JPS60238317A - Alkyd resin - Google Patents

Abstract

PURPOSE:To provide the titled resin giving a coating film having excellent hardness, gloss, gasoline resistance and weather resistance, by carrying out the ring- opening reaction of a cyclic ester in the presence of an OH-containing cellulose derivative, and using the resultant graft polymer as a polyhydric alcohol component. CONSTITUTION:A cyclic ester (preferably epsilon-caprolactone) is subjected to the ring-opening reaction in the presence of a cellulose derivative containing OH group in the molecule [preferably cellulose acetate (butyrate), etc.] using a catalyst such as tetrabutyl titanate. The obtained graft polymer is used as a polyhydric alcohol component, and is made to react with a polybasic acid such as phthalic anhydride to obtain the objective alkyd resin.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an alexod resin containing a cellulose derivative and forming a coating film having excellent hardness, gloss, gasoline resistance, and weather resistance.

Alkyd resin is mainly a resin consisting of a condensate of polybasic acid and polyhydric 7 alcohol, and is widely used in paints.Most of the resins are oil-modified 7μ resins with fatty acids (oils) added to their components. By adding cellulose derivatives such as nitro to this alkyd resin, paints with excellent coating film hardness and gasoline resistance have been used for various purposes such as woodworking and metal coatings. However, nitrocellulose and cellulose acetate ghylate are inferior in compatibility to nitrocellulose, and there are restrictions on the composition of the alkyd resin to be mixed, making it difficult to obtain an alkyd resin with a sufficiently beautiful coating film.

There are also cellulose-modified fluid resins that use cellulose derivatives as alkyd resin components, but the hydroxyl groups of conventional cellulose derivatives are directly bonded to the cellulose skeleton, and there are many secondary hydroxyl groups in the hydroxyl groups. Due to the presence of bulky substituents around it,
An alkyd resin sufficiently modified with a cellulose derivative could not be obtained.

The present inventors solved these problems and improved hardness, gloss,
With the aim of creating a cell with excellent gasoline resistance and weather resistance, as a result of extensive research, we have developed a graft polymer with graft chains whose ends are hydroxyl groups obtained by ring-opening reaction of a cyclic ester in the presence of a cellulose derivative. The present invention has been completed by discovering that an alkyd resin using as a component of a polyhydric alcohol can improve the above-mentioned drawbacks.

That is, the present invention provides an alkyd resin characterized by containing, as a polyhydric alcohol component, a graft polymer obtained by subjecting a cyclic ester to a ring-opening reaction in the presence of a cellulose derivative having a hydroxyl group.

The alkyd resin of the present invention is not simply a mixture of a cellulose derivative and an alkyd resin, but the cellulose derivative is also chemically bonded as a component of the alkyd resin polymer molecule, and therefore there is a problem with the compatibility between the cellulose derivative and the alkyd resin. Moreover, since the graft polymer, which is a cellulose derivative used in the alkyd resin of the present invention, has a flexible graft chain formed by ring-opening of a cyclic ester, it can be sufficiently improved without adding a plasticizer. Because it has flexibility and strength, the alkyd resin of the present invention provides a coating film that does not develop racks even after a long period of time after being applied.

The cellulose derivative used in the present invention may be any cellulose derivative having a hydroxyl group in its molecule,
For example, cellulose acetate, cellulose acetate propionate, cellulose acetate gtylate, cellulose acetate phthalate, sulfuric acid superlose, cellulose nitrate-♀totenases, or ethyl cellulose,
Examples include cellulose ethers such as pencil cellulose. Among these cellulose derivatives, cellulose acetate, cellulose acetate glylate, cellulose acetate propionate, etc., which are industrially easily available, easy to handle, and have excellent weather resistance, are preferred. Note that these cellulose derivatives can be used alone or in combination of two or more.

The cyclic ester used in the present invention may be one that can be polymerized by a ring-opening reaction using a known method, such as propiolactone, β-butyrolactone, α,α-bischloromethylpropiolactone, α, α-dimethyl-
β-propiolactone, σ-valerolactone, β-ethyl-valerolactone, 3,4.5-)dimethoxy-
δ-valerolactone, 1,4. -Dioxan-2-one, glycolide, I-limethylene carbonate, *, t-pentyl carbonate, ethylene oxalate, propylene oxalate, α-methyl-ε-caprolactone, β
-Methyl-epsilon-caprolactone, gamma-methyl-epsilon-caprolactone, epsilon-caprolactone, 4-methyl-7-isopropyl-epsilon-caprolactone, 3,3.5-trimethyl-epsilon-caprolactone, cissudisali7lide, trisalinelide, etc. Can be mentioned.

Among these cyclic esters, industrially easy to obtain,
Easy to handle, and cellulose acetate butyrate, cellulose acetate prophylactic #711 Norosuma Bank / 7) Intuition! It is advantageous to use ε-caprolactone, which has good compatibility with the 1-nolose ester.

In the present invention, the graft polymer obtained by carrying out a cyclic ester ring-opening reaction in the presence of a cellulose derivative having a hydroxyl group is obtained by the following method. , catalysts used in the ring-opening reaction of cyclic esters, such as organic acids, inorganic acids, organic tin compounds, organic acid tin salts, alkali metals, organic compounds of alkali metals, alkylaluminums, organic compounds of titanium, tin chloride, etc. Catalysts such as halides (in addition, the catalysts used for the ring-opening reaction of cyclic esters are
)” P104 to P128 (■ Kagaku Doujin, published in 1973). ), and if necessary, add an organic solvent such as quinolene and heat at a temperature of 120 to 230 C for about 0.1 to 96 hours. can be obtained by the following method.

The graft polymer has a graft chain consisting of a cyclic lactone with a primary hydroxyl group at the end, and this graft chain is relatively flexible, which is a characteristic of cellulose derivatives. It has both a certain rigidity and flexibility due to the grafted chains. Moreover, since the graft polymer has a primary hydroxyl group that is more reactive than other alcoholic hydroxyl groups and is located away from the cellulose skeleton,
The hydroxyl group reacts more easily with other functional groups, ie, carboxyl groups and their derivatives, than the hydroxyl group directly bonded to the cellulose skeleton, and the polycondensation reaction during the production of alkyl resins is effectively carried out.

In the present invention, a polyhydric alcohol generally used for producing alkyd resins can be used together with the above-mentioned graft polymer.

Examples include t, ethylene glycol, zorobylene glycol, diethylene glycol, diethylene glycol, butanediol, hexanediol, glycerin, butanetriol, trimethylolethane, trimethylolpropane, pentaerythritol, sidaricerol, triglycerol, and the like. Other products include neopentyl glycol, neobenchi/l/glycol ester of hydroxyhybaric acid, dipentaerythritol, 1,4-cyclohexanedimethanol, trimethylbentanediol, hydrogenated bisphenol A1, ethylene oxide adduct of bisphenol A, propylene oxide to bisphenol. Also includes additives.

The polybasic acids used in the present invention may be those commonly used in the production of alkyd resins, such as butaric anhydride, isophthalic acid, terephthalic acid,
Examples include hydrogenated terephthalic acid, trimellitic anhydride, maleic anhydride, fumaric acid, adipic acid, cepacic acid, dotecanniic acid, het acid, and terpene maleic anhydride adducts. In addition to the above polybasic acids, a small amount of benzoic acid,
Monobasic acids such as P-tert-butylbenzoic acid may also be used.

In the present invention, together with the graft polymer and polybasic acid, fatty acids (oils) commonly used in the production of alkyd resins are used.
For example, linseed oil, soybean oil, castor oil, dehydrated castor oil, olive oil, cottonseed oil, safflower oil, dimer acid, tall oil, coconut oil, etc. may be used. - Furthermore, 1,2-epoxy aliphatic compounds, natural resins such as rosin, silicone resins, amine resins, etc. can also be used as appropriate as components of the alkyd resin of the present invention.

In the alkyd resin of the present invention, the graft polymer can be reacted with other components in any proportion to form an alkyd resin, but generally the graft polymer is
It is preferable that the alkyd resin be contained in an amount of 10 to 30% by weight, and it is particularly preferable to obtain an alkyd resin by containing the alkyd resin in an amount of 10 to 30% by weight, since the properties of the coating film such as hardness, gloss, and gasoline resistance are well-balanced.

It can be manufactured by any of the methods used to manufacture resins, the melting method, and the solvent method. That is, the alkyd resin of the present invention can be prepared by adding a polyhydric alcohol, a polybasic acid, and a fatty acid (oil) together and heating it, or by heating the fatty acid (oil) and a polybasic acid to perform exchange esterification ( A method in which a polyhydric alcohol is added to esterify a fatty acid (
Exchange esterification (alcolysis) is carried out by heating the oil) and polyhydric alcohol, then a polybasic acid or an esterification reaction catalyst is added, and the mixture is generally heated at 60°C to 320°C for 1 to 7 hours.
It can be produced by reaction for 2 hours, preferably at 160 to 250°C for 8 to 48 hours.

The alkyd resin of the present invention can be used alone or in combination with other resins as a coating resin. Furthermore, the alkyd resin of the present invention may contain a thinner, which is usually added to paints.
Organic solvents, crosslinking agents such as coating melamine compounds, polyisocyanate compounds, and epoxy compounds, viscosity modifiers, dyes, pigments, etc. can be added as appropriate.

The alkyd resin of the present invention is suitable for coating paints for metals, wood, ceramics, glasstics, concrete, mortar, and the like.

Next, it will be further explained in Examples.

Example 1 In a 1e glass flask equipped with a stirrer, a reflux condenser and a thermometer, ε~caprolactone 1502 containing 200 ppm of tetrabutyl titanate and cellulose acetate (manufactured by Daicel Chemical Industries, Ltd., LL-10) 1 which had been sufficiently dried in advance
502, heated to 120°C, and sufficiently stirred under a nitrogen atmosphere to dissolve. After that, the temperature was raised to 160℃,
The reaction was carried out for a period of time to obtain a pale yellow graft polymer.

1e equipped with a stirrer, reflux dehydrator and thermometer.
The above graft polymer 100F,
Dehydration and mustard oil 1422, p-Ler-butylbenzoic acid 33.32, tetrahydrophthalic anhydride 92. s
i, isofuku/l/acid 16.62, trimethylolpropane 202 and neopentyl glycol 43.7
+? was charged, and a dehydration esterification reaction was carried out at 200 °C for 24 hours under a nitrogen atmosphere. Thus acid value 18 KOH7n
g/2, hydroxyl value 32 KOHmy/f/7/L'
A kid resin was obtained.

This product was mixed with a toluene/ethyl acetate mixed solvent (mixed weight ratio, toluene/ethyl acetate = 70/30) to give a solid content of 55%.
After coating on a mild steel plate using a &30 bar coater, the performance of the dried coating film was evaluated. The results are shown in Table 1.

Example 2 In a 1e glass flask equipped with a stirrer, a reflux condenser, and a thermometer, ε-caprolactone 1502 containing 200 ppm of tetrabutyl titanate and cellulone acetate petitlate (manufactured by Eastman Chemical Co., Ltd. + CAB551-0) sufficiently dried in advance were added. .2) Prepare 150F, 12
Heat to 0°C and stir thoroughly under nitrogen atmosphere to dissolve. Thereafter, the temperature was raised to 160°C, and reaction was carried out for 16 hours to obtain a pale yellow graft polymer.

1 equipped with a stirrer, a reflux dehydrator and a thermometer.
The above graft polymer 1502 was placed in the glass flask of e.
Prepare and heat to 180℃. To this material, under a nitrogen atmosphere, 54.3 t of neopentyl glycol, 202 t of trimethylolpropane, 22.8 t of benzoic acid, and 1 t of soybean oil were added.
282 was added and the reaction was carried out at 200°C until the acid value became 5 or less. Then, tetrahydrophthalic anhydride 76
．． 4 g, adipic acid 15,81! , isophthalic acid 16
．． 8F was added and the dehydration esterification reaction was further carried out at 210°C for 24 hours. Thus, the acid value is 12 KOH1q
7Q, Alkyrad 81 fat with a hydroxyl value of 24 KOH%Q was obtained.

After diluting the mixture as follows and coating it on a mild steel plate using an &30 bar coater, the performance of the dried coating film was evaluated. The results are shown in Table 1t.

Pencil hardness/JISK-5400 pencil scratch.

The test was conducted in accordance with the above test.

Adhesion: The coating film was crimped with adhesive tape having 11 vertical and horizontal lines at 1n intervals, and the number of rice H left after the tape was pulled and peeled off was evaluated.

Bending resistance: Bend the test piece with the coating outside and bend it to a diameter of 2.
I bent it when I was drunk and observed the state of the paint film at this time.

Water resistance: The state of the coating film was observed after 3 hours of immersion in 20°C water.

Gasoline resistance: The painted surface is coated with 100% gasoline-containing absorbent cotton.
The condition after rubbing twice was evaluated.

Ultraviolet resistance: A 15W ultraviolet germicidal lamp was irradiated for 48 hours from a distance of 15G, and the condition of the painted surface was observed.

Claims (1)

[Claims] An alkyd resin comprising, as a polyhydric alcohol component, a graft polymer obtained by ring-opening a cyclic ester in the presence of a cellulose derivative having a hydroxyl group.