JPS5938963B2 - Resin manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for preparing a mixture of (a) an unsaturated aromatic hydrocarbon, (b) a monoacrylate or monomethacrylate of a polyhydric alcohol, and (c) an α,β monounsaturated carboxylic acid in an organic solvent. radical polymerization in the presence of acid value 5 to 150) hydroxyl value 3
The present invention relates to a method for producing a water-soluble or alcohol-soluble resin having a molecular weight of 0 to 120.

Printing inks using water and alcohol as solvents,
For example, water-based gravure inks, flexo inks, water-based or alcohol-soluble paints, and other coatings cause less air pollution than ink paints that use hydrocarbon solvents, and are advantageous in terms of pollution control. Development of alcohol-soluble or alcohol-soluble resins is underway. Such water-soluble resins include, for example, rosin-modified maleic acid resins with high acid values, and ceramics, but they have insufficient water resistance and abrasion resistance, and are made from natural products, so the price and supply are limited. It has the disadvantage of being unstable. Synthetic resins such as styrene-acrylic acid have also been developed, but this resin also has a high acid value, so when used as an ink resin, the ink may have insufficient stability, abrasion resistance, and water resistance. There are drawbacks. The present inventor has obtained a product obtained by radical copolymerization of an unsaturated aromatic hydrocarbon such as styrene, a monoacrylate or monomethacrylate of a polyhydric alcohol, and an α,β monounsaturated carboxylic acid such as acrylic acid or maleic anhydride. The present invention was completed by discovering that the resin has excellent performance as a water-soluble or alcohol-soluble resin, or a resin having both water-soluble and alcohol-soluble properties.

The resin according to the invention also has the following characteristics.

A large amount of acrylate or methacrylate is required to obtain an alcohol-soluble resin by radical copolymerization of monoacrylate or monomethacrylate of polyhydric alcohol, which is a monomer with alcohol affinity, and unsaturated aromatic hydrocarbon. By adding α, β monounsaturated carboxylic acids such as , acrylic acid, and maleic anhydride to form a ternary copolymer resin, the amount of monoacrylate or monomethacrylate of polyhydric alcohol can be greatly reduced. It is advantageous in terms of cost because it can be used as a resin, and since it has a suitable amount of acid groups, when this resin is used in various coatings such as inks and paints, it has good affinity with pigments.
A coating film or printed surface with excellent gloss and color density can be obtained.

Furthermore, in order to make a resin obtained from a two-component system of an unsaturated aromatic hydrocarbon and an α,β-unsaturated carboxylic acid, for example, styrene and acrylic acid, into a water-soluble resin by using an aqueous alkaline solution,
An acid value of about 200 is required.

Since such resins have a high acid value, the water resistance and abrasion resistance of the coating film are insufficient. According to the present invention, monoacrylate or monomethacrylate of a polyhydric alcohol is added to a system such as styrene and acrylic acid, and by ternary copolymerization, even if the acid value is small, it can be made water-soluble with an alkaline aqueous solution. When used as a resin component in various coatings such as paints and printing inks, the water resistance and abrasion resistance of the coated surface are significantly improved, and the gloss is good. The resin obtained in the present invention has an acid value of 5 to 150 and a hydroxyl value of 30 to 120.
belongs to.

Alcohol-soluble resins usually have an acid value of 5 to 801, preferably 10 to 601, hydroxyl value 30 to 100, preferably 40 to 80, and water-soluble resins usually have an acid value of 60 to 15.
0, preferably 70-1201, hydroxyl value 30-120,
Preferably, it can be produced in the range of 40 to 100. Hydroxyl value is 0gg, P0ter, Wi11it
s (Ind. Eng. Chem., Anal. Ed.,
17394 (1945)), and the amount of hydroxyl groups contained in resin 19 was determined by the corresponding KOHOmf! It was a hailstorm in numbers.

Acid value is measured according to JISK-5902. In the case of alcohol-soluble resins, if the acid value is less than 5, the affinity between the resin and the pigment will be insufficient, and the gloss and color development of the coated surface using this resin will not be sufficient, and if the acid value is higher than 80, However, the stability of coatings using this material over time tends to deteriorate.

Furthermore, if the hydroxyl value is lower than 30, it will become insoluble in alcohols such as isopropyl alcohol, and even if the hydroxyl value is higher than 100, the gloss and color development of the coated surface will not change, but it will be disadvantageous in terms of cost. is suitably 100 or less. In the case of a water-soluble resin, if the acid value is lower than 60, it will be insoluble in an aqueous alkaline solution, and if it exceeds 150, the water resistance of the coating using it will be poor, which is not preferred.

If the hydroxyl group is lower than 30, it will be insoluble in alkaline water even if the acid value is 150. Further, even if the value is higher than 120, the gloss and color development of the coated surface will not change, so increasing the hydroxyl value even higher is disadvantageous in terms of cost, so a value of 120 or less is appropriate. Examples of the unsaturated aromatic hydrocarbons used in the present invention include styrene, vinyltoluene, α-methylstyrene, and naphtha cracked oil fractions.
It is also possible to use fractions containing styrene and its derivatives, indene and its derivatives, which have a boiling point of 20°C.

The monoacrylate or monomethacrylate of polyhydric alcohol referred to in the present invention is a monoester of acrylic acid or methacrylic acid and polyhydric alcohol.

Here, the polyhydric alcohol usually has 2 to 10 carbon atoms, preferably 2 to 5 carbon atoms, such as ethylene glycol, propylene glycol, butanediol,
Typical examples include glycerin, pentaerythritol, diethylene glycol, dipropylene glycol, and triethylene glycol. Therefore, the polyhydric alcohol monoacrylate or monomethacrylate referred to in the present invention includes, for example, 2-hydroxyethyl acrylate. , 2-hydroxyethyl methacrylate,
Examples include 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, and the like. In addition, α,β monounsaturated carboxylic acids include maleic anhydride, itaconic anhydride, acrylic acid,
Examples of organic solvents used during polymerization include carbonized solvents such as benzene, toluene, xylene, kyumene, cymene, isooctane, mineral spirits, solvent naphtha, kerosene, etc. Hydrogen solvent, methanol, ethanol, n-propanol, IPAln-butanol,
Examples include alcohols such as Sec-butanol, n-amyl alcohol, and 2-ethylhexyl alcohol, and glycol ethers such as butyl cellosolve and ethyl cellosolve.

The catalyst is appropriately selected from so-called radical polymerization catalysts that generate radicals when heated, depending on the operating temperature.

For example, benzoyl peroxide, lauroyl peroxide, ditertiary butyl peroxide, tertiary butyl hydroperoxide, cumene hydroperoxide, parathane hydroperoxide, tertiary butyl perbenzoate, tertiary butyl peracetate, azobisisobutyronitrile, etc. Select appropriately depending on the operating temperature. The amount used is usually 0.3 to 5% by weight, preferably 0.5 to 3% by weight, based on the total monomer amount. Polymerization time is 0.5 to 10 hours, preferably 1
~5 hours. In the present invention, in order to adjust the softening point of the resin, a chain transfer agent generally known in radical polymerization can be used as a molecular weight regulator.

Examples include mercaptans, halogenated hydrocarbons, halogen-substituted organic acids, aldehydes, and alcohols. Specific examples of these molecular weight regulators include n-
Examples include dodecyl mercaptan, t-dodecyl mercaptan, octyl mercaptan, butyl mercaptan, carbon tetrabromide, bromoacetic acid, butyraldehyde, octyl alcohol, and the like. The polymerization method is carried out by maintaining unsaturated aromatic hydrocarbons, monoacrylates or monomethacrylates of polyhydric alcohols, α,β monounsaturated carboxylic acids, solvents, radical polymerization initiators, etc. at a predetermined temperature and time. .

In addition, unsaturated aromatic hydrocarbons are added to the solvent kept at a predetermined temperature.
It can also be carried out by dropping a mixture of polyhydric alcohol monoacrylate or monomethacrylate, α,β-unsaturated carboxylic acid, solvent, radical polymerization initiator, etc. In the present invention, if the conditions are appropriately selected, the conversion rate of the monomer can be approximately 10,070, so the amount of each raw material to be supplied is determined so as to theoretically achieve the predetermined acid value and hydroxyl value. Depending on the desired acid value,
A resin having a hydroxyl value can be obtained.

Furthermore, if alcohol is used as the polymerization solvent, a resin dissolved in alcohol can be obtained without recovering the resin from the solution after polymerization. For example, when alcohol is used as a solvent, it can be used directly as an alcohol-soluble paint or printing ink varnish after polymerization. Furthermore, in order to recover solid resin from a resin-containing solution after polymerization, it is commercially advantageous to remove the solvent by distillation or evaporation, but in the present invention, the temperature of distillation or evaporation is an important factor. The distillation temperature is usually 230°C, preferably 210°C or lower. If the distillation temperature exceeds 230°C, the resin may gel and become insoluble in alcohol or alkaline aqueous solutions. The properties of the resins obtained by the above methods are usually softening points (JIS-K-25
31-60) 100-150°C, number average molecular weight 800-50001 Hue (Cardner scale AST
Measured by MD-1544-58T, resin 100%)7
It is as follows.

The water-soluble and alcohol-soluble resins of the present invention can be dissolved in alcohol, alcohol-alkaline aqueous solutions, and alkaline aqueous solutions to prepare varnishes.

Moreover, various coatings can be manufactured by kneading these varnishes and pigments. The alcohol used is usually an alcohol having 1 to 10 carbon atoms, preferably 2 to 6 carbon atoms, such as ethanol, IPAl ethyl cellosolve, etc. The alcohol used as the polymerization solvent may be used as it is. In order to make the resin soluble in alkaline water, examples of the alkali used for neutralization include ammonia, dimethylamine, trimethylamine, monoethanolamine, diethanolamine, triethanolamine, and morpholine.

The present invention will be explained in more detail with reference to Examples below. 〇Example 1 300 m capacity with 1 flux condenser, thermometer, stirrer, and dripping load! P-cymene 509 is placed in a four-bottle flask and kept at a temperature of 170°C in advance.

Styrene 509, 2-hydroxyethyl methacrylate 99, acrylic acid 49, ditertiary butyl peroxide 1f1, t-dodecyl mercaptan 0.5fI
, p-cymene 509 was added dropwise at 160°C.
The solution was added dropwise to p-cymene kept at a temperature of 1 hour or more. Next, after continuing stirring at the same temperature for 2 hours,
mmHgabs. Remove the solvent and low polymer under the conditions of 56
．． 59 resins were obtained. This resin had a softening point of 126° C., an acid value of 46, a hydroxyl value of 47, a hue of 2, and was soluble in ethanol and isopropyl alcohol. Example 2 In a 300 d four-bottle flask equipped with a flux condenser, a thermometer, a stirrer, and a dropper, 50 f. IPA509 and AIBN1.59 were added, and after purging the system with N2, stirring was continued at 70°C for 2 hours.

The temperature was then raised to 75°C and stirring continued for an additional 3 hours.
The solution was then allowed to cool to room temperature. The solid concentration of the solution was 54.3wt70, and it was partially soluble in ethanol, soluble in ethanol-isopropyl alcohol (1:1), and soluble in isopropyl alcohol. A resin obtained by distilling this solution in the same manner as in Example 1 had a softening point of 130°C, an acid value of 9, and a hydroxyl value of 78. Example 3 In the same flask as in Example 2, a cracked oil fraction with a boiling point range of 145 to 176°C produced as a by-product by steam cracking of naphtha (total unsaturated components by gas chromatography analysis: 46.
129 of 2-hydroxyethyl methacrylate, 19 of methacrylic acid, 0.59 of otatyl mercaptan, and 19 of ditertiary butyl peroxide were added to 1009 (which was 5 wt. Stirring was continued for 1 hour at a temperature of 145°C.

After that, the temperature was 210°C and the degree of vacuum was 5mmHgabs. The solvent and low polymers were removed under the following conditions to obtain a resin of 55.39. This resin has a softening point of 138°C, an acid value of 13, a hydroxyl value of 74, and a hue of 5. It is partially soluble in ethanol, soluble in ethanol-isopropyl alcohol (1:1), and soluble in isopropyl alcohol. Ta. Example 4 A mixture of 100 g of the cracked oil fraction with a boiling point of 145 to 176°C used in Example 3, 109 g of 2-hydroxyethyl methacrylate, 1.59 g of maleic anhydride, and 1 g of benzoyl peroxide was
After dropping the mixture into xylene 509 maintained at a temperature of 35 to 140° C. for 2 hours, unreacted components and low polymers were removed in the same manner as in Example 3 to obtain 539 in fat.

The softening point of this resin is 132°C, acid value 18, and hydroxyl value 52.
, hue 5, partially soluble in ethanol, ethanol-
It was soluble in isopropyl alcohol (1:1). Comparative Example 1 Same as Example 1, styrene 509, 2-hydroxyethyl acrylate 159, t-dodecylmercaptan 0.59, ditertiarybutyl peroxide 19, p-cymene 509
The mixture was added dropwise to p-cymene 509 kept at a temperature of 170°C, and the solvent and low polymers were removed to obtain resin 599.

The softening point of this resin is 128℃, the acid value is 1 or less, and the hydroxyl value is 8.
2, but it was insoluble in ethanol and isopropyl alcohol. Comparative Example 2 In the same manner as in Comparative Example 1, 50 g of styrene, 209 g of 2-hydroxyethyl metatallate, and 50 g of p-cymene were prepared.
63.4 g of resin was obtained from 9,n-DDM19 and 1.59 ditertiary butyl peroxide.

The softening point of this resin is 136℃, the acid value is 1 or less, and the hydroxyl value is 9.
8 and ethanol-isopropyl alcohol (1:
1) It was insoluble in isopropyl alcohol. Example 5 P-cymene 1009 is placed in the same apparatus as in Example 1 and kept at a temperature of 160°C in advance.

A mixture of 509 styrene, 109 2-hydroxyethyl acrylate, 139 acrylic acid, 29 n-dodecylmercaptan, 509 p-cymene, and 1 g ditertiarybutyl peroxide was dropped into p-cymene over 2 hours, and then the temperature The solvent and low polymer were removed under the conditions of 190° C. and a reduced pressure of 5 mT1LHg to obtain resin 699. This resin had a softening point of 133° C., an acid value of 95, a hydroxyl value of 44, and a hue of 3. This resin was soluble in isopropyl alcohol. Further, an aqueous solution having a resin concentration of 30wt70 was prepared using this resin and equivalent amounts of ammonia water and water.
The viscosity of this aqueous solution at 25°C was 110 cp. Example 6 p-cymene 1 heated to a temperature of 160°C in the same manner as in Example 5
2-hydroxyethyl acrylate 209 in 009
, methacrylic acid 109, n-dodecyl mercaptan 2
A mixture of 5 g of 9, p-cymene and 19 ditertiary butyl peroxide was added dropwise over a period of 2 hours from the dropwise loading, and resin 729 was obtained in the same manner as in Example 6. The softening point of this resin was 126°C, and the acid Value 82, hydroxyl value 94, hue 3
The viscosity of the ammonia aqueous solution prepared in the same manner as in Practical Example 6 was 230 cp.

Example 7 2-hydroxyethyl acrylate 159 and acrylic acid 159,n were added to the cracked oil fraction 1009 used in Example 3.
- A mixture of 1.59% of dodecyl mercaptan, 1.59% of benzoyl peroxide, and 509% of xylene was added dropwise from the dropwise loading over 2 hours.
Resin No. 9 was obtained.

Claims (1)

[Claims] 1 (a) unsaturated aromatic hydrocarbon, (b) monoacrylate or monomethacrylate of polyhydric alcohol, (c
) A mixture of α,β-unsaturated carboxylic acids is radically polymerized in the presence of an organic solvent to obtain an acid value of 5 to 150 and a hydroxyl value of 30 to 1.
A method for producing a water-soluble or alcohol-soluble resin having a composition of 20.