JPS58222158A - Coating resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. giving cured films excellent in weatherability, solvent resistance, flexibility, etc. to flexible substrates, by incorporating a particular polyester-modified acrylic resin, isocyanate by incorporating a particular polyester-modified acrylic resin, isocyanate compd., and amino resin. CONSTITUTION:A coating compsn. which consists of a hydroxyl group-contg. polyester-modified acrylic resin given by polymn. of an acrylic monomeric mixt. (b) in the presence of an epsilon-caprolactone-modified unsatd. polyester polyol having a hydroxyl value of 50-300 (a) with an isocyanate compd. or amino resin, and which is characterized in that the wt. ratio of compd. a to mixt. b is 10/90-90/ 10, mixt. b cnsists of 1-40pts.wt. hydroxyl group-contg. acrylic monomer, 30- 99pts.wt. (meth)acrylate other than hydroxyl group-contg. acrylic monomer, and 0-60pts.wt. other monomer copolymerizable therewith, and the total amt. of mixt. b is 100pts.wt.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a VK covering resin composition, and more particularly to a composition comprising a hydroxyl group-containing polyester-modified acrylic resin and an isocyanate compound or an amino resin.

Recently, the range of coating base materials has gradually expanded from metal bases such as iron to flexible materials such as plastics and rubber, and as a result, the number of coatings on the latter materials has increased significantly. Furthermore, there is a demand for flexible covering materials or coating materials used therein.

In this way, in order to obtain a coating material or coating material that provides a flexible cured coating film, as a coating film-forming resin component,
Acrylic polyols with low glass transition points, polyester polyols obtained from polyhydric alcohols, polyhydric carboxylic acids, and the like are effective.

However, although cured coatings obtained using such acrylic polyols with low glass transition points and isocyanate compounds or amino resins have flexibility, they do not have sufficient hardness and solvent resistance, and they are not compatible with polyester polyols. Cured coating films obtained using isocyanate compounds or amino resins do not have sufficient weather resistance or flexibility at low temperatures.

As described above, it is unlikely that a cured coating film that satisfies all of the weather resistance, solvent resistance, and flexibility can be obtained from the coating resin composition that has the above-mentioned combination.

However, the present inventors have developed a coating resin composition that can provide a cured coating film with excellent weather resistance, solvent resistance, and flexibility on flexible substrates such as plastics or rubber. As a result of intensive study to obtain specific polyester-modified acrylic resin and isocyanate...
The inventors have discovered that a resin composition comprising a compound and an amino resin is suitable for these purposes, and have completed the present invention.

That is, the present invention provides an acrylic monomer mixture (1-1) in the presence of an 8-caprolactone modified unsaturated polyester polyol (1-1) having a hydroxyl value of 50 to 300.
It is composed of a polyester-modified acrylic resin (1) having a hydroxyl group, obtained by polymerizing 2>, and a curing agent component (IT), which is an isocyanate-1 compound (IT-1> or an amino resin (If-2)). , the weight specific force of the polyester polyol N-1) and the monomer mixture (1-2>) is within the range of 0/90 to 90/10, and this monomer mixture (r-2) is 1 to 40 parts by weight of a hydroxyl group-containing acrylic monomer and 30 to 99 parts by weight of a (meth)acrylic acid ester excluding the hydroxyl group-containing acrylic monomer
0 to 6 parts by weight and one other copolymerizable monomer
0 parts by weight, and these monomer mixtures (1-
The present invention provides a coating resin composition in which the total amount of 2) is 100 parts by weight.

The present invention will be explained in detail, but first, the above-mentioned 50 to 300
In order to prepare the ε-caprolactone-modified unsaturated polyester polyol (I-1) having a hydroxyl value, for example, a polyhydric alcohol and a polyhydric carboxylic acid, and further a monoepoxide or a dieboxide are esterified. Then, ε-caprolactone may be added to the resulting polyester polyol having an unsaturated bond, or ε-caprolactone may be added to a polyhydric alcohol in advance, and then a polyhydric carboxylic acid may be added, and then a monoepoxide or A method of esterifying dieboxide or the like may also be used.

Here, typical polyhydric alcohols include ethylene glycol, 1.4-butanediol, 1.6-
Examples of the polyhydric carboxylic acids include hexanediyl, glycerin, trimethylolpropane, and pentaerythritol, but a mixture of these may also be used. , azelaic acid, sebacic acid, decane-1,10-dicarboxylic acid, terephthalic acid, isophthalic acid or phthalic acid (anhydride), which may also be used in the form of a mixture.

In addition to the above-mentioned compounds, examples of such acid components include itaconic acid,
Fumaric acid or maleic acid can be used, and there is no problem in using fatty acids obtained from fats or cores such as soybean oil, coconut oil, castor oil or tall oil in combination with the compounds mentioned above. do not have.

Furthermore, the representative monoepoxides or dieboxides mentioned above each include 1 Cardule E.
(glycidyl ester of persatic acid manufactured by Shell, Netherlands) or other compounds commonly used as epoxy resins.

Using the thus obtained unsaturated polyester polyol (I-1) modified with ε-caprolactone, the above-mentioned hydroxyl group-containing polyester-modified acrylic resin (r)
To prepare this ε-caprolactone-modified unsaturated polyester polyol N-j) and the acrylic monomer mixture (12) in a weight ratio in the range of 10/90 to 90/10, both are mixed in a known and customary manner. If the amount of polyester polyol (1-1) used is lower than 10% by weight, the solvent resistance will deteriorate throughout the year. If the amount increases, the flexibility of the coating film will not be obtained.

Preferably, the weight ratio of these two components is 20/80 to
80/2 (+ range, particularly preferably 30/70~
The range is 70/30.

5- Also, the composition of the acrylic monomer mixture (1-2) is C
is 1 to 40 parts by weight of a hydroxyl group-containing acrylic monomer,
30 to 99 parts by weight of (meth)acrylic acid ester, or 6 parts by weight of other copolymerizable monomers.
0Im may be used in a range up to 1 part, in any case when the total amount of this monomer mixture (1-2) is 10
The composition ratio of each monomer may be determined so that the amount is 0 parts by weight.

The acrylic monomer mixture (1-2) is prepared by dissolving the ε-caprolactone-modified unsaturated polyester polyol (I-1) in an aromatic solvent, an ester solvent, a ketone thread solvent, etc. in advance. The hydroxyl group-containing polyester-modified acrylic resin (r), which is the base resin component of the composition of the present invention, can be obtained by solution polymerization in the presence of a polymerization initiator that generates radicals, but this method is only an example. However, it is by no means limited to this method.

Here, typical examples of the acrylic monomer containing a hydroxyl group include β-hydroxyethyl (meth)acrylate, β-hydroxypropyl (meth)acrylate, and β-hydroxypropyl (meth)acrylate.
-Hydroxyisopropyl (meth)acryle-I or β-hydroxybutyl (meth)acrylate-1, and typical examples of the above (meth)acrylic esters include methyl 6-(meth)acrylate, Ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (
Examples include lauryl meth)acrylate and cyclohexyl (meth)acrylate, and representative monomers that can be copolymerized include styrene, (meth)acrylonitrile, and vinyl acetate. (meth)acrylic acid, fumaric acid, maleic acid,
This does not preclude the use of some monomers having an acid group or a functional group such as a glycidyl group, such as itaconic acid or (methyl)glycidyl (meth)acrylate, and furthermore, dibutyl fumarate, dimethyl ester or dibutyl titanate can be used similarly, and (meth)acrylic acid amide or N-methoxymethyl (meth)acrylamide as a derivative thereof can also be used.

On the other hand, the isocyane-1 compound (11-
Examples of 1) include active compounds such as tolylene diisocyanate or hexamethylene diisocyanate; adducts of these diisoleanates with polyhydric alcohols as described above; or reaction products of 1 mole of water with 3 moles of di-1 isocyanate. Known and commonly used so-called prepolymers having free isocyanate I groups that are reactive with hydrogen can be used, and such compounds (TI
-1) Commercially available products include “Burnock D
-750, 11N-950J (product of Dainippon Ink Chemical Industries) and "Desmodur N" (product of Bayer, West Germany).

Typical crosslinking agents for the amino resin (U-2>) include methylolization of an amino group-containing compound such as melamine, urea, or guanamine with an aldehyde such as formalin, and then further lower aliphatic There are alcohols in which at least two of the methylol groups are etherified, and typical commercially available products include "Beccamin P-138" and "Super Beckamine J-820J".
(The above are Dainippon Ink Chemical Industry products), [Cymel 3
00J (product of American Cyanamid Company), etc.

In order to obtain the composition of the present invention, the base resin component (
The blending ratio of 1) and the crosslinking agent or curing agent component (If) varies depending on the type of the crosslinking agent or curing agent component (II), but is generally as follows.

That is, the polyester-modified acrylic resin (1)
and the amino resin (IT-, 2) have a solid content weight ratio of 9
A range of 0/10 to 60/40 is appropriate; on the other hand,
The blending ratio of this polyester-modified acrylic resin (1) and the isocyanate i/compound (II-1) is determined by the ratio of the number of hydroxyl groups in the former resin (T) to the number of isocyanate groups in the latter compound (n-1). A range of 110.5 to 1/1.5 is appropriate, and flexibility and weather resistance are ensured at this blending ratio.

Recrosslinking agent or curing agent component (II) listed above
The cured coating film obtained using the coating resin composition of the present invention containing as essential components the base resin component of the polyester-modified acrylic resin (1) is extremely flexible,
It has excellent flexibility and impact resistance, especially at low temperatures.
Since the composition of the present invention also has excellent weather resistance and solvent resistance, it can be applied to a wide range of substrates.

For example, it can be applied not only to coating agents for metal coating, but also to flexible materials such as plastics or rubber, and in addition, to wood products or concrete products.

Next, the present invention will be specifically explained using reference examples, examples, comparative examples, applied examples, and comparative applied examples. In the following, unless otherwise specified, all parts and percentages are based on the III standard. .

Reference Example 1 (Preparation example of ε-caprolactone modified unsaturated polyester polyol (+-1)) 37.2 parts of 9-trimethylolpropane, 38.0 parts of phthalic anhydride, 3 parts of maleic anhydride and 5
These were subjected to an esterification reaction using 25.3 parts of EJ, and then 42.8 parts of 8-caprolactone were added to conduct an addition reaction. As a result, an ε-caprolactone-modified unsaturated polyester polyol with a hydroxyl value of 140 was obtained. Obtained.

Thereafter, this polyester polyol was dissolved in 80 parts of Kizilol and 15.2 parts of methyl isobutyl ketone to obtain an ε-caprolactone-modified unsaturated polyester polyol solution with a nonvolatile content of 60.5%. Hereinafter, this will be abbreviated as resin (■-1 to 1).

Reference Example 2 (same as above) 15.6 parts of trimethylolpropane, 36.8 parts of 1,3-butanediol, 9.9 all of phthalic acid, 2 parts of maleic anhydride, and 51.1 parts of adipic acid. The esterification reaction was carried out in the same manner as in Reference Example 1, except that the entire amount was changed to Kijirole as the solvent for the resulting polyester polyol, with a non-volatile content of 60.5%.
A solution of ε-caprolactone modified unsaturated polyester polyol was obtained. Hereinafter, this will be abbreviated as resin (1-1-2).

Example 1 A reactor equipped with a stirrer and a cooler was charged with 50 parts of the resin (1-il) obtained in Reference Example 1 and further 60 parts of doluol, and the temperature inside the reactor was adjusted. The temperature was raised to 100°C.

Then, 7 parts of hestylene, 40 parts of n-butyl methacrylate, 10 parts of n-butyl acrylate and β-
A monomer mixture consisting of 13 parts of hydroxyethyl methacrylate and a solution of 1.5 parts of azobisisobutyronitrile and 0.5 parts of di-tert-butyl peroxide in 20 parts of doluol. was added dropwise over a period of 4 hours, and the temperature was then maintained at the same temperature for 10 hours.
A hydroxyl group-containing polyester-modified acrylic resin with a nonvolatile content of 50.4% and a hydroxyl value of 98 (solid equivalent) was obtained. Hereinafter, this will be abbreviated as resin (1-a).

Then, for 100 parts of this resin (I-a), [
65 parts of Tybake R-820J (titanium oxide manufactured by Ishiya Sangyo ■) was blended and the pigment was dispersed in a sand mill, and then "Super Beckamine 1,117-60" (amino resin manufactured by Dainippon Ink & Chemicals ■) was mixed. 30 parts were added and diluted with thinner to adjust the coating viscosity to obtain the desired coating resin composition.

Example 2 [The amount used was 48 parts of Tybake R-820j, and 29.3 parts of Parnock DN-950J was used instead of [Super Beckamine L, -117-60J]. A coating resin composition was obtained in the same manner as in Example 1.

Examples 3 to 6 and Comparative Example 1.2 Hydroxyl group-containing polyester modified acrylic resin (1-b) and ( I-c) and an acrylic resin (I'-a) for comparison were prepared.

Thereafter, the same formulations as in Example 1 and Example 2 were used, except that 100 parts of each base resin component (1-b), (T-c) and (1'-a) were used. A resin composition for coating seeds was obtained.

Application Examples 1 to 3 and Comparative Application Example 1 Various coating resin compositions obtained in Example 1.3.5 and Comparative Example] were spray-coated onto an annealed copper plate, and then 140%
Bake for 20 minutes at 'c.

After testing the physical properties of each cured coating film obtained,
The results shown in Table 2 were obtained.

Application Examples 4 to 6 and Comparative Application Example 2 The various coating resin compositions obtained in Examples 2.4.6 and Comparative Example 2 were applied to a polystyrene molded plate, and then 8
Forced drying was performed at 0°C for 20 minutes.

When the coating performance of the obtained coating film was tested, the results shown in Table 3 were obtained.

13- 14- Table 2 Note 1) Using a 1/2 inch diameter mandrel,
I went with C.

2) 500g (load) x 50CM at -20℃ room temperature
(high) conditions.

15- Table 3 435- 16-

Claims (1)

[Claims] (1) Polyester having a hydroxyl group obtained by polymerizing an acrylic monomer mixture (■-2) in the presence of an ε-caprolactone-modified unsaturated polyester polyol (1-1) having a hydroxyl value of 50 to 300 A resin composition comprising a modified acrylic resin and (II) an isocyanate compound (I[-1) or an amino resin (n-2), comprising - the polyester polyol (1-1) and the acrylic monomer. The weight ratio with the body mixture (1-2) is 10/9.
0 to 90/10, and the acrylic monomer mixture (T-2) contains 1 to 40 parts by weight of the hydroxyl group-containing acrylic monomer and the hydroxyl group-containing acrylic monomer. consisting of 30 to 99 parts by weight of acrylic ester or methacrylic ester excluding the above, and further 0 to 60 parts by weight of other copolymerizable monomers, and the total amount of these monomer mixtures (1-2) 100 parts by weight of a coating resin composition.