JPS61247765A - Paint resin composition - Google Patents

Abstract

PURPOSE:To provide a paint resin compsn. having excellent adhesion, low- temperature curability, etc., by reacting a lactone with a base resin contg. hydroxyl and carboxyl groups and reacting the product with an alkyleneimine compd. contg. an alkyleneimine ring. CONSTITUTION:A lactone of the formula (wherein n is 4-10) such as epsilon- caprolactone is reacted with a base resin contg. hydroxyl and carboxyl groups such as alkyd resin, polyester resin or acrylic resin in the presence of a catalyst (e.g. stannous chloride) to modify the base resin with the lactone. An alkyleneimine compd. contg. at least one C2-C3 alkyleneimine ring (e.g. ethyleneimine or 1, 2-propyleneimine) is reacted with the modified base resin to modify it with the alkyleneimine, thus obtaining a paint resin compsn. having a lactone content of 5-40 wt% of resin solid and an alkyleneimine content corresponding to a quantity of resin acid value of 1-50.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a resin composition for paints, and more specifically, a resin composition for general-purpose paints that can be applied as a top coat, intermediate coat, or repair paint to various materials. It is related to.

BACKGROUND ART Conventionally, various top coats and intermediate coats have been provided for each material to be coated, but almost no paint compositions that are universal in terms of materials, application purposes, etc. have been put to practical use. This is largely due to the curing properties and adhesion of the paint, in addition to the general coating performance.

For example, it is possible to bake steel plates at relatively high temperatures, but plastics require low-temperature curing properties, and the adhesion of the paint must be considered for each material. This is because the adhesion requirements required for paints under various environments are not uniform, such as adhesion between paint and topcoat, and adhesion to substrates and interlayer adhesion such as when repairing automobiles.

Recently, there has been an increasing demand for paints that exhibit excellent adhesion and curing properties for various materials and for various painting purposes, such as integral painting of steel plates and plastics, or repair painting in the field of painting automobiles and other areas. There is.

The problem that the invention aims to solve: Therefore, a general-purpose product that exhibits excellent adhesion to various materials such as steel plates, plastics, or a combination thereof, as well as to old paint films or various paint films, and has particularly excellent low-temperature curing properties. It is an object of the present invention to provide a resin composition for paint.

Means for Solving the Problems The above-mentioned purpose of the invention was to react a lactone represented by the formula % with a base resin having a hydroxyl group and a carboxyl group, and then react with a lactone having 2 to 3 carbon atoms.
This can be achieved by a coating resin composition obtained by reacting an alkylene imine compound having at least one alkylene imine ring.

What is used as the base resin in the resin composition of the present invention is any paint resin having a hydroxyl group and a carboxyl group,
Examples include alkyd resins, polyester resins, acrylic resins, modified epoxy resins, and the like.

This base resin is first reacted with a lactone represented by the formula %, and after this lactone modification, alkylene imine modification with an alkylene imine compound having at least one alkylene imine ring having 2 to 3 carbon atoms is performed. It is done.

Examples of the above lactone include ε-caprolactone,
Examples include ξ-enantholactone, η-caprylolactone, and ring-substituted products thereof. For lactone modification, the usual method of adding a desired lactone to the resin and heating is used, and the lactone is incorporated into the resin by ring opening of the lactone and reaction of the hydroxyl groups.

In this reaction, it is preferable to use a catalyst such as a tin compound, an organic salt of lead or manganese, and particularly effective catalysts include a tin halide and a compound of the formula (where X is an alkyl, aryl, aralkyl, or allyloxy group, ′ is alkyl, aryl, aralkyl, acyloxy, halogen,
A compound represented by a hydroxyl group). For example, tetraphenyltin, tetraoctyltin, diphenyltin dilaurate, tri-n-butyltin hydroxide, tri-n-butyltin acetate, dimethyltin oxide, dibutyltin oxide, dilauryltin oxide, di-n-
Butyltin dichloride, dioctyltin dichloride. Also, lead acetate, manganese acetate, 2-ethylhexane lead acetate,
Lead salicylate, lead benzoate, etc. are also useful. The amount of lactone used for lactone modification is preferably 5 to 40% by weight based on the resin solid content. This is because if it is less than 5% by weight, the curing reaction of the resin composition and material will be slow, and a long curing reaction will be required at a relatively high temperature. Adhesion strength decreases, and solvent resistance decreases due to insufficient curing. On the other hand,
If it exceeds 40% by weight, the coating film becomes soft and its water resistance, chemical resistance, solvent resistance, and polishability decrease.

When selecting alkyd or polyester as the base resin, the resin can be modified with lactone, or lactone can be added as a synthetic component when synthesizing the resin, and in the case of acrylic resin, Lactone-denatured alcohol can also be used as part of the alcohol component.

After the base resin is modified with lactone, alkyleneimine modification is performed in the present invention. The alkylene imine compound used for this modification is an alkylene imine compound having at least one alkylene imine ring having 2 to 3 carbon atoms, such as a compound represented by the formula (in the formula, R1,
R2, R3, R1 and R5 are hydrogen, methyl,
Alkyl having 20 or less carbon atoms such as ethyl and propyl: Aryl such as phenyl; Alkyl such as tolyl and xylyl: Aralkyl such as benzyl and phenethyl; Rs is hydrogen or alkyl usually having 6 or less carbon atoms; n is 0 or 1
) can be given. Compounds in which two or more groups represented by the above formula are bonded are also included, but certain compounds are difficult to synthesize due to steric hindrance, and therefore in many cases R1 to R6 are hydrogen. Specific examples of the above alkylene imine compounds include the following.

Ethyleneimine, 1,2-propyleneimine, 1,3-
Probyleneimine, 1.2-dodecyleneimine, 1.1
-dimethylethyleneimine, phenylethyleneimine,
Tolylethyleneimine, benzylethyleneimine, 1.
2-diphenylethyleneimine, 2-hydroxyethylethyleneimine, aminoethylethyleneimine, 2-methylpropyleneimine, 3-chloropropyleneimine, p-chlorophenylethyleneimine, methoxyethylethyleneimine, carboethoxyethylethyleneimine, N-ethyl 1-ethyleneimine, N-butylethyleneimine, N-(2-aminoethyl)ethyleneimine, N
-(2-hydroxyethyl)ethyleneimine, N-(cyanoethyl)ethyleneimine, N-phenylethyleneimine, N-triethylethyleneimine, N-(p-chlorophenyl)ethyleneimine, N-(2-carboethoxy-1- Particularly preferred imines from the viewpoint of availability and effectiveness are ethyleneimine, 1,2-propyleneimine, and N-(2-ethyl)ethyleneimine.
Hydroxyethyl) ethyleneimine. In addition,
For example ethylene-1,2-bisaziridine and 1,2
．． Satisfactory results can also be obtained with alkylene imines containing one or more alkylene imine rings, such as 4-tris(2-1-aziridinylethyl) trimellitate. In this invention, the term alkylene imine compound includes all the above-mentioned alkylene imines, including substituted ones.

The reaction of the alkylene imine compound is carried out by mixing the alkylene imine compound with a lactone-modified base resin having a hydroxyl group and a carboxyl group and heating the mixture to a temperature of usually 20 to 150°C.

The alkylene imine compound has a resin acid value of the base resin of 1 to 50.
It is preferable to react with a firefly corresponding to . Particularly preferred is an amount corresponding to a resin acid value of 3 to 30. This is because if it is less than 3, the non-abrasive adhesion with the top coat tends to decrease when used for repair purposes, and the adhesion to plastic materials also decreases, and if it is less than 1, the effect of alkyleneimine modification cannot be obtained. If it exceeds 30, the curing speed with the curing agent, such as isocyanate, will be faster, resulting in a short pot life, and if it exceeds 50, water resistance and chemical resistance will decrease, and there will be extremely difficult problems such as poor coating film appearance. It is.

Function The thus obtained resin composition according to the present invention undergoes lactone modification to the base resin and is provided with a large number of primary hydroxyl groups, so that the reactivity with crosslinking agents such as melamine and isocyanate compounds is improved, and the sealing resistance is also improved. In addition, the methylene chain imparts flexibility, stress relaxation during curing does not impair adhesion to the substrate, and improved compatibility provides the effect of binrid formation, while alkylene imine modification provides cross-linking. The reactivity with the agent is further improved, and the adhesion of the material is improved, showing excellent adhesion to various materials such as steel plates and plastics. Combined with the excellent curing reactivity, it is suitable for top and intermediate coatings for automobiles, etc. The present invention provides a coating composition that is extremely useful as an integral coating for steel brushes, a repair primer, and the like.

Example 1 6.8 g of trimethylolpropane was placed in a reaction tank equipped with a heating device, a stirrer, a reflux device, a water separator, a purifier and a thermometer.
parts (by weight, the same applies hereinafter) neopentyl glycol 29.
4 parts of adipine, 125.7 parts of isophthalic acid, 20.0 parts of Cardura E (glycidyl ester of branched saturated fatty acids manufactured by Shell Petroleum ■), and 0.05 parts of dilobyltin oxide were charged and heated.

When the raw materials are melted and stirring becomes possible, stirring begins and the reaction tank s
Raise the temperature of i to 220'C. However, from 160°C to 220°C, raise the temperature at a constant rate over 3 hours. The condensed water produced is distilled out of the system. When the temperature reaches 220° C., the temperature is maintained, 2 parts of kijirole is added as a refluxing solvent into the reaction tank, and the condensation is switched to condensation in the presence of a solvent. Resin acid value is 3.0K
When the volume reaches 1 l+ (1 part g) of OH, it is cooled. Next, 8.4 parts of tetrachlorophthalic anhydride is added and reacted at 150'C. When the resin acid value reaches 18.0, the reaction is completed and the mixture is cooled. Reaction tank When the temperature reached 110°C, 20 parts of Plaxel M (trade name ε-cabrolactone, manufactured by Daicel Chemical Co., Ltd.) was added and the temperature was raised to 150°C under a nitrogen atmosphere.While keeping the temperature at this temperature, time-lapse sampling was carried out.
The amount of unreacted ε-caprolactone was monitored at R, and the reaction rate was 9.
The reaction is terminated when the concentration reaches 8% or more, and the temperature is reduced to 0 by cooling.
- Add 9 parts of 27°.

Then, at 80°C, 2.1 parts of N-(2- and droxyethyl)ethyleneimine (trade name: HEEI, manufactured by Sogo Yakuko Co., Ltd.) was added, and the reaction was allowed to proceed at this temperature for 1 hour, followed by the addition of 27.9 parts of butyl acetate to form a polyester resin. I got an A.

The special properties of this varnish are shown in Table 1.

Example 2 In a reaction tank similar to Example 1, 21.3 parts of coconut oil, 15.7 parts of trimethylolpropane, and 0.0 parts of lithium naphthenate were added.
After adding 1 part, transesterification was carried out at 240°C, and then 26.7 parts of isophthalic acid, 123.5 parts of adipine, 2484 parts of neopentyl glycol, and 0.05 parts of dilobyltin oxide were added, and the acid value was adjusted to 230°C. React up to 3.

Next, 8.3 parts of tetrachlorophthalic anhydride was added and heated to 160°C.
The acid value was 18. When it reaches O, cool it down. When the temperature of the reaction tank reached 100°C, 20 parts of Plaxel M was added and reacted at 150°C for 2 hours, then cooled and 27.9 parts of Kijirole was added. Then HEEI at 80℃
After adding 2.1 parts and causing a JFR reaction, the mixture was cooled and 2,769 parts of butyl acetate was added to obtain alkyd resin B.

The special properties of this varnish are shown in Table 1.

Examples 3 to 12 and Comparative Examples 1 to 8 Based on the compositions shown in Table 1, reactions were carried out in the same manner as in Example 1 to obtain polyester resin varnish C-L and comparative varnish 0 to ■.

Example 13 11.0% trimethylolpropane was placed in a reaction tank equipped with a heating device, a stirrer, a reflux device, a water separator, a purification tower, and a thermometer.
0 parts, neopentyl glycol 15.9 parts, adipic acid 20.6 parts, isophthalic acid 23.4 parts, Cardura E (
20.0 parts of glycidyl ester of saturated fatty acids (produced by Shell Petroleum @ Co., Ltd.), 17.4 parts of Plaxel M, and 0.05 part of di-n-butyltin oxide were charged and heated.

When the raw materials are melted and stirring becomes possible, stirring is started and the temperature of the reaction tank is raised to 220°C. However, from 160℃ to 22
The temperature is raised to 0°C at a constant rate over 3 hours. The condensed water produced is distilled out of the system.

When the temperature reaches 220° C., the temperature is maintained, and 2 parts of kijirole is added as a refluxing solvent into the reaction tank, and the condensation is switched to condensation in the presence of a solvent. When the resin acid value reaches 20.0 KOHmg/g, it is cooled and 21.9 parts of pheasant roll is added.

Next, 12.1 parts of I (EEI) was added at 80°C and the mixture was reacted for 1 hour, and then 21.9 parts of butyl acetate was added to obtain polyester resin M.

The special properties of this varnish are shown in Table 1.

Example 14 and Comparative Example 9 (Acrylic Resin Varnish N and Comparative Varnish W) In a reaction tank, 25 parts of Kijirole, 25 parts of butyl acetate, 35 parts of styrene (ST), and n-butyl acrylate (NBA>1
9.2 parts, 2.3 parts of methacrylic acid (MAA) and Plaxel FM-1 (trade name, manufactured by Daicel Chemical Co., Ltd., ε-caprolactone ring-opening addition product of 2-hydroxyethyl methacrylate, containing ε-caprolactone 1146.7 %)43.5
After raising the temperature to 110°C, a solution containing 25 parts of pheasant, 25 parts of butyl acetate, and 1 part of azoisobutyronitrile was added at a constant rate over 3 hours while keeping the temperature, and 2 hours after completion of the dropwise addition. After the reaction, acrylic resin varnish W was obtained by cooling. (Comparative Example 5) Furthermore, 100 parts of the resin varnish W obtained in Comparative Example 5 was added with H.
After adding 1.6 parts of EEl and reacting at 80° C. for 1 hour, the mixture was cooled. The characteristics of the obtained varnish N are as shown in Table 1. (Example 14) (Hereafter the margin) Reference example 1 Polyester resin varnish A obtained in Example 1 Solid content 3
5.0 parts, crosslinking agent (melamine resin, Super Beckamine L-117-60, trade name manufactured by Dainippon Ink Co., Ltd.) solid content 1
5.0 parts, Kijiroll 8゜0 parts, Tsurupets 100 4
．． 0 parts, n-butanol 7.0 parts, silicon KF-69
(manufactured by Shin-Etsu Chemical ■) to 0.015 parts of titanium CR-95 (manufactured by Ishito Sangyo ■), First Gen Blue NK (
Dainippon Ink (Iu) 2.3 parts dispersed in a light blue paint containing 20.0 parts of Tsurupetz 100, 50.0 parts of Dorol, 10.0 parts of Kijirol, and 20.0 parts of n-butanol. 20 in a Ford cup #4 by adding a diluent consisting of part O.
The viscosity-adjusted paint was spray-painted on urethane R-RIM, which had been adjusted to a temperature of 25° C./sec/25° C. and degreased with trichlene, and after being left for a certain period of time, it was baked at 100° C. for 30 minutes. The performance of each coating film was evaluated and the results are shown in Table 2.

Reference Examples 2 to 7 and Comparative Reference Examples 1 to 4 The resins of Examples 2 to 7 and Comparative Examples 1 to 4 were made into paints in the same manner as in Reference Example 1, and after baking at 100°C, the coating film performance was evaluated. The results are shown in Table 2.

(The following is a margin.) Note 2 in the table: Pencil height J Is-5400 Pencil scratch test according to the general test method for paints.

Note 3 Extract with a gel fraction Soxhlet extractor (extraction solvent: acetone/methanol-1/1 (wt ratio)) at 70°C for 5 hours, then dry in a dryer at 120°C for 30 minutes, and cool in a desiccator. After cooling, measure the weight and calculate the gel fraction.

Note 4 Adhesion to substrate JIs-5400 Paint general test method was used to evaluate the cross-cut test (1 mm).

◎100/100~95/100 (practical)
0 94/100~80/100 ()△ 79/
100~60/100 (Practical problem x 59
/100~O/100 ()Note 5 Water resistance The condition of the coated surface after immersion in warm water at 40°C for 10 days was evaluated according to the following criteria.

ONo abnormality Δ Some blisters occur X Bliss - appearance, shine Note 6 Painted surface condition Based on B value determination using color difference LAB display.

○ ΔB value 0.2 or less (practical) Δ 0
．． 2 to 0.5 (practical problems) x 0.5 or more () Note 7 Impact resistance (-20℃) Impact test according to J Is-5400 general paint test method (Dupont method, -20℃, 500 (IX50cm) No abnormality × Cracking, peeling Reference example 8 Polyester resin varnish H obtained in Example 8 Solid content 3
5.0 parts, Kijiroll 8.0 parts, Tsurupets 100 4
．． 0 parts, butyl acetate 7.0 parts, silicone KF-69 (manufactured by Shin-Etsu Chemical) 0.015 parts 1, titanium 0R-95 (manufactured by Ishigashira Sangyo @ J), First Gen Blue NK (Dainippon Ink) Desmodur N-75 (manufactured by Sumitomo Bayer side >1
Add 9.8 parts of Tsurpets 100, 20.0 parts of Doluol, 50.0 parts of Kijirole, 2 parts of butyl acetate.
Ford cup #4 with addition of diluent consisting of 0.0 part
The viscosity-adjusted paint was spray-coated onto urethane R-RIM which had been procured and degreased with trichlene until the temperature reached 25°C for 20 seconds at 90°C, and force-dried at 90°C for 20 minutes. After being allowed to stand for 2 days at the lowest temperature, the performance of each coating film was evaluated. The results are shown in Table 3.

Reference Examples 9 to 14 and Comparative Reference Examples 5 to 9 The resins of Examples 9 to 14 and Comparative Examples 5 to 9 were made into paints in the same manner as Reference Example 8, and the coating performance was evaluated.

The results are shown in Table 3.

Reference Example 15 In a stainless steel container, 36 parts of the polyester resin varnish of Example 8, 12 parts of butyl acetate, 12 parts of Kijirol, 12 parts of titanium R-820, 40 parts, and 100 parts of glass beads (1 mm diameter) were added to a stainless steel container, and after stirring uniformly, 1
Brymer surfacer paint for repair was manufactured over time.

Next, using the above paint as a main ingredient, 1 part of Coronate L (manufactured by Nippon Polyurethane Industries) was added to 100 parts by weight of the main ingredient.
After adding 7.5 parts, it was diluted with a mixed solvent consisting of 50 parts of Kijirole and 50 parts of butyl acetate for 22 to 24 seconds/
After adjusting to #4 Ford Cup (20°C), it was painted with air spray and its performance as a brimer surf bait was evaluated.

The results are shown in Table 4.

Reference Examples 16 to 21 and Comparative Reference Examples 10 to 14 Based on the compositions in Table 4, using the resins of Examples 9 to 14 and the resins of til15 to 9, Brimer Surfney+j tliF4 was prepared.
After making trH and forming it into a coating film in the same manner as in Reference Example 15, the performance as a brass suff was evaluated. The results are shown in Table 4.

(The following is a margin) Note 1 in the same table: The adhesion to the substrate is determined by degreasing a 5PC-dull steel plate with dimensions 100X150XO' and 8 m/m using a Kiji Roll, polishing the surface with #240 sandpaper, applying Brimar Surfacer, and leaving it at room temperature. After leaving it for a day and night, J Is-5400
Evaluation was carried out by a cross-cut test (1 ml) according to the paint general test method.

◎100/100~95/100 (practical)
094/ 100~80/100 ()△ 79/
100~60/100 (practical problem)X 5
9/100~0/100 (>Note 2, Note 3 Interlayer adhesion (#400) and non-polishing interlayer adhesion dimension 10
0x300x0.8 m/m 5Pc-1 dull steel plate #
After sanding with 240 sandpaper, Primer Surfacer was applied, and after leaving it for a day and night, half of the surface of Brimer Surfacer was sanded and dried with #400 waterproof paper, and then a commercially available top coat acrylic urethane paint for automobile repair was applied.

After standing at 60° C. for a day and night, a cross-cut test was conducted on both the polished and unpolished surfaces of the Brimer Surfacer surface to evaluate interlayer adhesion (#400) and unpolished interlayer adhesion, respectively.

◎100/100~95/100 (practical) 0 9
4/100~80/100 ()Δ 79/100
~60/100 (practical problem)X 59/1
00~O/100 (#') Note 4, Note 5 Sealing properties and solvent resistance Apply nitrocellulose lacquer on a 71J board with dimensions of 200 x 300 x 0.3 m/m and leave it at room temperature for 1 hour, then apply one side of the painted surface. Apply commercially available putty evenly. After 3 hours, a coat of modified primer Surfacer polished with #240 Sand Vapor was applied in five different thicknesses (10 to 50μ).

-Q After being left overnight, it was polished with #400 waterproof vapor and dried, then a commercially available top coat acrylic urethane paint for automobile repair (using toluene, butyl acetate, and methyl isobutyl ketone as solvents) was applied. Feather on the putty after being left at 60℃ for a day and night
The state of shrinkage on the edge part and the nitrocellulose lacquer surface was observed (1), and the sealing performance and solvent resistance were evaluated at the lowest film thickness without shrinkage.

However, in practical terms in the market, the minimum film thickness that does not shrink is 30μ.
The thickness is preferably 20μ or less, particularly preferably 20μ or less.

◎ (Minimum film thickness that does not shrink) 10~20μ (practical) 0 21~30μ (practical) △ 31~40μ (practical problems) x 41μ~ (
) Note 6 Based on visual judgment.

O No abnormality, practical) Δ Loss of shine (problems in practical use) - × Loss of gloss, skin roughness (problems in practical use) Patent application agent

Claims (3)

[Claims] (1) A base resin having a hydroxyl group and a carboxyl group is reacted with a lactone represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (n = 4 to 10), and then a carbon number of 2 to 3 is reacted.
A resin composition for coating material obtained by reacting an alkylene imine compound having at least one alkylene imine ring. (2) The lactone content is 5 to 40% by weight of the resin solids,
The resin composition according to claim 1, wherein the alkylene imine compound content is in an amount corresponding to a resin acid value of 1 to 50. (3) The resin composition according to claim 1, wherein the base resin is an alkyd resin, a polyester resin, an acrylic resin, or a modified epoxy resin.