JPH021167B2 - - Google Patents

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 paints, and more specifically, to a novel method for producing a polyester-modified acrylic copolymer that is particularly useful for coatings. This invention relates to a method for producing a copolymer. Because acrylic paint has excellent performance,
In recent years, it has been used in a variety of fields, but the performance required is also diverse. Especially recently, the required standards in fields such as automobiles, home appliances, and building exteriors - weather resistance and pollution resistance. The requirements for water repellency, pigment dispersibility, weather resistance, stain resistance, etc. are becoming even higher due to improvements in water repellency, prevention of water marks, prevention of ice adhesion, and trend toward multicolor. The appearance of even higher grade acrylic paints is expected. 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 reached the point where I have completed it. That is, the present invention provides (1) general formula [However, in the formula, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a phenyl group or an alkyl group of C ₁ to _{C 18} , and n is an integer of 1 to 3. ] 0.1 to 100% by weight of trialkylsiloxyalkyl (meth)acrylate and/or triphenylsiloxyalkyl (meth)acrylate represented by (2) a vinyl monomer copolymerizable with the above (meth)acrylates (1) 5-99.5% by weight of a monomer mixture consisting of 0-99.9% by weight
and (B) 0.5 to 95% by weight of a polyester having a hydroxyl equivalent of 100 to 5000 and having a copolymerizable unsaturated bond (hereinafter also referred to as unsaturated group-containing polyester) in the presence of a radical generator. By copolymerizing with
The present invention provides a method for producing a polyester-modified acrylic copolymer, which has excellent water repellency, pigment dispersibility, and texture, and is particularly useful for paints. The trialkyl- or triphenylsiloxyalkyl (meth)acrylate (1) used in carrying out the method of the present invention is a hydroxyalkyl (meth)acrylate in the presence of a hydrochloric acid scavenger such as triethylamine or pyridine. Examples include those obtained by reacting alkylchlorosilane or triphenylchlorosilane, and typical examples of those obtained in this way include trimethylsiloxyethyl (meth)acrylate, trimethylsiloxypropyl (meth)acrylate, and trimethylsiloxypropyl (meth)acrylate.
acrylate, trimethylsiloxybutyl (meth)acrylate, triethylsiloxyethyl (meth)acrylate, tributylsiloxypropyl (meth)acrylate, triphenylsiloxyethyl (meth)acrylate or dimethylmonophenylsiloxyethyl (meth)acrylate, these are It can be used alone or in a mixture of two or more. And, since the effect of using these substances is not seen if it is less than 0.1% by weight, 0.1%
It should be selected in the range from ~100% by weight, preferably from 0.5 to 95% by weight. Furthermore, typical copolymerizable vinyl monomers (2) include the following. First, hydroxyalkyl (meth)acrylates such as β-hydroxyethyl (meth)acrylate, β-hydroxypropyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate, or methylols such as M-methylolated (meth)acrylamide. Hydroxyl group-containing vinyl monomers such as (meth)alkylamides are
Furthermore, unsaturated carboxylic acids such as (meth)alkyl acids, fumaric acid, maleic acid or itaconic acid and monovalent carboxylic acids such as "Carduura E" (product of Siel, Netherlands), octylic acid glycidyl ester or coconut oil fatty acid glycidyl ester Also included are adducts with monoepoxy compounds typified by acid monoglycidyl esters and monoglycidyl ethers such as butylglycidyl ether. Next, epoxy group-containing vinyl monomers such as glycidyl (meth)acrylate, methylglycidyl (meth)acrylate or (meth)acrylic glycidyl ether, or
200, 400, 441, 850 or 1050" (all products of Dainippon Ink and Chemicals Co., Ltd.), "Epicoat 1001,
1004 or 1009" (all products from Ciel), "Araldite 6071 or 6084" (all products from Ciba-Geigy, West Germany), "Chitsonox 221"
At least 2 in one molecule such as (Chitsuso Co., Ltd. product)
Epoxy group-containing polymerizable addition obtained by addition reaction of a polyepoxy compound having 3 epoxy groups with an unsaturated mono- or dicarboxylic acid such as (meth)acrylic acid, fumaric acid, maleic acid or itaconic acid in an equimolar ratio. Also included are epoxy group-containing vinyl monomers such as epoxy group-containing vinyl monomers. In addition, α, β-unsaturated dicarboxylic acids such as (meth)acrylic acid, fumaric acid, maleic acid or itaconic acid, or monoesters of various α,β-unsaturated dicarboxylic acids such as these fumaric acid and maleic acid with monohydric alcohols, etc. β-unsaturated mono- or dicarboxylic acids;
Alternatively, a hydroxyl group-containing vinyl monomer as described above or an epoxy group-containing vinyl monomer as described above may be added to an unsaturated compound such as succinic acid, adipic acid, azelaic acid, phthalic acid, or succinic anhydride, phthalic anhydride, or trimellitic anhydride. Carbosyl group-containing vinyl monomers such as adducts obtained by addition reaction of polycarboxylic acids or their acid anhydrides are also included, and 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 C ₁ to _{C 8} monohydric alcohols, such as itaconate or diethyl itaconate;
(Meth) such as (meth)acrylamide or N-alkoxymethylated (meth)acrylamide
Acrylamides, N,N-dialkylaminoalkyl (meth)alcohols such as dimethylaminoethyl (meth)acrylate, or mono[β-hydroxyethyl (meth)acrylate]
Vinyl monomers having no functional group are also included, such as phosphoric acid group-containing vinyl monomers such as acid phosphate or mono[β-hydroxypropyl (meth)acrylate] monochloroacrylate phosphate. Therefore, when a vinyl monomer (2) copolymerizable with these (meth)alcohols (1) is also used together with the trialkyl- and/or triphenylsiloxyalkyl (meth)acrylate (1), In particular, when a vinyl film monomer containing a hydroxyl group, an epoxy group, and/or a carboxyl group as described above is used in combination, the range of 5 to 60% by weight of the total monomer mixture (A) should be used to improve paint viscosity, coating workability, and This is preferable from the viewpoint of coating film properties. That is, when the amount of the other copolymerizable vinyl monomer (2) used is less than 5% by weight,
In each case, when using no crosslinking agent component as described below, gasoline resistance, thinner resistance, adhesion, etc. are inevitably affected due to the low crosslinking density even when using a crosslinking agent component. , weather resistance, thinner resistance, stain resistance, gasoline resistance, etc. will decrease, and on the other hand, if the amount of monomer (2) used exceeds 60%, the use of crosslinking agent components will decrease. In the absence of any water resistance,
Alkali resistance, acid resistance, adhesion, etc. will be reduced. On the other hand, when using a crosslinking agent component, although the performance such as water resistance, acid resistance, and alkali resistance will be improved, the crosslinking density will become too high. This, on the contrary, results in a decrease in adhesion to the substrate and, in addition, increases the price of the paint, which is undesirable in either case. Therefore, the appropriate amount of the copolymerizable other monomer (2) is in the range of 5 to 60% by weight, preferably in the range of 10 to 50% by weight. Separately, of the other copolymerizable vinyl monomers (2), the amount of vinyl monomers that do not have the above-mentioned functional groups is determined by Depending on the amount of the monomer used and the desired coating film performance, the usage range (0
~99.9% by weight), it may be determined as appropriate. By the way, this copolymerizable vinyl monomer
As for (2), polyisocyanate compounds, amino resins, etc. are preferably used as crosslinking agent components when crosslinking and curing copolymers obtained using the above-mentioned hydroxyl group-containing vinyl monomers. To accelerate the curing reaction, it is recommended to use a small amount of a compound such as a carboxyl group-containing vinyl monomer, a phosphoric acid group-containing vinyl monomer, or N,N-dialkylaminoalkyl (meth)alkylate as an internal catalyst. It is known that the polyester-modified acrylic copolymer obtained by the method of the present invention is to be used as a cross-linked curable acrylic paint. When using a vinyl monomer having an internal catalytic action, preferably from 0.05 to
It is desirable to keep it within a range of about 5% by weight. Single use of the silicon monomers (1) listed above or monomers that can be copolymerized with these monomers (2)
If the amount of monomer mixture (A) used in combination with monomer mixture (A) is less than 5% by weight of the total monomer mixture (A), these effects cannot be obtained, and 99.5
If the amount exceeds % by weight, the properties of the unsaturated bond-containing polyester (B) as described below 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 (B) used in carrying out the method of the present invention may be drying oils, semi-drying oils, or polyesters modified with their fatty acids or non-drying oils. The polyester (B) may be a polyester that has not been modified at all with such oils or fatty acids.
Typical polyalcohols that can be used to prepare are (poly)ethylene glycol, (poly)
Propylene glycol, neopentyl glycol, 1,6-hexanediol, 1,3-butylene glycol, 1,4-butylene glycol, bis(hydroxyethyl) terephthalate, hydrogenated bisphenol A, trimethylolethane, trimethylolpropane, glycerin , pentaerythritol, etc. Epoxy compounds include polyepoxy compounds as mentioned above, monoglycidyl esters of monovalent carboxylic acids as mentioned above, and glycidyl polyhydric alcohols such as "Denacol EX-6111" (manufactured by Nagase Sangyo Co., Ltd.). Monocarboxylic acids and polycarboxylic acids include ``Versatellite acid (product of Siel Corporation), octylic acid, benzoic acid, p-tert-butylbenzoic acid, p-hydroxybenzoic acid, phthalic acid, and isophthalic acid. Acids include terephthalic acid, hectic acid, hexahydrophthalic acid, trimellitic acid, succinic acid, oxalic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid and their anhydrides, and are drying oils, semi-drying oils or non-drying oils. Oils include linseed oil, tung oil, safflower oil, dehydrated castor oil, tall oil, cottonseed oil, soybean oil, rice bran oil, castor oil, coconut oil, hydrogenated coconut oil, and their fatty acids, which contain unsaturated carboxylic acids. As (meta)
Acrylic acid, cylindrical acid, crotonic acid, (anhydrous) maleic acid, fumaric acid, itaconic acid, citraconic acid,
These include tetrahydrophthalic acid (anhydride), hymic acid (anhydride) (product of Hitachi Chemical Co., Ltd.), and methylcyclohexenetricarboxylic anhydride. Also,
The polyester (B) is a modified polyester that has been urethanized in advance with diisocyanates such as hexamethylene diisocyanate, hydrogenated hexamethylene diisocyanate, hydrogenated xylidene isocyanate, tolylene diisocyanate, etc. in place of a small amount of polycarboxylic acid. Of course, carboxylic acids may also be used. In order to prepare the polyester (B), the above-mentioned raw materials can be appropriately combined and calculated, and then reacted using a known method. (1) or a vinyl monomer (2) copolymerizable with these and the monomer mixture (A) component. Or, when only semi-drying oil is used, the oil length of polyester (B) 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 amount of unsaturated carboxylic acid used is 0.5 to 3% by weight
(vs. all-polyester (B); the same applies hereafter), and when non-drying oil and unsaturated carboxylic acid are used together, the oil length should be 5 to 60%, and the amount of unsaturated carboxylic acid should be It is best to set it at 0.5 to 5% by weight.
Further, when no oil modification is 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 graft points are introduced into the skeleton of the molecular structure, a saturated polyester having no unsaturated bonds is separately prepared, and this saturated polyester In the presence of a polymerization inhibitor, the hydroxyl and/or carboxyl groups contained in Copolymerizable with free isocyanate groups such as vinylsilanes or equimolar reaction products of fatty acid or alicyclic acid diisocyanates such as hexamethylene diisocyanate, hydrogenated xylidene diisocyanate, etc. and hydroxyl group-containing vinyl monomers. It is also possible to use a product obtained by carrying out an addition reaction with a compound having a vinyl group in an amount of 0.1 to 10% by weight, preferably 0.5 to 8% by weight. The unsaturated bond-containing polyester (B) is used to adjust the Mw/n ratio of the finally obtained polyester-modified acrylic copolymer to fall within the range of 3 to 30, and is the degree of unsaturation depending on the molecular weight of the polyester (B),
It is desirable that the grafting point in the polyester (B) is adjusted within the preferred range as described above, that is, within a range that does not cause gelation during the copolymerization reaction with the component (A). When the amount of the polyester (B) used is less than 0.5% by weight, almost no modification effect is observed, and on the other hand, when it exceeds 95% by weight, it becomes difficult to adjust the w/n ratio. In addition, pigment dispersion stability is also lowered, which is undesirable.In the end, the appropriate amount of the polyester (B) used is 0.5 to 95% by weight, preferably 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 ester solvents such as ethyl acetate, butyl acetate, and cellosolve acetate; Ketone solvents such as MEK and MIBK; Alcohol solvents such as butanol and isobutanol; Cellosolve solvents such as methyl cellosolve and butyl cellosolve. When using a polyisocyanate with free isocyanate groups as a component,
Alcohol-based solvents and cellosolve-based solvents are reactive and should be avoided. The initiator used in the polymerization can be one that is normally used in the polymerization of vinyl monomers, such as AIBN, BPO, di-t-butyl peroxide, t-butyl perbenzoate, etc.
Furthermore, if necessary, commonly used chain transfer agents such as mercaptans, "Dipentene T" (product of Nippon Terpen Co., Ltd.), and α-methylstyrene can also be used. When the w/n ratio of the polyester-modified acrylic copolymer thus obtained is less than 3, pigment dispersibility becomes poor for both single color and mixed color systems;
When it exceeds 30, the pigment dispersibility of mixed colors becomes worse, even if it is not so bad for single colors.
It is appropriate that the w/n ratio be within the range of 3 to 30. In order to keep the w/n 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 that purpose, the high molecular weight part is mainly produced. The desired w/n
The reaction conditions may be selected so that the ratio is the same. The polyester-modified acrylic copolymer obtained by the method of the present invention can be used as it is or in combination with resins such as vinyl resins, alkyd resins, and amino resins, cellulose compounds such as nitrified cotton and CAB, or plasticizers to form a lattice type. It can be used as a paint, and if a functional group-containing vinyl monomer as mentioned above is used as an essential component, it can be used as a crosslinked and cured paint by using a crosslinking agent component that is reactive with the functional group. You can also do that. When used as a crosslinked curable coating material, the following may be used depending on the combination with the functional group contained in the polyester-modified acrylic copolymer. When containing a hydroxyl group as a functional group component,
As a crosslinking agent component, aromatic diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; fatty acid diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, and trimethylhexane diisocyanate; isophorone diisocyanate, methylcyclohexane-2,4 (or 2,6)-diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), cycloaliphatic diisocyanate such as 1,3-(isocyanatomethyl)cyclohexane and ethylene glycol, propylene glycol, neopentyl glycol, trimethylolethane , polyhydric alcohols such as trimethylolpropane, extremely low molecular weight polyester resins (including oil-denatured types) that have functional groups that react with isocyanate groups, adducts or biuret forms with water, etc., and diisocyanate compounds. Polymers (including oligomers) or those blocked with known blocking agents such as low paper monohydric alcohols or methyl ethyl ketoxime are suitable. Commercially available examples include "Burnock D-750". , D-800, DN-950, DN-
960 or DN-970” (Dainippon Ink Chemical Industry Co., Ltd.)
products), “Takenate D-102, D-110N, D-
120N, D-140N or B-824N” (Takeda Pharmaceutical Co., Ltd. product), “Coronate L, HL or 2030”
(a product of Nippon Polyurethane Industries Co., Ltd.) and "Desmodeur L, N or HL" a product of Bayer, West Germany). Particularly preferred are polyisocyanates. The blending ratio of the polyisocyanate and the above polymer is preferably OH/NCO=1/0.5 to 1/1.5 (equivalent ratio) from the viewpoint of coating film performance and paint price. Next, it is a resin made by adding formaldehyde to urea, melamine, benzoguanamine, acetoguanamine, etc., and then etherifying it with a _C1 to _C8 monohydric alcohol. Commercially available examples include "Petscamine P-138 or G- 1800", "Super Bethcomin J-820-60, G-821-60 or L-
117-60” (all products of Dainippon Ink & Chemicals Co., Ltd.),
Examples include "Yuban 20SE" (manufactured by Mitsui Toatsu Chemical Co., Ltd.). These products consist of one or more types of copolymer/amino resin = 60-90/10-40 (weight ratio)
It is desirable to use such proportions from the viewpoint of various properties of the coating film. In some cases, a small amount of epoxy resin may also 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, typical crosslinking agent components include:
Any material that has a carboxyl group in its molecule may be used, such as high acid value polyester (including oil-modified types) or acrylic copolymers (even if they partially contain styrene monomers). ), epoxy compounds having two or more epoxy groups in one molecule (acrylic copolymers may be used) and excess polycarboxylic acid leaving free carboxyl groups, and rosin. Examples include adducts with maleic anhydride. in this case,
In order to obtain sufficient physical properties, the acid value of the resin should be at least 15 or more. All of these are used in a ratio such that epoxy group/carboxyl group=1/0.5 to 1/1.5 (equivalent ratio) from the viewpoint of various properties of the coating film. 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 that leave free epoxy groups to which at least two epoxy compounds are added in one molecule, or "Epicron 200,"
400, 441, 850 or 1050" (Dainippon Ink & Chemicals Co., Ltd. product), "Epicote 1001, 1004, 1009" Ciel product), "Araldite 6071 or 6084" (Ciba Geigy), "Titsonox 221" (Chitso
Examples include epoxy compounds having at least two or more epoxy groups in one molecule, such as "Denacol EX-611" (product of Nagase Sangyo Co., Ltd.). In terms of various properties of the coating film, all of these are carboxyl group / epoxy group = 1 / 0.5 ~
Used at a ratio of 1/1.5 (equivalent ratio). In this case, the curing time can be shortened by using known catalysts such as imidazoles and BF ₃ 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. Can be done. It goes without saying that, if desired, known and commonly used paint additives such as leveling agents, ultraviolet absorbers, pigment dispersants, etc. can also be used. As a coating method, known and commonly used methods such as brush coating, spray coating, and roll coating can be applied.
The curing conditions may also be selected depending on the combination of the polyester-modified acrylic copolymer and the crosslinking agent component, and the most suitable curing conditions for the combination. In other words, depending on the combination, drying at room temperature to drying by heating can be selected as appropriate. Next, the present invention will be specifically explained with reference to Examples, Comparative Examples, Applied Examples, and Comparative Applied Examples. In the following, parts and percentages are all based on weight unless otherwise specified. Example 1 513 parts of isophthalic acid, 18 parts of maleic anhydride, 111 parts of adipic acid, 350 parts of neopentyl glycol,
121 parts of trimethylolpropane and 30 parts of pentalithritol were added to an inert gas inlet, a stirring device,
Pour into a four-necked flask equipped with a thermometer and a discharge port for the produced water, raise the temperature to 180℃, and then raise the temperature from 180℃ to 220℃ over 5 hours. Maintain at ℃ to determine solid content hydroxyl value.
128, an unsaturated group-containing polyester having a solid content acid value of 8 was obtained. Next, the thus obtained polyester 20
1, 400 parts of butyl acetate, and 100 parts of toluene were charged into a four-necked flask equipped with a stirring copolymer, a thermometer, a reflux condenser, and an inert gas inlet, and the temperature was raised to 90°C. At 90℃, add 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, and 20 parts of BPO.
and 5 parts of t-butyl perbenzoate, then 195 parts of the mixture was first added dropwise over 1 hour, and after the addition was finished, the temperature was raised to 120°C over 30 minutes, and the temperature was increased to 120°C.
When the temperature reached ℃, the remaining mixture was added dropwise over 3 hours, and even after the addition was completed, the same temperature was maintained for 10 hours to obtain a mixture with a non-volatile content of 50%, a viscosity of X-Y, an acid value of 4.8, a hydroxyl value of 40,
A polyester-modified acrylic copolymer (CP-1) with Mw/n=5 was obtained. Example 2 104 parts of neopentyl glycol, 146 parts of adipic acid, and 134 parts of trimethylolpropane were placed in the same flask as in Example 1, and the temperature was raised to 160°C.
Once the temperature reached 160°C, the temperature was raised to 210°C over 3 hours. Hold at the same temperature until the acid value becomes 10 or less.
At the point below, 24 parts of maleic anhydride and 420 parts of phthalic anhydride were gradually added to the system while being careful not to generate heat. When the system became transparent and the acid value reached 215-220, 180 "Epicron 200" 1000 after cooling down to ℃
1 part and 2 parts of 2-methylimidazole were added, the reaction was stopped when the acid value became 5 or less, and diluted with a mixed solvent of toluene/n-butanol/MIBK = 60/20/20 (weight ratio). An epoxy group-containing unsaturated polyester resin solution having a nonvolatile content of 50%, a viscosity of U, and an acid value of 3 was obtained. Next, 600 parts (non-volatile content: 50%) of the resin solution obtained in this way was charged into a four-necked flask equipped with a stirrer, a thermometer, an inert gas inlet, and a reflux condenser, and the temperature was raised to 110°C. A mixture consisting of 100 parts of triethylsiloxypropyl acrylate, 50 parts of styrene, 10 parts of glycidyl methacrylate, 40 parts of butyl methacrylate, 5 parts of azobisisobutyronitrile, 5 parts of t-butyl perbenzoate and 50 parts of toluene was added dropwise over 3 hours. After the dropwise addition was completed, the temperature was maintained at the same temperature for 10 hours, and then 75 parts of butanol and 75 parts of MIBK were added to prepare an epoxy-based polyester-modified acrylic material with a nonvolatile content of 50%, viscosity Y, acid value 0.5, and w/n = 8. A polymer (CP-2) was obtained. Example 3 In a flask similar to Example 1, soybean oil fatty acid
478 parts, maleic anhydride 5 parts, phthalic anhydride 275 parts
128 parts of pentaerythritol and 178 parts of trimethylolpropane, heated to 220°C and held until the acid value became 10 or less to stop the reaction.
Cool and add 667 parts of toluene to reduce non-volatile content to 60
%, viscosity U, acid value 5.8, and OH value 80, an unsaturated group-containing soybean oil-modified alkyd resin solution 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 210 parts of trimethylsiloxyethyl methacrylate, 90 parts of methyl methacrylate, 47 parts of β-hydroxyethyl methacrylate, and acrylic of 350 parts of a monomer mixture consisting of 3 parts of acid.
50 parts, 3 parts of t-butyl peroctoate, and 200 parts of butyl acetate, heated to 90°C, and further heated to 90°C.
The temperature was raised to 115°C over 1 hour, and a mixture consisting of the remaining 300 parts of the monomer mixture, 200 parts of toluene, 7 parts of t-butyl peroctoate, and 5 parts of t-butyl perbenzoate was added dropwise over 4 hours. After the addition, the temperature was maintained at the same temperature for 10 hours, and the non-volatile content was 50%, the viscosity was Y, the acid value was 3.8, the hydroxyl value was 40,
A hydroxyl group- and carboxyl group-containing polyester-modified acrylic copolymer (CP-3) with w/n=13 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, 5 parts of a mixture consisting of 40 parts of triethylsiloxypropyl methacrylate, 8 parts of β-hydroxypropyl methacrylate, 2 parts of methacrylic acid, 50 parts of toluene, 5 parts of t-butyl peroctoate, and 2 parts of di-t-butyl peroxide was added. It was added dropwise over a period of time, and after being maintained at 110°C for 10 hours, 150 parts of toluene was added to give a solution containing hydroxyl and carboxyl groups with a non-volatile content of 50%, viscosity Z, acid value 2.8, hydroxyl value 63, w/n = 21. A polyester-modified acrylic copolymer (CP-4) was obtained. Example 5 In a flask similar to Example 1, 100 parts of pt-butylbenzoic acid, 501 parts of phthalic anhydride, 66 parts of trimethylpentanediol, and trimethylolpropane were added.
254 parts and 150 parts of neopentyl glycol were charged, and the temperature was raised to 160°C. Furthermore, from 160℃ to 210℃
The temperature was raised over 6 hours and maintained at the same temperature until the acid value became 10 or less. Afterwards, the temperature dropped to 180℃,
Add 315 parts of phthalic anhydride while being careful not to generate heat.
The temperature was maintained at the same temperature until the acid value was approximately 100 or less, and when the acid value reached approximately 96, the temperature was lowered and diluted with a toluene/MIBK = 20/80 mixed solvent to obtain a mixture with a nonvolatile content of 60% and a viscosity of Z. _2. A carboxyl group-containing saturated polyester resin solution with an acid value of 57 was obtained. Next, 667 parts of this resin solution was charged into a four-necked flask equipped with a stirrer, thermometer, inert gas inlet, and reflux condenser, and then hydroquinone monomethyl ether
0.08 parts of 2-methylimidazole, 0.2 parts of glycidyl methacrylate, 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 approximately 54. When the acid value reached about 54, the temperature was lowered to about 40°C, 100 parts of butyl acetate, 15 parts of dimethylmonophenylsiloxyethyl acrylate and 5 parts of BPO were added, and the temperature was raised to 110°C to give 80% of triphenylsiloxyethyl acrylate. parts, 133 parts of toluene, 3 parts of BPO,
A mixture consisting of 5 parts of t-butyl peroctoate was added dropwise over 2 hours and kept at the same temperature for about 10 hours to obtain a solution with a non-volatile content of 50%, viscosity V, acid value 36, w/n=
13 carboxyl group-containing polyester-modified acrylic copolymer (CP-5) was obtained. Example 6 In a flask similar to Example 1, coconut oil fatty acid 235
1 part, 427 parts of phthalic anhydride, 98 parts of neopentyl glycol, 213 parts of trimethylolpropane, and 100 parts of pentaerythritol were charged, and the temperature was first raised to 160°C, and then the temperature was raised from 160°C to 210°C over 6 hours. The temperature is maintained at the same temperature until the acid value becomes 10 or less, the temperature is lowered to about 100-110℃, and the mixture is diluted with a mixed solvent of toluene/isobutyl acetate = 40/60 (weight ratio).
A coconut oil-modified saturated polyester resin solution having a nonvolatile content of 60%, a viscosity of Z ₂ to _{Z 3} , an acid value of 4.8, and an OH value of 95 was obtained. Next, 83 parts of this resin solution was charged into a four-neck 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 the temperature was heated to 110°C. After raising the temperature to 40°C and keeping it at the same temperature for 30 minutes, cool it down to 40°C, add 150 parts of styrene, 100 parts of tributylsiloxypropyl methacrylate, 87 parts of β-hydroxyethyl acrylate, 108 parts of butyl methacrylate, 200 parts of isobutyl acetate, 255 parts of a mixture consisting of 5 parts of BPO, 3 parts of t-butyl peroctoate, and 2 parts of t-butyl perbenzoate were added and the temperature was raised to 100°C again, kept at the same temperature for 30 minutes, and then raised to 115°C. Raise the temperature and at this temperature the remaining 400 ml of the mixture
was added dropwise over 4 hours and kept at the same temperature for about 10 hours until the nonvolatile content was 50%, viscosity W-X, and acid value.
A polyester-modified acrylic copolymer (CP-6) containing hydroxyl groups and carboxyl groups with a hydroxyl temperature of 3.4, a hydroxyl cold value of 50, and w/n=8 was obtained. Example 7 Except that 50 parts of trimethylsiloxybutyl acrylate and 50 parts of triphenylsiloxyethyl methacrylate were used instead of tributylsiloxypropyl methacrylate.
In the same manner as in Example 6, NV was 50% and viscosity was
-Y, the acid value is 3.3, the hydroxyl value is 50, and
A polyester-modified acrylic copolymer (CP-7) having a hydroxyl value and a carboxyl group and having Mw/n=8 was obtained. Comparative Example 1 Polyester with non-volatile content of 50%, viscosity Z, acid value 4.9, hydroxyl value 40, w/n = 5 was prepared in the same manner as in Example 1, except that isobutyl methacrylate was used instead of trimethylsiloxyethyl acrylate. A modified acrylic copolymer (CP-1') was obtained. Comparative Example 2 Same as Example 2 except that isobutyl methacrylate was used instead of triethylsiloxypropyl acrylate, non-volatile content 50%, viscosity Z, acid value
0.5, an epoxy group-containing polyester-modified acrylic copolymer (CP-2') with w/n=8 was obtained. Comparative Example 3 Same as Example 3 except that isobutyl methacrylate was used instead of trimethylsiloxyethyl methacrylate, nonvolatile content 50%, viscosity Z ~
A polyester-modified acrylic copolymer (CP-3') containing hydroxyl and carboxyl groups with Z ₁ , acid value 4.0, hydroxyl value 40, w/n=10 was obtained. Comparative Example 4 Except for using isobutyl methacrylate instead of tributylsiloxypropyl methacrylate,
Same as Example 6, non-volatile content 50%, viscosity Y-
A polyester-modified acrylic copolymer (CP-4') containing hydroxyl groups and carboxyl groups was obtained, having an acid value of 3.5, a hydroxyl value of 50, and w/n=8. Application Examples 1 to 13 and Comparative Application Examples 1 to 8 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).

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Claims (1)

[Claims] 1 (A)(1) General formula [However, in the formula, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a phenyl group or an alkyl group of C ₁ to _{C 18} , and n is an integer of 1 to 3. ] 0.1 to 100% by weight of trialkylsiloxyalkyl (meth)acrylate and/or triphenylsiloxyalkyl (meth)acrylate represented by (2) a vinyl monomer copolymerizable with the above (meth)acrylates (1) 5-99.5% by weight of a monomer mixture consisting of 0-99.9% by weight
and (B) copolymerizing 0.5 to 95% by weight of a polyester having a hydroxyl equivalent of 100 to 5000 and having a copolymerizable unsaturated bond in the presence of a radical generator, and the polyester thus obtained. Water repellency, characterized in that the w/n ratio of the modified acrylic copolymer is 3 to 30;
A method for producing a polyester-modified acrylic copolymer for paints that has excellent pigment dispersibility and texture.