JPH02155949A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition which can be cured in a low- temperature region and can give a very hard film of excellent flexibility by mixing an alkyd resin having a (meth)acryloyl group with a polymerizable monomer and a cure accelerator. CONSTITUTION:29.999-97pts.wt. drying or semi-drying oil-modified alkyd resin having an acryloyl group and/or a methacryloyl group [e.g. a product obtained by effecting an addition reaction of the residual acid groups of an alkyd resin with glycidyl (meth)acrylate ethylene isocyanate] is mixed with 2-70pts.wt. polymerizable monomer and 0.001-10pts.wt. cure accelerator in a total amount of 100pts.wt. In this way, a resin composition which can be suitably cured in a relatively low temperature range from room temperature to 100 deg.C and can give a film excellent in hardness, flexibility, solvent resistance, chemical resistance, corrosion resistance, stain resistance, build and gloss can be obtained.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to novel and useful resin compositions.

More specifically, the present invention comprises an alkyd resin into which a (meth)acryloyl group has been introduced, a polymerizable monomer, and a curing accelerator as essential components. The present invention relates to a resin composition suitable for curing.

[Conventional technology]

As part of energy saving measures, or
As part of our efforts to coat large vehicles and large industrial machinery where it is difficult to increase the baking temperature, we have developed a resin system that can be cured at low temperatures and that exhibits satisfactory coating performance. Next time.

However, in the case of aminoalkyd resins, which are one of the typical examples of such resin systems, in order to improve low-temperature curability, it is basically necessary to add monoacid ``metal'' as a curing catalyst from outside. However, such systems often have problems with conventional resin-based systems, such as corroding the metals being coated or providing coatings that lack the properties of hardness and flexibility. naturally had its limits.

Separately, attempts have been made to combine alkyd resins or anhydrous maleic modified resins with polymerizable monomers, but in either case, it is difficult to achieve a sufficient balance between curability and coating performance. The reality is that there is no such thing.

[Problem to be solved by the invention]

However, in view of the various drawbacks and problems in the prior art as described above, the present inventors have conducted intensive studies to find a resin system that can be cured in a relatively low temperature range. A novel resin system that uses a so-called specific modified alkyd resin into which a specific functional group called a (meth)acryloyl group is introduced is:
The shortcomings and problems of conventional resin systems can be eliminated and solved; that is, they can be cured sufficiently at a relatively low temperature range from room temperature to 100C, and can be cured at a temperature of 10,000 yen, giving a very hard coating film. It provides a coating film with excellent flexibility.
So to speak, it was a great feat for the inventors to discover that the present invention exhibits similar behavior, and thus completed the present invention.

[Means to solve the problem]

In other words, the present invention uses (semi-)drying oil-modified alkyd resin (A) into which (meth)acryloyl groups are introduced as an essential component.
) and 29.999 to 97% by weight of polymerizable monomers (B
) and 0.001% of curing accelerator (C).
~10% by weight of these (A), (B) and (
It is an object of the present invention to provide a useful resin composition which contains the three components C) in a total amount of 100% by weight and has a number of excellent characteristics as described below.

Here, the (semi)drying oil-modified alkyd resin (4) into which the (meth)acryloyl group has been introduced is prepared by adding (meth)acryloyl The easiest method is to introduce a group, and the present inventors particularly recommend this modification method.

That is, in preparing the modified alkyd resin (A), first, the alkyd resin, which can also be called the base material, is
It can be prepared by a known method such as an alcohol exchange method, a fatty acid method or an acid exchange method, or by making full use of a solvent method or a melting method.

At that time, in order to promote the alcohol exchange reaction and esterification reaction, it is also possible to use a known and commonly used alcohol exchange catalyst or esterification reaction catalyst, respectively.

Used in the preparation of alkyd resins, respectively:
Typical alcohol components include ethylene glycol, glopyrendalicol, neo(/tyl glycol, glycerin, trimethylolethane, trimethylolethane 47, i or metaerythritol), and typical acid components include Examples include (anhydrous) phthalic acid, inphthalic acid, niphthalic acid, (anhydrous) maleic acid,
fumaric acid, itaconic acid, succinic acid or anopic acid,
or benzoic acid or p-tart-butylbenzoic acid. Typical (semi-)drying oils include linseed oil, tung oil, safflower oil, dehydrated castor oil, cottonseed oil, soybean oil, or rice bran oil. etc., and these thermopolymerized oils can also be used.

In addition, when using the fatty acid method, fatty acids constituting various oils such as fried oils and tall oil fatty acids can also be used.

Next, methods for modifying the alkyd resin thus obtained with (meth)acryloyl groups include adding glycidyl IL/(meth)acrylate to the remaining acid groups of the alkyd resin, or adding (meth)acrylate to the hydroxyl groups in the alkyd resin.
Typical methods include adding acrylate ethylene incyanate or adding anhydrous (meth)acrylic acid to the hydroxyl group in the alkyd resin, but the present invention is limited only to these methods. Rather, it is characterized by the use of the obtained modified alkyd resin (A)'.

In addition, the above-mentioned polymerizable monomers (barrels) have at least one polymerizable unsaturated double bond in one molecule and have a boiling point of 150°C or higher at normal pressure, preferably 200°C.
The above compounds are referred to, but the most representative ones are t'Rf, ethylene glycol,
diethylene glycol or polyethylene glycol, propylene glycol, diethylene glycol or
) mono- or tetra(meth)acrylates of various polyhydric alcohols such as trimethylol ethane, trimethylol propane, glycerin or pentaerythritol; glycerin, trimethylol ethane, trimethylol ethane or pentaerythritol; In particular, functional monomers having an allyl group such as mono- or tetraallyl ether, diallyl phthalate, diallyl fumarate or tetraallyloxyethane of polyhydric alcohols having a valence of 3 or more; or lataryl (meth)acrylate, 2-ethylhexyl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, glycitul (meth)acrylate, p-methoxyethyl ( meta) acrylate,
Hydroxyalkyl (meth)acrylate, dimethyl itaconate, soethyl itaconate, dibutyl itaconate, dioctyl itaconate, dibutyl fumarate or dibutyl maleate.

These various polymerizable monomers may be used alone, or two
Of course, 11 or more may be used in combination.

When the amount of the polymerizable monomers used is less than 2% by weight based on the total amount of the above-mentioned three essential components constituting the composition of the present invention, the resulting resin composition is sufficiently crosslinked. On the other hand, if it exceeds 70% by weight, the monomers may remain unreacted, or homopolymers may be formed, resulting in insufficient Since it becomes difficult to obtain a film with good performance, the amount of the monomers used is 2 to 70% by weight based on the total amount of the three essential components.
It is appropriate to fall within the following range.

Furthermore, to exemplify only typical curing accelerators, organic acids such as so-called metal soaps, such as fatty acids such as naphthenic acid or octylic acid, cobalt, manganese, sericum, lead, and zolconicum. or salts with metal elements such as tin; amines such as dimethylaniline, dimethyltoluidine, and N-ethyltoluidine; and amines such as ethanolamine; and various alcoholades such as titanium alcoholade or aluminum alcoholade, among others. , it is recommended to use metal soaps.

The curing accelerator (the amount used is o, based on the total amount of the three essential components constituting the composition of the present invention)
A suitable range is from ooi to -10% by weight.

If it is less than 0.001% by weight, the curing of the resulting resin composition may not proceed sufficiently, while if it exceeds 10% by weight, the adhesion, water resistance, etc. of the resulting film may be affected. Both of these methods are undesirable, since they lead to problems such as poor quality and coloring of the resin composition.

The thus obtained resin composition of the present invention can be put to practical use as it is without adding a diluent, but as a means of improving workability, it can be put to practical use in a form diluted with an organic solvent. You can also donate.

Such organic solvents include aromatic hydrocarbons such as toluene or xylene; ketones such as acetone, methyl ethyl lactone, methyl imbutyl ketone or cyclohexanone; esters such as ethyl acetate or n-butyl acetate; methanol, Typical examples include alcohols such as inglopanol or n-butanol; and petroleum hydrocarbons such as mineral spirits.

The resin composition of the present invention is characterized in that it can be easily and sufficiently cured even at room temperature.

In addition, the resin composition of the present invention has solvent resistance, chemical resistance,
It has excellent corrosion resistance, stain resistance, durability, and gloss, as well as excellent hardness and flexibility. In addition, in the present invention, baking hardening at temperatures exceeding 100°C is never excluded. Of course, this is not the case.

The composition of the present invention can be widely used as a paint, an adhesive, a molding material, etc., but it is especially suitable for use as a paint.

As described above, when using the composition of the present invention as a paint, various organic or inorganic pigments, various silicone-based or acrylic polymer-based paint surface conditioners, epoxy resin-based plasticizers, and ultraviolet rays are required. Known and commonly used additives for paints, such as absorbents, can be used as appropriate.

The resin composition of the present invention can be applied to gray paint, brush amount 9 paint,
Conventional coating methods such as dip coating or roller coating can be applied, and the applications, especially for coatings, include floors, wood, building materials, metals, glass or automobile repair, light electrical applications, etc. This is a revolutionary product that can be widely used in large vehicles and large industrial machinery.

In addition, one essential component of the composition of the present invention is the following (half)
The content of (meth)acryloyl groups in the drying oil-modified alkyd resin (A) is as follows:
7' per 1,000 grams? A range of +90.1 to 6, preferably 0.5 to 5 is appropriate.

If the number is less than 0 or 1, the number of so-called grafting points at which the above-mentioned polymerizable monomers (B) can be grafted to this (meth)acryloyl group will inevitably be reduced, and therefore, the present invention This is because it becomes difficult to obtain a sufficient effect.On the other hand, if the number exceeds 6, it becomes difficult to obtain a flexible film.

Further, the oil length of the (semi-)drying oil-modified alkyd resin (A) is suitably within the range of 5 to 80 inches.

If the oil length is less than 5%, the production of peroxide tends to decrease due to the absorption of oxygen from the air, which results in poor curing properties of the resulting resin composition.
If it exceeds 0%, it may become difficult to design the (semi-)drying oil-modified alkyd resin to meet the purpose of the present invention, and the molecular weight may be too high! 7 F'<
(2) In addition, the drying properties and low curing properties of the film deteriorate, so both are unfavorable.

- The suitable oil length range for the layer is 10-60%.

〔Effect of the invention〕

As mentioned above, the resin composition of the present invention has the advantage that it is suitable for curing at a relatively low temperature range from room temperature to 100'C, and secondly, it has excellent hardness. In addition, it has the unique effect of being easily flexible, and also has bath agent resistance, chemical resistance,
The present invention far exceeds the prior art in that it provides a film with excellent corrosion resistance, stain resistance, durability, and gloss.

〔Example〕

Next, the present invention will be explained based on Reference Examples, Examples and Comparative Examples.
The layer will be explained in detail. In the following, all parts and parts are based on weight unless otherwise specified.

Reference Example 1 [Preparation example of (meth)acryloyl group-introduced n-alkyd resin (A)] In a four-way flask equipped with a stirrer, thermometer, air condenser, and reflux condenser, 500 parts of linseed oil and glycerin were added. Charge 102.6 parts of Resurge and 0.125 parts of Resurge, carry out a transesterification reaction at 240°C, cool it, and add 33.8 parts of pentaerythritol, 36.9 parts of glycerin, and 372 parts of phthalic anhydride. .0 part of gold was added, the temperature was raised to 220-230°C, and in a nitrogen stream,
The reaction was carried out until the acid value reached 45, the temperature was lowered to 130°C, 0.1 part of monohydroquinone and 100 parts of glycitul methacrylate were added, stirred well, and according to the table, the mixture was kept at the same temperature for 4 hours. After the reaction, xylene 730
A viscous solution of the desired resin with a non-volatile content of 60% and an acid value of 10 was obtained by adding 1.5 parts of the solution and cooling. Hereinafter, this will be abbreviated as resin (A-1).

Reference Example 2 (same as above) In a reaction vessel similar to Reference Example 1, 390 parts of soybean oil fatty acid, 190 parts of glycerin, 300 parts of phthalic anhydride, and 90 parts of ethylene glycol were charged, and heated to 220°C over 5 hours. Raise the temperature and keep it at the same temperature to react until the acid value becomes 10 or less, then lower the temperature to 140"C,
To this, 250 parts of xylene was added, and the mixture was rapidly cooled to 70°C. Then, 0.1 part of hydroquinone and 0.200 parts of methacrylate ethyl isocyanate were added, and the reaction was continued by keeping at the same temperature for 2 hours. The temperature was raised to 80°C and maintained at this temperature for an additional 5 hours to continue the reaction,
To this, 200 parts of le-butanol and 3 parts of xylene
50 parts were added to obtain a viscous solution of the target resin with a nonvolatile content of 60%. Hereinafter, this will be abbreviated as resin (A-2).

Reference Example 3 (same as above) Into a reaction vessel similar to Reference Example 1, 300 parts of dehydrated castor oil was charged, the temperature was raised to 270°C, kept at the same temperature for 3 hours, and then 80 parts of pentaerythritol and 0% of Resurge were added. After adding .1 part and keeping it at 250℃ for 1 hour,
Cool to 00°C or below, add 44 parts of antaerythitol, 110 parts of ethylene glycol, and 75 parts of neopentyl glycol, maintain at 180°C for 2 hours, and then raise to 230°C over 2 hours. After heating and reacting until the acid value reached 10, it was cooled to 100°C, 0.2 parts of hydroquinone and 500 parts of methacrylic anhydride were added, kept at 150°C for 4 hours, and then cooled. After washing with water, excess methacrylic anhydride and free methacrylic acid were removed by vacuum distillation.

Next, 600 parts of xylene and 200 parts of i-butanol were added to the reaction vessel to obtain a viscous solution of the desired resin having a non-volatile content of 60% and an oil length of 25%. Hereinafter, this will be abbreviated as resin (A-3).

Reference Example 4 [Preparation example of alkyd resin containing no (meth)acryloyl group] In a reaction vessel similar to Reference Example 1, 47 parts of coconut oil fatty acid,
47 parts of pentaerythritol, 6 parts of maleic anhydride
5 parts of ethylene glycol, 31 parts of ethylene glycol, 77 parts of fumaric acid, and 540 parts of phthalic anhydride were heated to 180°C while stirring well, and kept at the same temperature for 2 hours.
The temperature was further raised to 230°C over 2 hours, and maintained at the same temperature until the acid value reached 2. Then, 250 parts of xylene was added thereto, and the temperature was lowered to 140°C with stirring. Add 23 parts of acid, hold at the same temperature for 2 hours, cool to below 10.0°C, then add 200 parts of n-butanol and 450 parts of xylene, with a non-volatile content of 60 parts. A viscous control resin solution with an oil length of 5 inches was also obtained. Hereinafter, this will be abbreviated as resin (A'-1).

Reference Example 5 (same as above) Into a reaction vessel similar to Reference Example 1, 340 parts of soybean oil fatty acid, 200 M of pentaerythritol, 150 parts of -11-terene glycol, and 420 parts of phthalic anhydride were charged, and the mixture was heated for 5 hours. The temperature was raised to 230℃, and the acid value was 10.
Hold at the same temperature until
70 parts were added to form a viscous control resin solution with 60% non-volatile content. Hereinafter, this will be abbreviated as resin (A'-2).

Examples 1 to 4 and Comparative Examples 1 and 2 The resin obtained in each reference example, polymerizable monomers, and curing accelerator were added to the first
A resin composition of the present invention and a control resin composition were obtained by blending the resin compositions in the proportions shown in Table 2 or Table 2.

Next, each resin composition was dried and cured on the one hand under the baking conditions shown in Table 1 for baking drying, and on the other hand, it was dried and cured by being left at 25°C for room temperature drying. and they are shown in Table 2.

After evaluating the performance of each cured film,
The consistent results shown in Tables 1 and 2 were obtained.

The performance of each film was evaluated according to the following procedure.

Hardness: The hardness of the ship's end at which the paint film is no longer damaged.

Blistering resistance 4: The appearance of the film after a 96-hour test on blister 1x at 50°C was visually judged.

Water resistance: Visually judge the appearance of the film after immersed in water for 96 hours.

Solvent resistance: Visually judge the appearance of the film after 50 2-pin tests with xylene.

Acid resistance: Visually judge the appearance of the film after a 24-hour cup test with a 5% sulfuric acid aqueous solution.

Alkali resistance: Visually judge the appearance of the film after 24 hours of Kagtist with 5% sodium hydroxide aqueous solution.

Among these various performances, the evaluation criteria for the above-mentioned nine blister resistance, water resistance, solvent resistance, acid resistance, and alkali resistance are as follows: 00... Completely no luster No O...The gloss is hardly extinguished Δ...The gloss fades a little ×...The gloss disappears completely or the film dissolves.

Stain resistance: Comprehensive evaluation based on whether or not each color remains after 24 hours of coloring with red, black, and colored magic ink, and lipstick. .

O...None of the colors remain on the paint film@...
...Almost none of the colors remain on the paint film△...Depending on the color, some colors remain clearly on the paint film×... ...All four colors remain on the paint film.

Shock resistant near-h Yupon type, concave, with 1/2 inch notch, load = sooy.

O...40I:In or more Δ・・・・・・Within the range of 15 to 35 sub ×・・・・・・10c+++ or less Erichsen value: by Erichsen extruder.

○・・・7■ or more@・・・4- or more but less than 71m Δ・・・2m+ or more 4■ Unfinished X・・・less than 2■／ / / / As is clear from the results in Tables 1 and 2, the resin composition of the present invention has excellent hardness and flexibility both when dried at room temperature and when dried by forced drying or baking. Not only does it have the unique effect of being excellent in terms of performance, but it also provides a coating film that is well-balanced in terms of solvent resistance, chemical resistance, moisture resistance, water resistance, and gloss.

Representative Patent Attorney Katsutoshi Takahashi

Claims (1)

[Scope of Claims] 1. Drying oil or semi-drying oil-modified alkyd resin (A
) and 29.999 to 97% by weight of polymerizable monomers (B
) and 0.001% of curing accelerator (C).
~10% by weight, and (A), (B)
and (C), wherein the total amount of the three components is 100% by weight. 2. The resin according to claim 1, wherein the drying oil or semi-drying oil-modified alkyd resin (A) into which an acryloyl group and/or methacryloyl group has been introduced has an oil length of 5 to 80%. Composition. 3. The number of drying oil or semi-drying oil-modified alkyd resin (A) into which the above-mentioned acryloyl group and/or methacryloyl group is introduced is within the range of 0.1 to 6 per 1,000 g of the alkyd resin (A). The resin composition according to claim 1, which has an acryloyl group and/or a methacryloyl group. 4. The polymerizable monomers (B) described above are compounds that have at least one polymerizable unsaturated double bond in one molecule and have a boiling point of at least 200°C under normal pressure. , the resin composition according to claim 1.