JPS58149962A - Novel polyester-modified acrylic resin varnish and production thereof - Google Patents

Abstract

PURPOSE:To advantageously obtain the titled varnish which can lower curing temp., shorten curing time and has excellent solvent solubility, by reacting a specified oil-free polyester with a vinyl monomer in the presence of a radical polymn. initiator. CONSTITUTION:An oil-free polyester contg. an alpha-beta-ethylenically unsaturated bond and an amino sulfonic acid type zwitter-ion group of the formula (wherein A is a 1-6C straight-chain or branched alkylene, phenylene, substd. phenylene) in the molecule, is reacted with a vinyl monomer in the presence of a redical polymn. initiator in an inert org. solvent. Examples of the vinyl monomers are carboxyl group-contg. monomers such as (meth)acrylic acid and maleic acid, and copolymerizable vinyl monomers such as alkyl (meth)acrylate and (meth)acrylamide. Examples of the radical polymn. initiators are benzoyl peroxide and t-butyl peroxide.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel polyester-modified acrylic resin varnish and its manufacturing method. The present invention relates to a novel polyester-modified acrylic resin varnish useful for paints containing a graft polymer of polyester and a vinyl monomer, and a method for producing the same.

Oil-free polyester is obtained through the polycondensation reaction of polybasic acids, polyhydric alcohols, and/or oxirane compounds, and the main chain itself is plasticized using acids and alcohols that are flexible and have good molecular mobility. It is widely used in the paint field as a resin that does not require internal circuit layering and has a linear structure, and has excellent hardness and flexibility, as well as good weather resistance, stain resistance, and chemical resistance. There is. On the other hand, resins made by polymerizing vinyl monomers, especially acrylic resins, are highly transparent, hard, and have excellent gloss, and the reactive components can be freely changed to obtain 1# resins that can be hardened or softened, so they are also widely used in the paint field. ing. Attempts have been made for a long time to mix these different types of resins to create coatings that take advantage of the properties of each resin, but in this case, both resins are compatible and the paint It is necessary to show common solubility in the solvent used. Moreover, it goes without saying that they are chemically superior to each other than a simple mixture of different types of resins, and resins modified with such resins have the excellent properties of both. Many attempts have been made to obtain this. Now, when modifying acrylic resin with polyester, the conventional method is to graft polymerize a vinyl monomer to an alkyd resin modified with unsaturated oil or unsaturated fatty acid, or to graft polymerize a vinyl monomer to an unsaturated polyester resin. There were known ways to do this. All of these methods involve graft polymerization of vinyl monomers onto unsaturated groups of alkyd resins, and if the content of unsaturated groups is large, gelation tends to occur during resin production. The range of unsaturated group content that does not cause kelization was limited to a relatively narrow range. As a result, the grafting rate is low, and the resulting resin has poor compatibility between the non-grafted vinyl resin component and the alkyd resin component, which limits the amount and combination of vinyl monomers that can be put into practical use. The resin component was limited to a narrow internal pressure range.

At the laboratory of the present applicant, the formula (wherein R1 has at least one hydroxyl group,
C1 containing -0- or -C00- in the chain
~C8, alkyl group, R1 and R8 are the same or different groups, hydrogen atom, C,-'-e,, alkyl group,
an alkyl group or an extended ring group having at least one hydroxyl group and/or sulfonic acid group, A is C1-C
A hydroxyl group-containing aminosulfonic acid type zwitterionic compound represented by (representing a linear or branched alkylene group, phenylene group, or substituted phenylene group) is used as part of the alcohol component, and polybasic acid and polyhydric alcohol are used. By polycondensing and/-strapping oxirane compound, a novel oil-free polyester having an aminosulfo/acid type zwitterionic group represented by the formula (the characters in the formula are as described above) in the molecule can be obtained. maintains the excellent properties of oil-free polyester, such as high hardness and flexibility, as well as excellent weather resistance, chemical resistance, and stain resistance. It was found to be extremely useful as a paint resin because it has active and electrochemical properties, is soluble in many organic solvents, and has excellent miscibility with solvent-based resin compositions, and a patent application was filed. . (Special application 55-560
No. 48) As a result of continuing research on the above-mentioned oil-free polyester, the present inventors found that an excessive amount of the above-mentioned hydroxyl group-containing aminosulfonic acid type zwitterionic compound was added to a polyhydric alcohol and/or an oxirane compound containing as part of the alcohol component. By polycondensing polybasic acids, an oil-free polyester containing an aminosulfo/acid-type zwitterionic group and a carboxyl group represented by the formula % (the characters in the formula are as described above) in the molecule can be obtained. When a glycidyl ester of α,β-ethylenically unsaturated fatty acid is applied to a polymer in the presence of a polymerization inhibitor, the remaining carboxyl group and glycidyl group react, forming the formula (the characters in the formula are as described above) in the molecule. Aminosulfonic acid type zwitterionic group represented by α, β
- An oil-free polyester having ethylenically unsaturated groups is obtained, which also retains the unique surface activity and electrochemical properties derived from the zwitterionic groups, and also has 1
It also has reactivity due to the radically polymerizable unsaturated group in the molecule, and it was found that it is extremely useful as a reactive emulsifier for, for example, Emulsi, 7 resin, etc., and a separate patent was granted on the same date as this application. I applied. (February 2, 1981
The aminosulfonic acid type zwitterionic group and α shown in Patent Application (1) and Patent Application (2)) filed on May 5th.

Particular attention was paid to the polymerization reactivity of oil-free polyesters having β-ethylenically unsaturated bonds.

That is, the present inventors believe that the above-mentioned polyester has radically polymerizable α,β-unsaturated bonds at its terminals due to its manufacturing method, so it can be radically polymerized directly with vinyl monomers to form a graft polymer. There is no restriction on the pressure of the constituent components of the polyester or vinyl copolymer, and the design can be carried out arbitrarily, so it is extremely suitable for the production of polyester-modified acrylic resins. This method is extremely advantageous as an industrial method for producing polyester-modified acrylic resins, as there is no gelation during the production of the resin when the monomers are grafted, and the grafting rate can be arbitrarily designed.
Moreover, the resulting modified resin has unique surface activity and electrochemical properties due to the presence of the amphoteric ionic group, which helps lower the curing temperature and shorten the curing time, and has excellent solvent solubility and pigment dispersion. The present invention was completed after discovering that this resin has excellent properties such as properties and flexibility and is extremely useful as a paint resin.

That is, according to the present invention, an aminosulfonic acid type zwitterion represented by the formula (in the formula, a straight chain or branched alkylene group of C to C, a phenylene group, or a thtm phenylene group) is used in the molecule. Base, α, β
- a polyester-modified acrylic resin face containing as a main component a graft polymer of an oil-free polyester having an ethylenically unsaturated bond and at least one vinyl monomer, and the oil-free polyester; A novel method for producing a polyester-modified acrylic resin face is provided, which comprises reacting various vinyl monomers with a vinyl monomer in the presence of a radical polymerization initiator.

The resin obtained in the present invention is a new type of graft polymer that has not been previously known in that it is modified with an oil-free polyester having an amphoteric ionic group represented by the formula in the molecule.

The oil-free polyester having an aminosulfonic acid type zwitterionic group represented by the formula and an α,β-ethylenically unsaturated bond in the molecule used in the present invention is disclosed in a separate application filed by the present inventors on the same date. The patent lit (1. Title of the invention: "Novel oil-free polyester and method for producing the same." obtain an oil-free polyester having groups,
Next, α for 1 equivalent of carboxyl group of the polyester,
It is advantageously produced by reacting glyc7dyl ester of β-ethylenically unsaturated fatty acid with an epoxy group equivalent of 0.2 to zO equivalent in the presence of a polymerization inhibitor. (For details of the manufacturing method, refer to the same patent application (1).) The hydroxyl group-containing aminosulfo/acid type zwitterionic compound used in the above reaction is described in the patent application filed by the present inventors in 1983.
-56048, the representative ones are N-(2-hydroxyethyl)aminomethanesulfonic acid, N-(2-hydroxy-1-methylethyl)aminomethanesulfonic acid, N-(2-hydroxyethyl)aminomethanesulfonic acid, -hydroxypropyl)aminomethanesulfonic acid, N-(3-hydroxypropyl)aminomethanesulfonic acid, N-(2-propyl-2-hydroxyethyl)amine,
Methanesulfonic acid, N-(2-methyl-2-ethyl-2-hydroxyethyl)aminomethanesulfonic acid, N-(1,2-dimethyl-2-hydroxyethyl)aminomethanesulfonic acid, N-(1,1 , 2,2-tetramethyl-2-hydroxyethyl)aminomethanesulfonic acid, N-(1-methyl-
5,5-dimethyl-5-hydroxypentyl)aminomethanesulfonic acid, N-(1,2-diisopropyl-2-
hydroxyethyl)aminomethanesulfonic acid, N-(2,3-dihydroxypropyl)aminomethanesulfonic acid, N-(1-hydroxymethyl-2-hydroxyethyl)
Aminomethanesulfonic acid, 2-(1-methyl-2-dihydroxyethyl)aminomethanesulfonic acid, N-(1-hydroxymethyl-3-hydroxypropyl)aminomethanesulfonic acid, N -(1-(r-hydroxypropyl)-2-hydroxyethyl)aminomethanesulfonic acid, N-(1,1-bis(hydroxymethyl)-2-hydroxyethyl)aminomethanesulfonic acid 1,N-(2, 2-bis(hydroxymethyl)-3-hydroxypropyl)aminomethanesulfonic acid, and each of the above N-alkyl and KN,N-dialkyl substituted products, N,N-bis(2-hydroxyethyl)aminomethanesulfonic acid, N-(2-hydroxyethyl)-N-(2-hydroxypropyl)aminomethanesulfonic acid, N,N-bix(2
-hydroxypropyl)aminomethanesulfonic acid, N,N-bis(4-hydroxybutyl)aminemethanesulfonic acid, N-(2-hydroxyethyl)-N-(1,4-bis(
hydroxymethyl)-2-hydroxyethyl)aminomethanesulfonic acid, N-(3-hydroxypropyl)-N-(1゜1-bis(hydroxymethyl)-2-hydroxyethyl)amino, methanesulfonic acid, N, N-bis(2,3-dihydroxypropyl)aminomethanesulfonic acid, N,N-bis-(1-hydroxymethyl)-2-hydroxyethyl)aminomethanesulfonic acid, N,N-bis-
(1,1-(bishydroxymethyl)-2-hydroxyethyl)aminomethanesulfonic acid, and each of the above N-alkyl substituents, N,N,N-)lis-(2-hydroxyethyl)ammoniomethanesulfone Acid betaine, N,N-bis-(2-
hydroxyethyl) -N=(3-hydroxypropyl)ammoniomethane sulfo/acid betaine, N,N,N-)lis(3-hydroxypropyl)ammoniomethane sulfonic acid betaine, aminomethane sulfonic acid corresponding to each of the above , aminopropanesulfonic acid-
(1), aminopentanesulfonic acid-(1), sulfonic acid, N-(2-hydroxypropyl)ibanodiethanesulfo/11% N-(2,3-dihydroxyfurovir)iminodiethanesulfonic acid N-(1) , 1-bis(hydroxymethyl)-2-hydroxyethyl)iminodiethanesulfonic acid, N-(2-hydroxyethyl)ibanoethanesulfonic acid, propanesulfonic acid, N-(2-hydroxypropyl)iminoethanesulfonic acid Propanesulfonic acid, N-(2,3-dihydroxypropyl)iminoethanesulfonic acid Propanesulfonic acid, N-(1,1-bis(hydroxymethyl)-2-hydroxyethyl)iminoethanesulfonic acid Propanesulfonic acid, N- (2-hydroxyethyl)orthanylic acid N-(2-
Hydroxyethyl>mep=h acid N-(2-hydroxyethyl)sulfanilic acid, N,N-bis-(2-hydroxyethyl)orthanylic acid, N,N-bis-(2-hydroxyethyl)metanilic acid, N,N-bis-(2-hydroxyethyl)sulfanilic acid, etc., and one or more of these are used as part of the alcohol component. Furthermore, polyhydric alcohols, oxirane compounds, or polybasic acids to be reacted with them are of the type normally used in the production of oil-free polyester, and α,β-ethylenically unsaturated fatty acids include glycidyl acrylate. , glycidyl methacrylate, etc. are preferably used. Please refer to the above-mentioned patent application (1) for details of the reaction.

As is clear from the above, this zwitterionic group and α.

Reactive oil-free polyester having β-ethylenically unsaturated bonds has an ethylenically unsaturated group at the end that can be radically polymerized due to its manufacturing method, and polyhydric alcohol, polybasic acid, etc. must be selected appropriately. An arbitrary property from K,
It is possible to design polyesters with specific properties, and by carrying the above-mentioned zwitterionic groups that exhibit unique surface activity and electrochemical properties, it is possible to create new copolymers through Gunft polymerization with vinyl monomers. have.

In the present invention, the novel reactive oil-free polyester described above is copolymerized with at least one vinyl monomer in the presence of a radical polymerization initiator.

Examples of vinyl monomers include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid, alkyl (meth)acrylates, hydroxy (meth)acrylates, nitrogen-containing alkyl (Meth)acrylate, (meth)acrylamide, (meth)acrylonitrile, styrene, alpha methylstyrene, vinyltoluene, vinyl acetate, vinyl propionate, butadiene, isoprene, and other co-monogenous vinyl monomers It is understood that these may be used alone or in any combination of two or more, and in this sense, the design of the acrylic resin is completely free.As the polymerization initiator, radical polymerization initiators such as benzoyl peroxide, benzoyl peroxide, Organic peroxides such as t-butyl peroxide and methyl ethyl ketone peroxide, azobisisobutyronitrile, azobis-(2,4-dimethyl)valeronitrile,
Any organic azo compound such as azobiscyanovaleric acid can be used, and the amount used is approximately 0.05 to 5%, preferably 0.1 to 3%, based on the total reaction components.

The reaction is conveniently carried out in solution polymerization in an inert organic solvent.

The polymerization temperature depends on the reaction components, catalyst, solvent, etc., but is usually 4.
The temperature is selected to be 0 to 180°C, preferably 50 to 140°C. If necessary, a suitable amount of a conventional chain transfer agent such as mercaptans such as lauryl mercaptan and hexyl mercaptan may be used in combination.

The present invention can be carried out using ordinary resin varnish manufacturing methods,
Although no special operations are required, the initiator and monomer are usually dropped into a solvent maintained at the reaction temperature, reacted for a certain period of time, and then, if necessary, after the initiator is removed. It is advantageously produced by adding the kernels to the kernels, keeping them warm for 1 to 2 hours, and then cooling them.

The resin obtained by the method of the present invention is an oil-free polyester-modified acrylic resin in which a large number of oil-free polyesters having amphoteric ionic groups are chemically bonded as side chains to an acrylic resin obtained by polymerizing or copolymerizing vinyl monomers,
Moreover, it is a completely new resin in that it has the above-mentioned special aminosulfonic acid type zwitterionic group in the grafted oil-free polyester part, and the polyester and acrylic resin can be freely designed to have various properties such as sharpness, image clarity, etc. It is possible to obtain a resin that is extremely useful for coatings, etc., and has excellent gloss, pigment dispersibility, flexibility, chemical resistance, hardness, and low-temperature curability. Therefore, it is useful for example in thermosetting acrylic paints.

The present invention will be explained below with reference to Examples and Comparative Examples. In addition, "part" in the example sentence means "part by weight, J1&-.

Example 1 (a) 169 parts of hydroxyethyl taurine and 1 part of trimethylolpropane were placed in a 2-ton colben equipped with a stirrer, a nitrogen inlet tube, a temperature control device, a condenser, and a decanter.
34 parts of $opentyl glycol, 148 parts of phthalic anhydride, 404 parts of sebacic acid, and 32 parts of xylene were charged, and the temperature was raised. Water produced by the reaction was removed by azeotropic reflux with xylene.

After about 2 hours and 30 minutes from the start of reflux, the temperature was raised to 200°C.
The reaction was continued with stirring and dehydration until the acid value equivalent to carboxylic acid reached 110.

After lowering this to 80℃, 0.07i of hydroquinone
1S and 108 parts of methylglycidyl methacrylate were added, the temperature was raised to 110°C, and the reaction was completed for 4 hours.

This product has an acid value of 9B, a hydroxyl value of 138, and a number average molecular weight of 75.
5, the iodine value was 27.4.

(b) Take 156 parts of the resin obtained in (a) above into a 1 ton beaker, add 237.9 parts of methyl methacrylate, 9 and 3 parts of butyl acrylate, 81.1 parts of 2-hydroxyethyl methacrylate, and 7.0 parts of acrylic acid. 7 parts of styrene and 75 parts of styrene.

Furthermore, 6 parts of azobisisobutyronitrile was dissolved in this solution to obtain a mixed solution of monomer and initiator. 220 parts of 1-methyl in butyl ketone, 270 parts of xylene, and 40 parts of methyl cellosolve were charged into a separately prepared FC-21 Kolben equipped with a stirrer, a nitrogen inlet pipe, a temperature control device, and a condenser, and the temperature was raised to 110°C. After the temperature reached 110°C, the previously prepared mixed solution of monomer and initiator was added dropwise over 3 hours, and after the dropwise addition, 0.5 parts of azobisisobutyro nitride dissolved in 10 parts of amethane was added. The solution was added and kept at the same temperature for an additional hour to complete the reaction. This festival
It had a nonvolatile content of 54.2%, a number average molecular weight of 8,500, and was completely transparent.

The characteristics of the festival are shown in Table 1.

Example 2 (a) 213 parts of bishydroxyethyl taurine, 236 parts of 1.6=hexanediol, 296 parts of phthalic anhydride, Azelaic acid 37
6 parts and 44 parts of Xyrev were added and the temperature was raised. Water produced by the reaction was removed by azeotropic reflux with xylene. Over about 3 hours from the start of reflux, the temperature was raised to 210°C, and the reaction was continued with stirring and dehydration until the acid value equivalent to carboxylic acid reached 125. After lowering the temperature to 140°C, the temperature was maintained and 250 s of Cardura E10J (grindyl persatic acid ester manufactured by Shell) was added dropwise over 30 minutes, and stirring was continued for 2 hours.The temperature was then lowered to 80°C. 0.05 part of hydroquinone monomethyl ether, 140 parts of xylene, 128 parts of glycidyl methacrylate)
7.0 parts of ethylamine was added and the reaction was completed at 90° C. for 3 hours.

This product has an acid value of 68, a hydroxyl value of 57, and a number average molecule Φ). Take out 308 parts of the reaction product of (a) above into a 1 ton beaker, add 143.9 parts of methyl methacrylate, and 2 parts of methacrylic acid.
-Dissolved in a mixed solution of 55.6 parts of hydroxyethyl, 4.8 parts of methacrylic acid, 80 parts of styrene, 51.7 parts of ethyl acrylate, and 64 parts of dibutyl fumarate. Furthermore, 3 parts of azobisinobutyronitrile was dissolved in this solution to obtain a mixed solution of monomer and initiator. 70 parts of butyl acetate and 210 parts of xylene were placed in a 2-ton colben equipped with a separately prepared stirrer, nitrogen inlet tube, temperature control device, and condenser.
50 parts of n-butanol was charged and the temperature was raised to 120°C. 1
After the temperature reached 20° C., the mixed solution of monomer and initiator that had already been prepared was added dropwise over a period of 3 hours and 30 minutes. After finishing dropping, 10
Azobisisobutyronitrile dissolved in 70%
．． After the reaction was completed by keeping at the same temperature for an additional 1 hour and 30 minutes, 70 parts of butyl acetate, 200 parts of xylene, and 50 parts of n-7' tanol were added to the mixture at 80°C. The nonvolatile content of this varnish is 49.2'16, and the number average molecular weight is 1.
6300 and was completely transparent.

The properties of the varnish are shown in Table 1.

Comparative Example l Under the same reaction conditions as in Example 1, 170 parts of methyl in butyl ketone, 210 parts of xylene, and 30 parts of methyl cellosolve were used as solvents, and 2 methyl methacrylate was used as a reaction monomer.
37.9 parts, butyl acrylate 98.3 parts, methacrylic 112-hydroxyethyl 81.1 parts, acrylic acid 7.
A varnish was synthesized in the same manner as in Example 1 except that 7 parts of styrene and 75 parts of styrene were used.

This varnish has a nonvolatile content of 54.4% and a number average molecular weight of 620.
It was 0.

The properties of the varnish are shown in No. 19NK.

Comparative Example 2 Under the same reaction conditions as in Example 2, 42 parts of butyl acetate, 127 parts of xylene, and 30 parts of n-butanol were used as solvents during the reaction.
1 part and 42 parts of butyl acetate and 1 part of xylene as a diluting solvent.
21 parts, 30 parts of n-7' tanol and as additives 14 & 9 parts of methyl methacrylate, 55.6 parts of 2-hydroxyethyl methacrylate, 4.8 parts of methacrylic acid, 80 parts of styrene, 51 parts of ethyl acrylate. A varnish was synthesized in the same manner as in Example 2 except that .7 parts and 64 parts of dibutyl fumarate were used.

This varnish has a nonvolatile content of 49.3% and a number average molecular weight of 980.
It was 0.

The properties of the varnish are shown in Table 1.

Claims (2)

[Claims] (1) An aminosulfonic acid type zwitterionic group represented by the formula (wherein A represents C, -C, linear or branched alkylene group, phenylene group or substituted phenylene group) in the molecule, α ,
Novel polyester-modified acrylic resin varnish containing as a main component a graft polymer of oil-free polyester having β-ethylenically unsaturated bonds and at least one vinyl monomer 0 (2) an aminosulfonic acid type zwitterionic group represented by the formula (wherein A represents C1-C, linear or branched alkylene group, phenylene group or substituted phenylene group) in the molecule; α, β
- A novel polyester-modified acrylic characterized by reacting an oil-free polyester having an ethylenically unsaturated bond with at least one vinyl monomer in an inert organic solvent in the presence of a radical polymerization initiator. Method for producing resin varnish.