CN108291109A - Coating composition - Google Patents
Coating composition Download PDFInfo
- Publication number
- CN108291109A CN108291109A CN201680055827.XA CN201680055827A CN108291109A CN 108291109 A CN108291109 A CN 108291109A CN 201680055827 A CN201680055827 A CN 201680055827A CN 108291109 A CN108291109 A CN 108291109A
- Authority
- CN
- China
- Prior art keywords
- range
- component
- composition
- purchased
- polymer
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
Abstract
The present invention relates to a kind of compositions, and it includes A) photocurable component；B) photoinitiator；And C) coating containing polymer, wherein component A and component C physical mixeds, or be bonded with the polymer chemistry of component C.The invention further relates to the methods and thus obtained film of a kind of method preparing the composition and a kind of applying said compositions.
Description
Technical field
The present invention relates to a kind of coating composition, preparation method and the usages.Specifically, the present invention relates to inside
With the coating composition of applications, particularly applications.The invention further relates to preparation method and the usages.
Background technology
Coating composition is widely used in the various base materials for for example decorating and/or protecting.In numerous applications, especially
In applications, since applying its that time, film is exposed in the pollution from environment.The pollution include dirt and
Dust, these dirts and dust connect by water droplet in rainwater, air, air-flow or with people, animal or the direct physics of other objects
It touches and takes film coated surface to.In addition, the microorganism on coated wall can also accelerate the accumulation of dust.It is expected that having in the entire of film
During imitating service life, film keeps cleaning and does not have dust, soil or other pollutants.Therefore, it is desirable to by Coating material composition
The film that object is formed has excellent stain resistance (DPUR), stain resistance, resistance to blocking etc..
On the other hand, the base material for being usually applied onto coating may have defect, such as crackle and rough surface, this is wanted
Ask film that there is the bridging capability for covering these defects.In addition, with the passage of base material ageing time, new defect also will produce
And/or existing defect may further develop, if the flexibility of coating is inadequate, this may lead to the film in formation
On crack.Therefore, it is desirable to which coating has excellent flexibility, to avoid causing due to substrate imperfection or base material aging
Film defect.
In general, stain resistance needs coating hard on base material, and in order to avoid the paint film defect on base material, it is expected that film
With excellent flexibility.They are typically the attribute of conflict.
2010105938 A1 of WO, which are described, is introduced into the silica dioxide granule that surface is modified in coating to improve film
Hardness, to obtain improved DPUR.But final coating bridges the crackle of base material without enough flexibilities.
CN1256295A is described balances DPUR and flexible by using the dispersion of multistage emulsion polymer
Method.It is using multistage emulsion polymerization to have hard and soft polymer area on final film.But CN1256295A
To a certain extent DPUR is obtained by cost of flexibility.The final film of CN1256295A has medium DPUR and flexible
Property characteristic, does not protrude both.
US 8993667 describes a kind of redox polymerization for the DPUR improving elastomeric walls coating.In US8993667
In, the glass transition temperature of the polymer of acquisition is low to obtain good flexibility.In US 8993667, DPUR is still very
Difference, this is because bulk polymer is too soft.
JP2007224084A discloses a kind of Photocurable composition for kitchen and the film of gangway-floor.Root
According to JP2007224084A, Photocurable composition includes the phtotpolymerizable of the double bond with two or more free redical polymerizations
Oligomer is closed, the wherein oligomer (a) of photopolymerization should contain the low of the regioselective photopolymerization with limited ratio
The oligomer (a2) of polymers (a1) and photopolymerization.In addition, the volatility that the composition of JP2007224084A contains high-content has
Machine compound, and additional UV lamp is needed to help to cure.Photoinitiator due to high-content and double/polyfunctional monomer agent
Amount, the final membrane rigidity obtained by the composition of JP2007224084A is too strong and cannot provide enough flexibilities.
Therefore, people are still finding for various applications not only with good DPUR but also with good flexible painting
Film, while the coating of film prepares simple and saves cost.
Invention content
The object of the present invention is to provide a kind of compositions, will be formed while having good DPUR and good flexibility
Film.
On the one hand, the present invention relates to a kind of compositions, including：
A. photocurable component；
B. photoinitiator；With
C. the coating containing polymer does not include component A；
Wherein component A and component C physical mixeds, or be bonded with the polymer chemistry of component C to be formed with chemical bond
The component A's of conjunction is polymer-modified.
It is a further object to provide a kind of methods preparing the present composition, including：
Step 1：Form the coating containing polymer；
Step 2：During step 1 or after forming the coating containing polymer, by photocurable component and photoinitiator
It mixes in the coating containing polymer,
The wherein described photocurable component and the coating physical mixed containing polymer, or with described containing polymer
The polymer chemistry of coating is bonded.
In addition, the present invention relates to the methods of the application present composition comprising the composition of the present invention is applied to base
On material.
The invention further relates to the films that the composition by the present invention is formed.
There is excellent stain resistance (DPUR), stain resistance, resistance to blocking by the film that the composition of the present invention is formed
Deng.Meanwhile film of the invention has excellent flexibility.
Specific implementation mode
Unless otherwise defined, otherwise all technical and scientific terms used herein have with it is of the art general
The normally understood identical meanings of logical technical staff.
When for defining term, statement " one (a) ", " one (an) ", " should (the) " include the term plural form and
Singulative.
Terms used herein " polymer " include homopolymer (polymer prepared by single reaction compound) and
Copolymer (forms polymer prepared by the reactive monomer compound reaction of polymer) by least two.
In the first aspect of the present invention, the present invention relates to a kind of compositions, including：
A. photocurable component；
B. photoinitiator；With
C. the coating containing polymer does not include component A.
In another aspect of this invention, the present invention relates to a kind of compositions, including：
A. photocurable component；
B. photoinitiator；With
C. the coating containing polymer does not include component A；
Wherein component A and component C physical mixeds, or be bonded with the polymer chemistry of component C to be formed with chemical bond
The component A's of conjunction is polymer-modified.
The component A of the present composition is photocurable component.The photocurable component includes having two or more
Monomer, oligomer and/or the polymer of the double bond of a free redical polymerization.Any photocurable material that can be used for coating composition
Material is used equally in the composition of the present invention.For example, component A can be photo curable (methyl) acrylate, photocurable
(poly-) urethane, photo curable epoxide polymer etc..Preferably, the component A of the present composition is polyester acrylic
Ester, polyether acrylate, epoxy acrylate, urethane acrylate, or mixtures thereof monomer and/or oligomer.It is more excellent
Selection of land, the component A of the present composition can be selected from the monomer and/or oligomer of following substances：Urethane acrylate,PE55WIN、LR8765、LR 8983、LR 8889、LR8949 and 1,4-butanediol diacrylate, all of which can from BASF SE, Ludwigshafen,
Germany is obtained.It is highly preferred that the component A of the present composition isWA9057 or
LR8949。
The preferred ingredient A of the present composition contains the unsaturated double-bond with different polymerisation reactivities.Component A includes
(methyl) acrylic acid, maleic acid, fumaric acid, the allyl ester of itaconic acid, the monomer of vinyl esters and/or oligomer and/or poly-
Close object；Allyl ether, ethylene-ethyl base ether or thioether；Etc..It is highly preferred that component A includes (methyl) acrylic acid, Malaysia
The monomer and/or oligomer of acid, fumaric acid, the allyl ester of itaconic acid, vinyl esters；Allyl ether, ethylene-ethyl base ether
Or mixtures thereof or thioether,.
The amount of component A can be in the range of 0.01 to 9.9 weight %, preferably in 0.05 to 8 weight in the present composition
In the range of measuring %, more preferably in the range of 0.1 to 6 weight %, most preferably in the range of 0.5 to 5 weight %, based on this
The total weight of the solid component of inventive composition.
In the preferred embodiment of wherein component A and component C physical mixeds, the amount of component A in the compositions of the present invention
It can be in the range of 0.1 to 9.9 weight %；It is preferred that in the range of 0.1 to 8 weight %；More preferably in 0.1 to 6 weight %
In the range of, such as in the range of 0.5 to 5 weight %, the total weight of the solid component based on the present composition.
In the preferred embodiment that wherein component A is bonded with the polymer chemistry of component C, component in the present composition
The amount of A can be in the range of 0.01 to 9.9 weight %；It is preferred that in the range of 0.05 to 8 weight %；More preferably 0.1 to 6
In the range of weight %, such as in the range of 0.5 to 5 weight %, the total weight of the solid component based on the present composition
Meter.
Any photoinitiator can be used as the component B of composition for the purpose of the present invention, and condition is that it can be used for coating group
It closes in object.For example, photoinitiator can be selected from but not limited to benzophenone or acetophenone or sub- with benzophenone or acetophenone
The derivative of structure, such as substituted benzophenone, such as 4- methyl benzophenones, 2,4,6- tri-methyl benzophenones；Thioxanthene
Ketone, such as isopropyl thioxanthone；Or the ethylenic bond unsaturation derivative of benzophenone or acetophenone, example are with (methyl) third
Those of olefin(e) acid group, such as (methyl) acryloyloxyethoxy benzophenone, or with those of vinyl, such as 4- ethylene oxies
Base benzophenone；Or the mixture of these active constituents, such as 4- methyl benzophenones and 2,4,6- tri-methyl benzophenones.Group
Divide B that can be added before, during or after actually preparing A and/or C.
Preferably, the component B of the present composition can be selected from benzophenone, purchased from BASF's
754、500 and purchased from Lamberti SPA companiesTZM、TZT.It is more excellent
The component B of selection of land, the present composition can be selected fromTZM and500。
The amount of component B can be in the range of 0.01 to 5 weight %, preferably in 0.01 to 1 weight in the present composition
In the range of measuring %, more preferably in the range of 0.01 to 0.5 weight %, most preferably in the range of 0.1 to 0.5 weight %,
The total weight of solid component based on the present composition.
The component A and component B of the present composition can be used with the proper proportion of 1 to 990 (by weight).It is preferred that
Ground, in the present compositions, component A and component B can be up to 200 with the ratio of component A/ components B, more preferably up to
It is used up to 100.Preferably, in the present compositions, component A and component B can be equal to the ratio of component A/ components B
Or it is more than 1.6, preferably equal to or greater than 2, more preferably equal to or greater than 5 to use.
The component C of the present composition can be any coating containing polymer.Component C itself is to can be directly used for base material
To form the coating composition of film.Preferably, component C can be directly used for applications, such as the exterior wall for building.This
Any conventional coating composition containing polymer can be employed as component C in field.Component C can by those skilled in the art according to
Prepared by conventional method or component C is commercially available.For example, component C can be with trade name290、
7035、7079 are purchased from BASF.In other embodiments of the present invention, component C can by
(this two documents are included in this each by the mode of reference for method acquisition disclosed in US2014107249 or US2013079462
In specification).
The polymer of the component C of the present composition can be any polymerization being suitable for inclusion in coating composition
Object.For example, the polymer can be polyester, polyurethane-epoxy resin, poly- (methyl) acrylate etc..Technical staff will be easy
The appropriate polymer of component C is selected, and the polymer is easy to get by routine techniques.
The glass transition temperature (Tg) of the polymer of component C is in the range of -20 to 60 DEG C, preferably at -10 to 50 DEG C
In the range of, more preferably in the range of -10 to 40 DEG C, most preferably in the range of 0 to 30 DEG C.
The Mw of the polymer of component C is in the range of 25,000 to 10,000,000 dalton, preferably 30,000 to 5,
In the range of 000,000 dalton, more preferably in the range of 100,000 to 2,000,000 dalton, most preferably 300,
In the range of 000 to 1,000,000 dalton, and Mn is in the range of 4,000 to 1,000,000 dalton, preferably 5,000
To 500,000 dalton, more preferably in the range of 10,000 to 200,000 dalton, most preferably 40,000
To 100,000 dalton.
Component C constitutes the balance of the present composition.In general, component C can also contain additive.These additives can be with
It is pigment, such as purchased from Kerr-McGee Corporation, the TiCl of Oklahoma, U.S.A2CR828；Filler, such as purchase
From the CaCO of Omya3 5；Coalescents, such as purchased from Eastman Chemical companies
Thickener, such as purchased from Ashland's250HBR；And antifreeze additive, such as purchased from GuoYao
The propylene glycol of Reagent companies；Etc..Any conventional additives for coating composition may be embodied in component C.It is logical
Often, these additives are used with its convention amount respectively.
In the second aspect of the present invention, the present invention relates to a kind of methods preparing the present composition comprising：
Step 1：Form the coating containing polymer；
Step 2：During step 1 or after forming the coating containing polymer, by photocurable component and photoinitiator
It mixes in the coating containing polymer,
The wherein described photocurable component and the coating physical mixed containing polymer, or with described containing polymer
The polymer chemistry of coating is bonded.
The step 1 for being used to prepare the method for the present composition can be in any ordinary temperature and pressure for being used to form coating
It is carried out under the conditions of power.Technical staff can select the condition for being suitble to step 1.In one embodiment of the invention, step 1 is logical
The aqueous emulsion polymerization for crossing free radical initiation is realized.This method has been widely described before this, therefore for art technology
It is well known [see, e.g., Encyclopedia 0f Polymer Science and enough for personnel
Engineering, volume 8, page 659 to 677, John Wiley＆Sons, Inc., 1987；D.C.Blackley,
Emulsion Polymerisation, page 155 to 465, Applied Science Publishers, Ltd., Essex,
1975；D.C.Blackley, Polymer Latices, second edition, volume 1, the 33-415 pages, Chapman＆Hall, 1997；
H.Washon, The Applications 0f Synthetic Resin Emulsions, page 49 to 244, Ernest
Benn, Ltd., London, 1972；J.Piirma, Emulsion Polymerisation, page 1 to 287, Academic
Press, 1982；F.Holscher, Dispersionen synthetischer Hochpolymerer, page 1 to 160,
Springer-Verlag, Berlin, 1969；With patent specification DE-A 40 03 422].The aqueous emulsion that free radical causes
Polymerization usually by the way that ethylenically unsaturated monomers are dispersed in water-bearing media, usually using dispersing aid such as emulsifier and/or
Protecting colloid, and so that its polymerization is completed by least one water-soluble radical polymerization initiator.In general, in the aqueous of acquisition
In polymeric dispersions, by technical staff it is also known that chemistry and/or physical method reduce unreacted ethylenic bond not
The residual volume of monomer is saturated [see, e.g., EP-A 771328, DE-A 19624299, DE-A 19621027, DE-A
19741184、DE-A 19741187、DE-A 19805122、DE-A 19828183、DE-A 19839199、DE-A
19840586 and 19847115], by diluting or concentrating or by other conventional additives such as fungicide, foaming modifying dose or viscosity
Modifying agent is added in aqueous polymer dispersion is adjusted to required level by polymer solids content.
As for the step 2 of this method, can be carried out under any suitable temperature and pressure.For convenience and save at
This, the method for preparing the present composition can be under environment temperature and environmental pressure, such as is carried out under room temperature and normal pressure.
In the third aspect of the present invention, the present invention relates to a kind of methods using the present composition comprising incite somebody to action this
The composition of invention is applied to base material.
The composition of the present invention can be applied by conventional method of administration, such as brushing or roller coating；Spraying such as air mist
Change spraying, air-assisted spray, without air-atomizing, high power capacity low pressure atomizing, air-assisted airless spraying, electrostatic spray etc.；
Spin coating；Curtain coating etc..
Any suitable base material can be employed as the base material of the composition using the present invention, such as polymeric substrate, cement, mixed
Solidifying soil, ceramics, metal, timber, leather etc., condition, which is the base material of coating, will be exposed under light such as daylight.
After being administered on base material, the film formed by the composition of the present invention can have any appropriate dried film thickness
Degree.Preferably, the thickness of dry film of the film formed by the present composition is up to 2000 μm, preferably up to 1000 μm, example
Such as up to 500 μm, more preferably up to 300 μm, and especially up to up to 200 μm, and it is not less than 10 μm, it is preferably not small
In 50 μm, more preferably no less than 100 μm.
For internal applications, the thickness of dry film of the film usually formed by the composition of the present invention exists
In the range of 50 μm to 500 μm, more preferably in the range of 50 μm to 300 μm, such as in the range of 100 μm to 300 μm.
For applications, the thickness of dry film of the film usually formed by the composition of the present invention is in 10 μ
In the range of m to 2000 μm, such as in the range of 30 μm to 1000 μm, more preferably in the range of 50 μm to 1000 μm, still
It is preferred that in the range of 50 μm to 500 μm, such as in the range of 50 μm to 300 μm.
In the certain preferred embodiments for the present invention of applications, base material is timber, and by the present invention's
The thickness of dry film for the film that composition is formed is in the range of 30 μm to 200 μm, more preferably in the range of 50 μm to 150 μm,
Still preferably in the range of 50 μm to 100 μm.
In the fourth aspect of the present invention, the present invention relates to a kind of films that the composition by the present invention obtains.
In conclusion the present invention includes following embodiments.
1. a kind of composition, including
A. photocurable component；
B. photoinitiator；With
C. the coating containing polymer does not include component A.
2. a kind of composition, including
A. photocurable component；
B. photoinitiator；With
C. the coating containing polymer does not include component A；
Wherein component A and component C physical mixeds.
3. a kind of composition, including
A. photocurable component；
B. photoinitiator；With
C. the coating containing polymer does not include component A；
Wherein component A is bonded with the polymer chemistry of component C to form the modified poly of the component A with chemical bonding
Object.
4. the composition of any one of embodiment 1-3, the wherein amount of component A be in the range of 0.01 to 9.9 weight %,
It is preferred that in the range of 0.05 to 8 weight %, more preferably in the range of 0.1 to 6 weight %, most preferably in 0.5 to 5 weight %
In the range of, the total weight of the solid component based on the present composition.
5. the composition of any one of embodiment 1-3, the amount of component A can be in 0.1 to 9.9 weight in the present composition
In the range of amount %；It is preferred that in the range of 0.1 to 8 weight %；More preferably in the range of 0.1 to 6 weight %, such as
In the range of 0.5 to 5 weight %, the total weight of the solid component based on the present composition.
6. the composition of any one of embodiment 1-3, the wherein Tg of the polymer of component C are in -20 to 60 DEG C of range
It is interior, preferably in the range of -10 to 50 DEG C, more preferably in the range of -10 to 40 DEG C, most preferably in the range of 0 to 30 DEG C.
7. the composition of any one of embodiment 1-3, the wherein Mw of the polymer of component C be 25,000 to 10,000,
In the range of 000 dalton, preferably in the range of 30,000 to 5,000,000 dalton, more preferably 100,000 to 2,
In the range of 000,000 dalton, most preferably in the range of 300,000 to 1,000,000 dalton, and Mn is 4,000
To 1,000,000 dalton, preferably in the range of 5,000 to 500,000 dalton, more preferably 10,000 to
In the range of 200,000 dalton, most preferably in the range of 40,000 to 100,000 dalton, according to ISO 13885-1
It is measured by gel permeation chromatography.
8. the composition of any one of embodiment 1-3, wherein in the present composition amount of component A can 0.1 to
In the range of 9.9 weight %；The Tg of the polymer of component C in the range of -10 to 50 DEG C, the Mw of the polymer of component C 30,
In the range of 000 to 5,000,000 dalton, Mn is in the range of 5,000 to 500,000 dalton, according to ISO
13885-1 is measured by gel permeation chromatography.
9. the composition of any one of embodiment 1-3, wherein in the present composition amount of component A can 0.1 to
In the range of 9.9 weight %；In the range of -10 to 40 DEG C, Mw's Tg of the polymer of component C of the polymer of component C exists
In the range of 100,000 to 2,000,000 dalton, Mn is in the range of 10,000 to 200,00 dalton, according to ISO
13885-1 is measured by gel permeation chromatography.
10. the composition of any one of embodiment 1-9, the wherein amount of component B be in the range of 0.01 to 5 weight %,
It is preferred that in the range of 0.01 to 1 weight %, more preferably in the range of 0.01 to 0.5 weight %, most preferably 0.1 to 0.5
In the range of weight %, the total weight of the solid component based on the present composition.
11. the composition of any one of embodiment 1-10, the wherein ratio of component A and component B are 1 to 990 (with weight
Meter) in the range of, the ratio of preferred ingredient A and component B is up to 200, preferably up to 100, and component A and component B
Ratio is not less than 1.6, preferably not less than 2, more preferably no less than 5.
12. the composition of any one of embodiment 1-11, wherein component A are selected from photo curable (methyl) acrylic acid
Monomer, oligomer and/or the polymer of ester, photo curable (poly-) urethane and photo curable epoxides；(methyl) propylene
Acid, maleic acid, fumaric acid, the allyl ester of itaconic acid, the monomer of vinyl esters, oligomer and/or polymer；Allyl ether,
Ethylene-ethyl base ether or thioether；Etc.；Preferably, component A is selected from polyester acrylate, polyether acrylate, propylene oxide
The monomer of acid esters and 1,4-butanediol diacrylate, oligomer or polymer；More preferable component A is selected from urethane acrylate
The monomer, oligomer or polymer of (methyl) allyl acrylate.
13. the composition of any one of embodiment 1-12, wherein component B are selected from benzophenone, acetophenone, have hexichol
The derivative of ketone or acetophenone substructure, such as substituted benzophenone, such as 4- methyl benzophenones, 2,4,6- trimethyls two
Benzophenone；Thioxanthones, such as isopropyl thioxanthone；The ethylenic bond unsaturation derivative of benzophenone or acetophenone, example are tool
Have those of (methyl) acrylic acid groups such as (methyl) acryloyloxyethoxy benzophenone, or with those of vinyl as
4- vinyl oxygroup benzophenone；Or the mixture of these active constituents, such as 4- methyl benzophenones and 2,4,6- trimethyls
Benzophenone.
14. a kind of method for the composition preparing any one of embodiment 1-13, including：
Step 1：Form the coating containing polymer；
Step 2：During step 1 or after forming the coating containing polymer, by photocurable component and photoinitiator
It mixes in the coating containing polymer,
The wherein described photocurable component and the coating physical mixed containing polymer, or with described containing polymer
The polymer chemistry of coating is bonded.
15. a kind of method of composition using any one of embodiment 1-13, including will appoint in embodiment 1-13
One composition is applied on base material.
16. a kind of film is obtained by the composition of any one of embodiment 1-13.
17. the thickness of dry film of the film of embodiment 13, wherein film is up to 1000 μm, preferably up to 500 μm, more
Preferably up to 300 μm, and especially up to up to 200 μm, and it is not less than 30 μm, it is preferably not less than 50 μm, more preferably not small
In 30 μm.
18. the film of embodiment 13, wherein for internal applications, the thickness of dry film of film is at 50 μm to 500 μm
In the range of, more preferably in the range of 50 μm to 300 μm, such as in the range of 100 μm to 300 μm.
19. the film of embodiment 13, wherein for applications, the thickness of dry film of film is at 30 μm to 1000 μm
In the range of, more preferably in the range of 50 μm to 1000 μm, it is still preferred in the range of 50 μm to 500 μm, such as at 50 μm
To in the range of 300 μm.
20. the film of embodiment 19, wherein for wood substrates, the thickness of dry film of film is at 30 μm to 200 μm
In the range of, more preferably in the range of 50 μm to 150 μm, it is still preferred in the range of 50 μm to 100 μm.
Embodiment
Hereinafter, will be with reference to being only exemplary and explanatory, specific embodiment and not restrictive further illustrates
The present invention.
If without in addition defining, every part used and percentage provide by weight.
The material used：
Embodiment 1
By the way that nitrogen is passed through in 4L reactors 10 minutes by its inerting, it is then charged into 600g softened waters, 25g granularities are
The 33% polystyrene seed latex of 33nm.Then, the reactor containing above-mentioned material 85 DEG C are heated under stiring to be used for
Synthesis.Then, at 85 DEG C, 5g7% sodium persulfate aqueous solutions are added.It, will be by keeping 450g soft in 210 minutes after addition
Change water, the sodium salt of 28g fatty alcohol polyglycol ether sulfuric esters, 705g methyl methacrylates, 527g n-butyl acrylates, 23g
Methacrylic acid and 13gThe emulsion feed that TZM is mixed to get is added in reactor.It is parallel with emulsion feed,
The initiator feed of the sodium persulfate aqueous solution of 7 weight % of 95g is added in reactor in 240 minutes.To be triggered dose of charging
After addition, the reaction mixture of gained is cooled to 75 DEG C.Then, 45g is added into reaction mixture in 5 minutes
8% sodium hydrate aqueous solution.Later, 10% tert-butyl hydroperoxide aqueous solutions of 26g are added in 60 minutes and 36g 13% is sub-
260g is then added in metabisulfite solutionLR 8765.After charging, reaction mixture is cooled to room temperature.
Produce latex.The glass transition temperature of resulting polymers is 31 DEG C.Pass through gel permeation chromatography according to ISO 13885-1
Measure molecular weight.Mw is about 373,000 dalton, and Mn is about 86,000 dalton.
Latex obtained by 310g is purchased to the dispersant of BASF with 270g softened waters, 5gAA4140,1g are purchased from
Antifoaming agent DC065,220g of Dow Corning is purchased from the TiO of Kerr-McGee2CR828,165g are purchased from the CaCO of Omya3 5,16g is purchased from Eastman's3g is purchased from Ashland's250HBR and
Propylene glycol of the 10g purchased from GuoYao Reagent companies is formulated together, to form composition.It is all inorganic in resulting composition
The volumetric concentration of object is about 45%.
In the composition of gained,The content of LR 8765 is about 5.01%,TZM's contains
Amount about 0.25%.
Comparative example 1
By the way that nitrogen is passed through in 4L reactors 10 minutes by its inerting, it is then charged into 600g softened waters, 25g granularities are
The 33% polystyrene seed latex of 33nm.Under stiring, the reactor containing above-mentioned material is heated to 85 DEG C for synthesizing.
Then, at 85 DEG C, 7% sodium persulfate aqueous solutions of 5g are added.After addition, in 210 minutes, will by make 450g softened waters,
The sodium salt of 28g fatty alcohol polyglycol ether sulfuric esters, 705g methyl methacrylates, 527g n-butyl acrylates, 23g methyl-props
The emulsion feed that olefin(e) acid is mixed to get is added in reactor.It is parallel with emulsion feed, by 7 weight %'s of 95g in 240 minutes
The initiator feed of sodium persulfate aqueous solution is added in reactor.After to be triggered dose of charging addition, by the reaction of gained
Mixture is cooled to 75 DEG C.Then, 8% sodium hydrate aqueous solutions of 45g are added into reaction mixture in 5 minutes.Later,
Then 10% tert-butyl hydroperoxide aqueous solutions of 26g and 13% sodium sulfite solutions of 36g are added in 60 minutes will react
Mixture is cooled to room temperature.Produce latex.
Latex obtained by 310g is purchased to the dispersant of BASF with 270g softened waters, 5gAA4140,1g are purchased from
Antifoaming agent DC065,220g of Dow Corning is purchased from the TiO of Kerr-McGee2CR828,165g are purchased from the CaCO of Omya3 5,16g is purchased from Eastman's3g is purchased from Ashland's250HBR and
Propylene glycol of the 10g purchased from GuoYao Reagent companies is formulated together, to form composition.It is all inorganic in resulting composition
The volumetric concentration of object is about 45%.
In the composition of gained, without photocurable component and photoinitiator is free of.
Embodiment 2
By the way that nitrogen is passed through in 4L reactors 10 minutes by its inerting, it is then charged into 600g softened waters, 25g granularities are
The 33% polystyrene seed latex of 33nm.Under stiring, the reactor containing above-mentioned material is heated to 85 DEG C for synthesizing.
Then, at 85 DEG C, 7% sodium persulfate aqueous solutions of 5g are added.After addition, in 210 minutes, will by make 450g softened waters,
The sodium salt of 28g fatty alcohol polyglycol ether sulfuric esters, 625g methyl methacrylates, 607g 2-EHAs, 23g first
Base acrylic acid and 13g500 emulsion feeds being mixed to get are added in reactor.It is parallel with emulsion feed,
The initiator feed of the sodium persulfate aqueous solution of 7 weight % of 95g is added in reactor in 240 minutes.To be triggered dose into
After material addition, the reaction mixture of gained is cooled to 75 DEG C.Then, 45g is added into reaction mixture in 5 minutes
8% sodium hydrate aqueous solution.Later, 10% tert-butyl hydroperoxide aqueous solutions of 26g are added in 60 minutes and 36g 13% is sub-
260g is then added in metabisulfite solutionLR 8765.After charging, reaction mixture is cooled to room temperature.
Produce latex.The glass transition temperature of resulting polymers is 4 DEG C.Pass through gel permeation chromatography according to ISO 13885-1
Measure molecular weight.Mw is about 467,000 dalton, and Mn is about 91,000 dalton.
Latex obtained by 310g is purchased to the dispersant of BASF with 270g softened waters, 5gAA4140,1g are purchased from
Antifoaming agent DC065,220g of Dow Corning is purchased from the TiO of Kerr-McGee2CR828,165g are purchased from the CaCO of Omya3 5,16g is purchased from Eastman's3g is purchased from Ashland's250HBR and 10g
Propylene glycol purchased from GuoYao Reagent companies is formulated together, to form composition.Whole inorganic matters in resulting composition
Volumetric concentration be about 45%.
In the composition of gained,The content of LR 8765 is about 5.01%,500
Content be about 0.25%.
Comparative example 2
By the way that nitrogen is passed through in 4L reactors 10 minutes by its inerting, it is then charged into 600g softened waters, 25g granularities are
The 33% polystyrene seed latex of 33nm.Under stiring, the reactor containing above-mentioned material is heated to 85 DEG C for synthesizing.
Then, at 85 DEG C, 7% sodium persulfate aqueous solutions of 5g are added.After addition, in 210 minutes, will by make 450g softened waters,
The sodium salt of 28g fatty alcohol polyglycol ether sulfuric esters, 625g methyl methacrylates, 607g 2-EHAs, 23g first
The emulsion feed that base acrylic acid is mixed to get is added in reactor.It is parallel with emulsion feed, by 7 weights of 95g in 240 minutes
The initiator feed for measuring the sodium persulfate aqueous solution of % is added in reactor.After to be triggered dose of charging addition, by gained
Reaction mixture be cooled to 75 DEG C.Then, 8% sodium hydrate aqueous solutions of 45g are added into reaction mixture in 5 minutes.
Later, 10% tert-butyl hydroperoxide aqueous solutions of 26g and 13% sodium sulfite solutions of 36g are added in 60 minutes, then will
Reaction mixture is cooled to room temperature.Produce latex.
Latex obtained by 310g is purchased to the dispersant of BASF with 270g softened waters, 5gAA4140,1g are purchased from
Antifoaming agent DC065,220g of Dow Corning is purchased from the TiO of Kerr-McGee2CR828,165g are purchased from the CaCO of Omya3 5,16g is purchased from Eastman's3g is purchased from Ashland's250HBR and
Propylene glycol of the 10g purchased from GuoYao Reagent companies is formulated together, to form composition.It is all inorganic in resulting composition
The volumetric concentration of object is about 45%.
In the composition of gained, without photocurable component and photoinitiator is free of.
Embodiment 3
By the way that nitrogen is passed through in 4L reactors 10 minutes by its inerting, it is then charged into 1000g softened waters, 25g granularities are
The 33% polystyrene seed latex of 33nm.Under stiring, the reactor containing above-mentioned material is heated to 85 DEG C for synthesizing.
Then, at 85 DEG C, 7% sodium persulfate aqueous solutions of 5g are added.After addition, in 180 minutes, will by make 450g softened waters,
Sodium salt, 1000g allyl methacrylates, the 25g n-dodecyl mercaptans of 28g fatty alcohol polyglycol ether sulfuric esters mix
To emulsion feed be added reactor in.It is parallel with emulsion feed, by the sodium peroxydisulfate water of 7 weight % of 95g in 210 minutes
The initiator feed of solution is added in reactor.After to be triggered dose of charging addition, the reaction mixture of gained is cooled down
To 75 DEG C.Then, 8% sodium hydrate aqueous solutions of 25g are added into reaction mixture in 5 minutes.Later, in 60 minutes
10% tert-butyl hydroperoxide aqueous solutions of 26g and 13% sodium sulfite solutions of 36g is added.After charging, reaction is mixed
Object is cooled to room temperature.Latex is produced, for further using.The glass transition temperature of polymer is 19 in gained latex
℃.Molecular weight is measured by gel permeation chromatography according to ISO 13885-1.Mw is about 98,000 dalton, and Mn is about 4,000
Dalton.
In this embodiment, allyl methacrylate is bonded with the polymer chemistry formed in latex.FT-IR analyses are aobvious
Show, in gained latex, remain the allyl of about 70 weight %, is active photocurable component.
Embodiment 4
By the way that nitrogen is passed through in 4L reactors 10 minutes by its inerting, it is then charged into 600g softened waters, 25g granularities are
The 33% polystyrene seed latex of 33nm.Under stiring, the reactor containing above-mentioned material is heated to 85 DEG C for synthesizing.
Then, at 85 DEG C, 7% sodium persulfate aqueous solutions of 5g are added.After addition, in 210 minutes, will by make 450g softened waters,
The sodium salt of 28g fatty alcohol polyglycol ether sulfuric esters, 594g methyl methacrylates, 577g 2-EHAs, 23g first
Base acrylic acid and 13g500 emulsion feeds being mixed to get are added in reactor.It is parallel with emulsion feed,
The initiator feed of the sodium persulfate aqueous solution of 7 weight % of 95g is added in reactor in 240 minutes.Work as emulsion feed
After being added 190 minutes, 62g allyl methacrylates are added in remaining emulsion feed, and continue to feed.To be triggered dose into
After material, reaction mixture is cooled to 75 DEG C.Then, 8% hydroxides of 45g are added into reaction mixture in 5 minutes
Sodium water solution.Later, 10% tert-butyl hydroperoxide aqueous solutions of 26g are added in 60 minutes and 13% sodium sulfites of 36g is molten
Liquid.After charging, reaction mixture is cooled to room temperature.Produce latex.The glass transition temperature of resulting polymers is
11℃.Molecular weight is measured by gel permeation chromatography according to ISO 13885-1.Mw is about 53,000 dalton of Isosorbide-5-Nitrae, and Mn is
108,000 dalton.
To prepare the latex of gained with the same way described in embodiment 1.
In this embodiment, allyl methacrylate is added during preparing latex.FT-IR analysis shows that,
In gained latex, the allyl of about 70 weight % is remained, is active photocurable component.In the composition of gained,
The content of allyl methacrylate is about 1.35%,500 content is about 0.28%.
Comparative example 3
By the way that nitrogen is passed through in 4L reactors 10 minutes by its inerting, it is then charged into 600g softened waters, 25g granularities are
The 33% polystyrene seed latex of 33nm.Under stiring, the reactor containing above-mentioned material is heated to 85 DEG C for synthesizing.
Then, at 85 DEG C, 7% sodium persulfate aqueous solutions of 5g are added.After addition, in 210 minutes, will by make 450g softened waters,
The sodium salt of 28g fatty alcohol polyglycol ether sulfuric esters, 625g methyl methacrylates, 607g 2-EHAs, 23g first
Base acrylic acid and 13g500 emulsion feeds being mixed to get are added in reactor.It is parallel with emulsion feed,
The initiator feed of the sodium persulfate aqueous solution of 7 weight % of 95g is added in reactor in 240 minutes.To be triggered dose into
After material addition, the reaction mixture of gained is cooled to 75 DEG C.Then, 45g is added into reaction mixture in 5 minutes
8% sodium hydrate aqueous solution.Later, 10% tert-butyl hydroperoxide aqueous solutions of 26g are added in 60 minutes and 36g 13% is sub-
Metabisulfite solution.After charging, reaction mixture is cooled to room temperature.Produce latex.
To prepare the latex of gained with the same way described in embodiment 1.
In the composition of gained, photocurable component is free of.
Embodiment 5
By 280g from dispersion commercially available BASF290 (latex A) and 1.4gTZT、
29gWA9057,270g softened water, 5g are purchased from the dispersant of BASFAA4140,1g are purchased from Dow
Antifoaming agent DC065,220g of Corning is purchased from the TiO of Kerr-McGee2CR828,165g are purchased from the CaCO of Omya3 5,16g is purchased from Eastman's3g is purchased from Ashland's250HBR and
Propylene glycol of the 10g purchased from GuoYao Reagent companies is formulated together, to form composition.It is all inorganic in resulting composition
The volumetric concentration of object is about 45%.The glass transition temperature of polymer is 20 DEG C in latex A.Passed through according to ISO 13885-1
Gel permeation chromatography measures molecular weight.Mw is about 512,000 dalton, and Mn is about 77,000 dalton.
In the composition of gained,The content of WA9057 is about 5.30%,TZT's contains
Amount about 0.26%.
Comparative example 4
By 309g latex A and 1.4gTZT, 270g softened water, 5g are purchased from the dispersant of BASFAntifoaming agent DC065, the 220g of AA4140,1g purchased from Dow Corning are purchased from Kerr-McGee's
TiO2CR828,165g are purchased from the CaCO of Omya3 5,16g is purchased from Eastman's3g is purchased from
Ashland'sPropylene glycol of the 250HBR and 10g purchased from GuoYao Reagent companies is formulated together, to be formed
Composition.The volumetric concentration of whole inorganic matters is about 45% in resulting composition.
In the composition of gained, photocurable component is free of.
Embodiment 6
By 303g latex A and 0.6g754、6.4gLR 8983,270g softened waters,
5g is purchased from the dispersant of BASFAntifoaming agent DC065, the 220g of AA4140,1g purchased from Dow Corning are purchased from
The TiO of Kerr-McGee2CR828,165g are purchased from the CaCO of Omya3 5,16g is purchased from Eastman's3g is purchased from Ashland's250HBR and 10g is purchased from the propylene glycol of GuoYao Reagent companies
It is formulated together, to form composition.The volumetric concentration of whole inorganic matters is about 45% in resulting composition.
In the composition of gained,The content of LR 8983 is about 1.16%,754
Content be about 0.11%.
Comparative example 5
By 280g latex A and 29gWA9057,270g softened water, 5g are purchased from the dispersant of BASFAntifoaming agent DC065, the 220g of AA4140,1g purchased from Dow Corning are purchased from Kerr-McGee's
TiO2CR828,165g are purchased from the CaCO of Omya3 5,16g is purchased from Eastman's3g is purchased from
Ashland'sPropylene glycol of the 250HBR and 10g purchased from GuoYao Reagent companies is formulated together, to be formed
Composition.The volumetric concentration of whole inorganic matters is about 45% in resulting composition.
In the composition of gained, photoinitiator is free of.
Embodiment 7
By 280g latex A and 0.3g- benzophenone, 29gLR 8949,270g softened waters, 5g are purchased from
The dispersant of BASFAntifoaming agent DC065, the 220g of AA4140,1g purchased from Dow Corning are purchased from Kerr-
The TiO of McGee2CR828,165g are purchased from the CaCO of Omya3 5,16g is purchased from Eastman's
3g is purchased from Ashland'sPropylene glycol of the 250HBR and 10g purchased from GuoYao Reagent companies is formulated together,
To form composition.The volumetric concentration of whole inorganic matters is about 45% in resulting composition.
In the composition of gained,The content of LR 8949 is about 5.15%, and the content of benzophenone is about
It is 0.05%.
Embodiment 8
By 284g from dispersion commercially available BASF7079 (latex B) and 1gTZM、
25gPE55WIN, 270g softened water, 5g are purchased from the dispersant of BASFAA4140,1g are purchased from Dow
Antifoaming agent DC065,220g of Corning is purchased from the TiO of Kerr-McGee2CR828,165g are purchased from the CaCO of Omya3 5,16g is purchased from Eastman's3g is purchased from Ashland's250HBR and
Propylene glycol of the 10g purchased from GuoYao Reagent companies is formulated together, to form composition.It is all inorganic in resulting composition
The volumetric concentration of object is about 45%.The glass transition temperature of polymer is 10 DEG C in latex B.Passed through according to ISO 13885-1
Gel permeation chromatography measures molecular weight.Mw is about 917,000 dalton, and Mn is about 190,000 dalton.
In the composition of gained,The content of PE55WIN is about 4.49%,TZM's contains
Amount about 0.18%.
Embodiment 9
By 408g latex B and 1.3g500、35.7gLR 8889,185g soften
Water, 5g are purchased from the dispersant of BASFAntifoaming agent DC065, the 196g of AA4140,1g purchased from Dow Corning are purchased from
The TiO of Kerr-McGee2CR828,139g are purchased from the CaCO of Omya3 5,16g is purchased from Eastman's3g is purchased from Ashland's250HBR and 10g is purchased from the propylene glycol of GuoYao Reagent companies
It is formulated together, to form composition.The volumetric concentration of whole inorganic matters is about 34% in resulting composition.
In the composition of gained,The content of LR 8889 is about 6.15%,500
Content be about 0.22%.
Comparative example 6
445g latex B and 185g softened waters, 5g are purchased to the dispersant of BASFAA4140,1g are purchased from Dow
Antifoaming agent DC065,196g of Corning is purchased from the TiO of Kerr-McGee2CR828,139g are purchased from the CaCO of Omya3 5,16g is purchased from Eastman's3g is purchased from Ashland's250HBR and
Propylene glycol of the 10g purchased from GuoYao Reagent companies is formulated together, to form composition.It is all inorganic in resulting composition
The volumetric concentration of object is about 34%.
In the composition of gained, without photocurable component and photoinitiator is free of.
Embodiment 10
By 427g latex B and 1gTZT、17gHDDA, 185g softened water, 5g are purchased from BASF
DispersantAntifoaming agent DC065, the 196g of AA4140,1g purchased from Dow Corning are purchased from Kerr-McGee's
TiO2CR828,139g are purchased from the CaCO of Omya3 5,16g is purchased from Eastman's3g is purchased from
Ashland'sPropylene glycol of the 250HBR and 10g purchased from GuoYao Reagent companies is formulated together, to be formed
Composition.The volumetric concentration of whole inorganic matters is about 34% in resulting composition.
In the composition of gained,The content of HDDA is about 2.98%,The content of TZT is about
It is 0.18%.
Embodiment 11
By 400g from dispersion commercially available BASF7035 (latex C) and 1g
754、44gWA9057,185g softened water, 5g are purchased from the dispersant of BASFAA4140,1g are purchased from
Antifoaming agent DC065,196g of Dow Corning is purchased from the TiO of Kerr-McGee2CR828,139g are purchased from the CaCO of Omya3 5,16g is purchased from Eastman's3g is purchased from Ashland's250HBR and
Propylene glycol of the 10g purchased from GuoYao Reagent companies is formulated together, to form composition.It is all inorganic in resulting composition
The volumetric concentration of object is about 34%.The glass transition temperature of polymer is 23 DEG C in latex C.Passed through according to ISO 13885-1
Gel permeation chromatography measures molecular weight.Mw is about 394,000 dalton, and Mn is about 62,000 dalton.
In the composition of gained,The content of WA9057 is about 7.93%,754
Content be about 0.18%.
Comparative example 7
445g latex C and 185g softened waters, 5g are purchased to the dispersant of BASFAA4140,1g are purchased from Dow
Antifoaming agent DC065,196g of Corning is purchased from the TiO of Kerr-McGee2CR828,139g are purchased from the CaCO of Omya3 5,16g is purchased from Eastman's3g is purchased from Ashland's250HBR and
Propylene glycol of the 10g purchased from GuoYao Reagent companies is formulated together, to form composition.It is all inorganic in resulting composition
The volumetric concentration of object is about 34%.
In the composition of gained, without photocurable component and photoinitiator is free of.
Embodiment 12
400g latex C and 1g benzophenone, 44g are purchased from by the dispersion of 3 gained of embodiment, 185g softened waters, 5g
The dispersant of BASFAntifoaming agent DC065, the 196g of AA4140,1g purchased from Dow Corning are purchased from Kerr-
The TiO of McGee2CR828,139g are purchased from the CaCO of Omya3 5,16g is purchased from Eastman's
3g is purchased from Ashland'sPropylene glycol of the 250HBR and 10g purchased from GuoYao Reagent companies is formulated together,
To form composition.The volumetric concentration of whole inorganic matters is about 35% in resulting composition.
In the composition of gained, the content of allyl methacrylate is about 2.89%, and the content of benzophenone is about
0.18%.
Comparative example 8
444g latex C and 1g benzophenone, 185g softened waters, 5g are purchased to the dispersant of BASF
Antifoaming agent DC065, the 196g of AA4140,1g purchased from Dow Corning are purchased from the TiO of Kerr-McGee2CR828,139g are purchased from
The CaCO of Omya3 5,16g is purchased from Eastman's3g is purchased from Ashland's
Propylene glycol of the 250HBR and 10g purchased from GuoYao Reagent companies is formulated together, to form composition.In resulting composition
The volumetric concentration of whole inorganic matters is about 34%.
In the composition of gained, photocurable component is free of.
Embodiment 13
408g latex A and 1.3g benzophenone, 36g are purchased from by the dispersion of 3 gained of embodiment, 185g softened waters, 5g
The dispersant of BASFAntifoaming agent DC065, the 196g of AA4140,1g purchased from Dow Corning are purchased from Kerr-
The TiO of McGee2CR828,139g are purchased from the CaCO of Omya3 5,16g is purchased from Eastman's
3g is purchased from Ashland'sPropylene glycol of the 250HBR and 10g purchased from GuoYao Reagent companies is formulated together,
To form composition.The volumetric concentration of whole inorganic matters is about 35% in resulting composition.
In the composition of gained, the content of allyl methacrylate is about 2.32%, and the content of benzophenone is about
0.23%.
Comparative example 9
400g latex C and 45g is purchased to the dispersant of BASF by the dispersion of 3 gained of embodiment, 185g softened waters, 5gAntifoaming agent DC065, the 196g of AA4140,1g purchased from Dow Corning are purchased from Kerr-McGee's
TiO2CR828,139g are purchased from the CaCO of Omya3 5,16g is purchased from Eastman's3g is purchased from
Ashland'sPropylene glycol of the 250HBR and 10g purchased from GuoYao Reagent companies is formulated together, to be formed
Composition.The volumetric concentration of whole inorganic matters is about 35% in resulting composition.
In the composition of gained, photocurable component is free of.
Comparative example 10
By the way that nitrogen is passed through in 4L reactors 10 minutes by its inerting, it is then charged into 600g softened waters, 25g granularities are
The 33% polystyrene seed latex of 33nm.Reactor containing above-mentioned material is heated to 85 DEG C, and in the whole of synthesis
Interior stirring.At 85 DEG C, 5g7% sodium persulfate aqueous solutions are added.After addition, proceed by emulsion feed, the lotion into
Material is by making 450g softened waters, the sodium salt of 28g fatty alcohol polyglycol ether sulfuric esters, 705g methyl methacrylates, 527g third
Olefin(e) acid N-butyl, 23g methacrylic acids and 13gTZM is mixed to get, and is added in 210 minutes.With lotion into
Material is parallel, starts the sodium persulfate aqueous solution for feeding 95g7 weight %, and added it in reactor in 240 minutes.It waits for
After initiator feed, reaction mixture is cooled to 75 DEG C.Then, it is added in 5 minutes into reaction mixture
45g8% sodium hydrate aqueous solutions.Later, 10% tert-butyl hydroperoxide aqueous solutions of 26g and 36g are added in 60 minutes
13% sodium sulfite solution, is then added 870g8765.After charging, reaction mixture is cooled to room
Temperature.
By latex obtained by 310g with 270g softened waters, dispersant N40, the 1g of 5g purchased from BASF purchased from Dow Corning's
Antifoaming agent DC065,220g are purchased from the TiO of Kerr-McGee2CR828,165g are purchased from the CaCO of Omya3 5、
16g is purchased from Eastman's3g is purchased from Ashland's250HBR and 10g are purchased from
The propylene glycol of GuoYaoReagent companies is formulated together.The volumetric concentration of whole inorganic matters is about 45% in resulting composition.
Comparative example 11
By 408g latex B and 35g500、35.7gLR 8889,185g softened waters,
Antifoaming agent DC065, the 196g of dispersant N40, the 1g of 5g purchased from BASF purchased from Dow Corning are purchased from Kerr-McGee's
TiO2CR828,139g are purchased from the CaCO of Omya3 5,16g is purchased from Eastman's3g is purchased from
Ashland'sPropylene glycol of the 250HBR and 10g purchased from GuoYao Reagent companies is prepared.Gained combines
The volumetric concentration of whole inorganic matters is about 34% in object.
Comparative example 12
By the way that nitrogen is passed through in 4L reactors 10 minutes by its inerting, it is then charged into 600g softened waters, 25g granularities are
The 33% polystyrene seed latex of 33nm.Reactor containing above-mentioned material is heated to 85 DEG C, and in the whole of synthesis
Interior stirring.At 85 DEG C, 7% sodium persulfate aqueous solutions of 5g are added.After addition, proceed by emulsion feed, the lotion into
Material is by making 450g softened waters, the sodium salt of 28g fatty alcohol polyglycol ether sulfuric esters, 998g methyl methacrylates, 304g third
Olefin(e) acid N-butyl, 23g methacrylic acids and 13gTZM is mixed to get, and is added in 210 minutes.With lotion into
Material is parallel, starts the sodium persulfate aqueous solution for feeding 7 weight % of 95g, and added it in reactor in 240 minutes.It waits for
After initiator feed, reaction mixture is cooled to 75 DEG C.Then, 45g is added into reaction mixture in 5 minutes
8% sodium hydrate aqueous solution.Later, 10% tert-butyl hydroperoxide aqueous solutions of 26g are added in 60 minutes and 36g 13% is sub-
260g is then added in metabisulfite solution8765.After charging, reaction mixture is cooled to room temperature.Gained
The glass transition temperature of polymer is 59 DEG C.
By latex obtained by 310g with 270g softened waters, dispersant N40, the 1g of 5g purchased from BASF purchased from Dow Corning's
Antifoaming agent DC065,220g are purchased from the TiO of Kerr-McGee2CR828,165g are purchased from the CaCO of Omya3 5、
16g is purchased from Eastman's3g is purchased from Ashland's250HBR and 10g is purchased from GuoYao
The propylene glycol of Reagent companies is formulated together.The volumetric concentration of whole inorganic matters is about 45% in resulting composition.
Comparative example 13
By the way that nitrogen is passed through in 4L reactors 10 minutes by its inerting, it is then charged into 600g softened waters, 25g granularities are
The 33% polystyrene seed latex of 33nm.Reactor containing above-mentioned material is heated to 85 DEG C, and in the whole of synthesis
Interior stirring.At 85 DEG C, 7% sodium persulfate aqueous solutions of 5g are added.After addition, proceed by emulsion feed, the lotion into
Material is by making 450g softened waters, the sodium salt of 28g fatty alcohol polyglycol ether sulfuric esters, 247g methyl methacrylates, 1055g third
Olefin(e) acid N-butyl, 23g methacrylic acids and 13gTZM is mixed to get, and is added in 210 minutes.With lotion into
Material is parallel, starts the sodium persulfate aqueous solution for feeding 7 weight % of 95g, and added it in reactor in 240 minutes.It waits for
After initiator feed, reaction mixture is cooled to 75 DEG C.Then, 45g is added into reaction mixture in 5 minutes
8% sodium hydrate aqueous solution.Later, 10% tert-butyl hydroperoxide aqueous solutions of 26g are added in 60 minutes and 36g 13% is sub-
260g is then added in metabisulfite solution8765.After charging, reaction mixture is cooled to room temperature.Gained
The glass transition temperature of polymer is -23 DEG C.
By latex obtained by 310g with 270g softened waters, dispersant N40, the 1g of 5g purchased from BASF purchased from Dow Corning's
Antifoaming agent DC065,220g are purchased from the TiO of Kerr-McGee2CR828,165g are purchased from the CaCO of Omya3 5、
16g is purchased from Eastman's3g is purchased from Ashland's250HBR and 10g is purchased from GuoYao
The propylene glycol of Reagent companies is formulated together.The volumetric concentration of whole inorganic matters is about 45% in resulting composition.
Comparative example 14
By the way that nitrogen is passed through in 4L reactors 10 minutes by its inerting, it is then charged into 600g softened waters, 25g granularities are
The 33% polystyrene seed latex of 33nm.Reactor containing above-mentioned material is heated to 85 DEG C, and in the whole of synthesis
Interior stirring.At 85 DEG C, 7% sodium persulfate aqueous solutions of 5g are added.After addition, proceed by emulsion feed, the lotion into
Material is by making 450g softened waters, the sodium salt of 28g fatty alcohol polyglycol ether sulfuric esters, 705g methyl methacrylates, 527g third
Olefin(e) acid N-butyl, 23g methacrylic acids, 52g n-dodecyl mercaptans and 13gTZM is mixed to get, and 210
It is added in minute.It is parallel with emulsion feed, start the sodium persulfate aqueous solution for feeding 7 weight % of 95g, and will in 240 minutes
It is added in reactor.After to be triggered dose of charging, reaction mixture is cooled to 75 DEG C.Then, in 5 minutes to anti-
Answer addition 8% sodium hydrate aqueous solutions of 45g in mixture.Later, 10% tert-butyl hydroperoxide of 26g is added in 60 minutes
13% sodium sulfite solution of aqueous solution and 36g, is then added 260g8765.It is after charging, reaction is mixed
Object is closed to be cooled to room temperature.Molecular weight Mw according to the ISO13885-1 resulting polymers measured by gel permeation chromatography is
25421 dalton and Mn are 4789 dalton.
By latex obtained by 310g with 270g softened waters, dispersant N40, the 1g of 5g purchased from BASF purchased from Dow Corning's
Antifoaming agent DC065,220g are purchased from the TiO of Kerr-McGee2CR828,165g are purchased from the CaCO of Omya3 5、
16g is purchased from Eastman's3g is purchased from Ashland's250HBR and 10g is purchased from GuoYao
The propylene glycol of Reagent companies is formulated together.The volumetric concentration of whole inorganic matters is about 45% in resulting composition.
Apply film preparation and test method
All composition samples from above-described embodiment and comparative example are according to SS500：Method described in 2002
It is cast and is solidified into dry film, machine is carried out according to BASF Advanced Chemicals Company, Shanghai Site
Tool is tested and outdoor exposure.Mechanical test is carried out according to ASTM D412 using mold C, rate of extension 50mm/min.
According to JGT 172-2014,9754 GB/T, GB/T 9761 and GB/T 11186.2 carry out D. Lab PUR tests,
Film preparation, ash content explanation and ash content application.
By differential scanning calorimetry (TA DSC Q100, Waters TA, -80 to 120 DEG C, the second heating curves " in
Point temperature ", 10 DEG C/min of the rate of heat addition) measure Tg.
Data according to the table, the elongation at break values obtained through the embodiment of the present invention are about 100% or higher,
This means there is enough flexibilities by the film that the present composition obtains.
As for D. Lab PUR, the highest D. Lab PUR Δ E values obtained through the embodiment of the present invention are 7.34 (embodiments
6), it is still below comparative example 2-9.D. Lab PUR Δ E values are lower to mean that stain resistance is better.
As for 3 months outdoor exposures, the peak obtained through the embodiment of the present invention was 9.78 (embodiments 6), still low
In comparative example 2-9.The Δ E values of 3 months outdoor exposures are lower, and stain resistance is better.
Comparative example 1, although which give 6.04 low DPUR values, the fracture of the film of obtained comparative example 1
Elongation is 16%, and the value is too low and not applicable.
Can be seen that the film obtained by the present composition according to the data provided in table realizes excellent flexibility
And stain resistance.
Each file mentioned above is included in this specification by reference.
Other than explicitly pointing out in embodiment or in addition, the amount of material specified in this specification, reaction condition
Deng all quantity be understood as by " about " word modify.
It should be understood that upper and lower bound amount, range and ratio limit as described herein can be combined independently.It is similar
Ground, the range and amount of each element of the invention can be used together with the range of any other element or amount.
The scope of the present invention is not limited to described herein specific embodiment and embodiment.In fact, in addition to herein
Except those of described, various modifications of the invention become aobvious and easy by description before to those skilled in the art
See.These modifications are intended to fall within the scope of the appended claims.
Claims (20)
1. a kind of composition, including
A. photocurable component；
B. photoinitiator；With
C. the coating containing polymer does not include component A.
2. a kind of composition, including
A. photocurable component；
B. photoinitiator；With
C. the coating containing polymer does not include component A；
Wherein component A and component C physical mixeds.
3. a kind of composition, including
A. photocurable component；
B. photoinitiator；With
C. the coating containing polymer does not include component A；
Wherein component A is bonded with the polymer chemistry of component C to form the polymer-modified of the component A with chemical bonding.
4. the composition described in any one of claim 1-3, the wherein amount of component A be in the range of 0.01 to 9.9 weight %,
It is preferred that in the range of 0.05 to 8 weight %, more preferably in the range of 0.1 to 6 weight %, most preferably in 0.5 to 5 weight %
In the range of, the total weight of the solid component based on the present composition.
5. the composition described in any one of claim 1-3, the amount of component A can be in 0.1 to 9.9 weight in the present composition
In the range of amount %；It is preferred that in the range of 0.1 to 8 weight %；More preferably in the range of 0.1 to 6 weight %, such as
In the range of 0.5 to 5 weight %, the total weight of the solid component based on the present composition.
6. the composition described in any one of claim 1-3, the Tg of the polymer of component C is excellent in the range of -20 to 60 DEG C
It is selected in the range of -10 to 50 DEG C, more preferably in the range of -10 to 40 DEG C, most preferably in the range of 0 to 30 DEG C.
7. the composition described in any one of claim 1-3, the Mw of the polymer of component C is 25,000 to 10,000,000
In the range of you pause, preferably in the range of 30,000 to 5,000,000 dalton, more preferably 100,000 to 2,000,000
In the range of dalton, most preferably in the range of 300,000 to 1,000,000 dalton, and Mn is 4,000 to 1,000,
In the range of 000 dalton, preferably in the range of 5,000 to 500,000 dalton, more preferably 10,000 to 200,000
In the range of dalton, most preferably in the range of 40,000 to 100,000 dalton, passed through according to ISO 13885-1 solidifying
Glue penetration chromatography determination.
8. the composition described in any one of claim 1-3, wherein in the present composition amount of component A can 0.1 to
In the range of 9.9 weight %；The Tg of the polymer of component C in the range of -10 to 50 DEG C, the Mw of the polymer of component C 30,
In the range of 000 to 5,000,000 dalton, Mn is in the range of 5,000 to 500,000 dalton, according to ISO
13885-1 is measured by gel permeation chromatography.
9. the composition described in any one of claim 1-3, wherein in the present composition amount of component A can 0.1 to
In the range of 9.9 weight %；In the range of -10 to 40 DEG C, Mw's Tg of the polymer of component C of the polymer of component C exists
In the range of 100,000 to 2,000,000 dalton, Mn is in the range of 10,000 to 200,000 dalton, according to ISO
13885-1 is measured by gel permeation chromatography.
10. the composition described in any one of claim 1-9, the wherein amount of component B be in the range of 0.01 to 5 weight %,
It is preferred that in the range of 0.01 to 1 weight %, more preferably in the range of 0.01 to 0.5 weight %, most preferably 0.1 to 0.5
In the range of weight %, the total weight of the solid component based on the present composition.
11. the composition described in any one of claim 1-10, the wherein ratio of component A and component B by weight 1 to
In the range of 990, the ratio of preferred ingredient A and component B is up to 200, preferably up to 100, and component A and component B
Ratio is not less than 1.6, preferably not less than 2, more preferably no less than 5.
12. the composition described in any one of claim 1-11, wherein component A are selected from photo curable (methyl) acrylic acid
Monomer, oligomer and/or the polymer of ester, photo curable (poly-) urethane and photo curable epoxides；(methyl) propylene
Acid, maleic acid, fumaric acid, the allyl ester of itaconic acid, the monomer of vinyl esters, oligomer and/or polymer；Allyl ether,
Ethylene-ethyl base ether or thioether；Etc.；Preferably, component A is selected from polyester acrylate, polyether acrylate, propylene oxide
Acid esters, the monomer of urethane acrylate and 1,4-butanediol diacrylate, oligomer or polymer；More preferable component A choosings
From monomer, oligomer or the polymer of urethane acrylate and (methyl) allyl acrylate.
13. the composition described in any one of claim 1-12, wherein component B are selected from benzophenone, acetophenone, have hexichol
The derivative of ketone or acetophenone substructure, such as substituted benzophenone, such as 4- methyl benzophenones, 2,4,6- trimethyls
Benzophenone；Thioxanthones, such as isopropyl thioxanthone；The ethylenic bond unsaturation derivative of benzophenone or acetophenone, such as have
Have those of (methyl) acrylic acid groups such as (methyl) acryloyloxyethoxy benzophenone, or with those of vinyl as
4- ethyleneoxy benzophenone；Or the mixture of these active constituents, such as 4- methyl benzophenones and 2,4,6- trimethyls two
Benzophenone.
14. a kind of method for the composition preparing any one of claim 1-13, including：
Step 1：Form the coating containing polymer；
Step 2：Photocurable component and photoinitiator incorporation are contained during step 1 or after forming the coating containing polymer
In the coating of polymer,
The wherein described photocurable component and the coating physical mixed containing polymer, or with the coating containing polymer
Polymer chemistry bonding.
15. a kind of method of composition using any one of claim 1-13, including by any one of claim 1-13
Composition be applied on base material.
16. a kind of film is obtained by the composition of any one of claim 1-13.
17. the thickness of dry film of the film described in claim 16, wherein film is up to 1000 μm, preferably up to 500 μm, more
Preferably up to 300 μm, and especially up to up to 200 μm, and it is not less than 30 μm, it is preferably not less than 50 μm, more preferably not small
In 30 μm.
18. the film described in claim 16, wherein for internal applications, the thickness of dry film of film is at 50 μm to 500 μm
In the range of, more preferably in the range of 50 μm to 300 μm, such as in the range of 100 μm to 300 μm.
19. the film described in claim 16, wherein for applications, the thickness of dry film of film is at 30 μm to 1000 μm
In the range of, more preferably in the range of 50 μm to 1000 μm, it is still preferred in the range of 50 μm to 500 μm, such as at 50 μm
To in the range of 300 μm.
20. the film described in claim 19, wherein for wood substrates, the thickness of dry film of film is at 30 μm to 200 μm
In the range of, more preferably in the range of 50 μm to 150 μm, it is still preferred in the range of 50 μm to 100 μm.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNPCT/CN2015/085351 | 2015-07-28 | ||
| CN2015085351 | 2015-07-28 | ||
| PCT/EP2016/067876 WO2017017128A1 (en) | 2015-07-28 | 2016-07-27 | Coating compositions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108291109A true CN108291109A (en) | 2018-07-17 |
| CN108291109B CN108291109B (en) | 2021-07-09 |
Family
ID=56551399
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680055827.XA Active CN108291109B (en) | 2015-07-28 | 2016-07-27 | Coating composition |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP3328949A1 (en) |
| JP (1) | JP2018528995A (en) |
| KR (1) | KR20180030705A (en) |
| CN (1) | CN108291109B (en) |
| AU (1) | AU2016299363A1 (en) |
| BR (1) | BR112018001462A2 (en) |
| CL (1) | CL2018000243A1 (en) |
| MX (1) | MX2018001216A (en) |
| WO (1) | WO2017017128A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11945967B2 (en) | 2020-07-02 | 2024-04-02 | Behr Process Corporation | Dirt pick up resistant latex resin |
| WO2022017570A1 (en) | 2020-07-20 | 2022-01-27 | Bodotex International A/S | Uv curable epoxy resin compositions comprising reactive dilu-ents |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6653394B1 (en) * | 1998-11-30 | 2003-11-25 | Basf Coatings Ag | Coating agent consisting of at least three components, method for producing same and its utilization |
| CN1203143C (en) * | 1998-12-08 | 2005-05-25 | 罗姆和哈斯公司 | Dust-proof pick-up coating binding material and coating |
| CN100336877C (en) * | 2001-04-26 | 2007-09-12 | Jsr株式会社 | Aqueous paint compositions and floor polishing compositions |
| CN102140149A (en) * | 2010-12-30 | 2011-08-03 | 长兴化学工业(中国)有限公司 | Aqueous emulsion composition, and emulsion resin prepared by using same and use thereof |
| WO2012160891A1 (en) * | 2011-05-20 | 2012-11-29 | 関西ペイント株式会社 | Coating composition and method for forming coating film |
| CN102925062A (en) * | 2011-08-12 | 2013-02-13 | 汉高股份有限公司 | Optically-transparent dual-curing adhesive |
| CN102959679A (en) * | 2010-07-02 | 2013-03-06 | 株式会社德山 | Composition for photocurable imprint, and method for formation of pattern using the composition |
| WO2015013900A1 (en) * | 2013-07-31 | 2015-02-05 | Dow Global Technologies Llc | Aqueous coating composition with improved durability |
-
2016
- 2016-07-27 JP JP2018504212A patent/JP2018528995A/en active Pending
- 2016-07-27 BR BR112018001462A patent/BR112018001462A2/en not_active Application Discontinuation
- 2016-07-27 AU AU2016299363A patent/AU2016299363A1/en not_active Abandoned
- 2016-07-27 CN CN201680055827.XA patent/CN108291109B/en active Active
- 2016-07-27 WO PCT/EP2016/067876 patent/WO2017017128A1/en active Application Filing
- 2016-07-27 EP EP16744741.6A patent/EP3328949A1/en not_active Withdrawn
- 2016-07-27 KR KR1020187005755A patent/KR20180030705A/en unknown
- 2016-07-27 MX MX2018001216A patent/MX2018001216A/en unknown
-
2018
- 2018-01-26 CL CL2018000243A patent/CL2018000243A1/en unknown
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6653394B1 (en) * | 1998-11-30 | 2003-11-25 | Basf Coatings Ag | Coating agent consisting of at least three components, method for producing same and its utilization |
| CN1203143C (en) * | 1998-12-08 | 2005-05-25 | 罗姆和哈斯公司 | Dust-proof pick-up coating binding material and coating |
| CN100336877C (en) * | 2001-04-26 | 2007-09-12 | Jsr株式会社 | Aqueous paint compositions and floor polishing compositions |
| CN102959679A (en) * | 2010-07-02 | 2013-03-06 | 株式会社德山 | Composition for photocurable imprint, and method for formation of pattern using the composition |
| CN102140149A (en) * | 2010-12-30 | 2011-08-03 | 长兴化学工业(中国)有限公司 | Aqueous emulsion composition, and emulsion resin prepared by using same and use thereof |
| WO2012160891A1 (en) * | 2011-05-20 | 2012-11-29 | 関西ペイント株式会社 | Coating composition and method for forming coating film |
| CN102925062A (en) * | 2011-08-12 | 2013-02-13 | 汉高股份有限公司 | Optically-transparent dual-curing adhesive |
| WO2015013900A1 (en) * | 2013-07-31 | 2015-02-05 | Dow Global Technologies Llc | Aqueous coating composition with improved durability |
Also Published As
| Publication number | Publication date |
|---|---|
| CL2018000243A1 (en) | 2018-05-04 |
| WO2017017128A1 (en) | 2017-02-02 |
| MX2018001216A (en) | 2018-04-24 |
| EP3328949A1 (en) | 2018-06-06 |
| CN108291109B (en) | 2021-07-09 |
| JP2018528995A (en) | 2018-10-04 |
| BR112018001462A2 (en) | 2018-09-11 |
| KR20180030705A (en) | 2018-03-23 |
| AU2016299363A1 (en) | 2018-02-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103517928B (en) | Waterborne multistage polymer dispersion, its preparation method and the purposes as the tackiness agent for coated substrate thereof | |
| CN106883323B (en) | The method for being used to prepare aqueous vinyl polymer dispersion | |
| CN1205286C (en) | External-use mat coat composition | |
| CN104781351B (en) | Aqueous polymer dispersions are used for the purposes for improving colour retention in coating | |
| JP4991736B2 (en) | Aqueous binder composition | |
| CN104854202B (en) | Water-based paint compositions and the coating that there is special glossiness to be distributed formed by it | |
| CN107108815A (en) | Finely divided aqueous emulsion polymer and its be used for the purposes of hydrophobic coating | |
| EP3452519B1 (en) | Amine functional anionic polymer dispersion and coating compositions thereof | |
| CN108430953A (en) | coating composition for coating fiber cement board | |
| TW425421B (en) | Multicolor coating composition | |
| CN108291109A (en) | Coating composition | |
| JP3041189B2 (en) | Aqueous basement conditioning material and method for finishing building exterior walls using it | |
| JP3169085B2 (en) | Emulsion paint for building interior and exterior | |
| JP5219110B2 (en) | Water-based paint composition | |
| JP2003301139A (en) | Aqueous coating material composition for inorganic building material and board coated therewith | |
| CN110268026A (en) | Environmental-friendly water-based paint compositions | |
| JPH1190325A (en) | Applycation of external coating material on building | |
| JP4914599B2 (en) | Emulsion production method and paint using the same | |
| CN109689793A (en) | Aqueous polymeric composition | |
| JP4096273B2 (en) | Curable one-part silicone-modified acrylic emulsion paint composition | |
| CN107177263A (en) | Base material Mk system | |
| JP2752862B2 (en) | One-component aqueous primer composition | |
| CN109486333A (en) | Water-based paint compositions | |
| JP4637471B2 (en) | Water-based paint composition | |
| JP3242713B2 (en) | Manufacturing method of resin for matte paint |
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 |