JPS5920317A - Production of polyester-modified acrylic copolymer for paint - Google Patents

Abstract

PURPOSE:To produce the titled copolymer excellent in water repellency, pigment dispersibility, and feeling of thickness and suitable for use in paints, by copolymerizing a specified Si-containing acrylic monomer with an unsaturated polyester having a copolymerizable unsaturated bond. CONSTITUTION:A polyester-modified acrylic copolymer having a weight-average MW to number-average MW ratio of 3-30 is prepared by copolymerizing 5 99.5wt% monomer mixture consisting of (a) 0.1-100wt% trialkyl- or triphenylsioxy-alkyl (meth)acrylate of the formula (wherein R1 is H, or methyl, R2 is phenyl, or 1-16C alkyl, and n is 1-3), and 0-99.9wt% (b) vinyl monomer copolymerizable with component (a), e.g., beta-hydroxyethyl (meth)acrylate with 95- 0.5wt% polyester containing a copolymerizable unsaturated bond (hydroxyl group equivalent weight of 100-5,000) in the presence of a radical generator in a solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a polyester-modified acrylic copolymer that is particularly useful for coatings, and more specifically to a specific silicon-containing acrylic monomer (hereinafter also abbreviated as silicon monomer). The present invention relates to a method for producing a novel copolymer comprising using.

Acrylic paints have been used in a variety of fields in recent years due to their excellent performance, but the performance required is also diverse, and in recent years, they have been especially used for automobiles, home appliances, and the exterior of buildings. Required standards in fields such as water repellency, pigment dispersibility, weather resistance and stain resistance, etc. The required standards are becoming higher and higher, and the appearance of even higher grade acrylic paints is desired.

Therefore, as a result of intensive research in response to these circumstances, the present inventors discovered that the above-mentioned performance could be amazingly improved by using a specific silicone monomer as an essential acrylic monomer. I have finally completed the .

That is, the present invention provides (1) trialkylsiloxyalkyl (meth)acrylate and/or triphenylsiloxyalkyl (meth)acrylate cL1 to 100% by weight represented by the general formula;
) 5 to 995% by weight of a monomer mixture consisting of the above (meth)acrylates (1) and 0 to 999% by weight of a copolymerizable vinyl monomer;
) Hydroxyl group equivalent is 100-5. D[l[l, and
0.5 to 9 of polyester having copolymerizable unsaturated bonds
5% by weight in the presence of a radical generator, the My/Mn ratio is 6 to 6D, which has excellent water repellency, pigment dispersibility, and texture, especially for paints. The present invention provides a method for producing a polyester-modified acrylic copolymer useful as a polyester-modified acrylic copolymer.

The trialkyl- or triphenylsiloxyalkyl (meth)acrylate fl) used in carrying out the method of the present invention is hydroxyalkyl (meth)acrylate fl).
Examples include those obtained by reacting acrylate with trialkylchlorosilane or triphenylchlorosilane in the presence of a hydrochloric acid scavenger such as triethylamine or pyridine. Trimethylsiloxyethyl (meth)acrylate, trimethylsiloxypropyl (meth)acrylate, trimethylsiloxybutyl (meth)acrylate, triethylsiloxyethyl (meth)acrylate, tributylsiloxypropyl (meth)acrylate, triphenylsiloxyethyl (meth)acrylate or dimethyl Examples include monophenylsiloxyethyl (meth)acrylate, and these can be used alone or in a mixture of two or more. If these are less than 0.1% by weight, the effect of use will not be seen, so they should be selected in a range of 0.1 to 100% by weight, preferably 0.5 to 95% by weight.

Moreover, the following are typical examples of the copolymerizable vinyl monomer (2). First, hydroxyalkyl (meth)acrylates such as β-hydroxyethyl (meth)acrylate, β-hydroxypropyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate, or methylols such as N-methylolated (meth)acrylamide. Hydroxyl group-containing vinyl monomers such as (meth)acrylamides are further combined with unsaturated carboxylic acids such as (meth)acrylic acid, fumaric acid, maleic acid or itaconic acid and "Cardura E" (a product of Shell, Netherlands). , adducts with monoepoxy compounds typified by monoglycidyl esters of monovalent carboxylic acids such as octylic acid glycidyl ester or coconut oil fatty acid glycidyl ester, and monoglycidyl ethers such as butyl glycidyl ether.

Then, epoxy-containing vinyl monomers such as glycidyl (meth)acrylate, methylglycidyl (meth)acrylate or (meth)allyl glycidyl ether, or [Epicron 200,400.441.850
or 1o50J (all Dainippon Ink & Chemicals products), [Epicoat 1001.1004 or 100
9” (all Shell products), [Araldite 6071
Or 6084" (all products of Ciba-Geigy in West Germany), [Chissonox 221j (Chisso product)
A polyepoxy compound having at least two epoxy groups in one molecule such as (meth)acrylic acid, fumaric acid,
It also includes epoxy group-containing vinyl monomers such as epoxy group-containing polymerizable adducts obtained by addition reaction with unsaturated carboxylic acids such as maleic acid or itaconic acid in equimolar ratios.

Additionally, polycarboxylic anhydrides such as phthalic anhydride can be added to unsaturated carboxylic acids such as (meth)acrylic acid, fumaric acid, maleic acid, or itaconic acid, or to hydroxyl group-containing vinyl monomers such as those mentioned above. It also includes carboxyl group-containing vinyl monomers such as adducts obtained by oxidation, as well as aromatic vinyl compounds such as styrene, α-methylstyrene or vinyltoluene,
(Meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate or isobutyl (meth)acrylate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl maleate, dimethyl Diesters of fumaric acid, maleic acid or itaconic acid and C8 to C8 monohydric alcohols such as itaconate or diethyl fumarate, (meth)acrylamides such as (meth)acrylamide or N-alkoxymethylated (meth)acrylamide , N,N-dialkylaminoalkyl (meth)acrylates such as dimethylamine ethyl (meth)acrylate, or mono[β-hydroxyethyl (meth)acrylate coacid phosphate or mono[β-hydroxypropyl (meth)acrylate]. Vinyl monomers without functional groups, such as phosphoric acid group-functionalized vinyl monomers such as -tocomochloroacid phosphate, are also included.
Along with meth)acrylate (1), a vinyl monomer (11) copolymerizable with these (meth)acrylates (11)
When 2) is also used, especially when the above-mentioned vinyl monomers containing hydroxyl groups, epoxy groups and/or carboxyl groups are used together, preferably 5 to 60% by weight of the total monomer mixture N is added to the coating material. It is preferable in terms of viscosity, coating workability, and physical properties of the coating film.

Separately, among the copolymerizable monomers (2), the amount of vinyl monomers that do not have the above-mentioned functional groups is determined by the amount of vinyl monomers containing functional groups such as the above-mentioned hydroxyl groups, epoxy groups, and/or carboxyl groups. The amount may be appropriately determined depending on the amount and desired physical properties of the coating film.

By the way, as the copolymerizable vinyl monomer (2), in particular when crosslinking and curing a copolymer obtained by using the above-mentioned hydroxyl group-containing vinyl monomer, examples of crosslinking agent components include polyisocyanate compounds and amino resins. etc. are preferably used, but the internal catalyst is preferably a carboxyl group-containing vinyl monomer as described above.
It is known that the combined use of small amounts of compounds such as monophosphoric acid group-containing vinyl monomers or N,N-dialkylaminoalkyl (meth)acrylates is extremely effective in accelerating the curing reaction. In order to use the polyester-modified acrylic copolymer obtained by the method of the present invention as a type acrylic paint, when a vinyl monomer having an internal catalytic action as described above is used in combination with the copolymer, In terms of storage stability and pigment dispersion stability of the obtained copolymer, preferably 0.
It is desirable to keep the content within the range of about 0.05 to 5% by weight.

If the amount of the silicon monomer listed above (monomer mixture vAA used alone or in combination with monomer (2) that can be copolymerized with these) is less than 5% by weight of the total monomer mixture kn. In some cases, these effects cannot be obtained, and in cases where the amount exceeds 995% by weight, unsaturated bond-containing polyester/L(B) as described below may be used.
The denaturing effect cannot be obtained.

Therefore, the appropriate amount of the monomer mixture to be used is 5 to 99.5% by weight.

On the other hand, the unsaturated bond-containing polyester/L (Bl) used in carrying out the method of the present invention may be a drying oil, a semi-drying oil, a non-drying oil, or a polyester modified with their fatty acids. Polyesters that have not been modified at all with such oils or fatty acids may also be used. Typical polyhydric alcohols that can be used to prepare the polyesters (Bl) include (poly)ethylene glycol and (poly)propylene glycol. , neopentyl glycol, 1,6-hexanediol, 1,3-butylene glycol, 1,4-butylene glycol, bis(hydroxyethyl) terephthalate, hydrogenated bisphenol A,) limethylolethane, trimethylolpropane,
Examples of epoxy compounds include glycerin and pentaerythritol, and epoxy compounds include polyepoxy compounds as mentioned above,
As mentioned above, there are monoglycidyl esters of monovalent carboxylic acids and [Bunacol EX-611J (glycidyl ether of polyhydric alcohol manufactured by Nagase Sangyo Co., Ltd.)]. (Shell product), Octylic acid, Benzoic acid, Talic acid, Inphthalic acid, Terephthalic acid, Het's acid, Hexahydrophthalic acid, Trimellitic acid, Succinic acid, Oxalic acid, Adipic acid, Sebacic acid, Dodecanedicarboxylic acid Drying oils, semi-drying oils, and non-drying oils include linseed oil, tung oil, safflower oil, dehydrated castor oil, tall oil, cottonseed oil, soybean oil, rice bran oil, castor oil,
There are coconut oil, hydrogenated coconut oil, and their fatty acids, and unsaturated carboxylic acids include (meth)acrylic acid, cinnamic acid,
Crotonic acid, (anhydrous) maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydro (anhydrous) 7-talic acid,
[(Anhydrous) noimitsucic acid] (Hitachi Chemical ■product),
Examples include methylcyclohexenetricarboxylic anhydride. Further, the polyester (B) has been urethanized in advance with a diisocyanate such as hexamethylene diisocyanate, hydrogenated hexamethylene diisocyanate, hydrogenated xylidene diisocyanate, tolylene diinocyanate, etc., in place of the original polycarbo/acid. Of course, a modified polycarboxylic acid may also be used.

In order to prepare the polyester A (B), the above-mentioned raw materials may be appropriately combined, calculated, and reacted using a known method. (11 or the monomer mixture A) with the vinyl monomer (2) copolymerizable with these, taking into account the copolymerization conditions of the component A, the grafting points in the polyester/1(B) are: When using only drying oil or semi-drying oil, use Polyester A (B)
The oil length is 20 to 80%, and when drying oil or semi-drying oil and unsaturated carboxylic acid are used together, the oil length is 5%.
~80% and the fecal dose of unsaturated carboxylic acid is 0.5
~6 weight it% (vs. all polyester qBl; same below)
When using a non-drying oil and an unsaturated carboxylic acid in combination, the oil length should be 5 to 60% and the unsaturated carboxylic acid powder should be 0.5 to 5% by weight. Furthermore, when oil modification is not carried out, the amount of unsaturated carboxylic acid used is preferably in the range of 0.5 to 5% by weight.

In carrying out the method of the present invention, in addition to the method in which grafting points are introduced into the skeleton of the molecular structure, a saturated polyester having no unsaturated bonds is separately prepared, and the saturated polyester The hydroxyl groups and/or
f or the carboxyl group, in the presence of a polymerization inhibitor, unsaturated polycarboxylic anhydride, epoxy group-containing vinyl monomer, vinyl silanes such as vinyl silanes, or hexamethylene diisocyanate, hydrogenated xylidene diisocyanate, etc. 0.1 to 10% by weight of a compound having a free isocyanate group and a copolymerizable vinyl group, such as an equimolar reaction product of an aliphatic or alicyclic diisocyanate and a hydroxyl group-containing vinyl monomer; It is also possible to use the products obtained by carrying out the addition reaction, preferably in a range of 0.5 to 8% by weight.

The unsaturated bond-containing polyester/L (Bl is the MwZ of the finally obtained polyester-modified acrylic copolymer
It is used to adjust the Mn ratio, and for this purpose, the degree of unsaturation is adjusted according to the molecular weight of the polyester A (Bl) to within the preferred range as a grafting point in the polyester/L (Bl) as described above. In other words, it is desirable to adjust the amount within a range such that gelation does not occur during the copolymerization reaction with the N component, but the polyester/1(B)
When the amount used is less than 0.5% by weight, almost no modification effect is observed; on the other hand, when it exceeds 95% by weight, it becomes difficult to adjust the MW24Wn ratio and the pigment dispersion becomes unstable. This is not a good thing because it also reduces sex, and in the end,
The amount of polyester/l used (B) is 0.5~
A suitable amount of N is 95% by weight, preferably from 1 to 90% by weight.

Typical solvents that can be used to obtain the polyester-modified acrylic copolymer of the present invention include aromatic hydrocarbons such as toluene and xylene; acetate-based solvents such as ethyl acetate, butyl acetate, and cellosolve acetate;
M.E.K.

Ketone solvents such as MIBK; alcohol solvents such as butanol and isobutanol; cellosolve solvents such as butyl cellosolve and butyl cellosolve; however, when using polyisocyanate with free isocyanate groups as a crosslinking agent component, Alcohol-based solvents and cellosolve-based solvents are reactive and should be avoided. The initiator used for polymerization is also AIB.
If necessary, mercaptans, [dipentene TJ (Nippon Terpene Product), α-methylstyrene, and other commonly used chain transfer agents can also be used.

If the Mw/vrn ratio of the polyester-modified acrylic copolymer thus obtained is less than 30, the pigment dispersibility will be poor in both single color and mixed color systems, and conversely, if it exceeds 30, the pigment dispersibility will be poor for single colors. (However, the pigment dispersibility of the mixed color system will be poor, so the Mw1Mn ratio should be 6.
It is appropriate to set it within the range of .about.60. In order to keep the M★/Mn ratio within the above range, the ratio and amount of the relatively high molecular weight part and the relatively low molecular weight part are important factors, and for this purpose, it is necessary to mainly generate the high molecular weight part. The reaction conditions can be selected so that the desired Mw/'n ratio is obtained by combining the step of producing a low molecular weight portion, the step of producing mainly a low molecular weight portion, and the reaction rate.

The polyester-modified acrylic copolymer obtained by the method of the present invention can be used up to its full length or in combination with resins such as vinyl resins, alkyd resins, and amino resins, cellulose compounds such as nitrified cotton and CAB, or plasticizers. It can be used as a lacquer-type paint, and if a functional group-containing vinyl monomer as mentioned above is used as an essential component, it can be used as a cross-linked curable paint using a crosslinking agent component that is reactive with the functional group. You can also use Depending on the combination with the functional group used as a cross-linked curable coating material, the following may be mentioned.

When containing a hydroxyl group as a functional group component, the crosslinking agent component is first an aromatic diisocyanate such as tolylene diisocyanate, diphenylmethane diisocyanate, or xylylene diisocyanate; or a fat such as tetramethylene diisocyanate, hexamethylene diisocyanate, or trimethylhexane diisocyanate. Group diisocyanates; alicyclic diisocyanates such as isophorone diisocyanate, methylcyclohexane-2°4 (or 2,6)-diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), 1,3-(isocyanatomethyl)cyclohexane and ethylene; Polyhydric alcohols such as glycogel, propylene glycol, neopentyl glycol, trimethylolethane, trimethylolpropane, etc., and electrodes (low molecular weight polyester resins (including oil-modified types) having functional groups that react with incyanate groups). ), adducts or billet forms with water, polymers (including oligomers) of diisocyanates, or those blocked with known blocking agents such as lower-hydric alcohols or methyl ethyl ketoxime, etc. are suitable. Commercially available examples include “Burnock D-750, D-800, D
N-950, DN-960 or DN-97DJ (Inu Nippon Ink Chemical Industry ■ product), [Takene] D-102,
D-11ON, D-12ON, D-14ON or B-842NJ (Takeda Pharmaceutical ■product), [Coronate L, HL or 203DJ (Japan Polyurethane Industries ■product), Desmodur L, N or HLJ (West German Bayer Polyisocyanates other than aromatic diisocyanates, which do not yellow due to ultraviolet rays, are particularly preferred from the viewpoint of weather resistance.

The blending ratio of polyisocyanate and the above polymer is OH/
NC0=110.5 to 1/1.5 (equivalent ratio) is preferable from the viewpoint of coating film performance and paint price.

Next, formaldehyde is added to urea, melamine, benzoguanamine, acetoguanamine, etc., and further C2
A resin etherified with a monohydric alcohol called ~C6, commercially available examples include "Beccamin P-168 or G-1800J" and "Super Beckamine J-820-6".
0, G-821-60 or L-117-6DJ (all Dainippon Ink & Chemicals products), [Kneepan 20S
Examples include EJ (Mitsui Toatsu Chemical ■ product). These materials are one or more copolymers/amino resins = 6
It is preferable to use it in a ratio of 0 to 90/10 to 40 (weight ratio). In some cases, a small amount of epoxy resin may be used to further improve corrosion resistance and adhesion, or a known acid catalyst such as phosphoric acid may be used as a curing accelerator.

In addition, when containing an epoxy group as a functional group component, the typical crosslinking agent component may be any compound having a carboxyl group in its molecule (for example, polyester with a high acid value (oil (including modified types), acrylic copolymers (which may partially contain styrene monomers), and epoxy groups containing two epoxy groups in one molecule.
Examples include epoxy compounds (acrylic copolymers may also be used) having more than 100 carboxyl groups, which are reacted with an excess of polycarboxylic acid to leave free carboxyl groups, and adducts of rosin and maleic anhydride. In this case, in order to obtain sufficient physical properties, the acid value of the resin may be at least 15 or more. These are epoxy group/carboxyl group = 1
They are used at a ratio of 10.5 to 1/1.5 (equivalent ratio).

Furthermore, when a carboxyl group is contained as a functional group component, the crosslinking agent component may have at least two epoxy groups in one molecule; An acrylic copolymer (which may partially contain a styrene monomer) containing monomers as an essential component is not suitable for polyesters (including oil-modified ones) or polycarboxylic acids having a certain degree of acid value. In order to introduce epoxy groups, epoxy oligoesters with free epoxy groups obtained by adding an excessive amount of an epoxy compound having at least two or more per molecule are used, or [Evicron 200.400, 441.8
50 or ID50J (Inu Nippon Ink Chemical Industry ■ product)
, [Epicote 1001.1004.1009j (Shell product), [Araldite 6071 or 6084J]
(Ciba Geigy), [Chissonox 221J (Chisso ■ product), [Bunacol EX-611J (Nagao Sangyo ■ product) These are carboxyl group/epoxy group=110.5-1
/1.5 (equivalent ratio). In this case, the curing time can be shortened by using known monomers such as imidazoles and BF3 complexes as curing accelerators.

The polyester-modified acrylic copolymer thus obtained by the method of the present invention can be used as a clear paint, or can be kneaded with known pigments such as titanium oxide, carbon black, and cyanine blue to be used as an enamel paint. I can do it.

Further, if desired, further known and commonly used leveling agents,
Of course, paint additives such as ultraviolet absorbers, pigment dispersants, etc. can also be used.

As the coating method, known and commonly used methods such as brush coating, spray coating, and roll coating can be applied, and the curing conditions are also determined depending on the combination of the polyester-modified acrylic copolymer and the crosslinking agent component. All you have to do is choose the curing conditions. In other words, depending on the combination of the six combinations, drying at room temperature to drying with heat can be selected as appropriate.

Next, the present invention will be specifically explained using Examples, Comparative Examples, Application Examples, and Comparative Application Examples.
Unless otherwise specified, all are based on the amount of N.

Example 1 516 parts of inphthalic acid, 18 parts of maleic anhydride, 111 g of adipic acid, 350 parts of neopentyl glycol, 121 parts of trimethylolpropane, and 30 parts of pentaerythritol were added to an inert gas inlet, a stirring device, a thermometer, and a live water spray. Pour into a four-eye flask with a discharge port, and bring to a boiling point of 18
Raised the temperature to 09G and 220'C from 180℃ for 5 hours.
22 until the solid content acid value becomes 10 or less.
Maintained at 0°C, solid content hydroxyl value 128, solid content acid value 8
An unsaturated group-containing polyester was obtained. Next, 20 parts of the polyester thus obtained, 400 parts of butyl acetate, and 100 parts of toluene were charged into a four-eye flask equipped with a stirrer, a thermometer, a reflux condenser, and an inert gas inlet.
The temperature was raised to 90°C. When the temperature reached 90'C, 400 parts of trimethylsiloxyethyl acrylate, 200 parts of styrene, 10 parts of acrylic acid, 100 parts of methyl methacrylate,
90 parts of butyl acrylate, 500 parts of toluene, BPO
195 parts of a mixture consisting of parts 2D and 5 parts of t-butyl perbenzoate were first added dropwise over 1 hour;
Once the dropping is finished, the temperature is raised to 120℃ over 60 minutes, and then the temperature is increased to 120℃.
When the temperature reached 50%, the remaining mixture was added dropwise over 6 hours, and the temperature was kept at the same temperature for 10 hours until the non-volatile content was 50%.
Viscosity X-Y, acid value 4.8, hydroxyl value 40. Mw/“n-
A polyester-modified acrylic copolymer (CP-1) of No. 5 was obtained.

Example 2 Neopentyl glycol 1 was added to the same flask as in Example 1.
04m, 146 parts of acyhinic acid, and 134 parts of trimethylolpropane were charged, and the temperature was raised to 160°C. Once the temperature reached 160°C, the temperature was raised to 210°C over 6 hours. The system was maintained at the same temperature until the acid value became 10 or less, and when the acid value became 1o or less, 24 parts of maleic anhydride and 2420 parts of phthalic anhydride were gradually added to the system while being careful not to generate heat. When it becomes transparent and the acid value reaches 215-220, the temperature is lowered to 180'C [1,000 parts of Ebicuron 200J and 2-
2 parts of methylimidazole was added to stop the reaction when the acid value became 5 or less, and toluene/n-butanol/MI
It was diluted with a mixed solvent of BK=60/20/20 (weight ratio) to obtain an epoxy group-containing unsaturated polyester resin solution having a nonvolatile content of 50%, a viscosity of U, and an acid value of 3. Next, 600 parts (non-volatile content: 50%) of the resin solution thus obtained was charged into a four-eye flask equipped with a stirrer, a thermometer, an inert gas inlet, and a reflux condenser, and the temperature was raised to 110°C. 100 parts of triethylsiloxypropyl acrylate, 50 parts of styrene, 10 parts of glycidyl methacrylate, 40 parts of butyl methacrylate, 5 parts of azobisisobutyronitrile,
A mixture consisting of 5 parts of t-butyl perbenzoate and 50 parts of toluene was added dropwise over 3 hours, and after the dropwise addition was completed, the same temperature was maintained for 10 hours, and then 75 parts of butanol and M
75 parts of IBK was added to obtain an epoxy group-containing polyester-modified acrylic copolymer (CP-2) having a nonvolatile content of 50%, a viscosity of Y11 parts, 0.5, and Mw/M n =8.

Example 3 In a flask similar to Example 1, 478 parts of soybean oil fatty acid,
5 parts maleic anhydride, 275 parts phthalic anhydride, 128 parts pentaerythritol and 1 part trimethylolpropane.
78 parts of toluene was added, heated to 220°C, held until the acid value became 10 or less to stop the reaction, cooled, and toluene 6
67 parts, non-volatile content 60%, viscosity phosphoric acid value 5.8,
An unsaturated group-containing soybean oil-modified alkyd resin solution with an OH value of 8° was obtained.

Next, 250 parts of this resin solution was charged into a stirrer, a thermometer, an inert gas inlet and a reflux condenser, and 350 parts of a monomer mixture consisting of torino and 6 parts of acrylic acid was added.
50 parts of 1 part, 3 parts of t-butyl peroctoate, and 200 parts of butyl acetate were charged, the temperature was raised to 90'C, and the temperature was further raised from 90'C to 115°C for 1 hour to obtain the monomer mixture. remaining 300 parts, 200 parts of toluene, t
- dropwise addition of a mixture of 7 parts of butyl peroctoate and 5 parts of t-butyl perbenzoate over a period of 4 hours;
After the dropwise addition, the same temperature was maintained for 10 hours until the non-volatile content was 50%.
%, viscosity Y, acid value 6.8, hydroxyl value 40, Mw/Mn=
A polyester-modified acrylic copolymer containing 13 hydroxyl groups and carboxyl groups (cp-3) was obtained.

Example 4 750 parts of the unsaturated group-containing soybean oil-modified alkyd resin solution obtained in Example 3 was charged into a flask similar to that used in Example 1, and the temperature was raised to 110°C. To this, 40 parts of triethylsiloxypropyl methacrylate, 8 parts of β-hydroxyglopyl methacrylate, 2 parts of methacrylic acid, 50 parts of toluene, 5 parts of t-butyl peroctoate, di-
A mixture consisting of 2 parts of t-butyl peroxide was added dropwise over 5 hours, maintained at 110°C for 10 hours, and then 150 parts of toluene was added to give a non-volatile content of 50% and a viscosity of 2. Acid value 2.
A polyester-modified acrylic copolymer (CP-4) containing hydroxyl groups and carboxyl groups with a hydroxyl value of 66, an M value of ηn = 21 was obtained.

Example 5 In a flask similar to Example 1, 100 parts of p-t-butylbenzoic acid, 501 parts of phthalic anhydride, 66 parts of trimethylbentanediol, 254 parts of trimethylolpropane, and 150 parts of hineopentyl glycol were charged. '
The temperature was raised to C. Furthermore, the temperature was raised from 160° C. to 210° C. over 6 hours and maintained at the same temperature until the acid value became 10 or less. Then, the temperature was lowered to 180°C, 315 parts of phthalic anhydride was added while being careful not to generate heat, and the temperature was maintained until the acid value became about 100 or less, and when the acid value reached about 96, the temperature was lowered. Diluted with toluene/MIBK=20/80 mixed solvent, non-volatile content 60%, viscosity 27, acid value 5
A carboxyl group-containing saturated polyester resin bath liquid of No. 7 was obtained. Next, 667 parts of this resin bath liquid was charged into a four-eye flask equipped with a stirrer, a thermometer, an inert gas inlet, and a reflux condenser, and then 0.08 parts of hydroquinone monomethyl ether and 2 -0.2 parts of methylimidazole and 5 parts of glycidyl methacrylate were charged, the temperature was raised to 80°C, and the temperature was maintained until the acid value reached about 54. When the acid value reached about 54, the temperature was lowered to about 40°C, 100 g of butyl acetate, 15 parts of dimethylmonophenylsiloxyethyl acrylate and 4 parts of BPO were added, and the temperature was raised to 1106°C to give 80% triphenylsiloxyethyl acrylate.
A mixture consisting of 133 parts of toluene, 4 parts of BPO, and 5 parts of t-butyl peroctoate was added dropwise over 2 hours and maintained at the same temperature for about 10 hours to obtain a mixture with a non-volatile content of 50%, a viscosity of V,
A carboxyl group-containing polyester-modified acrylic copolymer (CP-5) having an acid value of 36 and Mw/Mn=13 was obtained.

Example 6 In a flask similar to Example 1, 235 parts of coconut oil fatty acid, 427 parts of phthalic anhydride, and 98 ft of neopentyl glycol were added.
B.) 213 parts of limethylolpropane and 100 parts of pentaerythritol were charged and the temperature was first raised to 160°C.
Furthermore, the temperature was raised from 160℃ to 210℃ over 6 hours, and maintained at the same temperature until the acid value became 10 or less.
The temperature was lowered to 10°C, and toluene/isobutyl acetate = 40/6
0 (weight ratio) to dilute with a mixed solvent to reduce the non-volatile content to 6.
A coconut oil-modified saturated polyester resin solution with a viscosity of 0%, a viscosity of 22 to 25, an acid value of 4.8, and an OH value of 95 was obtained. Next, 86 parts of this resin solution was charged into a four-eye flask equipped with a stirrer, a thermometer, an inert gas inlet, and a reflux condenser, and then 267 parts of toluene and 5 parts of maleic anhydride were charged. ℃ and held at the same temperature for 60 minutes, then 4
After cooling to 0°C, 150 parts of styrene, 100 parts of tributylsiloxypropyl methacrylate, 87 parts of β-hydroxyethyl 7-acrylate, 108 parts of butyl methacrylate, 200 parts of isobutyl acetate, 4 parts of BPO, t
- Add 255 parts of a mixture consisting of 6 parts of butyl peroctoate and 2 parts of t-butyl perbenzoate, raise the temperature to 100°C again, maintain the same temperature for 30 minutes, and then raise the temperature to 115°C. and at this temperature the remaining 4
00 parts was added dropwise over 4 hours and kept at the same temperature for about 10 hours to obtain a nonvolatile content of 50%, viscosity W-X, and acid value 6.4.
A polyester-modified acrylic copolymer (CP-6) containing hydroxyl groups and carboxyl groups and having a hydroxyl value of 50 and Mw/Mn=8 was obtained.

Comparative Example 1 A nonvolatile content of 50%, viscosity of 2, acid value of 4.9, hydroxyl value of 4o, Mw/Mn=5 was prepared in the same manner as in Example 1 except that isobutyl methacrylate was used instead of trimethylsiloxyethyl acrylate. A polyester-modified acrylic copolymer (CP-1') was obtained.

Comparative Example 2 Same as Example 2 except that inbutyl methacrylate was used instead of triethylsiloxypropyl acrylate, non-volatile content 50%, viscosity Z, acid value 05, Mw/Mn=8
Epoxy group-containing polyester-modified acrylic copolymer (
CP-2') was obtained.

Comparative Example 3 Same as Example 3 except that isobutyl methacrylate was used instead of trimethylsiloxyethyl methacrylate, non-volatile content 50%, viscosity 2-21, acid value 4.0, hydroxyl value 40, Mw/fill”n= A polyester-modified acrylic copolymer (CP-3) containing 10 hydroxyl groups and carboxyl groups was obtained.

Comparative Example 4 Same as Example 6 except that isobutyl methacrylate was used instead of tributylsiloxypropyl methacrylate, non-volatile content 50%, viscosity Y-Z, acid value 6.5, hydroxyl value 50, Mw/in = 8. A polyester-modified acrylic copolymer (CP-4') containing hydroxyl groups and carboxyl groups was obtained.

Application Examples 1 to 12 and Comparative Application Examples 1 to B Paints were prepared in a conventional manner using the paint formulations shown in Tables 1 and 2, and the performance of the various paints obtained was evaluated.

The results are summarized in Table 1 for application examples of the present invention and in Table 2 for application examples of comparative products (comparative application examples).

Claims (1)

Scope of Claims: (A) (f) 0.1 to 100% by weight of trialkylsiloxyalkyl (meth)acrylate and/or triphenylsiloxyalkyl (meth)acrylate represented by the general formula; (2)
(B
) Copolymerizing 0.5 to 95% by weight of a polyester having a hydroxyl group density of 100 to 5,000 and a copolymerizable unsaturated bond in the presence of a radical generator, and the thus obtained A method for producing a polyester-modified acrylic copolymer for paints, which has excellent water repellency, pigment dispersibility, and texture, and is characterized in that the Mw/Mn ratio of the polyester-modified acrylic copolymer is 6 to 30. .