JPH0138418B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel polyester-modified acrylic resin varnish and a method for producing the same, and more specifically, the present invention relates to a novel polyester-modified acrylic resin varnish and a method for producing the same. The present invention relates to a novel polyester-modified acrylic resin varnish containing a graft polymer useful for paints 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 plasticization and has a linear structure, has excellent hardness and flexibility, and has good weather resistance, stain resistance, and chemical resistance. On the other hand, resins made by polymerizing vinyl monomers, especially acrylic resins, are highly transparent, hard, and glossy, and can be made into hard or soft resins by freely changing the reaction components, so they are also widely used in the paint field. . 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. Furthermore, it goes without saying that a coating film in which different resins are chemically bonded and integrated is better than a simple mixture of different resins; Many attempts have been made to obtain resins that combine the excellent properties of both. 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. These methods all involve graft polymerization of vinyl monomers onto unsaturated groups of an alkyd resin, and if the content of the unsaturated groups is large, gelation tends to occur during resin production. The range of unsaturated group content that does not cause gelation 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 components were limited within a narrow range. At the applicant's laboratory, a ceremony was held first. (In the formula, R ₁ is a C ₁ to C ₂₀ alkyl group having at least one hydroxyl group and may contain -O- or -COO- in the chain, R ₂ and R ₃ are the same or different groups. , a hydrogen atom, a C ₁ to _{C 20} alkyl group, an alkyl group or a cyclic group having at least one hydroxyl group and/or a sulfonic acid group, A is a C ₁ to _{C 6} linear or branched alkylene group, By using a hydroxyl group-containing aminosulfonic acid type zwitterionic compound represented by (representing a phenylene group or a substituted phenylene group) as part of the alcohol component, and polycondensing a polybasic acid with a polyhydric alcohol and/or an oxirane compound. , the formula in the molecule (In the formula, A is as described above) A novel oil-free polyester having an aminosulfonic acid type zwitterionic group is obtained,
This product 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.
Due to the characteristics of the zwitterionic group, it has unique reactivity, surface activity, and electrochemical properties, and is soluble in many organic solvents and has excellent miscibility with solvent-based resin compositions, making it an extremely useful resin for coatings. It was found to be useful and a patent application was filed. (Special request 1984
-56048) As a result of continuing research on the above-mentioned oil-free polyester, the present inventors found that the above-mentioned hydroxyl group-containing aminosulfonic acid type zwitterionic compound was added to the polyhydric alcohol and/or oxirane compound containing the above-mentioned hydroxyl group-containing aminosulfonic acid type zwitterionic compound as part of the alcohol component in an excessive amount. If polybasic acids are polycondensed, the formula An oil-free polyester containing an aminosulfonic acid type zwitterionic group and a carboxyl group represented by the formula (where A is as described above) was obtained, and this was treated with α,β-
When glycidyl esters of ethylenically unsaturated fatty acids are reacted, the remaining carboxyl groups and glycidyl groups react, creating a formula within the molecule. (In the formula, A is as described above) An aminosulfonic acid type zwitterionic group represented by
An oil-free polyester having α,β-ethylenically unsaturated groups is obtained, which also retains the unique surface activity and electrochemical properties derived from the zwitterionic groups, and is capable of intramolecular radical polymerization. It also has reactivity due to the unsaturated group, and it was found that it is extremely useful as a reactive emulsifier for emulsion resins, etc., and a separate patent application was filed on the same date as the present application. (February 1982
Patent application (1) and patent application (2) filed on the 25th) The present invention further provides that the formula Particular attention was paid to the polymerization reactivity of an oil-free polyester having an aminosulfonic acid type zwitterionic group and an α,β-ethylenically unsaturated bond shown in the following. That is, the present inventors believe that the above polyester originates from its manufacturing method and has radically polymerizable α,
Because it has β-unsaturated bonds, it is possible to obtain graft polymers by direct radical polymerization with vinyl monomers, and there are no restrictions on the constituent components of polyesters and vinyl copolymers, and they can be designed as desired. It is extremely suitable for the production of modified acrylic resins, and unlike when vinyl monomers are grafted onto the unsaturated groups of conventional alkyd resins, there is no gelation during the production of the resin, and the grafting rate is low. It is extremely advantageous as an industrial manufacturing method for polyester-modified acrylic resins because it can be arbitrarily designed.Moreover, the modified resins obtained have unique surface activity and electrochemical properties due to the presence of the zwitterionic groups, and the curing temperature is very low. The present invention was completed after discovering that this resin is extremely useful as a resin for coatings because it is useful for lowering the temperature and shortening the curing time, has excellent solvent solubility, and has excellent pigment dispersibility and flexibility. It is. That is, according to the present invention, the formula (wherein A represents a C ₁ to C ₆ linear or branched alkylene group, phenylene group, or substituted phenylene group);
A novel polyester-modified acrylic resin varnish containing as a main component a graft polymer of an oil-free polyester having an α,β-ethylenically unsaturated bond and at least one vinyl monomer, and the oil-free polyester; A novel method for producing a polyester-modified acrylic resin varnish is provided, which comprises reacting at least one vinyl monomer in the presence of a radical polymerization initiator. The resin obtained by the present invention has a formula in its molecule. This is a new type of graft polymer that has not been previously known in that it has been modified with an oil-free polyester having amphoteric ionic groups as shown in the figure below.
In the molecule used in the present invention, the formula an aminosulfonic acid type zwitterionic group represented by;
The oil-free polyester having α,β-ethylenically unsaturated bonds is described in the patent application (1) title of the invention “Novel oil-free polyester and its manufacturing method” filed separately on the same date by the present inventors. The way it is done, i.e. the general formula (In the formula, R ₁ is a C ₁ to C ₂₀ alkyl group having at least one hydroxyl group and may contain -O- or -COO- in the chain, R ₂ and R ₃ are mutually the same or A is a hydrogen atom, a _C1 - _C20 alkyl, an alkyl group or a cyclic group having at least one hydroxyl group and/or a sulfonic acid group, A is a _C1 - _C6 straight-chain or branched alkylene group, phenylene A polyhydric alcohol and/or an oxirane compound containing a hydroxyl group-containing aminosulfonic acid type zwitterionic compound represented by (representing a group or a substituted phenylene group) as part of the alcohol component and an excess amount of a polybasic acid are polycondensed. , the formula in the molecule (In the formula, A is as described above) An oil-free polyester having an aminosulfonic acid type zwitterionic group and a carboxyl group is obtained, and then α,β-ethylenically unsaturated fatty acid is added to 1 equivalent of the carboxyl group of the polyester. It is advantageously produced by reacting glycidyl ester of 0.2 to 2.0 equivalents of epoxy group in the presence of a polymerization inhibitor. (Details of the manufacturing method are in the same patent application.
(See (1)) Note that the hydroxyl group-containing aminosulfonic acid type zwitterionic compounds used in the above reaction are shown in Japanese Patent Application No. 56048/1983 by the present inventors, and a typical one is N-( 2-hydroxyethyl)aminomethanesulfonic acid, N-(2-hydroxy-1-methylethyl)aminomethanesulfonic acid, N-(2-hydroxypropyl)aminomethanesulfonic acid, N-(3-hydroxypropyl)aminomethane Sulfonic acid, N-(2-propyl-2-hydroxyethyl)
Aminomethanesulfonic 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, N-(1-hydroxy Methyl-2-methyl-2
-hydroxyethyl)aminomethanesulfonic acid, N-(1-hydroxymethyl-3-hydroxypropyl)aminomethanesulfonic acid, N-(1-(γ-hydroxypropyl)-2-hydroxyethyl)aminomethanesulfonic acid, N -(1,1-bis(hydroxymethyl)-2-
hydroxyethyl)aminomethanesulfonic acid, N-(2,2-bis(hydroxymethyl)-3-
hydroxypropyl)aminomethanesulfonic acid, and each of the above N-alkyl and N,N-
Dialkyl substituted product, N,N-bis(2-hydroxyethyl)aminomethanesulfonic acid, N-(2-hydroxyethyl)-N-(2-hydroxypropyl)aminomethanesulfonic acid, N,N-bis(2- hydroxypropyl)aminomethanesulfonic acid, N,N-bis(4-hydroxybutyl)aminomethanesulfonic acid, N-(2-hydroxyethyl)-N-(1,1-
Bis(hydroxymethyl)-2-hydroxyethyl)aminomethanesulfonic acid, N-(3-hydroxypropyl)-N-(1,1
-bis(hydroxymethyl)-2-hydroxyethyl)aminomethanesulfonic 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 -Tris-(2-hydroxyethyl)
Ammoniomethanesulfonic acid betaine, N,N-bis-(2-hydroxyethyl)-N-
(3-hydroxypropyl)ammoniomethanesulfonic acid betaine, N,N,N-tris(3-hydroxypropyl)ammoniomethanesulfonic acid betaine, aminoethanesulfonic acid corresponding to each of the above, aminopropanesulfonic acid-( 1), aminopentanesulfonic acid-(1), N-(2-hydroxyethyl)iminodiethanesulfonic acid, N-(2-hydroxypropyl)iminodiethanesulfonic acid, N-(2,3-dihydroxypropyl) Iminodiethanesulfonic acid N-(1,1-bis(hydroxymethyl)-2-
Hydroxyethyl)iminodiethanesulfonic acid, N-(2-hydroxyethyl)iminoethanesulfonic 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)methanilic acid N-(2-hydroxyethyl)sulfanilic acid, N,N-bis-(2 -hydroxyethyl)orthanilic acid, N,N-bis-(2-hydroxyethyl)methanilic acid, N,N-bis-(2-hydroxyethyl)sulfanilic acid, etc., and one or more of these are It is used as part of the alcohol component. moreover,
Polyhydric alcohols, oxirane compounds, or polybasic acids to be reacted with them are of the type used in the production of ordinary oil-free polyesters, and α,β-ethylenically unsaturated fatty acids include glycidyl acrylate and methacrylate. Glycidyl acid and the like are preferably used. For details of the reaction, please refer to the above-mentioned patent application (1). As is clear from the above, this reactive oil-free polyester having amphoteric ionic groups and α,β-ethylenically unsaturated bonds has radically polymerizable ethylenically unsaturated groups at the terminals due to its manufacturing method. By appropriately selecting polyhydric alcohols, polybasic acids, etc., it is possible to design polyesters with arbitrary characteristics and properties.
It has the property of producing a new copolymer through graft polymerization with vinyl monomers. 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 acrylic acid,
Carboxyl group-containing monomers such as methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, alkyl (meth)acrylates, hydroxy (meth)acrylates, nitrogen-containing alkyl (meth)acrylates
Acrylate, (meth)acrylamide, (meth)
Any copolymerizable vinyl monomer such as acrylonitrile, styrene, α-methylstyrene, vinyltoluene, vinyl acetate, vinyl propionate, butadiene, isoprene, etc. may be used alone or in any combination of two or more types, and this meaning is used. It will be understood that the design of the acrylic resin is completely free. Examples of polymerization initiators include those commonly used as radical polymerization initiators, such as organic peroxides such as benzoyl peroxide, t-butyl peroxide, and methyl ethyl ketone peroxide, azobisisobutyronitrile, and azobis-(2,4-dimethyl)valero. Any organic azo compound such as nitrile, azobiscyanovaleric acid, etc. can be used, and the amount used is approximately 0.05 to 5%, preferably 0.05 to 5% based on the total reaction components.
It is selected in the range of 0.1 to 3%. The reaction is conveniently carried out in solution polymerization in an inert organic solvent. Although the polymerization temperature depends on the reaction components, catalyst, solvent, etc., it is usually selected to be 40 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 is carried out using a normal resin varnish manufacturing method and does not require any special operations, but specifically, the initiator and monomer are usually added dropwise into a solvent maintained at the reaction temperature. After reacting for a certain period of time, if necessary, add an initiator later,
It is advantageously produced by keeping it warm for 1 to 2 hours and then cooling it. 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 particularly useful for coatings, etc., and has excellent gloss, pigment dispersibility, flexibility, chemical resistance, hardness, and low-temperature curability. Therefore, it is particularly useful for, for example, thermosetting acrylic paints. The present invention will be explained below with reference to Examples and Comparative Examples. Note that "parts" in the example sentences means "parts by weight." Example 1 (a) In a two-kolben equipped with a stirrer, a nitrogen inlet tube, a temperature control device, a condenser, and a decanter,
169 parts of hydroxyethyl taurine, 134 parts of trimethylolpropane, neopentyl glycol
104 parts, phthalic anhydride 148 parts, sebacic acid 404 parts,
32 parts of xylene was charged and the temperature was raised. Water produced by the reaction was removed by azeotropic reflux with xylene. It takes about 2 hours and 30 minutes from the start of reflux to lower the temperature.
The temperature was raised to 200°C, and the reaction was continued with stirring and dehydration until the acid value equivalent to carboxylic acid reached 110. this
After lowering the temperature to 80℃, add 0.07 parts of hydroquinone and 108 parts of methylglycidyl methacrylate.
The temperature was set to 110°C, and the reaction was completed for 4 hours. This product had an acid value of 98, a hydroxyl value of 138, a number average molecular weight of 755, and an iodine value of 27.4. (b) Take 156 parts of the resin obtained in (a) above into beaker 1, add 237.9 parts of methyl methacrylate,
It was dissolved in a mixed solution of 98.3 parts of butyl acrylate, 81.1 parts of 2-hydroxyethyl methacrylate, 7.7 parts of acrylic acid, and 75 parts of styrene. Further, 6 parts of azobisisobutyronitrile was dissolved in this solution to obtain a mixed solution of monomer and initiator. Separately prepared stirrer, nitrogen introduction tube, temperature control device,
220 parts of methyl isobutyl ketone, 270 parts of xylene, and 40 parts of methyl cellosolve were charged into a 2-kolben equipped with 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. After the dropwise addition, a solution of 0.5 parts of azobisisobutyronitrile dissolved in 10 parts of acetone was added, and the mixture was heated to the same temperature. The reaction was then completed for another 1 hour. This varnish had a nonvolatile content of 54.2%, a number average molecular weight of 8500, and was completely transparent. The properties of the varnish are shown in Table 1. Example 2 (a) 213 parts of bishydroxyethyltaurine, 1,6-
236 parts of hexanediol, 296 parts of phthalic anhydride,
376 parts of azelaic acid and 44 parts of xylene were charged 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 the temperature was lowered to 140° C. and maintained at this temperature, 250 parts of “Cardilla E10” (Versatellite glycidyl ester manufactured by Shell) was added dropwise over 30 minutes, and stirring was continued for 2 hours. Cool this to 80℃ and add 0.05 parts of hydroquinone monomethyl ether, 140 parts of xylene, 128 parts of glycidyl methacrylate, and triethylamine.
7.0 parts were 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 molecular weight.
940, and the iodine value was 18.8. (b) Take out 308 parts of the reaction product of (a) above into beaker 1, and add 143.9 parts of methyl methacrylate, 55.6 parts of 2-hydroxyethyl methacrylate, 4.8 parts of methacrylic acid, 80 parts of styrene, 51.7 parts of ethyl acrylate, It was dissolved in a mixture of 64 parts of dibutyl fumarate. Furthermore, 6.3 parts of azobisisobutyronitrile was dissolved in this solution to obtain a mixed solution of monomer and initiator. A stirrer prepared separately,
70 parts of butyl acetate and xylene in a 2-kolben equipped with a nitrogen inlet tube, temperature control device, and condenser.
210 parts and 50 parts of n-butanol were charged, and the temperature was raised to 120°C. After the temperature reached 120°C, a mixed solution of monomer and initiator that had already been prepared was added dropwise over a period of 3 hours and 30 minutes. After completing the dropping, add 0.5 part of azobisisobutyronitrile dissolved in 10 parts of acetone,
After the reaction was completed by keeping at the same temperature for another 1 hour and 30 minutes, the temperature was lowered to 80℃ and 70 parts of butyl acetate and xylene were added.
200 parts and 50 parts of n-butanol were added. The non-volatile content of this varnish is 49.2% and the number average molecular weight is 16300.
It was completely transparent. The properties of the varnish are shown in Table 1. Comparative Example 1 Under the same reaction conditions as in Example 1, 170 parts of methyl isobutyl ketone, 210 parts of xylene, and 30 parts of methyl cellosolve were used as solvents, and 237.9 parts of methyl methacrylate, 98.3 parts of butyl acrylate were used as reaction monomers.
A varnish was synthesized in the same manner as in Example 1, except that 81.1 parts of 2-hydroxyethyl methacrylate, 7.7 parts of acrylic acid, and 75 parts of styrene were used. This varnish had a nonvolatile content of 54.4% and a number average molecular weight of 6200. The properties of the varnish are shown in Table 1. Comparative Example 2 Under the same reaction conditions as in Example 2, 42 parts of butyl acetate, 127 parts of xylene, 30 parts of n-butanol and 42 parts of butyl acetate were used as a diluting solvent.
121 parts of xylene, 30 parts of n-butanol, and as monomers 143.9 parts of methyl methacrylate, 55.6 parts of 2-hydroxyethyl methacrylate, 4.8 parts of methacrylic acid, 80 parts of styrene, and ethyl acrylate.
A varnish was synthesized in the same manner as in Example 2 except that 51.7 parts and 64 parts of dibutyl fumarate were used. This varnish has a non-volatile content of 49.3% and a number average molecular weight
It was 9800. The properties of the varnish are shown in Table 1.

[Table] Ranking of performance judgment ◎＞○＞△＞×

Claims (1)

[Claims] 1 Formula in the molecule (wherein A represents a C ₁ to C ₆ linear or branched alkylene group, phenylene group or substituted phenylene group);
A novel polyester-modified acrylic resin varnish containing as a main component a graft polymer of an oil-free polyester having α,β-ethylenically unsaturated bonds and at least one vinyl monomer. 2 Formula in molecule (wherein A represents a C ₁ to C ₆ linear or branched alkylene group, phenylene group or substituted phenylene group);
A novel method characterized by reacting an oil-free polyester having α,β-ethylenically unsaturated bonds with at least one vinyl monomer in an inert organic solvent in the presence of a radical polymerization initiator. A method for producing polyester modified acrylic resin varnish.