JPS6323953A - Air-drying unsaturated polyester resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn, having excellent jet-blackness, gloss, depth and brightness, consisting of a specified unsaturated polyester and an ethylenically unsaturated monomer. CONSTITUTION:One mol of a polybasic acid component (a) contg. an unsaturated polybasic acid component is reacted with a polyhydric alcohol allyl ether component (b) and 0.05-0.5mol of a derivative component (c) having a glucidyl or alcoholic hydroxyl group, obtd, by reacting a phenol compd. selected from the group consisting of cardanol, cardol and their oligomers with epichlorohydrin or an alkylene oxide, in an inert gas atmosphere at 150-250 deg.C to obtain an unsaturated polyester (A). A soln. obtd. by dissolving the component A in an ethylenically unsaturated monomer (B) (e.g., styrene) is blended with a curing agent, a curing accelerator and a black dye or pigment (e.g., carbon black) (C).

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates primarily to air-drying unsaturated polyester resin compositions for obtaining black enamel coatings.

Conventional technology Lacquer was used in ancient times to paint high-end furniture, but the production volume of lacquer is limited, and the lacquer painting process only takes 11 days.
It is difficult to produce it industrially, as it involves as many as 27 steps and takes several weeks to several months to complete. However, the unique jet black feeling, high gloss, deep feeling, and sharpness of the product obtained by lacquer coating are the most preferable.

Therefore, as an alternative to lacquer coating, a polybasic acid component containing an unsaturated polybasic acid component and a polyhydric alcohol component are reacted to obtain an unsaturated polyester that has air drying properties (air drying properties). Saturated monomer and black dyeing
Various attempts have been made to prepare unsaturated polyester resin compositions by blending pigments and use them for coating, some of which have been put into practical use.

As one such attempt, when producing an air-drying unsaturated polyester by reacting a polybasic acid component containing an unsaturated polybasic acid component with a polyhydric alcohol component, cashew nut shell liquid or cardanol was used to produce an air-drying unsaturated polyester. A method of mixing and using cardanol glycidyl ether, and a method of reacting an adduct obtained by reacting cardanol glycidyl ether with dialcamelamine have been proposed (Japanese Patent Publication No. 12873/1987, Japanese Patent Publication No. 189/23/1989).
According to this method, although it is inexpensive,
Properties such as favorable air drying properties, internal plasticity, and pigment wettability can be imparted.

Problems to be solved by the invention
According to the method described in Publication No. 189, products with quality close to those of lacquered products can be obtained, but when painting pianos, etc., it is necessary to obtain the unique jet black feeling, high gloss, depth, and sharpness of the lacquered products. There is a strong desire to have sex.

The present invention was achieved as a result of extensive research in order to meet such market demands.

Means for Solving the Problems The air-drying unsaturated polyester resin composition of the present invention is an unsaturated polyester (X ) and an ethylenically unsaturated monomer (Y) as a main component, in which the unsaturated polyester (X) is a polyhydric alcohol allyl ether component (a) and cardanol, cardol or these. It is characterized by using an unsaturated polyester into which a derivative component (b) having a glycidyl group or an alcoholic hydroxyl group derived from a phenolic compound selected from the group consisting of oligomers is introduced.

The present invention will be explained in detail below.

The air-drying unsaturated polyester resin composition of the present invention is an unsaturated polyester (X) obtained by reacting a polybasic acid component containing an unsaturated polybasic acid component and a polyhydric alcohol component.
and an ethylenically unsaturated monomer (Y) as a main ingredient.

Unsaturated polyester

Examples include unsaturated polybasic acids such as itaconic acid and fumaric acid. Along with these unsaturated polybasic acids, phthalic anhydride,
Saturated polybasic acids such as phthalic acid, terephthalic acid, isophthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, het acid, citraconic acid, adipic acid, and sebacic acid can also be used together.

Further, as the polyhydric alcohol component constituting the unsaturated polyester (X), ethylene glycol, propylene glycol, diethylene glycol, and triethylene glycol are used. -l, dipropylene glycol, bisphenol dioxypropyl ether, 1,3-butylene glycol,
2.3-Butylene gellicol, 1.6-hexanediol, 2-ethyl-1.3-hexanediol, 2.2.

Examples include 4-trimethyl-1,3-bentanediol, neopentyl glycol, trimethylolethane, trimethylolpropane, glycerin, and pentaerythritol. Depending on the case, a polyether glycol such as polytetramethylene glycol, polypropylene glycol, or polyethylene glycol or a hydroxyl group-containing liquid polybutadiene may also be used in combination.

In the present invention, the unsaturated polyester (X
), (a) a polyhydric alcohol allyl ether component; (b) a derivative component having a glycidyl group or an alcoholic hydroxyl group derived from a phenolic compound selected from the group consisting of cardanol, cardol, or oligomers thereof; An unsaturated polyester containing the following components is used.

By using both components (a) and (b) above, a synergistic effect can be obtained, and if either one of (a) or (b) is missing, the desired effect may be obtained in terms of the jet black feeling of the coating film, etc. The improvement effect is not fully realized.

The polyhydric alcohol allyl ether component (a) includes pentaerythritol triallyl ether, pentaerythritol diallyl ether, trimethylolpropane diallyl ether, trimethylolpropane monoallyl ether, trimethylolethane diallyl ether, trimethylolethane monoallyl ether, and glycerin. Diallyl ether, glycerin monoallyl ether, tetramethylol cyclohexanol diallyl monocrotyl ether, hexamethylol melamine diallyl dicrotyl ether, hexanetriol diallyl ether, pentaerythritol diallyl ether, tetramethylol cyclohexanol triallyl ether, tetramethylol cyclohexanone Examples include allyl ethers having at least one hydroxyl group in the molecule, such as diallyl ether and hexamethylol melamine tetraallyl ether.

This polyhydric alcohol allyl ether component (a) is 0.05 to 0 as an allyl group per mole of the polybasic ugly component.
．． It is preferable to use it in a proportion of 5 mol.If it is less than 0.05 mol, air drying properties will be insufficient, while if it exceeds 0.5 mol, air curability will be strong and the balance with internal curability will be lacking, resulting in a sagging phenomenon on the surface of the coating film. appears. A particularly preferable range is 0.1 to
It is 0.4 mol.

As the derivative component (b) having a glycidyl group or an alcoholic hydroxyl group derived from a phenolic compound selected from the group consisting of cardanol, cardol, or oligomers thereof, the following are used.

Cardatonol, one of the raw material phenolic compounds, is obtained by heating and decarboxylating anacardic acid contained in cashew oak shell liquid. Since cardol is contained in cashew nut shell liquid, it can be isolated by appropriate means. Cardanol or cardolmer is obtained by condensing cardanol or cardol with formaldehyde or formaldehyde-generating substances. What is oligomer?
Dimers, trimers, tetramers, etc. Among the phenolic compounds that are raw materials, the chemical formulas of cardanol, cardol, and cardanol dimer are shown below.

Cardanol Power Cardanol Dimer OH OH When the above-mentioned phenolic compound is reacted with epichlorohydrin in the presence of a basic catalyst, the corresponding glycidyl ether is obtained. For example, in the case of cardanol, cardanol glycidyl ether represented by the formula is obtained. At this time, a compound represented by the formula is produced as a by-product, and this compound can also be used as the derivative component (b).

When the cardanol glycidyl ether obtained above is reacted with a dialkanolamine such as jetanolamine or dibrobanolamine, a dialkanolamine adduct represented by the formula (R is an alkylene group) is obtained.

If the above-mentioned phenolic compound is reacted with a fullylene oxide such as ethylene oxide or propylene oxide, an alkylene oxide adduct in which one or more of the phenolic hydroxyl groups is converted to 0 (CHz CHz O) n H can be obtained. n
is usually 1, but may be 2 or more. An example of an adduct obtained by adding ethylene oxide to cardanol, cardol, or cardanol glycimer is shown in the following formula.

Cardanol Alcohol Cardol Alcohol Cali'nol Dimer Alcohol OCH, CH20H OCH2, CH2, OH Among the derivative components (b), cardanol glycidyl ether is preferred.

The ratio of the derivative component (b) introduced into the unsaturated polyester (X) is 0 to 1 mole of the polybasic fiIk component.
Select from the range of 205 to 0.5 mol. This ratio is 0
．． If the amount is less than 0.5 mol, the air curing properties will be insufficient, and if it exceeds 0.5 mol, wrinkles etc. will appear on the coating surface, making it impossible to use it practically. A particularly preferred range is 0.1 to 0.4 mol.

By using each of the above components, that is, a polybasic acid component, a polyhydric alcohol component, and the above-mentioned (a) and (b) components, by reacting them at a temperature of about 150 to 250°C in an inert gas atmosphere according to a conventional method. , the desired unsaturated polyester (
X) can be obtained.

In addition, this air-drying unsaturated polyester (X) is modified by reacting with an incyanate compound, and the polyester segment portion is further chain-extended via an isocyanate bond, or an acrylic monomer containing an active hydrogen group is added to the isocyanate group. It is also possible to introduce a double bond.

Ethylenically unsaturated monomer Y The unsaturated polyester (X) obtained as described above is used for coating as a solution of the ethylenically unsaturated monomer (Y).

As the ethylenically unsaturated monomer (Y), styrene,
Vinyl toluene, monochlorostyrene, α-methylstyrene, diallyl phthalate, triallyl cyanurate,
Acrylic acid ester, methacrylic ester, glycidyl methacrylate, 2-hydroxy methacrylate glycidyl ether, vinyl acetate, vinyl chloride, methylene bisacrylamide, divinylbenzene, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, diethylene glycol diacrylate, neopentyl Glycol diacrylate, 1,6-hexanediol diacrylate, etc. are used.

The uninvented air-drying unsaturated polyester resin composition contains the above-mentioned unsaturated polyester (X) and ethylenically unsaturated monomer (Y) as main ingredients. A curing agent, curing accelerator, and dye/pigment are blended.

As a curing agent, methyl ethyl ketone peroxide,
Cyclohexanone peroxide, cumene hydroperoxide, benzoyl peroxide, dicumyl peroxide, t-butyl perbenzoate, etc. are used, and the curing accelerators include cobalt octenoate, cobalt naphthenate, manganese octenoate, and manganese naphthenate. etc. are used.

Further, instead of the above-mentioned curing agent, an ultraviolet sensitizer can be added to carry out curing with ultraviolet rays. In addition, it is also possible to perform curing with an electron beam without adding the above-mentioned ultraviolet curing agent.

Various colors are used as dyes and pigments, but black dyes and pigments such as aniline black, carbon black, and synthetic iron black are the most important, and in some cases titanium white,
Cyanine Blue, Chrome Yellow, Watching Red, Red Garla, Manganese Blue, Ultramarine Blue,
Hansa Red, Chrome Yellow, Chrome Green Natomo are used.

In addition, fillers (calcium carbonate, kaolin, clay, talc, mica, alumina, asbestos powder, finely divided silica, barium sulfate, lithopone, gypsum, perlite, etc.) and abrasives (zinc stearate, finely divided talc, etc.) are also available as necessary. ), leveling agents (silicone, cellulose acetate phthalate, surfactants, etc.), diluents (ethyl acetate, toluene, xylene, methanol, ethanol,
butanol, acetone, methyl isobutyl ketone, methyl ethyl ketone, cellosolves, diacetone alcohol, etc.), thermoplastic resins, trocellulose, vinyl chloride -
Vinyl acetate copolymer, vinyl acetate resin, acrylic resin,
butylated melamine, butylated urea, etc.), greening prevention agent (
phosphoric acid, phosphorous acid, tartaric acid, etc.), idle running aids (oils and fats,
Paraffin wax, etc.) can also be blended.

Function The air-drying unsaturated polyester resin composition of the present invention is suitably used for coating high-grade musical instruments such as pianos, furniture, furniture, and the like.

As the coating f step, any coating method such as spray coating, brush coating, curtain flow coating, roll coating, dipping, etc. can be adopted.

After painting, a puff is applied to create a jet black feel, high gloss, depth, and sharpness. However, this puffing may be omitted.

In the present invention, since the polyhydric alcohol allyl ether component (a) and the specific derivative component (b) are introduced into the unsaturated polyester (X), room temperature curability, curing drying properties, jet black feeling, high gloss, and deep feeling are achieved. In terms of image clarity and the like, a synergistic quality-improving effect is exhibited compared to when either one of these components (a) or (b) is introduced.

EXAMPLES Next, the compositions of the present invention will be further explained with reference to Examples. Hereinafter, "parts" and "%" are expressed on a volume basis.

Example 1 91.0 mol of anhydrous maleic, 0.53 mol of propylene glycol, 0.25 mol of diethylene glycol, 0.20 mol of triethylene glycol, and trimethylolpropane were placed in a flask equipped with a stirrer, a gas inlet tube, and a reflux condenser. 0.15 mol of diallyl ether and 0.20 mol of cardanol glycidyl ether were charged, and 3% of xylene and 0.02 mol of hydroquinone (polymerization inhibitor W agent) were added.
% and heated at 200℃ while blowing nitrogen gas.
A linear combination reaction was carried out for a period of time, and then the reaction was continued for 1 hour at 150° C. under reduced pressure, and xylene was distilled off.

Unsaturated polyester (X) 70 thus obtained
30 parts of styrene to make a solution.

A part of it was added with 10% of aniline black, and passed through three rolls once to create a mill base.
35 parts of this millbase was added to the unsaturated polyester (X
) and further diluted with 40 parts of styrene monomer (Y) to obtain a resin liquid having a solid content of 52.8% and a viscosity of 400 cps/20°C. (The blending amount of aniline black is 2%.) This resin liquid is further diluted with styrene monomer (Y) to a spray viscosity and contains cobalt octenoate (Octex Co manufactured by Nippon Kagaku Sangyo Co., Ltd., 8% cobal). 0
．． 5% and 1.0% of methyl ethyl ketone peroxide (Permetsu N, manufactured by NOF Corporation) were mixed to prepare a coating composition, which was then spray-painted on a wood (piano material) surface and cured at room temperature.

The results are shown in Table 1.

Comparative Example 1 The charge of cardanol glycidyl ether was omitted, the amount of diethylene glycol was changed to 0.73 mol, maleic anhydride was further reduced to 0.5 mol, and 0.5 mol of tetrahydrophthalic anhydride was used instead. Except for the above, unsaturated polyester (X) and a coating composition were produced in the same manner as in Example 1. The formulation of Comparative Example 1 is already in practical use for piano painting.

The results are also shown in Table 1.

Comparative Example 2 Production of unsaturated polyester (X) and coating composition were carried out in the same manner as in Example 1 except that the charging of trimethylolpropane diallyl ether was omitted and the amount of propylene glycol was changed to 0.88 mol. Manufactured.

The results are also shown in Table 1.

(See Table 1) Table 1 Measurements in this Table 1 and Tables 2 and 3 below,
The determination method is as follows.

The hue conformed to JIS K-5400 and 8901.

The turbidity was determined by the kaolin turbidity method (according to JIS K-0101).

To determine stability at 80°C, put 150m of resin solution into a 200mM glass bottle, seal it tightly, and place it in a constant temperature bath at 80°C, and measure the number of days until it gels.

Room temperature curability (gelation time, minimum curing time, maximum exothermic temperature) was in accordance with JIS KJ901.

Curing and drying properties were measured as follows.

Value) The pot life is 100% of the unsaturated polyester resin liquid.
Oftex Go (manufactured by Nihon Kagaku Sangyo Co., Ltd.)
0.5%, Vermec N (manufactured by Himi Yushi Co., Ltd.) 2.
Gelation time after adding 0%.

C) Touch is the time taken to dry to the touch after applying the above solution to a thickness of 0.5ml11 on a glass plate with an applicator.

■ Tack-free is the time it takes for the coated surface of the same coating solution to become tack-free.

The 60° specular gloss, lightness L, and Hunter's brightness were measured using a Nippon Heavy Color Gloss Color Difference Meter. In addition, in terms of brightness and hunter's seat, the smaller the numerical value, the more jet-black it tends to be.

As is clear from Table 1, the composition of the present invention has improved room temperature curing properties and curing drying properties, and has jet blackness, high gloss, depth, and sharpness comparable to that of lacquer-coated products. It can be seen that excellent results can be obtained.

Examples 2 to 4 Instead of 0.20 mol of cardanol glycidyl ether, 0.2 mol of cardanol glycidyl etherolamine adduct (Example N2), 0.2 mol of cardanol dimer alcohol (Example 3), cardanol 1 compound of alcohol with 0.10 mol of alcohol ("lllln1
The unsaturated polyester (X) and the coating composition were produced in the same manner as in Example 1, except that 4) was used. The results are shown in Table 2.

Table 2 Example 5 In a flask equipped with a stirrer, a gas inlet tube, and a reflux condenser, 1.0 mol of maleic anhydride, 0.525 mol of propylene glycol, 0.275 mol of diethylene glycol, and 0.20 mol of triethylene glycol were added. , 0.17 mol of trimethylolpropane diallyl ether, 0.10 mol of cardanol alcohol, and 3 mol of xylene.
% and hydroquinone (polymerization inhibiting IF agent) 0.02%
The reaction was carried out at 200° C. for 5 hours while blowing nitrogen gas, and then the reaction was continued at 150° C. under reduced pressure for 1 hour, and xylene was distilled off.

A part of the unsaturated polyester (X) thus obtained was added with 10% of carbon black, and passed through three rolls once to prepare a millbase, and 35 parts of this millbase was Unsaturated polyester (X) 100
1 part and further diluted with 40 parts of styrene monomer (Y) to give a solid content of 52.8% and a viscosity of 450 cps/20°.
A resin liquid of C was obtained. (The amount of carbon black is 2.
It becomes 0%. ) This resin liquid is further mixed with styrene monomer (
Y) to a spray viscosity of 0.5% cobalt octenoate (Cutex Co manufactured by Nihon Kagaku Sangyo Co., Ltd., containing 8% cobalt) and 1.0% methyl ethyl ketone peroxide (Permetsu N manufactured by Nippon Oil & Fats Co., Ltd.). This was then spray-painted onto a wood (piano material) surface and cured at room temperature.

The results are shown in Table 3.

Comparative Example 3 An unsaturated polyester (X ) and a coating composition.

The results are also shown in Table 3.

Comparative Example 4 Production of unsaturated polyester (X) and coating composition were carried out in the same manner as in Example 5, except that the charge of trimethylolpropane diallyl ether was omitted and the amount of propylene glycol was changed to 0.70 mol. Manufactured.

The results are also shown in Table 3.

(See Table 3) Table 3 Effects of the Invention In the air-drying unsaturated polyester resin composition of the present invention, the unsaturated polyester (X) contains a polyhydric alcohol allyl ether component (a) and a specific derivative component (b). Because of the introduction of these components, synergistic quality-improving curing is achieved compared to the case where either one of these components (a) or (b) is introduced. In other words, room temperature curability, curing and drying properties are suitable for fins,
In terms of jet blackness, high gloss, depth, and sharpness, it provides excellent results comparable to those of lacquer-coated products.

Patent applicant Nippon Gosei Kagaku Kogyo Co., Ltd. Patent applicant Kashu - Co., Ltd. Agent Patent attorney Seibu Oishi [-□-

Claims (1)

[Claims] 1. An unsaturated polyester (X) obtained by reacting a polybasic acid component containing an unsaturated polybasic acid component with a polyhydric alcohol component and an ethylenically unsaturated monomer (Y) as main ingredients In the air-drying unsaturated polyester resin composition, the unsaturated polyester (X) is derived from a polyhydric alcohol allyl ether component (a) and a phenolic compound selected from the group consisting of cardanol, cardol, or oligomers thereof. An air-drying unsaturated polyester resin composition characterized by using an unsaturated polyester into which a derivative component (b) having a glycidyl group or an alcoholic hydroxyl group is introduced. 2. Claim 1, wherein the proportion of the polyhydric alcohol allyl ether component (a) introduced into the unsaturated polyester (X) is 0.05 to 0.5 mol per 1 mol of the polybasic acid component. Compositions as described in Section. 3. The ratio of the derivative component (b) introduced into the unsaturated polyester (X) is 0.05 per mole of the polybasic acid component.
A composition according to claim 1, wherein the composition is 0.5 mol. 4. As the derivative component (b), use a reaction product obtained by reacting a phenolic compound selected from the group consisting of cardanol, cardol, or oligomers thereof with epichlorohydrin, epichlorohydrin and dialkanolamine, or alkylene oxide. A composition according to claim 1, characterized in that: 5. The composition according to claim 1, which is an air-drying unsaturated polyester resin composition for obtaining a black enamel coating.