Hydroxyl acrylate aqueous dispersion and preparation method thereof

Abstract

The invention relates to a hydroxyl acrylate aqueous dispersion and a preparation method thereof. The hydroxyl acrylic acid aqueous dispersion comprises copolymers prepared from the following raw materials: (A) a hydroxyl functional polymer I with low glass transition temperature, (B) a hydroxyl functional polymer II with high glass transition temperature, and (C) a carboxyl functional hydrophilic polymer. The hydroxyl functional polymer is obtained by at least carrying out polymerization reaction on raw materials comprising a monomer a, the structure of the monomer a is as shown in # imgabs0 # and / or # imgabs1 #, and the dispersion can be matched with a water-based / oil-based isocyanate curing agent for use to obtain quick-drying finish paint with high gloss and high bubble-free film thickness.

Description

Technical Field

[0001] The invention belongs to the field of water-based coatings, and particularly relates to a hydroxy acrylate aqueous dispersion and a preparation method thereof, as well as application in water-based industrial coatings. Background Art

[0002] Water-based coatings can largely avoid the serious environmental pollution problems caused by solvent-based coatings. At the same time, under the guidance of current environmental protection policies, water-based coatings, especially low-solvent water-based coatings, are the inevitable trend of the current coating industry. Water-based hydroxy acrylic dispersions have excellent properties such as high gloss, good weather resistance, color retention and gloss retention, and are widely used in high-end coatings including automotive coatings. However, when hydroxy acrylic acid ester aqueous dispersions are used in the field of 2K coatings, they cannot achieve high bubble-free film thickness on the basis of achieving quick drying, which limits their application scope to a certain extent. Patent document US8119729 discloses a method for preparing a hydroxy acrylic acid ester aqueous dispersion, using a special (meth) acrylic acid ester monomer with an alcohol part having a carbon number of 8 or more, and limiting its use to more than 12.5%. Although the patent can improve the bubble-free film thickness to a certain extent, the special monomers used are relatively expensive, and the longer chain length reduces the drying speed of the paint film, which is not conducive to downstream applications. Patent document US20040314164 discloses a method for preparing a hydroxyl acrylate aqueous dispersion, which uses a cyclic (meth) acrylate monomer, and its purpose is to improve glossiness and durability, and can improve the thickness of the bubble-free film, but the improvement is not large. Patent document CN115873366 discloses a low-cost quick-drying hydroxyl acrylic dispersion and its preparation method, which uses a low-viscosity, high-permeability hydroxyl acrylic emulsion as a dispersion medium, and replaces water in the dispersion stage to disperse and emulsify acrylic resin to obtain a hydroxyl acrylic dispersion, which aims to effectively improve the drying speed of the paint film, and the cost is low, but the addition of the emulsion reduces the fullness of the paint film to a certain extent, and the thickness of the bubble-free film of the paint film decreases to a certain extent.

[0003] In summary, a technology needs to be provided to obtain high bubble-free film thickness while meeting downstream requirements for drying speed and high gloss and fullness of appearance. Summary of the invention

[0004] The present invention provides a hydroxyl acrylate aqueous dispersion and a preparation method thereof, aiming to provide a hydroxyl acrylate dispersion. Firstly, the a-structured hydroxyl monomer is introduced into the polymer chain segment by solution polymerization. The introduction of this structural hydroxyl monomer can effectively balance the reactivity with the curing agent to obtain a rapid establishment of high bubble-free film thickness and hardness. At the same time, the hydroxyl-functional polymer with a low glass transition temperature has the characteristics of low viscosity and good leveling, which promotes the fusion and flow with the curing agent during the film-forming process, further increasing the bubble-free film thickness of the paint film. The introduction of the hydroxyl-functional polymer with a high glass transition temperature further promotes the establishment of the hardness of the paint film.

[0005] When this dispersion is applied to a 2K coating system, the paint film has a fast drying speed, and at the same time, the obtained paint film has a high bubble-free film thickness.

[0006] To achieve the above object, the present invention provides the following technical solutions.

[0007] A hydroxyl acrylate aqueous dispersion, comprising a copolymer prepared from the following components:

[0008] (A) Hydroxyl-functional polymer I with a low glass transition temperature: 10 wt% - 50 wt%, preferably 20 wt% - 40 wt%;

[0009] (B) Hydroxyl-functional polymer II with a high glass transition temperature: 20 wt% - 65 wt%, preferably 30 wt% - 60 wt%;

[0010] (C) Carboxyl-functional hydrophilic polymer III: 10 wt% - 35 wt%, preferably 15 wt% - 30 wt%;

[0011] Among them, at least one of the polymers I, II, and III, preferably at least one of polymers I and II, is prepared from a monomer a with the following structural formula,

[0012]

[0013] Among them,

[0014] R 1 、R 2 are respectively Among them, n ≥ 1, m ≥ 0, and n + m ≤ 5.

[0015] The TG of the hydroxyl-functional polymer I with a low glass transition temperature in the present invention is -30 to 10 °C, preferably -20 to 0 °C.

[0016] The TG of the hydroxyl-functional polymer II with a high glass transition temperature in the present invention is 20 to 65 °C, preferably 25 to 60 °C.

[0017] The TG of the carboxyl-functional hydrophilic polymer III described in the present invention is 30 to 90 °C, preferably 40 to 80 °C.

[0018] In the copolymer described in the present invention, the hydroxyl-functional (meth)acrylate monomer accounts for 8-40% of the total mass of polymers I, II, and III, preferably 10-35%; the monomer a is one of the hydroxyl-functional (meth)acrylate monomers, and the monomer a accounts for 25-65% of the total mass of the hydroxyl-functional (meth)acrylate monomers, preferably 30-50%.

[0019] A method for preparing a hydroxyacrylate aqueous dispersion according to the present invention comprises the following steps:

[0020] (1) In the presence of an organic solvent, polymer I is polymerized by free radical polymerization from non-functional (meth)acrylate monomers, hydroxyl-functional (meth)acrylate monomers, and other polymerization monomers;

[0021] (2) Then, on the basis of polymer I, non-functional (meth)acrylate monomers, hydroxyl-functional (meth)acrylate monomers, and other polymerization monomers are further polymerized to obtain polymer II;

[0022] (3) Then, on the basis of polymers I and II, non-functional (meth)acrylate monomers, hydroxyl-functional (meth)acrylate monomers, and carboxyl-functional (meth)acrylate monomers are obtained to obtain polymer III;

[0023] (4) A neutralizing agent is added for neutralization and then water dispersion is carried out to obtain a hydroxyacrylate aqueous dispersion;

[0024] Among them, monomer a is used in one or more of steps (1), (2), and (3), preferably used in step (1) and / or (2), and more preferably used in step (2).

[0025] In the preparation method described in the present invention, the monomer composition in step (1) is as follows:

[0026] Non-functional (meth)acrylate monomers: 20-60%;

[0027] Hydroxyl-functional (meth)acrylate monomers: 20-50%;

[0028] Other polymerization monomers: 0-40%;

[0029] The above proportions are based on the total of all monomers in step (1).

[0030] In the preparation method described in the present invention, the monomer composition in step (2) is as follows:

[0031] Non-functional (meth)acrylate monomers: 10-50%;

[0032] Hydroxy-functional (meth)acrylate monomers: 15-40%;

[0033] Other polymerizable monomers: 20-60%;

[0034] The above proportions are based on the total of all monomers in step (2).

[0035] In the preparation method of the present invention, the monomer composition in step (3) is as follows:

[0036] Non-functional (meth)acrylate monomers: 45-70%;

[0037] Hydroxy-functional (meth)acrylate monomers: 15-40%;

[0038] Carboxy-functional (meth)acrylate monomers: 8-20%;

[0039] The above proportions are based on the total of all monomers in step (3).

[0040] The non-functional (meth)acrylic monomers of the present invention include one or more of methyl (meth)acrylate, butyl (meth)acrylate, ethyl (meth)acrylate, isooctyl (meth)acrylate, dodecyl (meth)acrylate, isobornyl (meth)acrylate, and norbornyl (meth)acrylate.

[0041] Except for monomer a, the hydroxy-functional (meth)acrylic monomers of the present invention include one or more of 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 6-hydroxyhexyl acrylate, and 6-hydroxyhexyl methacrylate.

[0042] Monomer a of the present invention is selected from one or more of the following structures:

[0043]

[0044]

[0045] Among them, the above monomer a is preferably one or two of them. This secondary hydroxyl structure is beneficial to the control of the activity during the reaction process, is conducive to the formation of a product with a high bubble-free film thickness, and at the same time, the short side chain structure does not affect the rapid establishment of high hardness.

[0046] The carboxy-functional (meth)acrylic monomers of the present invention are selected from acrylic acid and / or methacrylic acid.

[0047] Other polymerization monomers include one or more of styrene, (meth)acrylonitrile, and acrylamide.

[0048] The application of a hydroxyacrylate aqueous dispersion of the present invention in the field of waterborne coatings.

[0049] The hydroxyacrylate dispersion obtained in the present invention can achieve rapid hardness establishment when used in combination with waterborne / oily isocyanate curing agents, and at the same time has the characteristics of high gloss and high bubble-free film thickness. Specific embodiments

[0050] The embodiments of the present invention are described in detail through the following examples. In these examples, all glass transition temperatures (TG) are calculated using the FOX formula; all drying rates are measured using a BGD261 linear drying rate recorder from Biaogeda Precision Instruments (Guangzhou) Co., Ltd.; all film thicknesses are tested using a QNIX 4500 film thickness gauge (the paint film is sprayed on the surface of tinplate); all glosses are measured on Leneta cardboard according to the standard of GB / T 9754-2007.

[0051] The sources of the raw materials are shown in Table 1 below.

[0052] Table 1

[0053]

[0054] Example 1:

[0055] Add 50 g of Pnb to a 1 L reactor equipped with a heating device, a condensing device, and a stirring device and heat to 140 °C. When the initial material is heated to 140 °C, start to uniformly dropwise add the following monomer mixture: 25 g of styrene, 30 g of butyl acrylate, 35 g of 2-hydroxyethyl methacrylate, 45 g of isooctyl acrylate, and 4 g of DTBP. The dropping time is about 2.5 hours. After the monomer mixture is dropped, keep the temperature at this temperature for 15 min.

[0056] Then uniformly dropwise add the following monomer mixture: 50 g of methyl methacrylate, 70 g of 2-hydroxypropyl acrylate, 67 g of styrene, 20 g of isooctyl acrylate, and 7 g of DTBP. The dropping time is about 2.5 hours. After the monomer mixture is dropped, keep the temperature at this temperature for 0.5 hour.

[0057] Then continue to uniformly add dropwise the following monomer mixture: 53 g of methyl methacrylate, 10 g of butyl acrylate, 20 g of 2-hydroxyethyl methacrylate, 13 g of acrylic acid and 1.8 g of DTBP. After the addition of the monomer mixture is completed, continue to keep the temperature for 1.0 h at this temperature, then cool down to below 105 °C, add 16.8 g of N,N-dimethylethanolamine and stir for 20 minutes, and then disperse with 530 g of 40 °C warm water dispersion for 1 hour to obtain a hydroxy acrylic acid dispersion product. The TG values of the I / II / III segments of this dispersion are -19 °C / 29 °C / 68 °C respectively.

[0058] Example 2:

[0059] Add 50 g of BCS to a 1 L reactor equipped with a heating device, a condensing device and a stirring device and heat to 140 °C. When the initial material is heated to 140 °C, start to uniformly add dropwise the following monomer mixture: 20 g of styrene, 15 g of 2-hydroxypropyl acrylate, 10 g of 2-hydroxyethyl methacrylate, 20 g of methyl methacrylate, 30 g of isooctyl acrylate and 2 g of DTBP. The dropping time is about 1.0 hour. After the addition of the monomer mixture is completed, keep the temperature for 15 min at this temperature.

[0060] Then uniformly add dropwise the following monomer mixture: 90 g of methyl methacrylate, 60 g of 2-hydroxypropyl acrylate, 87 g of styrene and 4 g of DTBP. The dropping time is about 2.5 hours. After the addition of the monomer mixture is completed, keep the temperature for 0.5 hour at this temperature.

[0061] Then continue to uniformly add dropwise the following monomer mixture: 50 g of methyl methacrylate, 3 g of butyl acrylate, 20 g of 2-hydroxyethyl methacrylate, 13 g of acrylic acid and 2.0 g of DTBP. After the addition of the monomer mixture is completed, continue to keep the temperature for 1.0 h at this temperature, then cool down to below 105 °C, add 16.8 g of N,N-dimethylethanolamine and stir for 20 minutes, and then disperse with 530 g of 40 °C warm water dispersion for 1 hour to obtain a hydroxy acrylic acid dispersion product. The TG values of the I / II / III segments of this dispersion are -4 °C / 45 °C / 83 °C respectively.

[0062] Example 3:

[0063] Add 70 g of Pnb to a 1 L reactor equipped with a heating device, a condensing device and a stirring device and heat to 140 °C. When the initial material is heated to 140 °C, start to uniformly add dropwise the following monomer mixture: 25 g of 2-hydroxyethyl methacrylate, 12 g of methyl methacrylate, 23 g of isooctyl acrylate and 1 g of DTBP. The dropping time is about 1.0 hour. After the addition of the monomer mixture is completed, keep the temperature for 15 min at this temperature.

[0064] Then, the following monomer mixture was added dropwise evenly: 95 g of methyl methacrylate, 60 g of 1,2-propanediol 2-methyl-2-propenoate, 107 g of styrene, 10 g of isooctyl acrylate, and 4 g of DTBP. The dropping time was about 3.0 hours. After the monomer mixture was added dropwise, it was kept warm at this temperature for 0.5 hour.

[0065] Then, the following monomer mixture was continued to be added dropwise evenly: 40 g of methyl methacrylate, 13 g of butyl acrylate, 20 g of 2-hydroxyethyl methacrylate, 13 g of acrylic acid, and 1.5 g of DTBP. After the monomer mixture was added dropwise, it was continued to be kept warm at this temperature for 1.0 h, and then cooled to below 105 °C. 16.8 g of N,N-dimethylethanolamine was added and stirred for 20 minutes, and then dispersed with 530 g of 40 °C warm water dispersion for 1 hour to obtain a hydroxy acrylic acid dispersion product. The TG of the I / II / III segments of this dispersion was -2 °C / 65 °C / 57 °C respectively.

[0066] Comparative Example 1:

[0067] 50 g of Pnb was added to a 1 L reactor equipped with a heating device, a condensing device, and a stirring device and heated to 140 °C. When the initial material was heated to 140 °C, the following monomer mixture was started to be added dropwise evenly: 25 g of styrene, 30 g of butyl acrylate, 35 g of 2-hydroxyethyl methacrylate, 45 g of isooctyl acrylate, and 4 g of DTBP. The dropping time was about 2.5 hours. After the monomer mixture was added dropwise, it was kept warm at this temperature for 15 min.

[0068] Then, the following monomer mixture was added dropwise evenly: 50 g of methyl methacrylate, 70 g of 2-hydroxyethyl methacrylate, 67 g of styrene, 20 g of isooctyl acrylate, and 7 g of DTBP. The dropping time was about 2.5 hours. After the monomer mixture was added dropwise, it was kept warm at this temperature for 0.5 hour.

[0069] Then, the following monomer mixture was continued to be added dropwise evenly: 53 g of methyl methacrylate, 10 g of butyl acrylate, 20 g of 2-hydroxyethyl methacrylate, 13 g of acrylic acid, and 1.8 g of DTBP. After the monomer mixture was added dropwise, it was continued to be kept warm at this temperature for 1.0 h, and then cooled to below 105 °C. 16.8 g of N,N-dimethylethanolamine was added and stirred for 20 minutes, and then dispersed with 530 g of 40 °C warm water dispersion for 1 hour to obtain a hydroxy acrylic acid dispersion product. The TG of the I / II / III segments of this dispersion was -19 °C / 52 °C / 68 °C respectively.

[0070] Comparative Example 2:

[0071] Add 50 g of Pnb to a 1 L reactor equipped with a heating device, a condensing device, and a stirring device, and heat it to 140 °C. When the initial material is heated to 140 °C, start to uniformly dropwise add the following monomer mixture: 25 g of styrene, 30 g of butyl acrylate, 35 g of 2-hydroxypropyl acrylate, 45 g of isooctyl acrylate, and 4 g of DTBP. The dropping time is about 2.5 hours. After the monomer mixture is added dropwise, keep the temperature at this level for 15 min.

[0072] Then uniformly dropwise add the following monomer mixture: 50 g of methyl methacrylate, 70 g of 2-hydroxypropyl acrylate, 67 g of styrene, 20 g of isooctyl acrylate, and 7 g of DTBP. The dropping time is about 2.5 hours. After the monomer mixture is added dropwise, keep the temperature at this level for 0.5 hour.

[0073] Then continue to uniformly dropwise add the following monomer mixture: 53 g of methyl methacrylate, 10 g of butyl acrylate, 20 g of 2-hydroxypropyl acrylate, 13 g of acrylic acid, and 1.8 g of DTBP. After the monomer mixture is added dropwise, continue to keep the temperature at this level for 1.0 h, then cool down to below 105 °C, add 16.8 g of N,N-dimethylethanolamine and stir for 20 minutes, and then disperse it with 530 g of 40 °C warm water dispersion for 1 hour to obtain a hydroxyacrylic acid dispersion product. The TGs of the I / II / III segments of this dispersion are -30 °C / 29 °C / 52 °C respectively.

[0074] Comparative Example 3:

[0075] Add 50 g of Pnb to a 1 L reactor equipped with a heating device, a condensing device, and a stirring device, and heat it to 140 °C. When the initial material is heated to 140 °C, start to uniformly dropwise add the following monomer mixture: 30 g of styrene, 30 g of methyl methacrylate, 35 g of 2-hydroxyethyl methacrylate, 40 g of isooctyl acrylate, and 4 g of DTBP. The dropping time is about 2.5 hours. After the monomer mixture is added dropwise, keep the temperature at this level for 15 min.

[0076] Then uniformly dropwise add the following monomer mixture: 50 g of methyl methacrylate, 70 g of 2-hydroxypropyl acrylate, 67 g of styrene, 20 g of isooctyl acrylate, and 7 g of DTBP. The dropping time is about 2.5 hours. After the monomer mixture is added dropwise, keep the temperature at this level for 0.5 hour.

[0077] Then continue to uniformly dropwise add the following monomer mixture: 53 g of methyl methacrylate, 10 g of butyl acrylate, 20 g of 2-hydroxyethyl methacrylate, 13 g of acrylic acid, and 1.8 g of DTBP. After the addition of the monomer mixture is completed, continue to keep the temperature for 1.0 h at this temperature, then cool down to below 105 °C, add 16.8 g of N,N-dimethylethanolamine and stir for 20 minutes, and then disperse with 530 g of 40 °C warm water dispersion for 1 hour to obtain a hydroxyl acrylic acid dispersion product. The TG of the I / II / III segments of this dispersion is 19 °C / 29 °C / 68 °C respectively.

[0078] Table 2 Paint formulation: Component A

[0079]

[0080] Note: Raw materials without specified manufacturers can be used interchangeably as long as they are of the same type.

[0081] Table 3 Paint formulation: White paste

[0082]

[0083] Note: Raw materials without specified manufacturers can be used interchangeably as long as they are of the same type.

[0084] Table 4 Paint formulation: Component B

[0085]

[0086] According to the formulations in Tables 2, 3, and 4, perform the following preparations:

[0087] White paste preparation: While stirring at 1500 r with a disperser, sequentially add water, BYK190, R996, and Tego904w, and then stir for 150 min. Add 35 g of zirconium beads and grind with a grinding disc at 3000 r for 2 h. The fineness of the white paste is less than 10. Component A: While stirring, sequentially add the raw materials of Component A and stir sufficiently at 600 r for 30 - 40 min to obtain Component A;

[0088] Component B: Dilute HT600 with PGDA to 80%;

[0089] Add Component B to Component A, stir at 1000 r for 3 min according to the NCO / OH = 1.5 ratio. After film formation, place it at room temperature of 25 °C for 20 min (for thick coating, level for 15 min), and bake in an oven at 60 °C for 25 min.

[0090] Perform gloss, drying speed, and bubble-free film thickness tests on the waterborne paints prepared from the hydroxyl acrylate resin dispersions of each example and comparative example. The test results are shown in Table 5:

[0091] Table 5 Test results of gloss, drying speed, and bubble-free film thickness of waterborne paints

[0092]

[0093] In Comparative Example 1, there is no a structure in the hydroxy acrylic monomer. Although it has a good drying speed, it is impossible to obtain a high gloss and a bubble-free film thickness. In Comparative Example 2, the content of the a structure monomer is too high. Although it has a high bubble-free film thickness, its drying speed is slow. In Comparative Example 3, there is no hydroxy polymer with a low glass transition temperature, and its gloss and bubble-free film thickness are poor.

[0094] Finally, it should be noted that the above embodiments are only used to describe the preferred embodiments of the present invention, rather than limiting the protection scope of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that various modifications or equivalent substitutions made to the technical solutions of the present invention should fall within the protection scope determined by the claims of the present invention.

Claims

1. A hydroxyacrylate aqueous dispersion comprising a copolymer prepared from the following components: (A) A low glass transition temperature hydroxy-functional polymer I: 10 wt% - 50 wt%, preferably 20 wt% - 40 wt%; (B) A high glass transition temperature hydroxy-functional polymer II: 20 wt% - 65 wt%, preferably 30 wt% - 60 wt%; (C) A carboxyl-functional hydrophilic polymer III: 10 wt% - 35 wt%, preferably 15 wt% - 30 wt%; wherein, at least one of the polymers I, II, and III, preferably at least one of polymers I and II, is prepared from a monomer a having the following structural formula, and / or wherein, R 1 and R 2 are respectively where n≥1, m≥0, and n + m≤5.

2. The aqueous dispersion according to claim 1, characterized in that the TG of the low glass transition temperature hydroxy-functional polymer I is -30 to 10 °C, preferably -20 to 0 °C; the TG of the high glass transition temperature hydroxy-functional polymer II is 20 to 65 °C, preferably 25 to 60 °C; the TG of the carboxyl-functional hydrophilic polymer III is 30 to 90 °C, preferably 40 to 80 °C.

3. The aqueous dispersion according to claim 1 or 2, characterized in that in the copolymer, the hydroxy-functional (meth)acrylate monomers account for 8 - 40% of the total mass of polymers I, II, and III, preferably 10 - 35%; the monomer a is one of the hydroxy-functional (meth)acrylate monomers, and monomer a accounts for 25 - 65% of the total mass of the hydroxy-functional (meth)acrylate monomers, preferably 30 - 50%.

4. A method for preparing the aqueous dispersion according to any one of claims 1 - 3, comprising the following steps: (1) In the presence of an organic solvent, polymerize non-functional (meth)acrylate monomers, hydroxy-functional (meth)acrylate monomers, and other polymerization monomers by free radical polymerization to form polymer I; (2) Then, on the basis of polymer I, continue to polymerize non-functional (meth)acrylate monomers, hydroxy-functional (meth)acrylate monomers, and other polymerization monomers to obtain polymer II; (3) Then, on the basis of polymers I and II, obtain polymer III by using non-functional (meth)acrylate monomers, hydroxy-functional (meth)acrylate monomers, and carboxyl-functional (meth)acrylate monomers; (4) Add a neutralizing agent for neutralization and aqueous dispersion to obtain the hydroxyacrylate aqueous dispersion; wherein, monomer a is used in one or more of steps (1), (2), and (3), preferably used in step (1) and / or (2), more preferably used in step (2).

5. The method according to claim 4, characterized in that the monomer composition in step (1) is as follows: Non-functional (meth)acrylate monomers: 20 - 60%; Hydroxy-functional (meth)acrylate monomers: 20 - 50%; Other polymerization monomers: 0 - 40%; The above ratios are based on the total of all monomers in step (1).

6. The method according to claim 4, characterized in that the monomer composition in step (2) is as follows: Non-functional (meth)acrylate monomer: 10-50%; Hydroxy-functional (meth)acrylate monomer: 15-40%; Other polymerizable monomers: 20-60%; The above ratios are based on the total of all monomers in step (2).

7. According to the method described in claim 4, wherein, the monomer composition in step (3) is as follows: Non-functional (meth)acrylate monomer: 45-70%; Hydroxy-functional (meth)acrylate monomer: 15-40%; Carboxy-functional (meth)acrylate monomer: 8-20%; The above ratios are based on the total of all monomers in step (3).

8. According to the method described in claim 4, wherein, the non-functional (meth)acrylic acid monomers include one or more of methyl (meth)acrylate, butyl (meth)acrylate, ethyl (meth)acrylate, isooctyl (meth)acrylate, dodecyl (meth)acrylate, isobornyl (meth)acrylate, and norbornenyl (meth)acrylate.

9. According to the method described in claim 4, wherein, in addition to monomer a, the hydroxy-functional (meth)acrylic acid monomers include one or more of 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 2-hydroxyhexyl acrylate, and 2-hydroxyhexyl methacrylate.

10. According to the method described in claim 4, wherein, monomer a is selected from one or more of the following structures:

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