JPH0116406B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel method for producing a coating copolymer. In recent years, paint and coating industries have been eagerly looking for paints that are maintenance-free and provide highly weather-resistant coatings from the viewpoint of saving resources, saving energy, and reducing pollution. Traditionally, in fields that require high weather resistance,
Fluorine-modified resin paints, silicone-modified resin paints, etc. are being considered, but these resin paints have low initial gloss, are expensive, require the selection of solvents, and have problems with pigment dispersibility, especially pigments with high oil absorption, e.g. It has problems such as inferior dispersibility to carbon black, cyanine blue, etc., and is used only for special purposes and has not been widely used. Also, a coating copolymer made by copolymerizing dicyclopentadiene acrylate or dicyclopentadiene methacrylate is well known (U.S. Pat. No. 4,097,677), but this copolymer has a dicyclopentenyl group structure. , especially poor weather resistance. The present invention solves these problems and provides a copolymer for coating materials that is excellent not only in weather resistance but also in heat resistance, gloss, and pigment dispersibility. That is, the present invention provides (A) general formula () (However, in the formula, R is hydrogen, a lower alkyl group, or a halogen, and R' is a divalent organic group,
n is 0 or 1) (hereinafter referred to as "component (A)") 20 to 99.9% by weight (B) unsaturated monomer having a carboxyl group (hereinafter referred to as "( (c) 0 to 30% by weight of an unsaturated monomer copolymerizable with component (A) and/or component (B) (hereinafter referred to as "component (C)")
Blended 79.9% by weight to 100% by weight,
The present invention relates to a method for producing a copolymer for coating material, which is characterized by polymerization. The copolymer obtained according to the present invention can be dissolved in an organic solvent to form an organic solvent type paint, or can be diluted with water after neutralization to form a water-soluble paint. The hydrogenated dicyclopentadiene derivative shown in the general formula () as component (A) can be obtained by numbering the tricyclodecyl group carbon atoms in the compound as shown in the general formula () below.

[Formula] is bonded to the 8th or 9th position. R' is a divalent organic group having 1 to 18 carbon atoms, preferably 2 to 12 carbon atoms. R′ is preferably an alkylene group or -(R″-O-)mR-
It is a group represented by Here, R'' and R are alkylene groups having two or more carbon atoms, and R'' and R may be the same or different. m is an integer of 1 or more. Specifically, tricyclodecyloxyalkyl acrylates such as tricyclodecyl acrylate, tricyclodecyl methacrylate, tricyclodecyloxyethyl acrylate, tricyclodecyloxyethyl methacrylate, tricyclodecyloxypropyl acrylate, tricyclodecyloxypropyl methacrylate, or Examples include methacrylate, acrylic ester or methacrylic ester of polyalkylene glycol tricyclodecyl monoether, such as acrylic ester or methacrylate of diethylene glycol tricyclodecyl monoether. The amount of component (A) used is 20% by weight or more. If the amount used is less than 20% by weight, the characteristics of the present invention, such as high gloss, excellent weather resistance, heat resistance, and pigment dispersibility, cannot be obtained. (B) Components include acrylic acid, methacrylic acid,
These include maleic acid, fumaric acid, and itaconic acid.
The amount used is 0.1-30% by weight. If component (B) is less than 0.1% by weight, when this copolymer is used as a paint, the adhesion to the substrate will be poor. Moreover, if it exceeds 30% by weight, the water resistance of the coating film will be poor and there will be a practical problem. The preferred blending amount is 0.5~ especially when used dissolved in an organic solvent.
2% by weight is preferable, when making it into a water-soluble copolymer.
It is preferable to use it at 0.5% by weight or more, especially,
Preferably, it is used in an amount of 8 to 15% by weight. Component (C) includes methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate,
Alkyl acrylates such as isobutyl acrylate and 2-ethylhexyl acrylate; alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, and cyclohexyl methacrylate; styrene; vinyl toluene ,α
- Styrenic monomers such as methylstyrene, vinyl esters such as vinyl acetate and vinyl propionate,
Oxirane group-containing ethylenically unsaturated monomers such as glycidyl acrylate and glycidyl methacrylate, vinyl cyanides such as acrylonitrile and methacrylonitrile, unsaturated amides such as acrylamide, methacrylamide, N-methylolacrylamide, and N-butoxymethylacrylamide; 2
-Hydroxyalkyl acrylates such as hydroxyethyl acrylate and 2-hydroxypropyl acrylate, hydroxyalkyl methacrylates such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate, unsaturated phosphoric acid groups such as ethyl acrylate phosphate and ethyl methacrylate phosphate There are monomers, etc., which are used singly or in combination of two or more. In some cases, it is also possible to use a polyfunctional ethylenically unsaturated monomer such as ethylene glycol diacrylate in an amount of 0 to 2% by weight based on the total amount of monomers. The monomer having a reactive functional group other than a double bond is preferably used in an amount of 0 to 30% by weight, particularly 0 to 10% by weight based on the total amount of components (A), (B) and (C). It is preferably used in the case of Such functional monomers include hydroxyalkyl acrylate, hydroxyalkyl methacrylate, and the like. Such functional monomers include (A), (B) and (C)
Preferably, it is used in an amount of 0 to 30% by weight, based on the total amount of components. Too much of this monomer tends to reduce water resistance. Furthermore, as component (C), a copolymer of components (A), (B), and (C) has a particularly preferable glass transition temperature for paints.
In order to adjust the temperature to 30 to 70°C, it is preferable to use a soft monomer such as ethyl acrylate, butyl acrylate, or 2-ethylhexyl acrylate. Components (A), (B), and (C) are obtained by copolymerization using well-known polymerization methods such as solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization. The polymerization temperature is appropriately determined within the range of 50 to 150°C. As polymerization catalysts, peroxides such as benzoyl peroxide, t-butyl peroxide, and cumene hydroperoxide, and azo compounds such as azobisisobutyronitrile and azobisisobutylvaleronitrile can be used, but in emulsion polymerization, Preference is given to using persulfates such as ammonium persulfate, potassium persulfate and the like. The amount of polymerization catalyst used is 0.1 to 5% by weight based on the total amount of monomers.
is preferred. Furthermore, in the present invention, molecular weight regulators such as mercaptan, carbon tetrachloride, carbon tetrabromide, etc. can also be used if necessary. Organic solvents that can be used in solution polymerization include water-insoluble organic solvents such as toluene and xylene;
There are water-soluble organic solvents such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve. The copolymer obtained by the present invention can be made into a water-soluble polymer by further neutralizing some or all of the carboxyl groups of the copolymer with a neutralizing agent. In this case, it is preferable to use a water-soluble organic solvent as the organic solvent. At this time, after polymerization,
This can be followed by a neutralization step and dilution with water. Examples of neutralizing agents include amines such as ammonia, triethylamine, and dimethylaminoethanol. Emulsifiers used in emulsion polymerization include:
Examples include sodium lauryl sulfate, sodium dodecylbenzenesulfonate, and polyoxyethylene nonylphenol. In suspension polymerization, water-soluble polymers such as polyvinyl alcohol and methylcellulose, sparingly soluble inorganic salts such as calcium triphosphate, etc. can be used as suspending agents, and anionic surfactants such as sodium dodecylbenzenesulfonate can be used as suspension aids. It can be used as The copolymer according to the present invention can be used alone as a coating material, but if necessary, acrylic resin, alkyd resin, phenol resin, vinyl acetate copolymer resin, vinyl chloride copolymer resin, rosin, maleated rosin, ceramic, etc. Nitrified cotton and fiber derivatives can be blended. Further, this copolymer can be used in combination with an epoxy resin, a polyisocyanate compound, an aminoplast resin, etc. as a curing agent. The paint obtained using the polymer according to the present invention can be applied by dipping, brushing, spraying, roll coating, etc., and can be applied to wood, paper, fiber, plastic, etc.
Can be painted on surfaces such as ceramic, iron, and non-ferrous metals. Next, examples of the present invention will be shown. Example 1 (Solution polymerization method) Add toluene to a 500ml flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and gas introduction tube.
Charge 100g and heat to 100℃ under _N2 gas stream.
Then, a mixed solution of 80 g of tricyclodecyl acrylate, 0.5 g of methacrylic acid, 19.5 g of butyl acrylate, and 1 g of azobisisobutyronitrile was uniformly dropped from the dropping funnel over 2 hours. Then, the mixture was kept at this temperature for 3 hours to complete the polymerization. The obtained copolymer has a polymerization rate of 98% or more,
The heating residue was 50% and the viscosity was Gardner UV. Example 2 (Solution polymerization method) Using the same apparatus as in Example 1, 80 g of isopropyl alcohol was charged and the temperature was raised to 80°C. Then, a mixed solution containing 60 g of tricyclodecyloxyethyl acrylate, 12 g of methacrylic acid, 28 g of butyl acrylate, and 2 g of azobisisobutyronitrile was uniformly added dropwise from the dropping funnel over a period of 2 hours. Then, the mixture was kept at this temperature for 4 hours to complete the polymerization.
The obtained copolymer was cooled to 40°C, and the pH was adjusted to 8 with aqueous ammonia. Next, about 70g of ion exchange water
to obtain a water-soluble polymer. This polymer had a heating residue of 40% and a Gardner viscosity of Z. Example 3 (Emulsion polymerization method) Using the same equipment as in Example 1, 150 ml of ion-exchanged water was used.
Add 2 g of sodium lauryl sulfate and raise the temperature to 80°C. Then, 0.3 g of ammonium persulfate was added and dissolved. Tricyclodecyl acrylate 60
g, 1 g of acrylic acid, and 39 g of 2-ethylhexyl acrylate were uniformly dropped from the dropping funnel over 2 hours. Insulate at 80℃ for another 2 hours and cool. The pH of this copolymer was adjusted to 7 with aqueous ammonia. The resulting emulsion copolymer had a heating residue of 40% and a B-type viscosity of 250 centipoise. Example 4 (Suspension polymerization method) Using the same apparatus as in Example 1, 100 ml of ion-exchanged water was used.
g, 2% of polyvinyl alcohol (degree of polymerization 1500)
25g of aqueous solution, 80% of tricyclodecyl acrylate
g, methacrylic acid 0.3g, butyl acrylate
19.7 g and 2 g of benzoyl peroxide were charged and polymerized at 80°C for 4 hours to complete the polymerization. The obtained slurry was dehydrated and dried using a centrifugal separator to obtain a bead-like polymer. Example 5 (Solution polymerization method) 30 g of tricyclodecyloxyethyl acrylate and methyl methacrylate were prepared in the same manner as in Example 2.
30g, methacrylic acid 12g, butyl acrylate 28g
A water-soluble copolymer was obtained from g and 2 g of benzoyl peroxide. The heating residue was 40% and the viscosity was _Z2 . Example 6 (Solution polymerization method) In the same manner as in Example 2, 30 g of tricyclodecyl acrylate, 30 g of styrene, 12 g of methacrylic acid,
A water-soluble copolymer was obtained from 28 g of butyl acrylate and 2 g of benzoyl peroxide. The heating residue was 40% and the viscosity was Y to Z. Comparative Example 1 Methyl methacrylate 80 in the same manner as Example 1
g, methacrylic acid 0.5g, butyl acrylate
An organic solvent-based copolymer was obtained from 19.5 g and 1 g of azobisisobutyronitrile. The heating residue was 50% and the viscosity was _Z2 . Comparative Example 2 An organic solvent-based copolymer consisting of 30 g of styrene, 50 g of methyl methacrylate, 20 g of butyl acrylate, and 1 g of azobisisobutyronitrile was obtained in the same manner as in Example 1. The viscosity is Z~Z ₁ when the heating residue is 50%.
It was hot. Comparative Example 3 Methyl methacrylate 60 was prepared in the same manner as in Example 1.
g, methacrylic acid 12g, butyl acrylate 28g
A water-soluble copolymer was obtained from 2 g of azobisisobutyronitrile. The heating residue is 40% and the viscosity is X-
It was Y. Comparative Example 4 A water-soluble copolymer was obtained in the same manner as in Example 2 from 10 g of tricyclodecyl acrylate, 50 g of methyl methacrylate, 12 g of methacrylic acid, 28 g of butyl acrylate, and 2 g of azobisisobutyronitrile. The heating residue was 40% and the viscosity was Z. Table 1 below shows the properties of paints using the polymers obtained in Examples 1, 2, 5, and 6 and Comparative Examples 1 to 4.

[Table] When the coating copolymer obtained by copolymerizing hydrogenated dicyclopentadiene derivatives according to the present invention is used in coatings, it significantly improves the gloss, weather resistance, heat resistance, and pigment dispersion of conventional acrylic resins. You can improve.

Claims (1)

[Claims] 1 (A) General formula () (However, in the formula, R is hydrogen, lower alkyl, or halogen, R' is a divalent organic group, and n
is 0 or 1) (hereinafter referred to as "component (A)")
20 to 99.9% by weight (B) 0.1 to 30% by weight of an unsaturated monomer having a carboxyl group (hereinafter referred to as "component (B)") and (c) together with component (A) and/or component (B) A method for producing a copolymer for coating material, which comprises blending 0 to 79.9% by weight of a polymerizable unsaturated monomer so that the total amount is 100% by weight, and polymerizing the mixture.