according to claim 1 or 8, it is characterised in that: institute
The organic base stated is one of ethylenediamine, triethylamine, dimethylethanolamine, triethanolamine, diethanol amine and ethanol amine or more
The mixture of any proportion of kind；
The drier is one of cobalt naphthenate, manganese naphthenate, cobalt iso-octoate and manganese iso-octoate or a variety of any proportions
Mixture.
10. a kind of hud typed surface sizing strengthening agent, it is characterised in that: the preparation method as described in claim 1 to 9 any one
It is made.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910408945.XA CN110183593B (en) | 2019-05-16 | 2019-05-16 | Core-shell type surface sizing reinforcing agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910408945.XA CN110183593B (en) | 2019-05-16 | 2019-05-16 | Core-shell type surface sizing reinforcing agent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110183593A true CN110183593A (en) | 2019-08-30 |
| CN110183593B CN110183593B (en) | 2021-11-23 |
Family
ID=67716527
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910408945.XA Active CN110183593B (en) | 2019-05-16 | 2019-05-16 | Core-shell type surface sizing reinforcing agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110183593B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04119195A (en) * | 1990-09-06 | 1992-04-20 | Arakawa Chem Ind Co Ltd | Transparentizing agent for paper |
| US6783847B1 (en) * | 1999-08-19 | 2004-08-31 | Nippon Paper Industries Co., Ltd. | Offset printing paper |
| CN1957048A (en) * | 2004-05-25 | 2007-05-02 | 阿克佐诺贝尔国际涂料股份有限公司 | Coating composition comprising a vinyl modified alkyd resin |
| CN101880358A (en) * | 2003-08-13 | 2010-11-10 | 威士伯采购公司 | Water-based polyurethane-polyethylene compositions |
| CN102432797A (en) * | 2011-08-18 | 2012-05-02 | 山东圣光化工集团有限公司 | Hydroxyl-terminated alkyd resin-modified waterborne polyurethane and preparation method thereof |
| CN102643416A (en) * | 2012-05-08 | 2012-08-22 | 合众（佛山）化工有限公司 | Isocyanate modified alkyd resin and preparation method thereof |
| CN108623754A (en) * | 2018-05-25 | 2018-10-09 | 浙江恒达新材料股份有限公司 | The preparation method of cationic nucleocapsid fluorinated acrylate -ol acid resin Cypres |
-
2019
- 2019-05-16 CN CN201910408945.XA patent/CN110183593B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04119195A (en) * | 1990-09-06 | 1992-04-20 | Arakawa Chem Ind Co Ltd | Transparentizing agent for paper |
| US6783847B1 (en) * | 1999-08-19 | 2004-08-31 | Nippon Paper Industries Co., Ltd. | Offset printing paper |
| CN101880358A (en) * | 2003-08-13 | 2010-11-10 | 威士伯采购公司 | Water-based polyurethane-polyethylene compositions |
| CN1957048A (en) * | 2004-05-25 | 2007-05-02 | 阿克佐诺贝尔国际涂料股份有限公司 | Coating composition comprising a vinyl modified alkyd resin |
| CN102432797A (en) * | 2011-08-18 | 2012-05-02 | 山东圣光化工集团有限公司 | Hydroxyl-terminated alkyd resin-modified waterborne polyurethane and preparation method thereof |
| CN102643416A (en) * | 2012-05-08 | 2012-08-22 | 合众（佛山）化工有限公司 | Isocyanate modified alkyd resin and preparation method thereof |
| CN108623754A (en) * | 2018-05-25 | 2018-10-09 | 浙江恒达新材料股份有限公司 | The preparation method of cationic nucleocapsid fluorinated acrylate -ol acid resin Cypres |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110183593B (en) | 2021-11-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101914185B (en) | Hydroxy acrylic resin aqueous dispersion and water-based coating prepared therefrom | |
| CN102605648B (en) | Textile water-based pigment printing binding agent and preparation method | |
| CN105273557B (en) | A kind of aqueous woodware paint and preparation method thereof | |
| WO2017020513A1 (en) | Hydroxyl polyacrylate emulsion and preparation method and application thereof | |
| CN106749856B (en) | Silica solution and preparation method thereof, acrylic resin, acrylic acid double-component polyurethane coating | |
| CN106009454A (en) | High-solid low-viscosity hydroxy acrylic resin as well as preparation method and application thereof | |
| CN103360561A (en) | Polyurethane modified acrylic emulsion, preparation method of acrylic emulsion and prepared artificial stone | |
| CN104311716A (en) | Organic silicon modified styrene-acrylate microemulsion reinforcing agent as well as preparation method and application thereof | |
| CN101270225A (en) | Method for preparing binary dispersion composite emulsion of polyurethane acrylic acid | |
| CN105646762A (en) | High-solid-content high-gloss quick-drying water-soluble hydroxy acrylic resin and preparation method thereof | |
| CN105237676A (en) | Water-soluble organosilicon-modified acrylic resin and preparation method thereof | |
| CN109929067A (en) | A kind of core-shell structure acrylic acid ester emulsion and its preparation method and application | |
| CN101967211A (en) | Preparation method of low molecular weight polyacrylic ester acrylic ester for photo-curing | |
| CN110511388A (en) | A kind of modified hydroxyl acrylic emulsion and preparation method thereof for aqueous coatings for tin plate printing | |
| CN107513124A (en) | A kind of polyester acrylic ester aqueous dispersion and preparation method thereof | |
| CN103980791B (en) | Waterborne organic silicon polyurethane-polyacrylate nano hybridization coating that a kind of VOC free is chitin modified and preparation method thereof | |
| CN114044847B (en) | High-water-resistance and dirt-resistance acrylate emulsion and preparation method thereof | |
| CN103232566B (en) | Preparation method of high-solid-content low-viscosity acrylate emulsion for sealing gum | |
| CN101173030B (en) | Method for producing ultra-high solid content hydroxy acrylic resin | |
| CN107236440A (en) | A kind of preparation method of multiple modified high salt spray resistance acrylic acid dispersion | |
| CN102702438B (en) | Quick-drying weather-resistant high-solid-content acrylic resin and preparation method thereof | |
| CN104774287B (en) | Polyacrylate emulsion microgel and preparation method thereof | |
| CN109762095A (en) | Organic-silicon-modified hydroxy acrylate lotion and preparation method thereof | |
| CN110183593A (en) | A kind of hud typed surface sizing strengthening agent and preparation method thereof | |
| CN110003480A (en) | Preparation method with the cationic UV cure resin for cooperateing with water-soluble effect |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |