CN108291109B

CN108291109B - Coating composition

Info

Publication number: CN108291109B
Application number: CN201680055827.XA
Authority: CN
Inventors: 曾重; A·田边; Z·卫; Q·H·杨; C-L·赵
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2015-07-28
Filing date: 2016-07-27
Publication date: 2021-07-09
Anticipated expiration: 2036-07-27
Also published as: EP3328949A1; CN108291109A; CL2018000243A1; JP2018528995A; KR20180030705A; WO2017017128A1; MX2018001216A; AU2016299363A1; BR112018001462A2

Abstract

The present invention relates to a composition comprising A) a photocurable component; B) a photoinitiator; and C) a coating layer comprising a polymer, wherein component A is physically mixed with component C or chemically bonded to the polymer of component C. The invention also relates to a method for preparing said composition and a method for applying said composition, and to the coating film obtained thereby.

Description

Coating composition

Technical Field

The invention relates to a coating composition, a preparation method and application thereof. In particular, the present invention relates to coating compositions for interior and exterior applications, in particular exterior applications. The invention also relates to a preparation method and application thereof.

Background

Coating compositions are widely used for a variety of substrates for, for example, decoration and/or protection. In many applications, particularly exterior applications, the coating film is exposed to contamination from the environment from the moment it is applied. The contamination includes dirt and dust which is brought to the surface of the coating film by rain, water droplets in the air, an air current, or direct physical contact with a human, an animal, or other objects. In addition, microorganisms on the coated walls also accelerate dust accumulation. It is desirable that the film remain clean and free of dust, dirt, or other contaminants throughout the useful life of the film. Therefore, a coating film formed from the coating composition is desired to have excellent stain resistance (DPUR), stain resistance, blocking resistance, and the like.

On the other hand, the substrate on which the coating is usually applied may have defects such as cracks and a rough surface, which requires the coating film to have bridging ability to cover these defects. In addition, new defects may also be generated and/or existing defects may be further developed as the substrate ages, which may lead to cracks on the formed coating film if the flexibility of the coating is not sufficient. Therefore, it is desirable that the coating has excellent flexibility so as to avoid defects of the coating film due to substrate defects or substrate aging.

In general, stain resistance requires a hard coating on a substrate, and in order to avoid coating film defects on the substrate, excellent flexibility of the coating film is desired. They are usually a pair of contradictory attributes.

WO 2010105938 a1 describes the incorporation of surface modified silica particles into a coating to improve the hardness of the film and thereby obtain an improved DPUR. However, the final coating does not have sufficient flexibility to bridge cracks in the substrate.

CN1256295A describes a method of balancing DPUR and flexibility by using a dispersion of a multistage emulsion polymer. It uses multistage emulsion polymerization to have hard and soft polymer domains on the final film. However, CN1256295A gained DPUR to some extent at the expense of flexibility. The final coating film of CN1256295A had moderate DPUR and flexibility properties, neither of which were outstanding.

US8993667 describes a redox polymerization of DPUR to improve elastomeric wall coatings. In US8993667, the glass transition temperature of the obtained polymer is low to obtain good flexibility. In US8993667, DPUR is still poor because the bulk polymer is too soft.

JP2007224084A discloses a photocurable composition for coating films for kitchen and access floors. According to JP2007224084A, the photocurable composition comprises photopolymerizable oligomers having two or more free-radically polymerizable double bonds, wherein the photopolymerizable oligomer (a) should contain a specific selection of photopolymerizable oligomer (a1) and photopolymerizable oligomer (a2) in defined proportions. Furthermore, the composition of JP2007224084A contains high levels of volatile organic compounds and requires an additional UV lamp to aid curing. Due to the high level of photoinitiator and the di/multifunctional monomer dosage, the final film obtained from the composition of JP2007224084A is too rigid to provide sufficient flexibility.

Therefore, coating films having both good DPUR and good flexibility for various applications are still being sought, while the coating preparation of the coating films is simple and cost-effective.

Disclosure of Invention

It is an object of the present invention to provide a composition which will form a coating film having both good DPUR and good flexibility.

In one aspect, the present invention relates to a composition comprising:

A. a photocurable component;

B. a photoinitiator; and

C. a coating comprising a polymer, not comprising component a;

wherein component a is physically mixed with component C or chemically bonded to the polymer of component C to form a modified polymer having chemically bonded component a.

It is another object of the present invention to provide a process for preparing the composition of the present invention comprising:

step 1: forming a polymer-containing coating;

step 2: incorporating a photocurable component and a photoinitiator into the polymer-containing coating during step 1 or after forming the polymer-containing coating,

wherein the photocurable component is physically mixed with the polymer-containing coating or chemically bonded to the polymer of the polymer-containing coating.

Furthermore, the present invention relates to a method of applying the composition of the present invention, comprising applying the composition of the present invention to a substrate.

The present invention also relates to a coating film formed from the composition of the present invention.

The coating film formed from the composition of the present invention has excellent stain resistance (DPUR), stain resistance, blocking resistance, and the like. Meanwhile, the coating film of the present invention has excellent flexibility.

Detailed Description

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

When used to define a term, the expressions "a", "an", "the" include plural as well as singular forms of the term.

The term "polymer" as used herein includes homopolymers (i.e., polymers prepared from a single reactive compound) and copolymers (i.e., polymers prepared by reacting at least two polymer-forming reactive monomeric compounds).

In a first aspect of the invention, the invention relates to a composition comprising:

A. a photocurable component;

B. a photoinitiator; and

C. a coating comprising a polymer, not comprising component a.

In another aspect of the invention, the invention relates to a composition comprising:

A. a photocurable component;

B. a photoinitiator; and

C. a coating comprising a polymer, not comprising component a;

Component A of the composition of the present invention is a photocurable component. The photocurable component includes monomers, oligomers, and/or polymers having two or more free radically polymerizable double bonds. Any photocurable material useful in coating compositions can be used in the compositions of the present invention. For example, component A may be a photocurable (meth) acrylate, a photocurable (poly) urethane, a photocurable epoxy polymer, or the like. Preferably, component a of the composition of the present invention is a monomer and/or oligomer of a polyester acrylate, a polyether acrylate, an epoxy acrylate, a polyurethane acrylate, or a mixture thereof. More preferably, component a of the composition of the invention may be selected from monomers and/or oligomers of: urethane acrylate,

PE55WIN、

LR8765、

LR 8983、

LR 8889、

LR8949 and 1, 4-butanediol diacrylate, all of which are available from BASF SE, Ludwigshafen, Germany. More preferably, component A of the composition of the present invention is

WA9057 or

LR8949。

Preferred components A of the compositions according to the invention contain unsaturated double bonds with different polymerization reactivity. Component a comprises monomers and/or oligomers and/or polymers of (meth) acrylic acid, allyl esters of maleic acid, fumaric acid, itaconic acid, vinyl esters; allyl ethers, vinyl-vinyl ethers or thioethers; and so on. More preferably, component a comprises monomers and/or oligomers of allyl esters, vinyl esters of (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid; allyl ethers, vinyl-vinyl ethers or thioethers, or mixtures thereof.

The amount of component a in the present composition may be in the range of 0.01 to 9.9 wt%, preferably in the range of 0.05 to 8 wt%, more preferably in the range of 0.1 to 6 wt%, most preferably in the range of 0.5 to 5 wt%, based on the total weight of the solid components of the present composition.

In preferred embodiments wherein component a is physically mixed with component C, the amount of component a in the present composition may range from 0.1 to 9.9 wt%; preferably in the range of 0.1 to 8 wt.%; more preferably in the range of from 0.1 to 6 wt%, for example in the range of from 0.5 to 5 wt%, based on the total weight of the solid components of the composition of the present invention.

In preferred embodiments wherein component a is chemically bonded to the polymer of component C, the amount of component a in the composition of the present invention may range from 0.01 to 9.9 wt.%; preferably in the range of 0.05 to 8 wt%; more preferably in the range of from 0.1 to 6 wt%, for example in the range of from 0.5 to 5 wt%, based on the total weight of the solid components of the composition of the present invention.

Any photoinitiator may be used as component B of the composition for the purposes of the present invention, provided that it can be used in a coating composition. For example, the photoinitiator may be selected from, but is not limited to, benzophenone or acetophenone or derivatives having benzophenone or acetophenone substructures, such as substituted benzophenones, e.g., 4-methylbenzophenone, 2,4, 6-trimethylbenzophenone; thioxanthones, such as isopropyl thioxanthone; or ethylenically unsaturated derivatives of benzophenone or acetophenone, examples being those having a (meth) acrylic group, such as (meth) acryloxyethoxybenzophenone, or those having a vinyl group, such as 4-vinyloxybenzophenone; or mixtures of these active ingredients, such as 4-methylbenzophenone and 2,4, 6-trimethylbenzophenone. Component B can be added before, during or after the actual formulation of A and/or C.

Preferably, component B of the composition of the invention may be selected from benzophenones, available from BASF

754、

500 and available from Lamberti SPA corporation

TZM、

TZT. More preferably, component B of the composition of the invention may be selected from

TZM and

500。

the amount of component B in the present composition may be in the range of 0.01 to 5 wt.%, preferably in the range of 0.01 to 1 wt.%, more preferably in the range of 0.01 to 0.5 wt.%, most preferably in the range of 0.1 to 0.5 wt.%, based on the total weight of the solid components of the present composition.

Component a and component B of the composition of the present invention may be used in an appropriate ratio of 1 to 990 (by weight). Preferably, in the composition of the invention, component a and component B may be used in a ratio of component a/component B of up to 200, more preferably up to 100. Preferably, in the composition of the present invention, component a and component B may be used in a ratio of component a/component B equal to or greater than 1.6, preferably equal to or greater than 2, more preferably equal to or greater than 5.

Component C of the composition of the present invention may be any polymer-containing coating. Component C is itself a coating composition that can be applied directly to a substrate to form a coating film. Preferably, the groupThe molecule C can be used directly for external applications, for example for the outer walls of buildings. Any polymer-containing coating composition conventional in the art may be used as component C. Component C can be prepared by a person skilled in the art according to conventional methods, or component C is commercially available. For example, component C may have the trade name

290、

7035、

7079 from BASF. In other embodiments of the present invention, component C may be obtained by the methods disclosed in US2014107249 or US2013079462 (each of these two documents is incorporated by reference in the present specification).

The polymer of component C of the composition of the present invention may be any polymer suitable for inclusion in a coating composition. For example, the polymer may be a polyester, a urethane epoxy, a poly (meth) acrylate, or the like. The skilled person will readily select an appropriate polymer of component C and the polymer is readily obtained by conventional techniques.

The glass transition temperature (Tg) of the polymer of component C is in the range of-20 to 60 ℃, preferably in the range of-10 to 50 ℃, more preferably in the range of-10 to 40 ℃, most preferably in the range of 0 to 30 ℃.

The Mw of the polymer of component C is in the range of 25,000 to 10,000,000 daltons, preferably in the range of 30,000 to 5,000,000 daltons, more preferably in the range of 100,000 to 2,000,000 daltons, most preferably in the range of 300,000 to 1,000,000 daltons, and Mn is in the range of 4,000 to 1,000,000 daltons, preferably in the range of 5,000 to 500,000 daltons, more preferably in the range of 10,000 to 200,000 daltons, most preferably in the range of 40,000 to 100,000 daltons.

Component C constitutes the balance of the composition of the present invention. Typically, component C may also contain additives. These additives may be pigmentsMaterials such as TiCl available from Kerr-McGee Corporation, Oklahoma, U.S.A₂CR 828; fillers, e.g. CaCO from Omya₃

5; film-forming auxiliaries, e.g. from Eastman Chemical

Thickeners, e.g. from Ashland

250 HBR; and antifreeze additives such as propylene glycol available from GuoYao Reagent; and so on. Any conventional additive used in coating compositions may be included in component C. Generally, these additives are used in their respective conventional amounts.

In a second aspect of the invention, the invention relates to a process for preparing a composition of the invention comprising:

step 1: forming a polymer-containing coating;

Step 1 of the process for preparing the composition of the present invention may be carried out under any conventional temperature and pressure conditions for forming a coating. The skilled person can select conditions suitable for step 1. In one embodiment of the present invention, step 1 is achieved by free radical initiated aqueous emulsion polymerization. This method has been described extensively before and is therefore sufficiently well known to the person skilled in the art [ see, for example, Encyclopedia 0f Polymer Science and Engineering, Vol.8, pp.659 to 677, John Wiley & Sons, Inc., 1987; blackley, Emulsion polymerization, pages 155 to 465, Applied Science Publishers, ltd, Essex, 1975; black, Polymer Latices, 2 nd edition, volume 1, pages 33-415, Chapman & Hall, 1997; washon, The Applications 0f Synthetic Resin Emulsions, pages 49 to 244, Ernest Benn, Ltd., London, 1972; piirma, Emulsion polymerization, pages 1 to 287, Academic Press, 1982; holscher, dispersion synthesis themischer Hochpolymerer, pages 1 to 160, Springer-Verlag, Berlin, 1969; and patent specification DE-A4003422 ]. Free-radically initiated aqueous emulsion polymerization is generally carried out by dispersing ethylenically unsaturated monomers in an aqueous medium, generally using dispersing assistants such as emulsifiers and/or protective colloids, and polymerizing them by means of at least one water-soluble free-radical polymerization initiator. In general, the residual amount of unreacted ethylenically unsaturated monomers in the aqueous polymer dispersions obtained is reduced by chemical and/or physical methods likewise known to the skilled worker [ see, for example, EP-A771328, DE-A19624299, DE-A19621027, DE-A19741184, DE-A19741187, DE-A19805122, DE-A19828183, DE-A19839199, DE-A19840586 and 19847115], by adjusting the polymer solids content to the desired level by dilution or concentration or addition of further customary additives such as fungicides, foam modifiers or viscosity modifiers to the aqueous polymer dispersions.

As for step 2 of the process, it may be carried out at any suitable temperature and pressure. For convenience and cost savings, the process for preparing the compositions of the present invention may be carried out at ambient temperature and pressure, e.g., room temperature and pressure.

In a third aspect of the invention, the invention relates to a method of applying the composition of the invention comprising applying the composition of the invention to a substrate.

The compositions of the invention can be applied by conventional application methods, such as brushing or rolling; spray coating such as air atomized spray, air assisted spray, airless spray, high volume low pressure spray, air assisted airless spray, electrostatic spray, and the like; spin coating; curtain coating, and the like.

Any suitable substrate can be used as the substrate to which the composition of the present invention is applied, for example, polymeric substrates, cement, concrete, ceramics, metal, wood, leather, and the like, provided that the coated substrate will be exposed to light, such as sunlight.

The coating film formed from the composition of the present invention may have any suitable dry film thickness after application to a substrate. Preferably, the dry film thickness of the coating film formed from the composition of the invention is up to 2000. mu.m, preferably up to 1000. mu.m, for example up to 500. mu.m, more preferably up to 300. mu.m, and especially up to 200. mu.m, and not less than 10 μm, preferably not less than 50 μm, more preferably not less than 100. mu.m.

More preferably, for internal applications, the dry film thickness of the coating film typically formed from the composition of the invention is in the range of 50 μm to 500 μm, more preferably in the range of 50 μm to 300 μm, for example in the range of 100 μm to 300 μm.

Preferably, for external applications, the dry film thickness of the coating film typically formed from the composition of the invention is in the range of 10 μm to 2000 μm, for example in the range of 30 μm to 1000 μm, more preferably in the range of 50 μm to 1000 μm, still preferably in the range of 50 μm to 500 μm, for example in the range of 50 μm to 300 μm.

In some preferred embodiments of the invention for external applications, the substrate is wood and the dry film thickness of the coating film formed from the composition of the invention 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 a fourth aspect of the invention, the invention relates to a coating film obtained from the composition of the invention.

In summary, the present invention includes the following embodiments.

1. A composition comprising

A. A photocurable component;

B. a photoinitiator; and

C. a coating comprising a polymer, not comprising component a.

2. A composition comprising

A. A photocurable component;

B. a photoinitiator; and

C. a coating comprising a polymer, not comprising component a;

wherein component A is physically mixed with component C.

3. A composition comprising

A. A photocurable component;

B. a photoinitiator; and

C. a coating comprising a polymer, not comprising component a;

wherein component a is chemically bonded to the polymer of component C to form a modified polymer having chemically bonded component a.

4. The composition of any of embodiments 1-3, wherein the amount of component a is in the range of 0.01 to 9.9 wt.%, preferably in the range of 0.05 to 8 wt.%, more preferably in the range of 0.1 to 6 wt.%, most preferably in the range of 0.5 to 5 wt.%, based on the total weight of the solid components of the composition of the present invention.

5. The composition of any of embodiments 1-3, the amount of component a in the composition of the present invention may range from 0.1 to 9.9 weight percent; preferably in the range of 0.1 to 8 wt.%; more preferably in the range of from 0.1 to 6 wt%, for example in the range of from 0.5 to 5 wt%, based on the total weight of the solid components of the composition of the present invention.

6. The composition of any of embodiments 1-3 wherein the polymer of component C has a Tg in the range of-20 to 60 ℃, preferably in the range of-10 to 50 ℃, more preferably in the range of-10 to 40 ℃, most preferably in the range of 0 to 30 ℃.

7. The composition of any of embodiments 1-3, wherein the Mw of the polymer of component C is in the range of 25,000 to 10,000,000 daltons, preferably in the range of 30,000 to 5,000,000 daltons, more preferably in the range of 100,000 to 2,000,000 daltons, most preferably in the range of 300,000 to 1,000,000 daltons, and Mn is in the range of 4,000 to 1,000,000 daltons, preferably in the range of 5,000 to 500,000 daltons, more preferably in the range of 10,000 to 200,000 daltons, most preferably in the range of 40,000 to 100,000 daltons, as determined by gel permeation chromatography according to ISO 13885-1.

8. The composition of any of embodiments 1-3, wherein the amount of component a in the composition of the present invention may range from 0.1 to 9.9 wt.%; the Tg of the polymer of component C is in the range of-10 to 50 ℃, the Mw of the polymer of component C is in the range of 30,000 to 5,000,000 dalton, and the Mn is in the range of 5,000 to 500,000 dalton, determined by gel permeation chromatography according to ISO 13885-1.

9. The composition of any of embodiments 1-3, wherein the amount of component a in the composition of the present invention may range from 0.1 to 9.9 wt.%; the Tg of the polymer of component C is in the range of-10 to 40 ℃, the Mw of the polymer of component C is in the range of 100,000 to 2,000,000 dalton, the Mn is in the range of 10,000 to 200,00 dalton, determined by gel permeation chromatography according to ISO 13885-1.

10. The composition of any of embodiments 1-9, wherein the amount of component B is in the range of 0.01 to 5 weight percent, preferably in the range of 0.01 to 1 weight percent, more preferably in the range of 0.01 to 0.5 weight percent, most preferably in the range of 0.1 to 0.5 weight percent, based on the total weight of the solid components of the composition of the present invention.

11. The composition of any of embodiments 1-10 wherein the ratio of component a and component B is in the range of 1 to 990 (by weight), preferably the ratio of component a and component B is up to 200, preferably up to 100, and the ratio of component a and component B is no less than 1.6, preferably no less than 2, more preferably no less than 5.

12. The composition of any of embodiments 1-11, wherein component a is selected from the group consisting of monomers, oligomers, and/or polymers of photocurable (meth) acrylates, photocurable (poly) urethanes, and photocurable epoxides; monomers, oligomers and/or polymers of allyl esters, vinyl esters of (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid; allyl ethers, vinyl-vinyl ethers or thioethers; and the like; preferably, component a is selected from monomers, oligomers or polymers of polyester acrylates, polyether acrylates, epoxy acrylates and 1, 4-butanediol diacrylate; more preferably component A is selected from monomers, oligomers or polymers of urethane acrylates and allyl (meth) acrylates.

13. The composition of any of embodiments 1-12, wherein component B is selected from benzophenone, acetophenone, derivatives having benzophenone or acetophenone substructures, for example substituted benzophenones such as 4-methylbenzophenone, 2,4, 6-trimethylbenzophenone; thioxanthones, such as isopropyl thioxanthone; ethylenically unsaturated derivatives of benzophenone or acetophenone, examples being those having a (meth) acrylic group such as (meth) acryloxyethoxybenzophenone, or those having a vinyl group such as 4-vinyloxybenzophenone; or mixtures of these active ingredients, such as 4-methylbenzophenone and 2,4, 6-trimethylbenzophenone.

14. A method of making the composition of any one of embodiments 1-13, comprising:

step 1: forming a polymer-containing coating;

15. A method of applying the composition of any of embodiments 1-13, comprising applying the composition of any of embodiments 1-13 to a substrate.

16. A coating film obtained from the composition of any one of embodiments 1-13.

17. The coated film of embodiment 13, wherein the coated film has a dry film thickness of up to 1000 μm, preferably up to 500 μm, more preferably up to 300 μm, and particularly up to 200 μm, and not less than 30 μm, preferably not less than 50 μm, more preferably not less than 30 μm.

18. The coating film of embodiment 13, wherein the dry film thickness of the coating film for internal applications is in the range of 50 μm to 500 μm, more preferably in the range of 50 μm to 300 μm, for example in the range of 100 μm to 300 μm.

19. The coating film of embodiment 13, wherein the dry film thickness of the coating film for external applications is in the range of 30 μm to 1000 μm, more preferably in the range of 50 μm to 1000 μm, still preferably in the range of 50 μm to 500 μm, for example in the range of 50 μm to 300 μm.

20. The coated film of embodiment 19, wherein the dry film thickness of the coated film 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 for a wood substrate.

Examples

The present invention will be further described hereinafter with reference to specific examples, which are intended to be illustrative and explanatory only and not limiting.

Each part and percentage used is provided by weight if not otherwise defined.

The materials used were:

example 1

It was inertized by passing nitrogen through a 4L reactor for 10 minutes and then charged with 600g of demineralized water, 25g of 33% polystyrene seed latex with a particle size of 33 nm. The reactor containing the above materials was then heated to 85 ℃ with stirring for synthesis. Then, 5g of 7% aqueous sodium persulfate solution was added at 85 ℃. After the addition, 450g of demineralized water, 28g of the sodium salt of fatty alcohol polyglycol ether sulfate, 705g of methyl methacrylate, 527g of n-butyl acrylate, 23g of methacrylic acid and 13g of

The emulsion feed resulting from the TZM mixing was added to the reactor. In parallel with the emulsion feed, 95g of an initiator feed of a 7 wt.% aqueous sodium persulfate solution was fed to the reactor over 240 minutes. After the initiator charge addition was complete, the resulting reaction mixture was cooled to 75 ℃. Then, 45g of an 8% aqueous solution of sodium hydroxide was added to the reaction mixture over 5 minutes. Thereafter, 26g of a 10% aqueous solution of tert-butyl hydroperoxide and 36g of 13% methylene chloride were added over 60 minutesSodium sulfate solution, then 260g

LR 8765. After the end of the feed, the reaction mixture was cooled to room temperature. A latex is produced. The glass transition temperature of the resulting polymer was 31 ℃. The molecular weight was determined by gel permeation chromatography according to ISO 13885-1. The Mw was about 373,000 daltons and the Mn was about 86,000 daltons.

310g of the latex obtained were mixed with 270g of demineralized water and 5g of dispersant from BASF

AA4140, 1g defoamer DC065 from Dow Corning, 220g TiO 06E from Kerr-McGee₂CR828, 165g CaCO from Omya₃

5. 16g from Eastman

3g from Ashland

250HBR and 10g of propylene glycol from GuoYao Reagent company were formulated together to form a composition. The volume concentration of all inorganic species in the resulting composition was about 45%.

In the composition obtained, the amount of the water-soluble polymer,

the content of LR 8765 is about 5.01%,

the TZM content was about 0.25%.

Comparative example 1

It was inertized by passing nitrogen through a 4L reactor for 10 minutes and then charged with 600g of demineralized water, 25g of 33% polystyrene seed latex with a particle size of 33 nm. The reactor containing the above materials was heated to 85 ℃ with stirring for synthesis. Then, 5g of a 7% aqueous solution of sodium persulfate was added thereto at 85 ℃. After the addition, an emulsion obtained by mixing 450g of demineralized water, 28g of the sodium salt of fatty alcohol polyglycol ether sulfate, 705g of methyl methacrylate, 527g of n-butyl acrylate, 23g of methacrylic acid was fed into the reactor over 210 minutes. In parallel with the emulsion feed, 95g of an initiator feed of a 7 wt.% aqueous sodium persulfate solution was fed to the reactor over 240 minutes. After the initiator charge addition was complete, the resulting reaction mixture was cooled to 75 ℃. Then, 45g of an 8% aqueous solution of sodium hydroxide was added to the reaction mixture over 5 minutes. Thereafter, 26g of a 10% aqueous solution of t-butyl hydroperoxide and 36g of a 13% sodium sulfite solution were added over 60 minutes, and then the reaction mixture was cooled to room temperature. A latex is produced.

5. 16g from Eastman

3g from Ashland

In the resulting composition, no photocurable component and no photoinitiator are present.

Example 2

It was inertized by passing nitrogen through a 4L reactor for 10 minutes and then charged with 600g of demineralized water, 25g of 33% polystyrene seed latex with a particle size of 33 nm. Under stirring, the mixture is reactedThe reactor was heated to 85 ℃ for synthesis. Then, 5g of a 7% aqueous solution of sodium persulfate was added thereto at 85 ℃. After the addition, 450g of demineralized water, 28g of the sodium salt of fatty alcohol polyglycol ether sulfate, 625g of methyl methacrylate, 607g of 2-ethylhexyl acrylate, 23g of methacrylic acid and 13g of

500 the resulting emulsion feed was mixed and fed to the reactor. In parallel with the emulsion feed, 95g of an initiator feed of a 7 wt.% aqueous sodium persulfate solution was fed to the reactor over 240 minutes. After the initiator charge addition was complete, the resulting reaction mixture was cooled to 75 ℃. Then, 45g of an 8% aqueous solution of sodium hydroxide was added to the reaction mixture over 5 minutes. Thereafter, 26g of 10% aqueous tert-butyl hydroperoxide and 36g of 13% sodium sulfite solution were added over 60 minutes, followed by 260g

LR 8765. After the end of the feed, the reaction mixture was cooled to room temperature. A latex is produced. The glass transition temperature of the resulting polymer was 4 ℃. The molecular weight was determined by gel permeation chromatography according to ISO 13885-1. Mw was approximately 467,000 daltons and Mn was approximately 91,000 daltons.

5. 16g from Eastman

3g from Ashland

250HBR and10g of propylene glycol from GuoYao Reagent company were formulated together to form a composition. The volume concentration of all inorganic species in the resulting composition was about 45%.

In the composition obtained, the amount of the water-soluble polymer,

the content of LR 8765 is about 5.01%,

the content of 500 is about 0.25%.

Comparative example 2

It was inertized by passing nitrogen through a 4L reactor for 10 minutes and then charged with 600g of demineralized water, 25g of 33% polystyrene seed latex with a particle size of 33 nm. The reactor containing the above materials was heated to 85 ℃ with stirring for synthesis. Then, 5g of a 7% aqueous solution of sodium persulfate was added thereto at 85 ℃. After the addition, an emulsion obtained by mixing 450g of demineralized water, 28g of the sodium salt of fatty alcohol polyglycol ether sulfate, 625g of methyl methacrylate, 607g of 2-ethylhexyl acrylate, 23g of methacrylic acid was fed into the reactor over 210 minutes. In parallel with the emulsion feed, 95g of an initiator feed of a 7 wt.% aqueous sodium persulfate solution was fed to the reactor over 240 minutes. After the initiator charge addition was complete, the resulting reaction mixture was cooled to 75 ℃. Then, 45g of an 8% aqueous solution of sodium hydroxide was added to the reaction mixture over 5 minutes. Thereafter, 26g of 10% aqueous tert-butyl hydroperoxide and 36g of 13% sodium sulfite solution were added over 60 minutes, and the reaction mixture was cooled to room temperature. A latex is produced.

5. 16g from Eastman

3g from Ashland

Example 3

It was inertized by passing nitrogen through a 4L reactor for 10 minutes and then charged with 1000g of demineralized water, 25g of 33% polystyrene seed latex with a particle size of 33 nm. The reactor containing the above materials was heated to 85 ℃ with stirring for synthesis. Then, 5g of a 7% aqueous solution of sodium persulfate was added thereto at 85 ℃. After the addition, an emulsion feed obtained by mixing 450g of demineralized water, 28g of the sodium salt of fatty alcohol polyglycol ether sulfate, 1000g of allyl methacrylate, 25g of n-dodecyl mercaptan was fed into the reactor over 180 minutes. In parallel with the emulsion feed, 95g of an initiator feed of a 7 wt.% aqueous sodium persulfate solution was fed to the reactor over 210 minutes. After the initiator charge addition was complete, the resulting reaction mixture was cooled to 75 ℃. Then, 25g of an 8% aqueous solution of sodium hydroxide was added to the reaction mixture over 5 minutes. Thereafter, 26g of a 10% aqueous solution of tert-butyl hydroperoxide and 36g of a 13% sodium sulfite solution were added over 60 minutes. After the end of the feed, the reaction mixture was cooled to room temperature. A latex is produced for further use. The glass transition temperature of the polymer in the latex obtained was 19 ℃. The molecular weight was determined by gel permeation chromatography according to ISO 13885-1. The Mw was about 98,000 daltons and the Mn was about 4,000 daltons.

In this example, allyl methacrylate is chemically bonded to the polymer formed in the latex. FT-IR analysis showed that about 70% by weight of allyl groups, which are active photocurable components, were retained in the resulting latex.

Example 4

It was inertized by passing nitrogen through a 4L reactor for 10 minutes and then charged with 600g of demineralized water, 25g of 33% polystyrene seed latex with a particle size of 33 nm. The reactor containing the above materials was heated to 85 ℃ with stirring for synthesis. Then, 5g of a 7% aqueous solution of sodium persulfate was added thereto at 85 ℃. After the addition, 450g of demineralized water, 28g of the sodium salt of fatty alcohol polyglycol ether sulfate, 594g of methyl methacrylate, 577g of 2-ethylhexyl acrylate, 23g of methacrylic acid and 13g of water were mixed in 210 minutes

500 the resulting emulsion feed was mixed and fed to the reactor. In parallel with the emulsion feed, 95g of an initiator feed of a 7 wt.% aqueous sodium persulfate solution was fed to the reactor over 240 minutes. After 190 minutes of emulsion feed addition, 62g of allyl methacrylate was added to the remaining emulsion feed and the feed was continued. After the initiator feed was complete, the reaction mixture was cooled to 75 ℃. Then, 45g of an 8% aqueous solution of sodium hydroxide was added to the reaction mixture over 5 minutes. Thereafter, 26g of a 10% aqueous solution of tert-butyl hydroperoxide and 36g of a 13% sodium sulfite solution were added over 60 minutes. After the end of the feed, the reaction mixture was cooled to room temperature. A latex is produced. The glass transition temperature of the resulting polymer was 11 ℃. The molecular weight was determined by gel permeation chromatography according to ISO 13885-1. Mw was about 1,453,000 daltons and Mn was 108,000 daltons.

The resulting latex was formulated in the same manner as described in example 1.

In this example, allyl methacrylate was added during the preparation of the latex. FT-IR analysis showed that about 70% by weight of allyl groups, which are active photocurable components, were retained in the resulting latex. In the resulting composition, the allyl methacrylate content was about 1.35%,

the content of 500 is about 0.28%.

Comparative example 3

It was inertized by passing nitrogen through a 4L reactor for 10 minutes and then charged with 600g of demineralized water, 25g of 33% polystyrene seed latex with a particle size of 33 nm. The reactor containing the above materials was heated to 85 ℃ with stirring for synthesis. Then, 5g of a 7% aqueous solution of sodium persulfate was added thereto at 85 ℃. After the addition, 450g of demineralized water, 28g of the sodium salt of fatty alcohol polyglycol ether sulfate, 625g of methyl methacrylate, 607g of 2-ethylhexyl acrylate, 23g of methacrylic acid and 13g of

500 the resulting emulsion feed was mixed and fed to the reactor. In parallel with the emulsion feed, 95g of an initiator feed of a 7 wt.% aqueous sodium persulfate solution was fed to the reactor over 240 minutes. After the initiator charge addition was complete, the resulting reaction mixture was cooled to 75 ℃. Then, 45g of an 8% aqueous solution of sodium hydroxide was added to the reaction mixture over 5 minutes. Thereafter, 26g of a 10% aqueous solution of tert-butyl hydroperoxide and 36g of a 13% sodium sulfite solution were added over 60 minutes. After the end of the feed, the reaction mixture was cooled to room temperature. A latex is produced.

In the resulting composition, no photocurable component is contained.

Example 5

280g of a commercially available dispersion from BASF

290 (latex A) with 1.4g

TZT、29g

WA9057, 270g demineralized water, 5g dispersant from BASF

5. 16g from Eastman

3g from Ashland

250HBR and 10g of propylene glycol from GuoYao Reagent company were formulated together to form a composition. The volume concentration of all inorganic species in the resulting composition was about 45%. The glass transition temperature of the polymer in latex A was 20 ℃. The molecular weight was determined by gel permeation chromatography according to ISO 13885-1. Mw was about 512,000 daltons and Mn was about 77,000 daltons.

In the composition obtained, the amount of the water-soluble polymer,

the content of WA9057 WAs about 5.30%,

the TZT content is about 0.26%.

Comparative example 4

309g of latex A was mixed with 1.4g of

TZT, 270g demineralized water, 5g dispersant from BASF

5. 16g from Eastman

3g from Ashland

In the resulting composition, no photocurable component is contained.

Example 6

303g of latex A are mixed with 0.6g

754、6.4g

LR 8983, 270g demineralized water, 5g dispersant from BASF

5. 16g from Eastman

3g from Ashland

In the composition obtained, the amount of the water-soluble polymer,

the content of LR 8983 was about 1.16%,

754 is present in an amount of about 0.11%.

Comparative example 5

280g of latex A were mixed with 29g of latex A

WA9057, 270g demineralized water, 5g dispersant from BASF

5. 16g from Eastman

3g from Ashland

In the resulting composition, no photoinitiator was present.

Example 7

280g of latex A were mixed with 0.3g of benzophenone and 29g of

LR8949, 270g demineralized water, 5g dispersant from BASF

5. 16g from Eastman

3g from Ashland

In the composition obtained, the amount of the water-soluble polymer,

the content of LR8949 was about 5.15%, and the content of benzophenone was about 0.05%.

Example 8

284g of a commercially available dispersion from BASF

7079 (latex B) with 1g

TZM、25g

PE55WIN, 270g demineralized water, 5g dispersant from BASF

5. 16g from Eastman

3g from Ashland

250HBR and 10g of propylene glycol from GuoYao Reagent company were formulated together to form a groupA compound (I) is provided. The volume concentration of all inorganic species in the resulting composition was about 45%. The glass transition temperature of the polymer in latex B was 10 ℃. The molecular weight was determined by gel permeation chromatography according to ISO 13885-1. The Mw was about 917,000 daltons and the Mn was about 190,000 daltons.

In the composition obtained, the amount of the water-soluble polymer,

the PE55WIN content was about 4.49%,

the TZM content was about 0.18%.

Example 9

408g of latex B were mixed with 1.3g of

500、35.7g

LR 8889, 185g demineralized water, 5g dispersant from BASF

AA4140, 1g defoamer from Dow Corning DC065, 196g TiO from Kerr-McGee₂CR828, 139g CaCO from Omya₃

5. 16g from Eastman

3g from Ashland

250HBR and 10g of propylene glycol from GuoYao Reagent company were formulated together to form a composition. The volume concentration of all inorganic species in the resulting composition was about 34%.

In the composition obtained, the amount of the water-soluble polymer,

the content of LR 8889 is about 6.15%,

the content of 500 is about 0.22%.

Comparative example 6

445g of latex B were mixed with 185g of demineralized water, 5g of dispersant from BASF

5. 16g from Eastman

3g from Ashland

Example 10

427g of latex B and 1g

TZT、17g

HDDA, 185g demineralized water, 5g dispersant from BASF

5. 16g from Eastman

3g from Ashland

In the composition obtained, the amount of the water-soluble polymer,

the content of HDDA is about 2.98%,

the TZT content is about 0.18%.

Example 11

400g of a commercially available dispersion from BASF

7035 (latex C) with 1g

754、44g

WA9057, 185g demineralized water, 5g dispersant from BASF

5. 16g from Eastman

3g from Ashland

250HBR and 10g of propylene glycol from GuoYao Reagent company were formulated together to form a composition. The volume concentration of all inorganic species in the resulting composition was about 34%. The glass transition temperature of the polymer in latex C was 23 ℃. The molecular weight was determined by gel permeation chromatography according to ISO 13885-1. Mw was about 394,000 daltons and Mn was about 62,000 daltons.

In the composition obtained, the amount of the water-soluble polymer,

the content of WA9057 WAs about 7.93%,

754 is present in an amount of about 0.18%.

Comparative example 7

445g of latex C were mixed with 185g of demineralized water, 5g of dispersant from BASF

5. 16g from Eastman

3g from Ashland

Example 12

400g of latex C were mixed with 1g of benzophenone, 44g of the dispersion obtained in example 3, 185g of demineralized water, 5g of dispersant from BASF

5. 16g from Eastman

3g from Ashland

250HBR and 10g of propylene glycol from GuoYao Reagent company were formulated together to form a composition. The volume concentration of all inorganic species in the resulting composition was about 35%.

The composition obtained had an allyl methacrylate content of about 2.89% and a benzophenone content of about 0.18%.

Comparative example 8

444g of latex C were mixed with 1g of benzophenone, 185g of demineralized water, 5g of dispersant from BASF

5. 16g from Eastman

3g from Ashland

250HBR and 10g from GuPropylene glycol from oYao Reagent was formulated together to form a composition. The volume concentration of all inorganic species in the resulting composition was about 34%.

In the resulting composition, no photocurable component is contained.

Example 13

408g of latex A were mixed with 1.3g of benzophenone, 36g of the dispersion from example 3, 185g of demineralized water, 5g of dispersant from BASF

5. 16g from Eastman

3g from Ashland

The composition obtained had an allyl methacrylate content of about 2.32% and a benzophenone content of about 0.23%.

Comparative example 9

400g of latex C were mixed with 45g of the dispersion obtained in example 3, 185g of demineralized water, 5g of dispersant from BASF

5. 16g from Eastman

3g from Ashland

In the resulting composition, no photocurable component is contained.

Comparative example 10

It was inertized by passing nitrogen through a 4L reactor for 10 minutes and then charged with 600g of demineralized water, 25g of 33% polystyrene seed latex with a particle size of 33 nm. The reactor containing the above materials was heated to 85 ℃ and stirred for the entire time of the synthesis. 5g of 7% aqueous sodium persulfate solution was added at 85 ℃. After the addition, an emulsion feed was started by bringing 450g of demineralized water, 28g of the sodium salt of fatty alcohol polyglycol ether sulfate, 705g of methyl methacrylate, 527g of n-butyl acrylate, 23g of methacrylic acid and 13g of

TZM was mixed and added over 210 minutes. In parallel with the emulsion feed, 95g of 7 wt.% aqueous sodium persulfate solution was initially fed and fed to the reactor over 240 minutes. After the initiator feed was complete, the reaction mixture was cooled to 75 ℃. Then, 45g of 8% aqueous sodium hydroxide solution was added to the reaction mixture over 5 minutes. Thereafter, 26g of 10% aqueous tert-butyl hydroperoxide and 36g of 13% sodium sulfite solution were added over 60 minutes, followed by 870g

8765. After the end of the feed, the reaction mixture was cooled to room temperature.

310g of the latex obtained were mixed with 270g of demineralized water, 5g of dispersant N40 from BASF, 1g of defoamer DC065 from Dow Corning, 220g of TiO 220 from Kerr-McGee₂CR828, 165g CaCO from Omya₃

5. 16g from Eastman

3g from Ashland

250HBR was formulated with 10g of propylene glycol from GuoYaoReagent. The volume concentration of all inorganic species in the resulting composition was about 45%.

Comparative example 11

408g of latex B and 35g of latex B

500、35.7g

LR 8889, 185g demineralized water, 5g dispersant N40 from BASF, 1g defoamer DC065 from Dow Corning, 196g TiO from Kerr-McGee₂CR828, 139g CaCO from Omya₃

5. 16g from Eastman

3g from Ashland

250HBR and 10g of propylene glycol from GuoYao Reagent were formulated. The volume concentration of all inorganic species in the resulting composition was about 34%.

Comparative example 12

It was inertized by passing nitrogen through a 4L reactor for 10 minutes and then charged with 600g of demineralized water, 25g of 33% polystyrene seed latex with a particle size of 33 nm. The reactor containing the above materials was heated to 85 ℃ and stirred for the entire time of the synthesis. 5g of a 7% aqueous solution of sodium persulfate was added at 85 ℃. After addingAn emulsion feed was started by bringing 450g of demineralized water, 28g of the sodium salt of a fatty alcohol polyglycol ether sulfate, 998g of methyl methacrylate, 304g of n-butyl acrylate, 23g of methacrylic acid and 13g of

TZM was mixed and added over 210 minutes. In parallel with the emulsion feed, 95g of a 7 wt.% aqueous solution of sodium persulfate was initially fed and fed to the reactor over 240 minutes. After the initiator feed was complete, the reaction mixture was cooled to 75 ℃. Then, 45g of an 8% aqueous solution of sodium hydroxide was added to the reaction mixture over 5 minutes. Thereafter, 26g of 10% aqueous tert-butyl hydroperoxide and 36g of 13% sodium sulfite solution were added over 60 minutes, followed by 260g

8765. After the end of the feed, the reaction mixture was cooled to room temperature. The glass transition temperature of the resulting polymer was 59 ℃.

5. 16g from Eastman

3g from Ashland

250HBR was formulated with 10g of propylene glycol from GuoYao Reagent. The volume concentration of all inorganic species in the resulting composition was about 45%.

Comparative example 13

It was inertized by passing nitrogen through a 4L reactor for 10 minutes and then charged with 600g of demineralized water, 25g of 33% polystyrene seed latex with a particle size of 33 nm. To be reacted withThe reactor was heated to 85 ℃ and stirred for the entire time of the synthesis. 5g of a 7% aqueous solution of sodium persulfate was added at 85 ℃. After the addition, an emulsion feed was started by bringing 450g of demineralized water, 28g of the sodium salt of the fatty alcohol polyglycol ether sulfate, 247g of methyl methacrylate, 1055g of n-butyl acrylate, 23g of methacrylic acid and 13g of

8765. After the end of the feed, the reaction mixture was cooled to room temperature. The glass transition temperature of the resulting polymer was-23 ℃.

5. 16g from Eastman

3g from Ashland

Comparative example 14

By passing nitrogen through a 4L reactor for 10 minutesInertised, then charged with 600g of demineralised water, 25g of 33% polystyrene seed latex with a particle size of 33 nm. The reactor containing the above materials was heated to 85 ℃ and stirred for the entire time of the synthesis. 5g of a 7% aqueous solution of sodium persulfate was added at 85 ℃. After the addition, an emulsion feed was started by bringing 450g of demineralized water, 28g of the sodium salt of fatty alcohol polyglycol ether sulfate, 705g of methyl methacrylate, 527g of n-butyl acrylate, 23g of methacrylic acid, 52g of n-dodecyl mercaptan and 13g of

8765. After the end of the feed, the reaction mixture was cooled to room temperature. The molecular weight Mw of the resulting polymer was 25421 daltons, as determined by gel permeation chromatography according to ISO13885-1, and Mn was 4789 daltons.

5. 16g from Eastman

3g from Ashland

250HBR and 10g from GuoYao reagentPropylene glycol from company t was formulated together. The volume concentration of all inorganic species in the resulting composition was about 45%.

Coating film preparation and testing method

All composition samples from the above examples and comparative examples were according to SS 500: 2002, cast and cured to a dry film, mechanically tested and exposed outdoors according to BASF Advanced Chemicals Company, Shanghai Site. Mechanical testing was performed according to ASTM D412 using die C, with a tensile rate of 50 mm/min.

Laboratory DPUR testing, membrane preparation, ash specification and ash application were performed according to JGT 172-.

The Tg is determined by differential scanning calorimetry (TA DSC Q100, Waters TA, -80 to 120 ℃, midpoint temperature of the second heating curve, heating rate 10 ℃/min).

According to the data shown in the table, the elongation at break values obtained by the inventive examples are about 100% or higher, which means that the coating films obtained from the inventive compositions have sufficient flexibility.

As for the laboratory DPUR, the highest value of the laboratory DPUR Δ E obtained by the inventive examples was 7.34 (example 6), which is still lower than that of the comparative examples 2-9. Lower values of laboratory DPUR Δ E mean better stain resistance.

For an outdoor exposure of 3 months, the maximum value obtained by the inventive example is 9.78 (example 6), still lower than that of comparative examples 2-9. The lower the delta E value for 3 months outdoor exposure, the better the stain resistance.

Comparative example 1, which obtained a low DPUR value of 6.04, but the elongation at break of the film of comparative example 1 obtained was 16%, which value was too low to be applicable.

As can be seen from the data provided in the table, the coating films obtained from the composition of the present invention achieve excellent flexibility and stain resistance.

Each of the documents mentioned above is incorporated by reference into this specification.

Except in the examples, or where otherwise explicitly indicated, all numbers in this description specifying amounts of materials, reaction conditions, and the like, are to be understood as modified by the word "about".

It is understood that the upper and lower amount, range, and ratio limits described herein may be independently combined. Similarly, the ranges and amounts for each element of the invention can be used with ranges or amounts for any of the other elements.

The scope of the invention is not limited to the specific embodiments and examples described herein. Indeed, various modifications of the invention in addition to those described herein will become apparent to those skilled in the art from the foregoing description. Such modifications are intended to fall within the scope of the appended claims.

Claims

1. A composition comprising

A. A photocurable component;

B. a photoinitiator; and

C. a coating comprising a polymer, not comprising component A,

wherein the amount of component A is in the range of from 0.01 to 9.9 wt%, based on the total weight of the solid components of the composition,

the Mw of the polymer of component C is in the range of 300,000 to 10,000,000 daltons, and the Mn is in the range of 62,000 to 1,000,000 daltons, as determined by gel permeation chromatography according to ISO 13885-1.

2. A composition comprising

A. A photocurable component;

B. a photoinitiator; and

C. a coating comprising a polymer, not comprising component a;

wherein component A is physically mixed with component C,

3. A composition comprising

A. A photocurable component;

B. a photoinitiator; and

C. a coating comprising a polymer, not comprising component a;

wherein component A is chemically bonded to the polymer of component C to form a modified polymer having chemically bonded component A,

4. The composition of any one of claims 1-3, wherein the amount of component A ranges from 0.05 to 8 weight percent, based on the total weight of the solid components of the composition.

5. The composition of claim 4, wherein the amount of component A ranges from 0.1 to 6 weight percent based on the total weight of the solid components of the composition.

6. The composition of claim 5, wherein the amount of component A is in the range of 0.5 to 5 weight percent, based on the total weight of the solid components of the composition.

7. The composition of any one of claims 1-3, the amount of component A in the composition being in the range of from 0.1 to 9.9 weight percent, based on the total weight of the solid components of the composition.

8. The composition of claim 7, wherein the amount of component A in the composition is in the range of 0.1 to 8 weight percent, based on the total weight of the solid components of the composition.

9. The composition of claim 8, wherein the amount of component a in the composition is in the range of 0.1 to 6 weight percent, based on the total weight of the solid components of the composition.

10. The composition of claim 9, wherein the amount of component a in the composition is in the range of 0.5 to 5 weight percent, based on the total weight of the solid components of the composition.

11. The composition of any of claims 1-3, the polymer of component C having a Tg in the range of-20 to 60 ℃.

12. The composition of claim 11, the polymer of component C having a Tg in the range of-10 to 50 ℃.

13. The composition of claim 12, the Tg of the polymer of component C being in the range of-10 to 40 ℃.

14. The composition of claim 13, the Tg of the polymer of component C is in the range of 0 to 30 ℃.

15. The composition of any of claims 1-3, the Mw of the polymer of component C is in the range of 300,000 to 5,000,000 daltons, as determined by gel permeation chromatography according to ISO 13885-1.

16. The composition of claim 15, the Mw of the polymer of component C is in the range of 300,000 to 2,000,000 daltons, as determined by gel permeation chromatography according to ISO 13885-1.

17. The composition of claim 16, the Mw of the polymer of component C is in the range of 300,000 to 1,000,000 daltons, as determined by gel permeation chromatography according to ISO 13885-1.

18. The composition of any of claims 1-3, the Mn of the polymer of component C is in the range of 62,000 to 500,000 daltons, as determined by gel permeation chromatography according to ISO 13885-1.

19. The composition of claim 18, the Mn of the polymer of component C is in the range of 62,000 to 200,000 daltons, as determined by gel permeation chromatography according to ISO 13885-1.

20. The composition of claim 19, the Mn of the polymer of component C is in the range of 62,000 to 100,000 daltons, as determined by gel permeation chromatography according to ISO 13885-1.

21. The composition of any one of claims 1-3, wherein the amount of component A in the composition is in the range of 0.1 to 9.9 wt.%; the Tg of the polymer of component C is in the range of-10 to 50 ℃, the Mw of the polymer of component C is in the range of 300,000 to 5,000,000 dalton, and the Mn is in the range of 62,000 to 500,000 dalton, determined by gel permeation chromatography according to ISO 13885-1.

22. The composition of any one of claims 1-3, wherein the amount of component A in the composition is in the range of 0.1 to 9.9 wt.%; the Tg of the polymer of component C is in the range of-10 to 40 ℃, the Mw of the polymer of component C is in the range of 300,000 to 2,000,000 dalton, and the Mn is in the range of 62,000 to 200,000 dalton, determined by gel permeation chromatography according to ISO 13885-1.

23. The composition of any one of claims 1-3, wherein the amount of component B is in the range of 0.01 to 5 weight percent, based on the total weight of the solid components of the composition.

24. The composition of claim 23, wherein the amount of component B is in the range of 0.01 to 1 weight percent, based on the total weight of the solid components of the composition.

25. The composition of claim 24, wherein the amount of component B is in the range of 0.01 to 0.5 weight percent, based on the total weight of the solid components of the composition.

26. The composition of claim 25, wherein the amount of component B is in the range of 0.1 to 0.5 weight percent, based on the total weight of the solid components of the composition.

27. A composition according to any one of claims 1-3, wherein the ratio of component a and component B is in the range of 1 to 990 by weight, and the ratio of component a and component B is not less than 1.6.

28. The composition of claim 27 wherein the ratio of component a and component B is up to 200.

29. The composition of claim 28 wherein the ratio of component a and component B is up to 100.

30. The composition of claim 27 wherein the ratio of component a and component B is not less than 2.

31. The composition of claim 30 wherein the ratio of component a and component B is not less than 5.

32. The composition of any of claims 1-3, wherein component A is selected from the group consisting of monomers, oligomers and/or polymers of photocurable (meth) acrylates, photocurable (poly) urethanes and photocurable epoxides; monomers, oligomers and/or polymers of allyl esters, vinyl esters of (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid; allyl ethers, vinyl-vinyl ethers or thioethers.

33. The composition of claim 32, wherein component a is selected from the group consisting of monomers, oligomers, or polymers of polyester acrylates, polyether acrylates, epoxy acrylates, urethane acrylates, and 1, 4-butanediol diacrylate.

34. The composition of claim 32, wherein component a is selected from monomers, oligomers, or polymers of urethane acrylates and allyl (meth) acrylates.

35. A composition according to any one of claims 1-3, wherein component B is selected from benzophenone, acetophenone, derivatives having benzophenone or acetophenone substructures; or mixtures of these active ingredients.

36. The composition of claim 35 wherein component B is selected from a substituted benzophenone, a thioxanthone, or an ethylenically unsaturated derivative of a benzophenone or an acetophenone.

37. The composition of claim 36, wherein the substituted benzophenone is 4-methylbenzophenone or 2,4, 6-trimethylbenzophenone.

38. The composition of claim 36, wherein the thioxanthone is isopropylthioxanthone.

39. The composition of claim 36 wherein the ethylenically unsaturated derivatives of benzophenone or acetophenone are those having a (meth) acrylic group or those having a vinyl group.

40. The composition of claim 39 wherein those having (meth) acrylic groups are (meth) acryloxyethoxybenzophenones.

41. The composition of claim 39 wherein those having a vinyl group are 4-vinyloxybenzophenones.

42. The composition according to claim 35, wherein the mixture of active ingredients is 4-methylbenzophenone and 2,4, 6-trimethylbenzophenone.

43. A method of making the composition of any one of claims 1-42, comprising:

step 1: forming a polymer-containing coating;

44. A method of applying the composition of any one of claims 1-42, comprising applying the composition of any one of claims 1-42 to a substrate.

45. A coating film obtained from the composition of any one of claims 1 to 42.

46. The coated film according to claim 45, wherein the coated film has a dry film thickness of up to 1000 μm and not less than 30 μm.

47. A coated film according to claim 46 wherein the dried film thickness of the coated film is up to 500 μm.

48. A coated film according to claim 47 wherein the dried film thickness of the coated film is up to 300 μm.

49. A coated film according to claim 48 wherein the dried film thickness of the coated film is up to 200 μm.

50. The coated film according to claim 46, wherein the coated film has a dry film thickness of not less than 50 μm.

51. The coated film according to claim 50, wherein the coated film has a dry film thickness of not less than 30 μm.

52. The coated film of claim 45, wherein the coated film has a dry film thickness in the range of 50 μm to 500 μm for interior applications.

53. The coated film of claim 52, wherein the coated film has a dry film thickness in the range of 50 μm to 300 μm for internal applications.

54. The coated film of claim 53, wherein the coated film has a dry film thickness in the range of 100 μm to 300 μm for internal applications.

55. The coated film of claim 45, wherein the coated film has a dry film thickness in the range of 30 μm to 1000 μm for external applications.

56. The coated film of claim 55, wherein the coated film has a dry film thickness in the range of 50 μm to 1000 μm for external applications.

57. The coated film of claim 56, wherein the coated film has a dry film thickness in the range of 50 μm to 500 μm for external applications.

58. The coated film of claim 57, wherein the coated film has a dry film thickness in the range of 50 μm to 300 μm for external applications.

59. The coated film of claim 55, wherein the dry film thickness of the coated film is in the range of 30 μm to 200 μm for a wood substrate.

60. The coated film of claim 59, wherein the dried film thickness of the coated film is in the range of 50 μm to 150 μm for a wood substrate.

61. The coated film of claim 60, wherein the dry film thickness of the coated film is in the range of 50 μm to 100 μm for a wood substrate.