JPS62195055A - Oil-modified alkyd resin coating composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition outstanding in storage stability, adhesivity to metal, corrosionproofness and weatherability, by blending an oil-modified alkyd, liquid acrylic polymerizable monomer, specific chlorinated polymer, epoxy compound and curing catalyst in specified proportion. CONSTITUTION:The objective composition can be obtained by blending (A) 100pts.wt. of an oil-modified alkyd (pref. with an oil length 30-65% and alpha,beta-unsaturated monocarboxylic acid content 2-15wt%), (B) 50-200pts.wt. of an acrylic polymerizable monomer liquid at 20 deg.C dissolvable for the component A [pref. having acryloyloxy group, e.g. 1,3-butanediol mono(meth)acrylate], (C) 5-50pts.wt. of a chlorinated polymer selected from chlorinated rubbers, chlorinated polyethylenes chlorinated polypropylenes each containing >=60wt% of chlorine (per 100pts.wt. of the components A plus B), (D) 0.05-5pts.wt. of an epoxy compound (per 100pts.wt. of the components A plus C), and (E) an appropriate amount of a curing catalyst.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides weather resistance, adhesion to metals, gloss, weather resistance,
This invention relates to a solvent-free coating composition that provides a coating film with excellent hardness and the like.

[Prior art]

Oil-modified alkyd resins are generally prepared from polybasic acids, polyhydric alcohols, and unsaturated fatty acids, and take advantage of the property of hardening when the double bonds of the unsaturated fatty acids in the ingredients participate in a crosslinking reaction with oxygen in the air. It is used in various types of paints such as air-drying paints and baking paints (Special Public Interest Publication in 1977).
No.-431, No. 58-46274, JP-A-53-52
No. 596, No. 53-67792, No. 56-50910
No. 53-69251).

When considering that fatty acids in the resin react with glycerin to form triglycerides in oil-modified alkyd resins, the weight percentage of the triglycerides in the resin is called the oil length, which depends on the physical properties of the paint, i.e., solubility, It is an important index for determining hardness, gloss, color retention, weather resistance, curing time, storage stability, etc. For example, increasing oil length helps increase coating flexibility and solubility in organic solvents, but tends to decrease coating hardness. On the other hand, while reducing oil length helps improve the gloss and color retention of the coating, it tends to reduce the spreadability of the paint. Of course, it is not only oil length that determines the physical properties of the above-mentioned coatings, but these properties are also governed by the nature of the components of the oil-modified alkyd resin pond.

Conventionally, oil-modified alkyd resins have an oil length of 30% to 80%.
% is generally dissolved in a solvent such as turpentine oil or toluene and used as an air-drying paint, and a mixture of this with an amine resin is used as a baking paint.

These solvent-based paints provide films with excellent weather resistance and adhesion to metals. However, the solvent evaporates and air pollution is a problem.

Air-drying oil-modified alkyd resin paint that does not use a solvent, that is, (A) oil-modified alkyd resin (B) acrylic polymerizable monomer that dissolves the above (E) component C) radical polymerization initiator and metal drying agent Solvent-free (pollution-free) paints made of curing catalysts are also known (Japanese Patent Application Laid-open No. 53-52596, 53-67792, 5
No. 3-69251).

This non-polluting paint is used as a heavy preservative paint in factory plants,
Used for painting ships.

[Problem that the invention seeks to solve]

The object of the present invention is to improve the storage stability and weather resistance of the above-mentioned pollution-free oil-modified alkyd resin paint, thereby further extending the life of the paint film.

[Specific measures to solve the problem]

The above object is achieved by incorporating specific chlorinated polymers and storage stabilizers, epoxy compounds, into conventional non-polluting paints.

(Structure of the Invention) The present invention provides: (A) Component: 100 parts by weight of oil-modified alkyd (B) Component: 50 to 200 parts of an acrylic polymerizable monosoft body that is liquid at 20°C and capable of dissolving the above-mentioned (A) component. Weight part 0 component: Chlorinated polymer selected from chlorinated rubber, chlorinated polyethylene, and chlorinated polypropylene having a chlorine content of 60% by weight or more. 5 to 5 parts by weight per 100 parts by weight of the sum of components (A) and (B) above. 50 parts by weight 0 component: 0.
05-5 parts by weight ■Ingredients: Curing catalyst Appropriate amount of the above, (1
The present invention provides an oil-modified alkyd resin coating composition characterized in that components 3), C), 0, and (2) are blended in the above proportions.

(Component A) The oil-modified alkyd resin of component (A) of the oil-modified alkyd resin composition according to the present invention is essentially the same as oil-modified alkyd resins that are conventional or that will be provided in the future (
It also includes those further modified with α,β-unsaturated monocarboxylic acids. The method of modification with α,β-unsaturated monocarboxylic acid is also the same as the method of modifying ordinary alkyd resins with fatty acids).

Therefore, the polybasic acid components of the alkyd resin include phthalic anhydride, isophthalic acid, tetrahydrophthalic anhydride, adipic acid, sebacic acid, azelaic acid, Diels of various isoprene dimers containing conjugated double bonds, and maleic anhydride.・1 with a side chain obtained by Alder addition reaction
, 2.3.6-tetrahydrophthalic anhydride 1 conductor such as myrcene maleic anhydride, alloocimene maleic anhydride, ocimene maleic anhydride, 3-(β-methyl-2-butenyl)-5-methyl-1,2, 3,6-titrahydrophthalic acid, hexahydrophthalic anhydride, 4-
Aromatic, aliphatic or alicyclic saturated or unsaturated polybasic acids such as methyltetrahydrophthalic anhydride and trimellitic acid are used alone or in combination. As long as gelation does not occur, part of the saturated polybasic acid may be replaced with an α,β-unsaturated polybasic acid such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, etc. Among these, particularly preferred polybasic acids are phthalic acid and 3-(β-methyl-2-butenyl)-5-methyl-1,2,,3,6-tetrahydrophthalic anhydride (hereinafter abbreviated as M13THP). ).

When MBTHP is used as part of the polybasic acid, it has a remarkable effect on lowering the viscosity of alkyd resins.

Polyhydric alcohol components include ethylene glycol, diethylene glycol, phlopylene gelylcol, dipropylene glycol, 1,4-butanediol, neopentyl glycol, glycerin, pentaerythritol, trimethylolpropane, trimethylolethane, tris(2-hydroxy Ethyl) incyanurate etc. are used alone or in combination. Generally, dihydric to tetrahydric alcohols having about 2 to 12 carbon atoms are common.

The oils and fatty acids forming the oil-modified alkyd resin include those having air-drying properties, such as oils and fats such as linseed oil, soybean oil, tall oil, and safflower oil, and fatty acids separated therefrom.

In the present invention, in order to obtain a film with better adhesion to metals, the oil-modified alkyd resin consisting of the above three essential components is preferably further modified with an α,β-unsaturated monocarboxylic acid. The α,β-unsaturated monocarboxylic acids used here are crotonic acid, sorbic acid or 2-(β-furyl)acrylic acid.

Particularly preferred among these is sorbic acid.

These α,β-unsaturated monocarboxylic acids introduced into the oil-modified alkyd resin are thought to react in the same way as oil-modified fatty acids and exist as side chains in the alkyd resin, but these acids are When an acrylic polymerizable monomer is used as component (B) in the composition of the invention, it radically copolymerizes with it and contributes to curing, so it has a great effect on improving the hardness and water resistance of the resulting coating film. bring about.

Oil-modified alkyd resins are produced from these three essential components or four components by conventional methods, but specifically, for example,
A method in which α, β-unsaturated monocarboxylic acids, fatty acids, polybasic acids, and polyhydric alcohols are simultaneously charged and reacted, or a fatty acid, a polybasic acid, and a polyhydric alcohol are first reacted, and then α, β-unsaturated There is a method of reacting monocarboxylic acids. The latter is preferred from the viewpoint of preventing gelation during production. These components can be subjected to the reaction in the form of their functional derivatives, such as esters such as fats and oils themselves. In addition, when using fats and oils, it is common to perform transesterification by reacting only a polyhydric alcohol and an ester in advance. Furthermore, in any method, it is desirable to add an antigelation agent such as hydroquinone to avoid gelation during the reaction.

The oil-modified alkyd resin as component (A) used in the present invention has an oil length of 25 to 70%, preferably 30 to 65%. If the oil length is less than 25%, it will cause a decrease in the water resistance of the resulting coating film, while if it is more than 70%, undesirable phenomena such as a decrease in the initial drying hardness of the resulting coating film and a decrease in surface smoothness will occur. In addition, in the present invention, the oil length is the electric % of the monobasic acid triglyceride derived from the oil or fat of the oil-modified alkyd resin after modification with an α,β-unsaturated monocarboxylic acid or a fatty acid separated from it.

The α,β-unsaturated monocarboxylic acid content in the α,β-unsaturated monocarboxylic acid-modified oil-modified alkyd resin used in the present invention is 0.5 to 30% by weight, preferably 2 to 15% by weight. be. If it is less than 0.5%, no effect of improving the water resistance and hardness of the resulting coating film can be expected, while if it exceeds 30%, gelation will occur significantly during alkyd production, making it difficult to produce.

The oil-modified alkyd resin used in the present invention is α, β-
The acid value of the unsaturated monocarboxylic acid-modified oil-modified alkyd resin is usually about 5 to 40.

It is also possible to replace 50 to 20% by weight of the component (A) with unsaturated polyester, heat-treat the mixture, and use a resin in which the two are uniformly compatible (Japanese Patent Laid-Open No. 58
-21459).

This unsaturated polyester is obtained by reacting an unsaturated dibasic acid, a saturated polybasic acid, and a polyhydric alcohol.

By heating the oil-modified alkyd or a mixture of the same and the unsaturated polyester, a resin in which both are uniformly compatible is dissolved and diluted with an acrylic polymerizable monomer (solubilized) to prepare a uniform solution.

(Component B) Preferred polymerizable monomers for dissolving the oil-modified alkyd of component (A) are acrylic compounds having an acryloyloxy group, such as alcohols having 2 to 20 carbon atoms and acrylic acid or methacrylic acid. mono- or polyacrylates and methacrylates which are esters of
(hereinafter referred to as (meth)acrylate). This compound may have a hydroxyl group, an alkoxy group, etc., and since the resin composition for coating material is intended to provide a coating material for drying at room temperature or by heating, one with a high boiling point is preferable. Specifically, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, 2
-Ethoxyethyl C meth)acrylate, 2-butoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate
acrylate, 2-hydroxyethyl (meth)acrylate, 3-allyloxy-2-hydroxypropyl (meth)acrylate, 3-butoxy-2-hy)'.

xypropylbimeta)acrylate, 2-hydroxy-
1-7enether (meth)acrylate, 2-hydroxy-2-phenethyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate), 1,3-butanediol (meth)acrylate, 1 .4-butanediol di(meth)
Acrylate, 1,6-hexanethiol di(meth)acrylate, neobentyl glycol di(meth)acrylate, glycerin monoacrylate monomethacrylate, chrycerin monomethacrylate monohalf maleate, trimethylolpropane tri(meth)acrylate,
These include pentaerythritol tri(meth)acrylate and the like, and these can be used alone or in combination of two or more. Among these polymerizable monomers, particularly preferred are 1.3-butanediol mono(meth)acrylate, 1.4-butanediol mono(meth)acrylate, neopentyl glycol mono(meth)acrylate, and trimethylolpropane. It is tri(meth)acrylate.

A part of these (meth)acrylates may be replaced with styrene. Furthermore, since tri(meth)acrylates have a high viscosity, they should not be used much for purposes other than improving coating film hardness, but when used, they are used in combination with other mono(acrylates), di(meth)acrylates, etc.

The polymerizable monomer as component (B) is used in an amount of 50 to 200 parts by weight based on 100 parts by weight of the prisoner component.

If the amount of the polymerizable monomer is less than 50 parts by weight, the viscosity of the coating material becomes high and coating becomes difficult. Moreover, if the amount exceeds 200 parts, not only the drying properties of the paint will be impaired, but also the impact resistance of the resulting paint film will be poor.

(Component E) This component (E), component (■), the chlorine-based polymer (
The mixed resin composition of 0 and epoxy compound 0 uses an organic peroxide or a redox catalyst consisting of an organic peroxide and a reducing agent, and if necessary, a metal desiccant such as manganese naphthenate or cobalt naphthenate. It can be hardened by

Examples of catalysts include: C () Combination of methyl ethyl ketone peroxide and cobalt naphthenate ←) Combination of redox catalyst consisting of benzoyl peroxide and dimethylaniline and cobalt naphthenate or manganese naphthenate (c) Cyclohexanone peroxide and Examples include combinations with cobalt naphthenate. In particular, cobalt naphthenate is suitable because it not only participates in radical generation as an M base but also participates in oxidative hardening of the oil-modified alkyd resin as a metal desiccant.

The number of organic peroxides or drying agents to be used is left to the discretion of the practitioner, but for example, 0.5 to 5 parts by weight of organic peroxide and 0 parts by weight of reducing agent per 100 parts by weight of the oil-modified alkyd resin composition.
．． 0.01 to 5 parts by weight, and 0.01 to 5 parts by weight of the desiccant.

(Component C) The chlorinated polymer of the Ω component is a chlorinated rubber having a chlorine content of 60% by weight or more, preferably 65% by weight or more, which is compatible with the oil-modified alkyd of the component (A), chlorinated polyethylene, or a chlorine ratio. An example is polypropylene.

Specifically, chlorinated polypropylene "Superchron 306" (chlorine content of about 66%) with an apparent specific gravity of 0.2 to 0.4 and a softening temperature of 120 to 130 °C, and a softening temperature of 100 °C
~120℃ chlorinated polyethylene “Super Chron 90”
7MA", 6 507', 1 510", 1 515"
(Chlorine content: about 70%), chlorinated rubber with a softening point of about 130 to 155°C "Super Chron CR-10", "Super Chron CR-2"
Four types of Deyu Kokusaku pulp■ such as 0'' (chlorine content approximately 66%) can be used.

These chlorinated polymers are preferably 10 to 50 parts by weight per 100 parts by weight of the sum of components (A) and (B).
15 to 30 parts by weight are used. If it is less than 10 parts by weight, the contribution to improving weather resistance is low. The use of large amounts of chlorinated polymers
Further improvement in weather resistance cannot be expected, and it is not economical.
It has the disadvantage that coating properties, leveling properties, hardness, and drying properties are reduced.

(Component D) Epoxy compounds that contribute to the storage stability of the coating composition include epoxidized soybean oil, such as Adeka Argus Chemical ■ (7) ADK CI ZERO-130p (trade name)
, epoxidized linseed oil, e.g. Adeka Argus Chemical■
ADK CIZgRO-180 (trade name), diglycidyl ether of bisphenols with an epoxy equivalent of 165 to 210, such as oil-based shell epoxy 828 (trade name), the company's Epicor) 827 (trade name), ADEKA・Argus Higaku ■ MARK EP-13 (
Product name) is available. These may be used in combination of two or more types, or in combination with the chlorinated polymer plasticizer described below [
For example, Adeka Argus Chemical (MARK) may be used.

The 0 component epoxy compound is used in a ratio of 0.05 to 5 parts by weight based on 100 parts by weight of the oil-modified alkyd component (A) and the chlorinated polymer (0 component).

If the amount is less than 0.05 part by weight, the effect of improving the stability of the composition will not be sufficient. If the amount exceeds 5 parts by weight, the strength of the coating film will decrease.

[Optional ingredients]

In addition to the above components (A), (B), Ic), (D) and , small amounts of solvents such as mineral spirits, fungicides and chlorinated paraffins, dibutyl terephthalate,
A plasticizer such as dioctyl phthalate may be added if necessary.

[Painting method]

The coating composition of the present invention is applied onto a base material such as a steel plate, zinc plate, stone plate, etc. using a roll, brush, spray, etc., and dried at room temperature.

〔effect〕

The coating composition of the present invention is a non-polluting coating with excellent storage stability, has excellent adhesion to metals, anti-corrosion properties, and weather resistance, and is relatively less likely to cause chalking than silver coatings containing aluminum powder. Even with white paints containing easily susceptible titanium oxide, clay, barium sulfate, calcium carbonate, etc., the period until chalking occurs is significantly postponed.

Production example of oil-modified alkyd Production example-1 60 parts of soybean oil fatty acid and 2 parts of phthalic anhydride were placed in a reactor equipped with a stirrer, thermometer, cooler, water separator, and nitrogen inlet pipe.
2 parts, 4.6 parts of glycerin, 15 parts of pentaerythritol
．． After adding 8 parts of hydroquinone and 4 parts of xylene, the reaction was carried out at 220° C. in a nitrogen stream. When the acid value of the generated alkyd reached 40, 5 parts of sorbic acid and 0.05 part of hydroquinone were added, and the reaction was continued until the acid value reached 10, resulting in a sorbic acid component concentration of 5.0% and an oil length of 62. A .7% oil-modified alkyd resin (resin-A) was obtained.

Production Example-2 60 parts of soybean oil fatty acid, 27 parts of phthalic anhydride, 15.1 parts of glycerin, and 5.1 parts of pentaerythritol were prepared.
After further adding 0.05 part of hydroquinone and 4 parts of xylene, the same reaction as in Production Example-1 was carried out at 220°C in a nitrogen stream to obtain an oil-modified alkyd resin (Resin-B) with an oil length of 62.7%. Ta.

Production Example-3 60 parts of dehydrated castor oil fatty acid, 27 parts of phthalic anhydride, 15.1 parts of glycerin, and 5.1 parts of pentaerythritol were reacted in exactly the same manner as in Production Example-2 to obtain an oil length of 62.7%.
An oil-modified alkyd resin (Resin-C) was obtained.

Production example-4 Dehydrated castor oil fatty acid 54.6 parts, phthalic anhydride 15.1 parts
part, MBTHP 12.0 parts, glycerin 7.7 parts, pentaerythritol 12.1 parts and 2-(β-furyl).
The reaction was carried out in exactly the same manner as in Production Example-1 except that 5.4 parts of acrylic acid was used to obtain an oil-modified alkyd resin (resin -E) was obtained. □Production Example-5 Dehydrated castor oil fatty acid 55.6 parts, phthalic anhydride 15.3 parts
7.9 parts of glycerin, 11 parts of pentaerythritol.
Production example except using 7 parts and 4.4 parts of sorbic acid -
1. Meanwhile, 222 parts of phthalic anhydride and 224.6 parts of neopentyl glycol were charged into the same manufacturing apparatus as in Production Example 1, and 20 parts of xylene was added thereto, followed by a nitrogen stream. Acid value 30 at 210℃
After reacting to a temperature of ~15, it was cooled. 58 parts of fumaric acid and 0.25 parts of hydroquinone were charged, and the acid value was 2 at 210°C.
The reaction was allowed to occur until the value became 5 or less. Water, xylene, etc. were removed to obtain a pale yellow unsaturated polyester resin with an acid value of 24.

Next, 100 parts of the oil-modified alkyd resin and 100 parts of the unsaturated polyester resin were placed in the same manufacturing apparatus as in Manufacturing Example-1.
After adding 10 d of xylene, the reaction was carried out at 180° C. under a nitrogen stream. Sequentially, a small amount of resin was taken out from the reactor, and the viscosity of the solution diluted to 50% by weight with toluene at 25°C was measured.

Its viscosity at 25°C is 150 cm
), water, xylene, etc. were removed to obtain a homogeneously compatible resin (resin-F).

Evaluation of Paints Examples 1 to 15 and Comparative Examples 1 to 5' Oil-modified alkyd resins were dissolved in the polymerizable monomers shown in Coating 1 below to the indicated concentrations. 60 parts by weight of this solution, 2 parts by weight of a hardening agent consisting of a metal desiccant and a polymerization initiator as described below, 25 parts by weight of titanium oxide "R-930'" (trade name) manufactured by Ishihara Sangyo ■, barium sulfate manufactured by Sakai Chemical ■ 15 parts by weight and 2 parts by weight of thixotropic agent, and chlorinated polymer from Deyu Kokusaku Pulp (■) shown in Table 1 or chlorinated paraffin "Enbara 40" from Ajinomoto (■) and an epoxy compound in the proportions shown in the table, and three A coating composition was prepared by kneading with this roll.

This paint composition was degreased with acetone and
G-3141 (SPCCB) polished mild steel plate (70cm
×150 dew, wall thickness 0.8m+, polished with 320 polishing cloth) to a film thickness of 50μ, and then heated at 22℃.
It was dried at room temperature in an atmosphere of 65% R'H.

The physical properties of the resulting coating film (after 7 days) were measured under the following conditions. The results are shown in Table-1 and Table-2.

Curing agent ■Metal drying agent ■Polymerization initiator cyclohexanone peroxide 1.0 parts Active Degree 2 B type viscometer (manufactured by Tokyo Keiki) Touch dry time: Compliant with JIS K-5400 Paint film physical properties Pencil hardness: JIS K-5652 Adhesion: JIS K-5401 goblin test Flexibility: JIS K-5400 (2-).

Pass (○), Break (×) Impact resistance: DuPont impact strength (7 inches, 5002 load, 50 cIn height) Pass (○), Break (×) Surface smooth Note 20 (smooth), Δ (Yuzuhada) ) Weather resistance: A test piece of a soft steel plate with a coating film was placed in the weather-o-meter of Suga Test Instrument ■, under conditions of a rain cycle of 12 minutes/60 minutes and a black panel temperature of 45 ± 2 degrees Celsius. An accelerated test was conducted to determine the gloss of the paint film over time (JISK-5400, 60°-60°) and the occurrence of chalking (conducted in accordance with JISK-J516, and the first time when chalking was observed). time) was investigated.

The abbreviations in Table 1 are as follows:

HPA: Hydroxyprobyl methacrylate BDDA:
1.4-Butanediol diacrylate TMP-TM
A:) Limethylolpropane trimethacrylate CP
P: Chlorinated polypropylene "Super Chron" made by Deyu Kokusaku Pulp ■ 306' CPE: Chlorinated polyethylene 1 Super Chron 510'' made by Deyu Kokusaku Pulp ■ Chlorinated rubber "Super Chron" made by Deyu Kokusaku Pulp ■
CR-10" o-tso Epoxidized linseed oil manufactured by Niadeka Argus Chemical ■" ADK CIZER0-t8o "Q-130
Epoxidized soybean oil manufactured by Niadeka Argus Chemical - AD
K CIZER0-130P "E-828: Diglycidyl ether of bisphenol A made by Yuka Shell Epoxy 1 Epicor) 82B' E-807: Bisphenol F made by Yuka Shell Epoxy ■
Diglycidyl ether of

Claims (1)

[Claims] 1), Component (A): 100 parts by weight of oil-modified alkyd Component (B): An acrylic polymerizable monomer that is liquid at 20°C and capable of dissolving the above component (A) 50 to 200 parts by weight Component (C): Chlorinated polymer selected from chlorinated rubber, chlorinated polyethylene, and chlorinated polypropylene with a chlorine content of 60% by weight or more, based on 100 parts by weight of the sum of components (A) and (B) above. , 5 to 50 parts by weight Component (D): epoxy compound 0.05 to 5 parts by weight per 100 parts by weight of the sum of the above components (A) and (C) Component (E): Curing catalyst Appropriate amount of the above (A) , (B), (C), (D) and (E) in the above ratios. 2), an oil-modified alkyd resin in which the oil-modified alkyd of component (A) is modified with an α,β-unsaturated monocarboxylic acid selected from sorbic acid, crotonic acid, and 2-(β-furyl)acrylic acid (however, The coating composition according to claim 1, characterized in that the content of α,β-unsaturated monocarboxylic acid is 0.5 to 30% by weight. 3) The epoxy compound of component (D) is a compound selected from epoxidized soybean oil, epoxidized linseed oil, and diglycidyl ethers of bisphenols having an epoxy equivalent of 165 to 210. A coating composition according to scope 1.