JP2814504B2 - Resin composition - Google Patents

Description

The present invention relates to a novel and useful resin composition.

More specifically, the present invention comprises an alkyd resin having a (meth) acryloyl group introduced therein, a polymerizable monomer, and a curing accelerator as essential components, in particular, curing at a low temperature range. The present invention relates to a resin composition suitable for:

[Prior art] Hardening in the low-temperature region has been possible as part of energy saving measures or as a measure for painting large vehicles and large industrial machines where it is difficult to raise the baking temperature. Development of a resin system exhibiting satisfactory coating performance has been carried out.

However, in the case of aminoalkyd resins, which are one of the typical examples of such resin systems, in order to enhance low-temperature curability, "acids" as a so-called curing catalyst are basically added from outside. However, such a system is obtained, and the conventional resin-based system is not provided so as to corrode the metal to be coated or to give only a coating film lacking a balance between hardness and flexibility. There was naturally a limit.

Separately, attempts have been made to combine polymerizable monomers with an alkyd resin or a maleic anhydride-modified resin, but in all cases, the balance between curability and coating film performance was sufficiently achieved. The fact is that it has not been done.

[Problems to be solved by the invention]

However, the present inventors, in view of the existence of various disadvantages or problems in the prior art as described above, as a result of intensive studies to find a resin system that can be cured in a relatively low temperature range, A novel resin system using a so-called specific modified alkyd resin in which a specific functional group called (meth) acryloyl group is introduced has been solved at once to solve the drawbacks or problems of the conventional resin system. That is, it hardens sufficiently in a relatively low temperature range from room temperature to 100 ° C., and gives a very hard coating film, while giving a coating film excellent in flexibility. The present invention has been completed by finding out that they show the same behavior as "out-of-office work".

[Means for solving the problem]

That is, the present invention comprises, as essential components, 29.999 to 97% by weight of a (semi) dry oil-modified alkyd resin (A) into which a (meth) acryloyl group is introduced, and 2 to 2 parts of a polymerizable monomer (B). 70% by weight and 0.001 to 10% by weight of curing accelerator (C)
(A), (B) and (C) in a total amount of 100% by weight to provide a useful resin composition having various excellent characteristics as described below. What you want to do.

Here, the preparation of the (semi) dry oil-modified alkyd resin (A) having the (meth) acryloyl group introduced thereinto is carried out by introducing a (meth) acryloyl group into an alkyd resin prepared in advance according to a known and conventional method. It is easiest to do this, and we particularly recommend such a modification method.

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

At that time, in order to promote the alcohol exchange reaction and the esterification reaction, a known and commonly used alcohol exchange catalyst and an esterification reaction catalyst can be used, respectively.

Typical examples of the alcohol component used in preparing the alkyd resin include ethylene glycol, propylene glycol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol. Typical acid components include (phthalic anhydride), isophthalic acid, elephthalic acid, (anhydride) maleic acid, fumaric acid, itaconic acid, succinic acid or adipic acid, or benzoic acid or p-tert-butylbenzoic acid. There are acids, etc., and typical examples of (semi) drying oils include linseed oil, tung oil, safflower oil, dehydrated castor oil, cottonseed oil, soybean oil, rice bran oil, and the like. Can also be used.

In the case of the fatty acid method, fatty acids constituting various oils as described above and tall oil fatty acids can also be used.

Then, the alkyd resin thus obtained can be modified with (meth) acryloyl groups by adding glycidyl (meth) acrylate to the remaining acid groups of the alkyd resin, or by adding (meth) acrylate ethylene isocyanate to hydroxyl groups in the alkyd resin. Or the addition of anhydrous (meth) to the hydroxyl groups in the alkyd resin
Typical methods include the method of adding acrylic acid, but the present invention is not limited to only these methods, and is characterized by using the obtained modified alkyd resin (A). .

The polymerizable monomer (B) has at least one polymerizable unsaturated double bond in one molecule and has a boiling point at normal pressure of 150 ° C. or higher, preferably 200 ° C. ° C
The above compounds are referred to, but among them, if only typical ones are exemplified, ethylene glycol, diethylene glycol or polyethylene glycol, propylene glycol, dipropylene glycol or polypropylene glycol glycol, butylene glycol, hexanediol, neopentyl glycol Mono-, di-, tri- or tetra (meth) acrylates of various polyhydric alcohols such as trimethylolethane, trimethylolpropane, glycerin or pentaerythrol; glycerin, trimethylolethane, trimethylolpropane or pentaerythritol In particular, tri- or higher polyhydric alcohols such as mono-, di-,
Functional monomers having an allyl group such as tri- or tetraallyl ether, diallyl phthalate, diallyl fumarate or tetraallyloxyethane; butadiene,
Oligomers such as pentadiene or neoprene; or lauryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth)
Acrylate, p-methoxyethyl (meth) acrylate, hydroxyalkyl (meth) acrylate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, dioctyl itaconate, dibutyl fumarate or dibutyl maleate.

These various polymerizable monomers may be used alone,
It goes without saying that two or more kinds may be used in combination.

When the amount of the polymerizable monomer used is less than 2% by weight based on the total amount of the essential three components constituting the composition of the present invention, the obtained resin composition is sufficiently crosslinked. However, if the content exceeds 70% by weight, the monomers remain unreacted or homopolymers are formed, resulting in sufficient performance. Since it becomes difficult to obtain a film having the following, the amount of the monomers used is 2 to 70% by weight based on the total amount of the essential three components.
A range within is appropriate.

Furthermore, if only a typical one is exemplified as a curing accelerator, it is called a so-called metal soap.
Salts of an organic acid such as a fatty acid such as naphthenic acid or octylic acid with a metal element such as cobalt, manganese, cerium, lead, zirconium or tin; amines such as dimethylaniline, dimethyltoluidine, N-ethyltoluidine or diethanolamine; Alternatively, various alcoholates such as titanium alcoholate or aluminum alcoholate may be used, and among them, metal soaps are preferred.

The amount of the curing accelerator (C) used is as follows.
With respect to the total amount of the three essential components constituting the composition of the present invention
A range of 0.001 to 10% by weight is appropriate.

When the amount is less than 0.001% by weight, the obtained resin composition hardly hardens sufficiently, and on the other hand, 10% by weight
In the case where it exceeds 2, the adhesion and water resistance of the resulting film are poor, and further, such disadvantages as coloring of the resin composition appear, so that neither is preferred.

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

Such organic solvents include aromatic hydrocarbons such as toluene or xylene; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; ester systems such as ethyl acetate or n-butyl acetate; methanol, isopropanol or n- Representative examples are alcohols such as butanol; and petroleum hydrocarbons such as mineral spirits.

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

In addition, the resin composition of the present invention can be dried at room temperature, forced drying, or baking drying to obtain a film having a solvent resistance, chemical resistance, corrosion resistance, and stain resistance. Excellent in meat durability and gloss,
Moreover, it has excellent hardness and flexibility.

In the present invention, baking hardening at a temperature exceeding 100 ° C. is, of course, not necessarily excluded.

The composition of the present invention can be widely used as an adhesive or a molding material, in addition to a paint, but is particularly preferably used as a paint.

As described above, when the composition of the present invention is used as a coating material, various organic or inorganic pigments, various coating surface preparations of silicone or acrylic polymer, epoxy resin plasticizer or ultraviolet absorber Known and commonly used additives for coatings, such as, for example, can be used as needed.

The resin composition of the present invention can be applied by a usual coating method such as spray coating, brush coating, dip coating or roller coating, and its use, particularly, for coating, flooring, woodworking, building material, metal It is an epoch-making product that can be widely used in large vehicles, large industrial machines, etc., including those for automobiles, plastics or automobile repairs, and light electric appliances.

The content of the (meth) acryloyl group in the sloping (semi) dry oil-modified alkyd resin (A), which is a position essential component of the composition of the present invention, is determined per 1,000 grams of the modified alkyd resin (A). 0.1-6, preferably 0.5
A range of ５5 is appropriate.

When the number is less than 0.1, the polymerizable monomer (B) which is tilted forward can be grafted to the (meth) acryloyl group. This is because it is difficult to sufficiently obtain the effect, while if the number exceeds six, it is difficult to obtain a flexible film.

The oil length of the (semi) dry oil-modified alkyd resin (A) is suitably in the range of 5 to 80%.

When the oil length is less than 5%, oxygen in the air is taken in, and the generation of peroxide is apt to be reduced, so that the curability of the obtained resin composition becomes inferior.
If it exceeds 80%, it becomes difficult to design the (semi) dry oil-modified alkyd resin so as to meet the purpose of the present invention, and it becomes difficult to increase the molecular weight,
As a result, the drying property of the film and the low curing method are deteriorated.

 A more suitable oil length range is 10-60%.

〔The invention's effect〕

As described above, the resin composition of the present invention firstly has the advantage of being suitable for curing in a relatively low temperature region from room temperature to 100 ° C., and then has excellent hardness. It also has a unique effect of being excellent in flexibility, and gives a film that is also excellent in solvent resistance, chemical resistance, corrosion resistance, stain resistance, stickiness and gloss. Thus, the present invention goes far beyond the prior art.

〔Example〕

Next, the present invention by reference examples, examples and comparative examples,
This will be described more specifically. In the following, all parts and percentages are by weight unless otherwise specified.

Reference Example 1 [Preparation Example of Alkyd Resin (A) Introduced with (Meth) acryloyl Group] In a four-necked flask equipped with a stirrer, a thermometer, an air condenser and a reflux condenser, 500 parts of linseed oil was added. Charge 102.6 parts of glycerin and 0.125 part of litharge,
After transesterification at 240 ° C, cool,
Add 33.8 parts of pentaerythritol, 36.9 parts of glycerin and 372.0 parts of phthalic anhydride, raise the temperature to 220 to 230 ° C, and in a nitrogen stream, conduct the reaction until the acid value becomes 45, and cool to 130 ° C. Then, 0.1 part of hydroquinone and 100 parts of glycidyl methacrylate were added, and the mixture was allowed to react at the same temperature for 4 hours while stirring well. Then, 730 parts of xylene was added and cooled, and the nonvolatile content was 60%. In addition, a viscous target resin solution having an acid value of 10 was obtained. Hereinafter, this is abbreviated as resin (A-1).

Reference Example 2 (same as above) In a reaction vessel similar to Reference Example 1, 390
Parts, 190 parts of glycerin, 300 parts of phthalic anhydride and 90 parts of ethylene glycol are charged and 220 ° C. over 5 hours
The temperature was raised until the acid value became 10 or less, and the reaction was maintained at the same temperature.Then, the temperature was lowered to 140 ° C., and 250 parts of xylene was added, and the mixture was rapidly cooled to 70 ° C. 0.1 part of hydroquinone and 200 parts of methacrylate ethyl isocyanate are added, and the reaction is continued at the same temperature for 2 hours, and then heated to 80 ° C. and further maintained at this temperature for 5 hours to continue the reaction. Here, 20 of n-butanol
0 parts and 350 parts of xylene were added to obtain a viscous target resin solution having a nonvolatile content of 60%. Hereinafter, the resin (A)
-2).

Reference Example 3 (same as above) In a reaction vessel similar to that of Reference Example 1, 300 parts of dehydrated castor oil was charged, heated to 270 ° C., kept at the same temperature for 3 hours, and then charged with 80 parts of pentaerythritol and 0.1 part of litharge.
After maintaining at 250 ° C. for 1 hour, the mixture was cooled to 200 ° C. or lower, and 44 parts of pentaerythritol, 110 parts of ethylene glycol and 75 parts of neopentyl glycol were added, and the mixture was heated to 180 ° C. for 2 hours. 230 ℃ over 2 hours after holding
Temperature until the acid value reaches 10, then 100
C., and 0.2 parts of hydroquinone and 500 parts of methacrylic anhydride were added. The mixture was kept at 150.degree. C. for 4 hours, cooled, washed with water, and distilled under reduced pressure to remove excess methacrylic anhydride and free radicals, respectively. Methacrylic acid was removed.

Next, 600 parts of xylene and 200 parts of n-butanol were added to the reaction vessel to obtain a nonvolatile matter of 60%, and
A viscous target resin solution having an oil length of 25% was obtained. Hereinafter, this is 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 was added.
47 parts of pentaerythritol, 65 parts of maleic anhydride,
Add 31 parts of ethylene glycol, 77 parts of fumaric acid and 540 parts of phthalic anhydride, raise the temperature to 180 ° C. with good stirring, maintain the temperature for 2 hours, and then add 23 hours over 2 hours.
After raising the temperature to 0 ° C. over 2 hours and maintaining the same temperature until the acid value becomes 2, 250 parts of xylene was added thereto,
The temperature was lowered to 140 ° C. with stirring, 23 parts of maleic anhydride was added, the temperature was maintained for 2 hours, and the temperature was cooled to 100 ° C. or less. Then, 200 parts of n-butanol and 450 parts of xylene were added. Thus, a viscous control resin solution having a nonvolatile content of 60% and an oil length of 5% was obtained. Hereinafter, the resin (A ′)
Abbreviated as -1).

Reference Example 5 (same as above) In a reaction vessel similar to Reference Example 1, 340
Parts, 200 parts of pentaerythritol, 150 parts of ethylene glycol and 420 parts of phthalic anhydride, raise the temperature to 230 ° C over 5 hours, keep the same temperature until the acid value reaches 10, then cool. Then, 670 parts of xylene was added to obtain a viscous control resin solution having a nonvolatile content of 60%. Hereinafter, this is abbreviated as resin (A'-2).

Examples 1 to 4 and Comparative Examples 1 and 2 The resins obtained in the respective reference examples, the polymerizable monomers, and the curing accelerator were blended in the proportions shown in Table 1 or Table 2. Thus, a resin composition of the present invention and a resin composition for control were obtained.

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

When the performance of each cured film was evaluated, the results shown in Tables 1 and 2 were obtained.

The evaluation of the performance of each film is based on the following procedure.

Hardness: The hardness of the pencil at which the coating is no longer damaged.

Blister resistance: The appearance of the film after a 96-hour test in a blister box at 50 ° C. was visually judged.

Water resistance: The appearance of the film after immersion in water for 96 hours was visually judged.

Solvent resistance: Visual evaluation of the appearance of the film after 50 rubbing tests with xylene.

Acid resistance: The appearance of the film was visually determined after a cup test with a 5% aqueous sulfuric acid solution for 24 hours.

Alkali resistance: The appearance of the film was visually determined after a 24 hour cup test with a 5% aqueous sodium hydroxide solution.

Among these various performances, the above-mentioned blister resistance,
The criteria for evaluation in water resistance, solvent resistance, acid resistance and alkali resistance are as follows.

Stain resistance: Colored with red, black and blue magic inks and lipstick, wiped 24 hours after coloring, and evaluated comprehensively by the presence or absence of residual color.

Impact resistance: DuPont type, concave, 1/2 inch notch, load = 500g.

…: 40 cm or more Δ: within the range of 15 to 35 cm ×: 10 cm or less Erichsen value: Depends on the Erichsen extruder.

As is clear from the results shown in Tables 1 and 2, the resin composition of the present invention is excellent in hardness and flexible in both cases of normal temperature drying, forced drying and baking drying. In addition to exhibiting the unique effect of being excellent in the properties, it also provides a coating film having a good balance of solvent resistance, chemical resistance, moisture / water resistance, gloss and the like.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08G 63/47 C08G 63/47

Claims (4)

(57) [Claims] (1) 29.999 to 97% by weight of a dry oil or semi-dry oil-modified alkyd resin (A) into which an acryloyl group and / or a methacryloyl group are introduced, and 2 to 70% by weight of a polymerizable monomer (B). % And 0.001-1 of curing accelerator (C)
0% by weight, and the total amount of the three components (A), (B) and (C) is 100% by weight. 2. The method according to claim 1, wherein the dry oil or semi-dry oil-modified alkyd resin (A) into which the acryloyl group and / or methacryloyl group has been introduced has an oil length of 5 to 80%. The resin composition as described in the above. 3. The drying oil or semi-drying oil-modified alkyd resin (A) into which the acryloyl group and / or methacryloyl group has been introduced is 1,000% of the alkyd resin (A).
The resin composition according to claim 1, having an acryloyl group and / or a methacryloyl group in a range of 0.1 to 6 per gram. 4. The polymerizable monomer (B) has at least one polymerizable unsaturated double bond in one molecule and has a boiling point of at least 200 ° C. under normal pressure. The resin composition according to claim 1, which is a compound.