JPS62283108A - Production of resin for paint - Google Patents

Abstract

PURPOSE:To obtain a resin containing phenolic hydroxyl group and imide ring in the molecule and having excellent quick-drying property, corrosion resistance, heat resistance and weather resistance, by reacting a specific vinyl polymer with a phenolic compound and subjected the reaction product to dehydration or dealcoholation. CONSTITUTION:The objective resin containing phenolic hydroxyl group and imide ring in the molecule can be produced by (1) reacting (A) a vinyl polymer produced by polymerizing (a) 1-70(wt)% vinyl monomer having carboxylic acid anhydride group (e.g. maleic anhydride, itaconic anhydride, etc.) and/or a monoalkyl ester compound of the vinyl monomer (e.g. monomethyl malate) and (b) other vinyl monomer copolymerizable with said vinyl monomer [e.g. methyl (meth)acrylate] with (B) a phenolic compound having one primary amine group in one molecule (e.g. aminophenol) and (2) subjecting the reaction product to dehydration or dealcoholation reaction.

Description

Detailed Description of the Invention 3. Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a new and useful method for producing a coating resin, and more specifically, to a method for producing a new and useful coating resin, and more specifically, a method for producing a vinyl resin having a carboxylic acid anhydride group. Excellent quick-drying, corrosion resistance, heat resistance, and weather resistance obtained by reacting a monoalkyl ester compound of the polymer and/or the anhydride group with a phenol compound having one primary amino group in one molecule. This invention relates to a method for producing paint resin.

[Conventional technology and its problems]

Phenol resin-modified alkyd resins, epoxy resin-modified alkyd resins, and epoxy ester resins have traditionally been used as anticorrosive paints1, and it is known that introducing phenolic hydroxyl groups and epoxy groups into resins is effective in improving corrosion resistance. generally known.

However, all of the resin systems are condensation systems, 1 and are ester compounds of animal and vegetable oils and their fatty acids or synthetic fatty acids, or condensates of formalin, so they have significant shortcomings in quick drying properties and chemical resistance.

Therefore, by introducing the above-mentioned functional groups, especially phenolic hydroxyl groups, into a vinyl polymer that has excellent quick-drying properties and excellent chemical resistance as a lacquer paint, a vinyl polymer that has excellent corrosion resistance, heat resistance, chemical resistance, and various physical properties can be obtained. will be obtained.

The method for producing such a vinyl polymer involves using a vinyl monomer containing a phenolic hydroxyl group, such as phenolmaleimide or oxystyrene, and, if necessary, another vinyl monomer that can be copolymerized with these monomers. It is conceivable to polymerize in the presence of a radical generator.

However, when such phenolic hydroxyl group-containing vinyl monomers are polymerized in the presence of a radical generator, the polymerization reaction slows down extremely or does not occur at all due to a phenomenon thought to be due to the radical scavenging effect of the phenolic hydroxyl group. It exhibits a phenomenon that does not occur.

[Problem that the invention seeks to solve]

However, as a result of intensive studies to solve the drawbacks of the prior art described above, the present inventors discovered that a vinyl polymer having a carboxylic acid anhydride group and/or a monoalkyl ester group of the anhydride group, and A phenolic hydroxyl group can be introduced into a vinyl polymer by addition reaction with a phenolic compound containing one primary amino group, and after the addition reaction, a phenolic hydroxyl group can be introduced into the molecule by dehydration or dealcoholization reaction. The inventors have discovered that an imide ring can also be formed, thereby producing a resin for coatings that is excellent in corrosion resistance, chemical resistance, and heat resistance, and has thus completed the present invention.

[Structure of the invention]

(Means for Solving the Problems) To summarize the present invention, the present invention has the following features: (A): 1. 1 to 70% by weight of a vinyl monomer having a carboxylic acid anhydride group and/or a monoalkyl ester compound of the vinyl monomer, and other vinyl monomers copolymerizable with the vinyl monomer. A vinyl polymer obtained by polymerizing 99 to 30% by weight of 99 to 30% by weight is reacted with (B): a phenol compound containing one IR amino group in one molecule, and then a dehydration reaction or dealcoholization reaction is performed. The aim is to produce a coating resin in which a phenolic hydroxyl group and an imide ring are introduced into a vinyl polymer.

Hereinafter, the configuration of the present invention will be explained in detail.

First, the vinyl polymer (A
) Explain the ingredients.

This vinyl polymer (A) component is.

(A)-1, a vinyl monomer having a carboxylic acid anhydride group, and/or a monoalkyl ester compound of the vinyl monomer; and (A)-2, copolymerizable with the vinyl monomer. It is composed of other vinyl monomers.

Typical examples of vinyl compounds having a carboxylic anhydride group (A)-1 include maleic anhydride.

Itaconic anhydride is 1, and the monoalkyl ester compound of the vinyl monomer has 1 to 1 carbon atoms with the monomer.
8 is obtained by reacting it with a monohydric alcohol having an alkyl group, and typical examples thereof include monomethyl maleate and monobutyl maleate.

Other vinyl monomers copolymerizable with these vinyl monomers of (A)-2 include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (
meth)acrylate, 1-propyl(meth)acrylate, n-butyl(meth)acrylate, 1-butyl(meth)acrylate, t-butyl(meth)acrylate,
2-ethylhexyl (meth)acrylate, lauryl (
(Meth)acrylic acid esters such as meth)acrylate, cyclohexyl (meth)acrylate, and benzyl (meth)acrylate; unsaturated dibases such as dimethyl maleate, dibutyl maleate, dimethyl fumarate, dibutyl fumarate, and dibutyl itaconate; Dialkyl esters of acids; Carboxyl group-containing monomers such as (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid; Cyano group-containing monomers such as acrylonitrile and methacrylonitrile; p -Styrene sulfonic acid.

Sulfonic acid group-containing monomers such as 2-acrylamido-2-methyl-propanesulfonic acid; vinyl esters such as vinyl acetate, vinyl benzoate, and "Beoba" (product of Shell, Netherlands); "Viscoat 8F, 8FM ,
3F or 3FMJ (fluorine-containing product manufactured by Osaka Organic Chemical Co., Ltd.)
meth)acrylic monomers], perfluorocyclohexyl (meth)acrylate, di-perfluorocyclohexyl fumarate or N-isopropyl perfluorooctanesulfonamide ethyl (meth)acrylate, or monomers containing a fluoroalkyl group or perfluoroalkyl group. halogenated olefins such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, and chlorotrifluoroethylene; aromatic vinyl monomers such as styrene, vinyltoluene, α-methylstyrene, and pt-butylstyrene and dialkylaminoalkyl (meth)acrylates such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and dimethylaminopropyl (meth)acrylate.

In addition, when (A)-1, a vinyl monomer containing a carboxylic acid anhydride group is used as the monomer, other vinyl monomers that can be copolymerized with this (A)-2, a hydroxyl group-containing monomer are used. Vinyl monomers cannot be used. This is because the carboxylic acid anhydride group-containing monomer easily undergoes a ring-opening reaction with the alcoholic 011 (hydroxyl group)-containing vinyl monomer, and the branched vinyl group becomes involved in polymerization to generate a three-dimensional structure. This is for gelatinization.

However, (A)-1, when using a monoalkyl ester compound of a vinyl monomer containing a carboxylic acid anhydride group as the monomer, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate,
A hydroxyl group-containing vinyl monomer such as 2-hydroxybutyl (meth)acrylate can be used.

In order to prepare the vinyl polymer (A) component from such monomers, any conventionally known polymerization method can be applied, but
Solution radical polymerization is the simplest method.

Typical solvents used in this case include hydrocarbon solvents such as toluene, xylene, cyclohexane, n-hexane, and octane; methyl acetate, ethyl acetate,
Ester solvents such as n-butyl vinegar and amyl acetate;
Examples include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, and cyclohexanone, and any mixtures thereof may of course be used.

Solution radical polymerization may be carried out by a conventional method using the solvent and various radical polymerization initiators such as azo type or peroxide type, and at this time, if necessary, the molecular weight W! Chain transfer agents such as lauryl mercaptan, octyl mercaptan, 2-mercaptoethanol, octyl thioglycolate, 3-mercaptopropionic acid or α-methylstyrene dimer can also be used as moderators.

The amount of the carboxylic anhydride group-containing vinyl monomer and/or the monoalkyl ester compound of the monomer used in the present invention is 1 to 70% by weight, preferably 5 to 60% by weight. If it is less than 1% by weight, no effect on corrosion resistance will be observed, and if it exceeds 70% by weight, the coating film will become extremely brittle.

Next, the (+3) component, a phenol compound containing a primary amino group that reacts with the carboxylic anhydride group and/or the carboxylic acid group of the monoalkyl ester compound of the seed water group, will be explained.

(B) Typical ingredients include aminocreso-
Examples include aminocresol, amylsorcinol, nitroaminophenol, 2-amino-4°6-sinitrophenol, p-(2-aminoethyl)phenol, and salicylic acid amide.

From the viewpoint of water resistance, aminophenol and aminocresol are preferred compounds.

In order to prepare the coating resin of the present invention from the vinyl polymer (A) component and the phenol compound (B) component described above, the carboxylic acid anhydride group and/or The amount of IR amino group in the compound (B) component is 0.5 to 3.0"4 fik, preferably 0.7 to 1.5 equivalent, per equivalent of the carboxylic acid group of the monoalkyl ester compound of the anhydride group. It is sufficient to mix both components in a ratio such that the reaction occurs in a temperature range from room temperature to about 100°C.If the amount is less than 0.5 equivalent, there will be no corrosion resistance effect, and if the amount exceeds 3.0 equivalent, there will be no corrosion resistance effect. If used, it will have a negative effect on water resistance.Afterwards.

Check the specified acid value and raise the temperature to about 70-150℃.
Ring closure occurs by retention, dehydration or dealcoholization to form an imide ring.

For example, an example of a reaction using a carboxylic anhydride group is as follows.

(Margins below) (A) (B) (However, n=0-
6. (R: H, alkyl group, OH group, NO, group, etc.) As shown in the reaction example above, a vinyl polymer (C) having both a phenolic hydroxyl group and an imide ring can be obtained.

The coating resin prepared by the method of the present invention may be used alone or in combination with other compatible coating resins or compounding components as required. For example, organic or inorganic pigments: known and commonly used. Flow W4!1 Agent 1 Various additives such as color separation inhibitors, ultraviolet absorbers, and antioxidants; Fiber derivatives such as nitrocellulose and cellulose acetate butyrate; chlorinated polyethylene, chlorinated polypropylene, Various resins such as petroleum resin and chlorinated rubber can be added as necessary.

(Example) Next, the present invention will be specifically explained using production examples, examples, and comparative examples. Unless otherwise specified, parts and percentages are as follows:
All are based on weight.

<Production example> Production example-1 [Preparation example of vinyl polymer containing phenolic hydroxyl group] 283 parts of xylene and di-butyl were placed in a four-bottle flask equipped with a thermometer, reflux condenser, stirrer, and nitrogen gas inlet. 2 parts of peroxide was charged and the temperature was raised to 120°C. When the temperature reached the same temperature, 130 parts of styrene, 100 parts of maleic anhydride, 170 parts of n-butyl methacrylate, and n-butyl methacrylate were added.
-100 parts of butyl acrylate, and 100 parts of dimethyl sulfoxide, 5 parts of azobisisobutyronitrile
A mixture of 1 part and 5 parts of ditertiary-butyl peroxide was added dropwise over 3 hours, and the reaction was further continued at the same temperature for 7 hours.

Lower the temperature to 100℃
05 parts was charged and the temperature was raised to 125°C to proceed with the reaction, and the produced water was removed from the flask over a period of 3 hours.

When the acid value is confirmed to be 0.5 or less, cool it and add xylene 2
30 parts and 100 parts of n-butanol were added to obtain the desired coating resin having a phenolic hydroxyl group and an imide ring. This product has a non-volatile content of 50% and a viscosity (Gardner 25℃
Same hereafter) Z3. The acid value was 0.3.

Production Example 2 [Preparation example of vinyl polymer containing phenolic hydroxyl group] Using the same apparatus as in Example 1, styrene, maleic anhydride, n-butyl methacrylate, n-butyl acrylate, and p-aminophenol were prepared. The same operation as in Example 1 was repeated except that 130 parts of styrene, 114 parts of itaconic anhydride, 156 parts of n-butyl methacrylate, 100 parts of n-butyl acrylate, and 108 parts of p-7 minofenol were used. A resin was obtained. This product has a non-volatile content of 50% and a viscosity of 2. -2. , the acid value was 0.4.

Production Example-3 [Preparation example of vinyl polymer containing phenolic hydroxyl group] The same operation as in Example 1 was repeated except that 150 parts of nitroaminophenol was used in place of p-aminophenol used in Example 1 to obtain the desired product. A resin was obtained. This product had a non-volatile content of 50%, a viscosity of Z2, and an acid value of 0.2. 190 parts of acrylate, 10 parts of ethyl acrylate
The desired resin was obtained by repeating the same operation as in Example 1 except for using 0 part of p-aminophenol and 68 parts of p-aminophenol. This product had a nonvolatile content of 50%, a viscosity Z, and an acid value of 0.2.

Production Example-5 [Comparative preparation example of vinyl polymer containing phenolic hydroxyl group] 155 parts of styrene, 4 parts of maleic anhydride, 211 parts of n-butyl methacrylate, 13 parts of lobutyl acrylate
The same operation as in Example 1 was repeated except that 4.8 parts of p-aminophenol and 4.8 parts of p-aminophenol were used to obtain a vinyl polymer containing a phenolic hydroxyl group and an imide ring for comparison.

This product had a nonvolatile content of 50%, a viscosity of W-X, and an M value of 0.4.

Production Example-6 [Comparative preparation example of vinyl polymer containing phenolic hydroxyl group] 130 parts of styrene, 100 parts of maleic anhydride, n-bu.
A comparative vinyl polymer containing a phenolic hydroxyl group and an imide ring was obtained by repeating the same operation as in Example 1 except for using 170 parts of tyl methacrylate, 100 parts of lobe tyl acrylate, and 43 parts of p-aminophenol. . This product has a non-volatile content of 50%, a viscosity of Y-Z, and an acid value of 0.
It was 4.

i Conventional Example-7 [Preparation Example of Comparative Control Epoxy Ester Resin] Dehydrated castor oil fat N140 was placed in the same flask as in Production Example 1.
0 parts and 600 parts of Epicron 4050 C (Epi-bis type epoxy resin manufactured by Dainippon Ink & Chemicals) were charged, and the temperature was raised to 240°C, and the reaction was proceeded at that temperature.

After confirming that the dilution viscosity with xylene was 50% and within the s-w range, the temperature was lowered to 120° C. or lower, 1000 parts of xylene was added, it was confirmed that a homogeneous solution was obtained, and the temperature was lowered to room temperature.

An epoxy resin is thus obtained, which has a non-volatile content of 5
0%, viscosity T-U, and acid value 1.2.

Production Example-8 [Am example of comparative control phenol resin-modified alkyd resin] 170 parts of isophthalic acid and 300 parts of linseed oil were charged into the same reactor as in Production Example 1, heated to 270°C in a nitrogen atmosphere, and held for 2 hours. . After that, it was cooled to below 180°C, and 170 parts of isophthalic acid and 26 parts of trimethylolethane were added.
After adding 5 parts of benzoic acid and 153 parts of benzoic acid, the temperature was raised to 230°C and maintained at that temperature. After confirming that the acid value was below 10, it was cooled to 180°C and turned into Super Veracasite 1001 [
After confirming that 60 parts of Dainippon Ink Chemical Industry ■Mr1100% phenol resin has been dissolved, add 1 part of xylene.
050 parts were added to obtain the desired resin. This product has a non-volatile content of 50.4% and a viscosity of R-8. The acid value was 3.1.

<Evaluation of physical properties of coating film> Polymer solution obtained in each production example and titanium oxide CR-9
130 parts of 3 (rutile type titanium oxide made by Ishihara Sangyo@): 3
They were mixed in a ratio of 5 parts and made into a paint by a conventional method. After that, it was diluted with a mixed solvent of toluene/n-butanol = 70,730 (weight ratio) to a viscosity that could be sprayed, and sprayed onto a zinc phosphate-treated steel plate to a film thickness of about 40%.6 The coated steel plate was baked at 80°C for 20 minutes. A cured coating film was obtained, and the physical properties of the coating film were evaluated. The test and evaluation results are shown in Table 1.

As is clear from Table 1, the coating material containing the specific vinyl polymer prepared by the method of the present invention is as follows.

The coating has excellent physical properties and maintains a good balance between physical properties.

(The following is a blank space) [Effects of the Invention] A vinyl polymer containing a phenolic hydroxyl group and an imide ring in the molecule obtained by the method of the present invention is as follows.

Forms a coating film with excellent quick drying, adhesion, corrosion resistance, hot air adhesion resistance, and chemical resistance.

Therefore, these vinyl polymers prepared by the method of the present invention are extremely useful as resin components for family 7Ii.

Claims (1)

[Claims] 1. (A): 1. 1 to 70% by weight of a vinyl monomer having a carboxylic acid anhydride group and/or a monoalkyl ester compound of the vinyl monomer 2. The vinyl monomer (B): Contains one primary amino group in one molecule. 1. A method for producing a coating resin having a phenolic hydroxyl group and an imide ring in its molecule, which comprises reacting a phenolic compound with a phenolic compound, followed by dehydration or dealcoholization. 2. For 1 equivalent of carboxylic acid of the carboxylic anhydride group and/or the monoalkyl ester compound of the anhydride group in the vinyl polymer (A), the primary in the primary amino group-containing phenol compound (B) 2. The method for producing a coating resin according to claim 1, which comprises reacting 0.5 to 3.0 equivalents of amino groups.