JPH082954B2 - Air-drying unsaturated polyester resin composition - Google Patents

Description

TECHNICAL FIELD The present invention mainly relates to an air-drying unsaturated polyester resin composition for obtaining a black enamel coating film.

Conventional technology Although lacquer was used to paint high-end furniture in the olden days, the production of lacquer is limited and even if the lacquer painting process is small, 11
The number of processes, many of which are 27, requires several weeks to several months for finishing, which makes industrial production difficult. However, the unique jet-blackness, high gloss, depth and sharpness of the product obtained by the lacquer coating are the most preferable.

Therefore, as an alternative to lacquer coating, a polybasic acid component containing an unsaturated polybasic acid component is reacted with a polyhydric alcohol component to obtain an unsaturated polyester having air-drying property (air-drying property). Various attempts have been made to prepare an unsaturated polyester resin composition by blending a saturated monomer and a black dye / pigment and to apply it to coating, some of which have been put to practical use.

As one of such attempts, in producing an unsaturated polyester having air-drying property by reacting a polybasic acid component containing an unsaturated polybasic acid component and a polyhydric alcohol component,
A method of blending and using cashew nut shell liquid or a mono- or poly-hydroalkyl ether of cardanol and a method of reacting an adduct obtained by the reaction of cardanol glycidyl ether and dialkanolamine have been proposed (Japanese Patent Publication No. 12873 gazette, Japanese Patent Publication No. 47-23189
(See the official gazette). According to this method, while being inexpensive,
Desirable dryness such as air-drying property, internal plasticity, and pigment wettability can be imparted.

Problems to be Solved by the Invention According to the methods described in JP-B-45-12873 and JP-B-47-23189, a quality close to a lacquer-coated product can be obtained, but when painting a piano or the like. There is a strong demand for a unique jet-black feeling, high gloss, depth and sharpness equivalent to lacquered products.

The present invention has been achieved as a result of earnest research conducted in order to meet such demands of the market.

Means for Solving the Problems 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 with a polyhydric alcohol component. )
And an air-drying unsaturated polyester resin composition comprising an ethylenically unsaturated monomer (Y) as a main component, wherein the unsaturated polyester (X) is a polyhydric alcohol allyl ether component (a) and cardanol, cardol or an oligomer thereof. An unsaturated polyester introduced with a derivative component (b) having a glycidyl group or an alcoholic hydroxyl group derived from a phenolic compound selected from the group consisting of the following:

 Hereinafter, the present invention will be described in detail.

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 with a polyhydric alcohol component.
And an ethylenically unsaturated monomer (Y) as a main agent.

Unsaturated Polyester (X) Among the polybasic acid components constituting the unsaturated polyester (X), examples of the unsaturated polybasic acid component include maleic anhydride, maleic acid, itaconic anhydride, itaconic acid and fumaric acid. An unsaturated polybasic acid may be used. Along with these unsaturated polybasic acids, saturated polybasic acid 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.

Moreover, as the polyhydric alcohol component constituting the unsaturated polyester (X), 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-
Examples include 1,3-pentadiol, neopentyl glycol, trimethylolethane, trimethylolpropane, glycerin and pentaerythritol. In some cases, a polyether glycol such as polytetramethylene glycol, polypropylene glycol or polyethylene glycol, or a hydroxyl group-containing liquid polybutadiene can be used in combination.

In the present invention, as the unsaturated polyester (X), glycidyl derived from a phenolic compound selected from the group consisting of (a) polyhydric alcohol allyl ether component, (b) cardanol, cardol or oligomers thereof. An unsaturated polyester in which both components of a derivative group having a group or an alcoholic hydroxyl group are introduced is used.
A synergistic effect can be obtained by using both the above components (a) and (b) together, and when either one of (a) and (b) is lacking, it is expected in terms of jetness of the coating film. The improvement effect of is not sufficiently achieved.

As the polyhydric alcohol allyl ether component (a),
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 monochlorotyl ether, hexamethylol melamine diallyl dicrotyl ether, hexanetriol diallyl ether, pentaerythritol diallyl crotyl ether, tetramethylol cyclohexanol triallyl ether, tetramethylol cyclohexanone diallyl ether, hexamethylol melamine tetraallyl ether, etc. Allyl ether having hydroxyl groups can be exemplified.

The polyhydric alcohol allyl ether component (a) has an allyl group of 0.05 to 0.5 per mol of the polybasic acid component.
It is desirable to use it in a molar ratio, and if it is less than 0.05 mol, air-drying property is insufficient, while if it exceeds 0.5 mol, air curability is strong and the balance with internal curability is lost, and a tingling phenomenon appears on the surface of the coating film. A particularly preferred range is 0.1 to 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 an oligomer thereof, the following compounds are used.

Cardanol, which is a raw material phenolic compound, is obtained by heating and decarboxylating anacardic acid contained in cashew nut shell liquid. Caldor
Since it is contained in the cashew nut shell liquid, it may be isolated by an appropriate means. Cardanol or cardol oligomers are obtained by condensing cardanol or cardol with formaldehyde or a formaldehyde generator. The oligomer means dimer, trimer, tetramer and the like. Among the phenolic compounds that are the raw materials, the chemical formulas of cardanol, cardol, and cardanol dimer are shown below.

By reacting the above phenolic compound with epichlorohydrin in the presence of a basic catalyst, the corresponding glycidyl ether can be obtained. For example, for cardanol, the formula A cardanol glycidyl ether represented by is obtained. At this time, the formula The compound represented by (1) is by-produced, and this compound can also be used as the above-mentioned derivative component (b).

By reacting the cardanol glycidyl ether obtained above with a dialkanolamine such as diethanolamine or dipropanolamine, the formula It is obtained with a dialkanolamine adduct represented by (R is an alkylene group).

By reacting the above phenolic compound with an alkylene oxide such as ethylene oxide or propylene oxide, an alkylene oxide adduct in which one or more phenolic hydroxyl groups are converted into O (CH ₂ CH ₂ O) nH can be obtained. n
Is usually 1, but may be 2 or more. The following formula shows an example of an adduct obtained by adding ethylene oxide to cardanol, cardol, or cardanol dimer.

Among the derivative components (b), cardanol glycidyl ether and cardanol alcohol are particularly preferable.

The ratio of the derivative component (b) introduced into the unsaturated polyester (X) is 0.05 to 1 mol with respect to 1 mol of the polybasic acid component.
Select from the range of 0.5 mol. If this ratio is less than 0.05 mol, the air-curability will be insufficient, while if it exceeds 0.5 mol, blemishes and the like will appear on the surface of the coating film, making it practically unusable. A particularly preferred range is 0.1 to 0.4 mol.

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

The air-drying unsaturated polyester (X) is reacted with an isocyanate compound for modification, and the polyester segment portion is chain-extended through an isocyanate bond, or an active hydrogen group-containing acrylic monomer is further added to the isocyanate group. It is also possible to introduce a double bond.

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

Examples of the ethylenically unsaturated monomer (Y) include styrene, vinyltoluene, monochlorostyrene, α-methylstyrene, diallyl phthalate, triallyl cyanurate, acrylic acid ester, methacrylic acid ester, glycidyl methacrylate and 2-hydroxymethacrylate glycidyl ether. , Vinyl acetate, vinyl chloride, methylenebisacrylamide, divinylbenzene, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-
Hexanediol diacrylate or the like is used.

Other Components The air-drying unsaturated polyester resin composition of the present invention contains the above-mentioned unsaturated polyester (X) and ethylenically unsaturated monomer (Y) as a main component, but usually, in addition to these, a curing agent and a curing accelerator. Add agents and dyes and pigments.

As the curing agent, methyl ethyl ketone peroxide, cyclohexanone peroxide, cumene hydroperoxide, benzoyl peroxide, dicumyl peroxide, t-butyl perbenzoate, etc. are used, and the curing accelerator is cobalt octenoate, cobalt naphthenate. , Manganese octenoate, manganese naphthenate and the like are used.

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

Although various color tones are used as dyes and pigments,
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 iron oxide, manganese blue, ultramarine blue, hansalet, chrome yellow. , Chrome green, etc. are also used.

In addition, if necessary, fillers (calcium carbonate, kaolin, clay, talc, mica, alumina, asbestos powder, fine silica, barium sulfate, lithopone, gypsum,
Perlite, etc., grinding agent (zinc stearate, fine powder talc, etc.), leveling agent (silicone, cellulose acetate butyrate, surfactant, etc.), diluent (ethyl acetate, toluene, xylene, methanol, ethanol, butanol, acetone, etc.) 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.), anti-greening agent (phosphoric acid) , Phosphorous acid, tartaric acid, etc.) and air-drying aids (oils, paraffin wax, etc.) can also be added.

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

As a coating means, any coating method such as spray coating, brush coating, curtain flow coating, roll coating and dipping can be adopted.

After painting, buffing is performed to develop jet black feeling, high gloss, depth feeling and sharpness. However, this buffing 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, cure drying property,
In terms of jet-black feeling, high gloss, depth feeling, and sharpness, synergistic quality improving action is exhibited as compared with the case where either of the components (a) or (b) is introduced.

EXAMPLES Next, the composition of the present invention will be further described with reference to Examples. Hereinafter, “part” and “%” are expressed on a weight basis.

Example 1 A flask equipped with a stirrer, a gas introduction tube and a reflux condenser was charged with 1.0 mol of maleic anhydride and propylene glycol.
0.53 mol, diethylene glycol 0.25 mol, triethylene glycol 0.20 mol, trimethyl roll propane diallyl ether 0.15 mol, cardanol glycidyl ether 0.20 mol were charged, xylene 3% and hydroquinone (polymerization inhibitor) 0.02% were charged, and nitrogen gas was blown. A condensation reaction was carried out at a temperature of 200 ° C. for 5 hours while stirring, and then the reaction was continued under reduced pressure at 150 ° C. for 1 hour to distill off xylene.

Unsaturated polyester (X) 70 thus obtained
To 30 parts of styrene, add 30 parts of styrene to make a solution, and take a part of it.
Add 10% aniline black and roll 3 rolls 1
A mill base was prepared by passing the solution through 35 times and 100 parts of the above-mentioned unsaturated polyester (X) was added to 100 parts of styrene solution.
And then 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 compounding amount of aniline black is 2%.) This resin liquid is further diluted with styrene monomer (Y) to a spray viscosity, and cobalt octenoate (Octex Co, 8% cobalt containing by Nippon Kagaku Sangyo Co., Ltd.) 0.5 is added. %
And 1.0% of methyl ethyl ketone peroxide (Permec-N manufactured by NOF CORPORATION) were mixed to form a coating composition, which was then spray-coated on a wood (piano material) surface and cured at room temperature.

 The results are shown in Table 1.

Comparative Example 1 Omitting the preparation of cardanol glycidyl ether,
And change the charge amount of diethylene glycol to 0.73 mol,
Further, the amount of maleic anhydride was reduced to 0.5 mol, and 0.5 mol of tetrahydrophthalic anhydride was used instead, and Example 1 was used.
The unsaturated polyester (X) and the coating composition were produced in the same manner as in. The formulation of Comparative Example 1 is
Currently, it is already in commercial use for piano painting.

 The results are also shown in Table 1.

Comparative Example 2 Except for omitting the charge of trimethylolpropane diallyl ether and changing the charge amount of propylene glycol to 0.68 mol, the unsaturated polyester (X) and the coating composition were manufactured in the same manner as in Example 1. went.

 The results are also shown in Table 1.

(See Table 1) The measurement and determination methods in Table 1 and Tables 2 and 3 described later are as follows.

 The hue was in accordance with JIS K-5400,6901.

Turbidity is based on the kaolin turbidity method (according to JIS K-0101).

For 80 ° C stability, 150 ml of resin solution was put into a 200 ml glass bottle, sealed and left in a constant temperature bath at 80 ° C, and the number of days until gelation was measured.

Room temperature curability (gelling time, minimum curing time, maximum exothermic temperature) was in accordance with JIS K-6901.

 The curing and drying property was measured as follows.

The pot life is the gelling time after adding Octex Co (manufactured by Nippon Kagaku Sangyo Co., Ltd.) 0.5% and Permec N (manufactured by NOF Corporation) 2.0% to 100 g of the unsaturated polyester resin liquid.

For finger touch, the same as the above liquid is applied to a glass plate to a thickness of 0.5 mm with an applicator, and the time until touch dry.

Tack-free is the same as the above until the coating surface of the coating solution becomes tack-free.

The 60 ° specular gloss, brightness L, and Hunter whiteness were measured using a Nippon Denshoku Gloss color difference meter. In addition, the lightness L and the whiteness of the hunter show a jet black tendency as the numerical values are smaller.

As is clear from Table 1, in the composition of the present invention, room temperature curability and curing / drying property are improved, and jet black feeling, high gloss, depth feeling and sharpness are the same as those of lacquered products. It turns out that excellent results are obtained.

Examples 2 to 4 Instead of 0.20 mol of cardanol glycidyl ether,
0.2 mol of cardanol glycidyl ether / diethanolamine adduct (Example 2), 0.2 mol of cardanol dimer alcohol (Example 3), and a mixture of 0.10 mol of cardanol alcohol and 0.10 mol of cardol alcohol (Example 4) were used. Except for this, the unsaturated polyester (X) and the coating composition were produced in the same manner as in Example 1.

 The results are shown in Table 2.

Example 5 A flask equipped with a stirrer, a gas introduction tube and a reflux condenser was charged with 1.0 mol of maleic anhydride and 0.5 mol of propylene glycol.
25 mol, diethylene glycol 0.275 mol, triethylene glycol 0.20 mol, trimethylolpropane diallyl ether 0.17 mol, cardanol alcohol 0.10 mol were charged, xylene 3% and hydroquinone (polymerization inhibitor) 0.02% were charged, and nitrogen gas was blown. While conducting a condensation reaction at a temperature of 200 ° C for 5 hours, then under reduced pressure
The reaction was continued at 50 ° C. for 1 hour, and xylene was distilled off.

Taking a part of the unsaturated polyester (X) thus obtained, adding 10% of carbon black, and passing it through three rolls once to prepare a mill base,
35 parts of this mill base was added to 100 parts of 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 450 cps / 20 ° C.
(The blending amount of carbon black is 2.0%.) This resin liquid is further diluted with styrene monomer (Y) to a spray viscosity, and cobalt octenoate (Octex Co, manufactured by Nippon Kagaku Sangyo Co., containing 8% cobalt) is added. 0.5
% And methyl ethyl ketone peroxide (Permec-N manufactured by NOF CORPORATION) 1.0% were mixed, and then this was spray-coated on the wood (piano material) surface and cured at room temperature.

 The results are shown in Table 3.

Comparative Example 3 Preparation of an unsaturated polyester (X) was carried out in the same manner as in Example 5 except that the charging of cardanol alcohol was omitted, the charging amount of maleic anhydride was 0.5 mol, and tetrahydrophthalic anhydride was 0.5 mol. A coating composition was produced.

 The results are also shown in Table 3.

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

 The results are also shown in Table 3.

(See Table 3) EFFECT OF THE INVENTION In the air-drying unsaturated polyester resin composition of the present invention, the polyhydric alcohol allyl ether component (a) and the specific derivative component (b) are introduced into the unsaturated polyester (X). ) Or (b) is introduced, synergistic quality improvement hardening is achieved. That is, room temperature curing and curing and drying properties are improved, and excellent results equivalent to a lacquer coated product are obtained in jet black feeling, high gloss, depth feeling and sharpness.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tetsuya Kanbara 300-66 Takagi, Omiya City, Saitama Prefecture

Claims (5)

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