JPH0730170B2 - Method for producing air-drying unsaturated polyester having good pigment dispersibility - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Industrial Field of the Invention The present invention uses a specific surfactant as a part of the polyhydric alcohol component and introduces it into the molecule, so that the pigment dispersibility is good and the crosslinkability is high. The present invention also relates to a method for obtaining an air-drying unsaturated polyester having good stability of a diluting solution with a monomer.

BACKGROUND ART Unsaturated polyester obtained by reacting a polyhydric alcohol component, a polybasic acid component, and a polyhydric alcohol allyl ether component has air-drying properties, is preferable in gloss and fleshness, and gives a beautiful finish. Therefore, it is useful as a raw material resin for paints for general woodworking or as a raw material resin for sealing materials.

Even the applicant of the present invention has a Japanese Patent Publication No. 57-60386.
No. 5-152752), an application has been filed for an unsaturated polyester resin paint comprising an unsaturated polyester prepolymer containing a hydroxylated tertiary amine component in the prepolymer molecule, a polymerizable monomer and carbon black. Here, the hydroxylated tertiary amine is (R ₁ and R ₂ are an alkyl group or an aryl group, R ₃ is an alkylene group), or (R ₁ is an alkyl group or an aryl group, R ₃ and R ₄ are alkylene groups).

Problems to be Solved by the Invention However, the conventional air-drying unsaturated polyester does not always have sufficient pigment dispersibility, so that the pigment precipitates before coating and drying, resulting in gloss and smoothness of the coated surface. Was sometimes damaged. In particular, sanding paints for woodworking and black enamel paints for pianos have been desired to be improved, because a slight change in the coating surface state due to poor dispersion of the pigment significantly deteriorates the quality of the product.

The unsaturated polyester resin paint disclosed in Japanese Patent Publication No. 57-60386 is intended to improve the dispersibility of carbon black and improve the image clarity of black.
As shown in ~ 3, there is a limit that the stability after dilution with a monomer such as styrene is insufficient.

Therefore, the present inventors have aimed to improve the pigment dispersibility,
The addition of various surfactants was investigated at the stage of making the air-drying unsaturated polyester into a coating material, but not only satisfactory pigment dispersibility was not obtained, but rather defects such as cissing were observed on the coated surface. There was a possibility that it would occur, and the intended purpose could not be achieved.

The present invention has been made for the purpose of solving such problems and providing an air-drying unsaturated polyester in which the dispersibility of a pigment and the stability of a diluting solution due to a crosslinking monomer are improved.

MEANS FOR SOLVING THE PROBLEMS The present invention provides a method for producing an air-drying unsaturated polyester by reacting a polyhydric alcohol component, a polybasic acid component and a polyhydric alcohol allyl ether component with a polyhydric alcohol allyl ether component. As an allyl ether group, 0.1 mol or more is used per 1 mol of the polybasic acid component, and as a part of the polyhydric alcohol component, a compound represented by the general formula (Wherein R is an alkyl group having 10 or more carbon atoms, n is an integer of 2 to 30), and is used in an amount of 0.05 to 5% by weight based on the total amount of the condensation component. A method for producing an air-drying unsaturated polyester having good pigment dispersibility.

The main point of this is to solve the above problems.

As described above, it is important to introduce the polyethylene glycol alkylamine-based surfactant into the prepolymer of the unsaturated polyester by a condensation reaction, and it is not necessary to simply add the surfactant at the stage of coating to make the pigment. The dispersion effect is not sufficient, and coating surface defects such as cissing are likely to occur.

Hereinafter, the present invention will be described in detail.

In the present invention, as a part of the polyhydric alcohol component,
General formula The use of a polyethylene glycol alkylamine-based surfactant represented by is essential. By introducing such a specific surfactant into the unsaturated polyester prepolymer, good pigment dispersibility and dilution of the cross-linkable monomer with good dispersibility can be achieved without impairing the excellent properties inherent to the air-drying unsaturated polyester. It becomes possible to have stability.

As the polyethylene glycol alkylamine-based surfactant represented by the above general formula, an alkyl group R having 10 or more carbon atoms and an integer of n of 2 to 30 is used, and the alkyl group R has less than 10 carbon atoms. In some cases, or when n is out of the above range, sufficient pigment dispersibility and stability of the diluting solution due to the crosslinkable monomer cannot be obtained, resulting in lack of practicality.

The amount of the polyethylene glycol alkylamine-based surfactant used is selected from the range of 0.05 to 5% by weight based on the total amount of the condensation component, and if it is less than 0.05% by weight, the desired pigment dispersibility cannot be obtained. Even if it is used in an amount exceeding 5% by weight, the effect does not reach a certain level, which is disadvantageous in terms of cost.
A particularly preferred range is 0.5 to 3% by weight.

As the polyhydric alcohol component in the present invention, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, bisphenol dioxypropyl ether, 1,3-
Butylene glycol, 2,3-butylene glycol, 1,6-
Hexanediol, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, neopentyl glycol, trimethylolethane, trimethylolpropane, glycerin, pentaerythritol and the like are used.

As the polybasic acid component, maleic anhydride, maleic acid,
Unsaturated polybasic acids such as itaconic anhydride, itaconic acid and fumaric acid are used.

Along with these unsaturated polybasic acids, saturated polybasic acids such as phthalic anhydride, phthalic acid, terephthalic acid, isophthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, het acid, citraconic acid, adipic acid, sebacic acid, etc. An acid can also be used together.

Furthermore, in the present invention, a polyhydric alcohol allyl ether component is used in order to impart air drying properties to the resulting unsaturated polyester. The polyhydric alcohol allyl ether component, pentaerythritol triallyl ether, pentaerythritol diallyl ether, trimethylolpropane diallyl ether, trimethylolpropane monoallyl ether, trimethylolethane diallyl ether, trimethylolethane monoallyl ether, glycerine diallyl ether, Glycerin monoallyl ether, tetramethylol cyclohexanol diallyl monochlorotyl ether, hexamethylol melamine diallyl dicrotyl ether, hexanetriol diallyl ether, pentaerythritol diallyl crotyl ether, tetramethylol cyclohexanol triallyl ether, tetramethylol cyclohexanone diallyl ether, hexamethylol melamine Te Ethers having at least one hydroxyl group in the molecule, such as La allyl ether can be exemplified.

The polyhydric alcohol allyl ether component is required to be used as an allyl group in an amount of 0.1 mol or more, particularly 0.3 mol or more, based on 1 mol of the polybasic acid component, and if it is less than 0.1 mol, air-drying property is insufficient. The upper limit can be up to the reaction limit.

The desired air-drying unsaturated polyester can be obtained by reacting each of the above components in an inert gas atmosphere at a temperature of about 150 to 250 ° C. according to a conventional method.

The air-drying unsaturated polyester thus obtained is
Usually, it is put to practical use as a solution of a crosslinkable monomer.

As the crosslinkable monomer, styrene, vinyltoluene,
Monochlorostyrene, α-methylstyrene, diallyl phthalate, triallyl cyanurate, acrylic acid ester, methacrylic acid ester, glycidyl methacrylate,
2-hydroxymethacrylate glycidyl ether, vinyl acetate, vinyl chloride, methylenebisacrylamide,
Divinylbenzene, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate,
Crosslinking for known unsaturated polyester such as diethylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, vinylcyclohexene monooxide, tung oil, linseed oil, soybean oil, cottonseed oil, safflower oil, coconut oil Examples of the monomer include a hydrophilic monomer.

As a curing agent, methyl ethyl ketone peroxide,
Cyclohexanone peroxide, cumene hydroperoxide, benzoyl peroxide, dicumyl peroxide, t-butyl perbenzoate, etc. are used, and as the curing accelerator, cobalt octenoate, cobalt naphthenate, manganese octenoate, manganese naphthenate, etc. Metal soap, dimethylaniline, diethylaniline, dimethyl-p-toluidine, methyl-β-hydroxyethylaniline, di-β-hydroxyethylaniline, di-β-hydroxyethyl-p-toluidine, methylaniline, methyl- An amine such as p-toluidine or a salt thereof such as hydrochloric acid, acetic acid or phosphoric acid is used.

Instead of the combination of the curing agent and the curing accelerator as described above,
Photopolymerization initiator, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyldiphenyl disulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, dibenzyl, diacetyl, acetophenone, 2,2-dimethoxy- An ultraviolet-curable unsaturated polyester can be obtained by using 2-phenylacetophenone, 2,2-diethoxyacetophenone, benzophenone, 2-chlorothioxanthone, 2-methylthioxanthone and the like.

Next, pigments (including fillers) used in the paint making stage include titanium white, cyanine blue, chrome yellow, watching red, red iron oxide, carbon black, graphite, aniline black, manganese blue, iron black, and ultra. Marine Blue, Hansa Red, Chrome Yellow, Chrome Green, Calcium Carbonate, Kaolin, Clay, Talc, Mica, Alumina, Asbestos Powder, Fine Silica, Barium Sulfate, Ritopon, Gypsum,
There are various known pigments such as pearlite and zinc stearate.

In addition, leveling agents (silicone, cellulose acetate butyrate, surfactants, etc.), diluents (ethyl acetate, toluene, xylene, methanol, ethanol, etc.)
Butanol, acetone, methyl isobutyl ketone, methyl ethyl ketone, cellosolves, diacetone alcohol, etc., thermoplastic resin (nitrocellulose, vinyl chloride-vinyl acetate copolymer, vinyl acetate resin, acrylic resin, butylated melamine, butylated urea, etc.) ), An anti-greening agent (phosphoric acid, phosphorous acid, iron tartrate, etc.) and an air-drying aid (oils, paraffin wax, etc.) can be added.

EXAMPLES Next, the method of the present invention will be described in more detail with reference to Examples. Hereinafter, “parts” and “%” are shown on a weight basis.

Example 1 A flask equipped with a stirrer, a gas introduction tube and a reflux condenser was charged with maleic anhydride, 1.0 mol, and propylene glycol.
0.5 mol, 0.25 mol of diethylene glycol, 0.25 mol of triethylene glycol and 0.2 mol of triallyl pentaerythritol were charged, and further 3% of xylene, 0.02% of hydroquinone (polymerization inhibitor) and formula Polyethylene glycol alkylamine type surfactant represented by (Nitmeen S-20 manufactured by Nitto Denki Kogyo Co., Ltd.
4) Charge 2% (the charge amount is based on the total amount of the condensation components), perform a condensation reaction at a temperature of 200 ° C for 5 hours while blowing nitrogen gas, and then continue the reaction under reduced pressure at 150 ° C for 1 hour to obtain xylene. Was distilled off.

The unsaturated polyester having an acid value of 16 KOH mg / g thus obtained was diluted with a styrene monomer to obtain a resin liquid having a solid content of 70% and a viscosity of 2000 cps / 20 ° C.

To 100 parts of this resin liquid, 3 parts of zinc stearate, 2 parts of talc (Nittarkuu SW manufactured by Nippon Talc Co., Ltd.), and finely divided silica (Aerosil # 200 manufactured by Nippon Aerosil Co., Ltd.) 1 part
Parts were mixed, dispersed with 3 rolls, then diluted with styrene monomer to spray viscosity, and then cobalt octenoate (Octex Co, manufactured by Nippon Kagaku Sangyo Co., Ltd.,
8% cobalt content) 0.5% and methyl ethyl ketone peroxide (NOF CORPORATION Permec-N) 1.0%
And were mixed, spray-coated on the wood surface, and cured at room temperature.

The results are shown in Table 1.

Comparative Example 1 An unsaturated polyester having an acid value of 18 KOHmg / g was obtained by performing a condensation reaction in the same manner as in Example 1 except that the addition of the polyethylene glycol alkylamine-based surfactant was omitted, and diluting it with a styrene monomer. , Solid content 70%, viscosity 19
A resin solution of 00cps / 20 ° C was obtained.

Thereafter, in the same manner as in Example 1, zinc stearate, talc and finely divided silica were mixed with this resin liquid, and then styrene monomer was added to dilute the mixture, and further cobalt octenoate and methyl ethyl ketone peroxide were mixed and sprayed on the wood surface. Coated

The results are also shown in Table 1.

As is clear from Table 1, the air-drying unsaturated polyester obtained by the method of the present invention can also have excellent pigment dispersibility without losing the characteristics of the conventional air-drying unsaturated polyester. Recognize.

Comparative Examples 2 to 3 Instead of the polyethylene glycol alkylamine-based surfactant in Example 1, the formula And the expression The same experiment as in Example 1 was conducted except that the compound represented by

The layer separation stability of the styrene diluted solution was only 35% in Comparative Example 2 and 27% in Comparative Example 3.

Example 2 In a flask equipped with a stirrer, a gas introduction tube and a reflux condenser, 1.0 mol of maleic anhydride, 0.6 mol of ethylene glycol, 0.2 mol of dipropylene glycol, 0.2 mol of 1,3-butylene glycol and 0.3 mol of triallyl pentaerythritol. Moles, charged with xylene 3%, hydroquinone (polymerization inhibitor) 0.02% and formula A polyethylene glycol alkylamine-based surfactant represented by (Niimein S-21 manufactured by Nitto Denki Kogyo Co., Ltd.
5) Charge 2% (the charge amount is based on the total amount of the condensation component), perform a condensation reaction at a temperature of 200 ° C for 5 hours while blowing nitrogen gas, and then continue the reaction at 150 ° C for 1 hour under reduced pressure.
Xylene was distilled off.

The unsaturated polyester having an acid value of 15 KOH mg / g thus obtained was diluted with a styrene monomer to obtain a resin liquid having a solid content of 69% and a viscosity of 2300 cps / 20 ° C.

To 100 parts of this resin solution, 1.0 part of carbon black and 1 part of finely divided silica (Aerosil # 200 manufactured by Nippon Aerosil Co., Ltd.) were mixed, dispersed with a three-roll mill, and then diluted to a spray viscosity with a styrene monomer. Cobalt octenoate (Octex Co, 8% made by Nippon Kagaku Sangyo Co., Ltd.)
0.5% of cobalt-containing) and 1.0% of methyl ethyl ketone peroxide (Permec-N manufactured by NOF CORPORATION) were mixed, spray-coated on a wood surface and cured at room temperature.

The results are shown in Table 2.

Comparative Example 4 An unsaturated polyester having an acid value of 12 KOHmg / g was obtained by carrying out a condensation reaction in the same manner as in Example 2 except that the addition of the polyethylene glycol alkylamine-based surfactant was omitted, and diluting this with a styrene monomer. , Solid content 70%, viscosity 19
A resin solution of 00cps / 20 ° C was obtained.

Thereafter, in the same manner as in Example 2, carbon black and finely divided silica were mixed with this resin liquid, and then styrene monomer was added to dilute the mixture, and further cobalt octenoate and methyl ethyl ketone peroxide were mixed and spray-coated on the wood surface. .

The results are shown in Table 2 together.

The air-drying unsaturated polyester obtained by the method of the present invention has excellent pigment dispersibility and stability of a diluting solution due to a crosslinkable monomer while maintaining the excellent characteristics inherent to conventional air-drying unsaturated polyesters. It is useful for sanding paints for woodworking, black enamel paints for pianos, and other applications that require a high degree of pigment dispersibility and stability of the diluting solution with a crosslinkable monomer.

Claims (1)

[Claims] 1. When a polyhydric alcohol component, a polybasic acid component and a polyhydric alcohol allyl ether component are reacted to produce an air-drying unsaturated polyester, the polyhydric alcohol allyl ether component is used as an allyl ether group to form the polybasic acid component. Using 0.1 mol or more per 1 mol, and as a part of the polyhydric alcohol component, the general formula (Wherein R is an alkyl group having 10 or more carbon atoms, n is an integer of 2 to 30), and is used in an amount of 0.05 to 5% by weight based on the total amount of the condensation component. A method for producing an air-drying unsaturated polyester having good pigment dispersibility.