JPH0556370B2 - - Google Patents

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention produces an air-drying unsaturated polyester resin having excellent coating suitability and physical properties of a coating film, and particularly an air-drying unsaturated polyester resin suitable as a raw material for wood coatings. It is about the method.

[Prior 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, has a desirable luster and texture, and has a beautiful finish. Therefore, it is useful as a raw material for general woodworking paints or as a raw material for sealants.

[Problems to be Solved by the Invention] However, such air-drying unsaturated polyester resin paints still have room for further improvement in terms of the coated surface and physical properties of the coated film. First, on the painted surface, for example, 2
When applying coating methods such as the head flow coater method or the reaction primer method, the coating surface discharged from the coating machine tends to cause a phenomenon called curtain breakage, so extreme caution is required in industrial implementation. There are some drawbacks such as:
In addition, in terms of physical properties of the coating, when a coating is formed on a wood surface, the coating may be absorbed into the conduit portion, and as a result, there is a risk of a scorching phenomenon in which unevenness occurs on the coating surface.

[Means for Solving the Problems] However, as a result of intensive research to solve these problems, the present inventors reacted a polyhydric alcohol component, a polybasic acid component, and a polyhydric alcohol allyl ether component, We have discovered that the purpose can be achieved when propylene glycol and bisphenol A/propylene oxide adducts are used as at least a part of the polyhydric alcohol component in the production of air-drying unsaturated polyester resins, and we have published this book. He has completed his invention.

In the present invention, it is essential to use two specific polyhydric alcohols, propylene glycol and bisphenol A/propylene oxide adduct, as at least part of the polyhydric alcohol component.

The bisphenol A/propylene oxide adduct is a compound represented by the following general formula.

(Here, n and m are both integers of 1 or more.) Although the upper limits of n and m are not particularly limited, adducts with 1≦n and m≦3 are preferably used practically.

The proportion of the total amount of propylene glycol and the above adduct in the polyhydric alcohol component is 60 to 100.
mol%, preferably 70 to 90 mol%, and the propylene glycol/adduct molar ratio is 95/5 to 40/60
Preferably it is 90/10 to 50/50.

The total amount of propylene glycol and the above adducts is
If it is less than 60 mol%, the curtain will easily break when using a two-head flow coater, etc., and on the other hand, if the molar ratio of both is
If it is less than 95/5, the hardness of the cured coating will be small,
If the ratio is 40/60 or more, the suitability for painting with a flow coater becomes poor, and the practicality decreases.

In addition to the above, polyhydric alcohol components include ethylene glycol, diethylene glycol,
Triethylene glycol, dipropylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,6-hexanediol, 2
-ethyl-1,3-hexanediol, 2,2,
General polyhydric alcohols such as 4-trimethyl-1,3-pentanediol, neopentyl glycol, trimethylolethane, trimethylolpropane, glycerin, and pentaerythritol can be used in combination.

Next, as the polybasic acid component in the present invention, unsaturated polybasic acids such as maleic anhydride, maleic acid, itaconic anhydride, itaconic acid, and fumaric acid are used.

Along with these unsaturated polybasic acids, phthalic anhydride, phthalic acid, terephthalic acid, isophthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, hettic acid, citraconic acid,
Saturated polybasic acids such as adipic acid and sebacic acid can also be used in combination.

Further, in the present invention, a polyhydric alcohol allyl ether component is used in order to impart air drying properties to the unsaturated polyester obtained. Polyhydric alcohol allyl ether components include pentaerythritol triallyl ether, pentaerythritol diallyl ether, trimethylolpropane diallyl ether, trimethylolpropane monoallyl ether, trimethylolethane diallyl ether, trimethylolethane monoallyl ether, glycerin diallyl ether, Glycerin monoallyl ether, tetramethylol cyclohexanol diallyl monocrotyl ether, hexamethylol melamine diallyl diallyl dicrothiether, hexanetriol diallyl ether,
Examples include allyl ethers having at least one hydroxyl group in the molecule, such as pentaerythritol diallyl crotyl ether, tetramethylolcyclohexanol triallyl ether, tetramethylolcyclohexanone diallyl ether, and hexamethylolmelamine tetraallyl ether.

The polyhydric alcohol allyl ether component is desirably used in an amount of 0.1 mol or more, particularly 0.3 mol or more, per 1 mol of the polybasic acid component as an allyl group; if it is less than 0.1 mol, air drying properties are insufficient. The upper limit is possible up to the reaction limit.

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

In addition, in the present invention, the air-drying unsaturated polyester obtained above is modified by reacting with an isocyanate compound, and the polyester segment portion is further chain-extended via an isocyanate bond,
The strength of the polyester of the present invention can be increased by adding an acrylic monomer containing an active hydrogen group to the isocyanate group and introducing a double bond to improve its properties, or by simply blending an isocyanate adduct. can be improved.

When reacting an air-drying unsaturated polyester with an isocyanate compound, the reaction ratio is, for example,
The equivalent ratio of NCO to OH is selected from the range of 1/2 to 1/1. In this way, it is possible to further improve the flexibility and strength compared to the case where the isocyanate modification is not performed. Examples of the isocyanate compound include tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, and 1,4-tetramethylene diisocyanate. Examples of isocyanate adducts include adducts of the above-mentioned isocyanate compounds with trimethylolpropane, triethylene glycol, and the like.

The air-drying unsaturated polyester thus obtained is usually put to practical use as a solution of a crosslinking monomer.

Examples of crosslinking monomers include styrene, vinyltoluene, monochlorostyrene, α-methylstyrene, diallyl phthalate, triallyl cyanurate, acrylic ester, methacrylic ester, glycidyl methacrylate, 2-hydroxymethacrylate glycidyl ether, vinyl acetate,
Vinyl chloride, methylenebisacrylamide, divinylbenzene, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, diethylene glycol diacrylate,
Examples of crosslinking monomers for unsaturated polyesters include 1,6-hexanediol diacrylate, vinylcyclohexane monooxide, tung oil, linseed oil, soybean oil, cottonseed oil, safflower oil, and coconut oil.

As the 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, etc. are used. , manganese octenoate, manganese naphthenate, etc. are used.

In place of the curing agents and curing accelerators mentioned above, photoinitiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl diphenyl disulfide, tetramethylthiuram monosulfide, azo Bisisobutyronitrile, dibenzyl, diacetyl, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2
-diethoxyacetophenone, benzophenone,
It is also possible to use 2-chlorothioxanthone, 2-methylthioxanthone, etc. to make an ultraviolet curable unsaturated polyester.

In addition, pigments (titanium white, cyanine blue, cream yellow, watching red, red iron, carbon black, aniline black, manganese blue, iron black, ultramarine blue, Hansared, chrome yellow, chrome green, etc.) and fillings are added as necessary. agents (calcium carbonate, kaolin, clay, talc, mica, alumina, asbestos powder, finely divided silica, barium sulfate, lithopone, gypsum, perlite, etc.), abrasives (zinc stearate, finely divided talc, etc.), leveling agents (silicone, xylene, methanol, ethanol, butanol, Aston, methyl isobutyl ketone, methyl ethyl ketone, cellosolves, diacetone alcohol, etc.), thermoplastic resins (nitrocellulose, vinyl chloride-vinyl acetate copolymer,
vinyl acetate resin, acrylic resin, butylated melamine, butylated urea, etc.), greening inhibitors (phosphoric acid,
(phosphorous acid, tartaric acid, etc.) and air-drying aids (oils and fats, paraffin wax, etc.) may also be added.

The resin of the present invention is suitably used for general wood coatings such as furniture, cabinets such as televisions, particle boards, and musical instruments such as pianos, organs, electronics, guitars, etc., but also for coating metals, mortar, concrete, artificial Of course, it can also be used for painting marble, FRP products, etc.

[Example] Next, the method of the present invention will be explained in more detail with reference to Examples.

Example 1 In a flask equipped with a stirrer and a reflux condenser, 1 mol of maleic anhydride, 0.6 mol of propylene glycol, 0.4 mol of bisphenol A/propylene oxide adduct (n=1, m=1), and 0.3 mol of trimethylolpropane diallyl ether Prepare the mole at 180℃
The reaction was carried out until the acid value reached 20 mmgKOH/g. Then, while cooling, styrene monomer was added so that the resin concentration was 70%.

The coating suitability and surface properties of the above were evaluated by the methods shown below.

Styrene monomer to 100 parts of the above 70% resin solution
A composition obtained by adding 30 parts of cobalt octylate and 1.5 parts of cobalt octylate (metal content: 8%) was used as No. 2 coating liquid for a two-head flow coater. Also, 30 parts of styrene monomer and 4 parts of methyl ethyl ketone peroxide (55% concentration) were added and mixed to 100 parts of the above resin to form No. 1.
It was made into a paint liquid.

Apply the above paint using a 2-head flow coater to oak plywood that has been pre-applied with urethane sealer.
No. 1 and No. 2 were applied at a rate of 50 g/m ² , and after setting for 30 minutes, they were heated in a hot air dryer at 60° C. for 10 minutes.

As a result, the condition of the curtain of the 2-head flow coater was very stable, and the coated surface of the oak wood had a textured feel and was beautiful with good surface smoothness.

Example 2 0.5 mol of propylene glycol, bisphenol A/propylene oxide adduct (n=1, m
= 1) The same experiment as in Example 1 was carried out using 0.2 mol and 0.3 mol of diethylene glycol as the polyhydric alcohol component. The results were the same as in Example 1.

Example 3 The same method as in Example 1 was carried out except that a bisphenol A/propylene oxide adduct with n=3 and m=3 was used, and the result was the same as in Example 1.

Example 4 The same experiment as in Example 1 was conducted except that the amount of propylene glycol used was changed to 0.8 mol and the amount of bisphenol A/propylene oxide adduct used was changed to 0.2 mol. The results were the same as in Example 1.

Control Examples 1 and 2 Examples except that 1 mol of propylene glycol (Control Example 1) and 1 mol of bisphenol A/propylene oxide adduct (n=1, m=1) (Control Example 2) were used as the polyhydric alcohol component. When the same method as in Example 1 was carried out, in Comparative Example 1, the curtain of the flow coater was unstable and the texture of the coating film was poor. In Control Example 2, the curtain did not form a film with the same coating amount, and it was necessary to apply a coating amount of 70 g/m ² for Liquid No. 1 and Liquid No. 2, resulting in insufficient smoothness of the coating film.

[Effect of the invention] By using propylene glycol and a bisphenol A/propylene oxide adduct together as a polyhydric alcohol component during the production of an air-drying unsaturated polyester resin, it is possible to achieve excellent coating properties with no fear of curtain breakage, etc. The physical properties of the film are also characterized by no fading.

Claims (1)

[Claims] 1. In producing an air-drying unsaturated polyester resin by reacting a polyhydric alcohol component, a polybasic acid component, and a polyhydric alcohol allyl ether component,
As at least a part of the polyhydric alcohol component,
A method for producing an air-drying unsaturated polyester resin, which comprises using propylene glycol and a bisphenol A/propylene oxide adduct. 2. The total proportion of propylene glycol and bisphenol A/propylene oxide adducts in the polyhydric alcohol component is 60 to 100 mol%,
and propylene glycol/bisphenol A.
Molar ratio of propylene oxide adduct is 95/5~
The manufacturing method according to claim 1, characterized in that the ratio is 40/60.