JPH03181573A - Resin composition for coating compound - Google Patents

Abstract

PURPOSE:To obtain the title composition useful as a coating composition for automobiles, having low volatility in baking and curing, not staining dryers, comprising a specific new amino compound as a main compound and a polymer of the compound as a subsidiary component. CONSTITUTION:The objective composition comprising (A) an amino compound shown by formula I (R1 to R8 are H, CH2OH or CH2OCH9) as a main compound and (B) a polymer of the component A as a subsidiary component. The component A, for example, is preferably obtained by reacting phthaloguanamine shown by formula II with formaldehyde in an alcohol solvent at pH10-12 at 60-75 deg.C and then with n-butyl alcohol at pH2-4 and at 60-75 deg.C.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to a resin composition for paint.

(Prior Art) Amine resin paints are widely used for coating automobiles, industrial machinery, steel furniture, electrical appliances, pre-coated metals, food and drink cans, etc. As an amino resin.

Urea resin, melamine resin, benzoguanamine resin, etc. are used in combination. Of this.

Products containing benzoguanamine resin have poor weather resistance, but are excellent in initial gloss, heat resistance, acid resistance, alkali resistance, water resistance, hardness, etc., so they are suitable for undercoating.

Widely used in paints for indoor applications.

(Problems to be Solved by the Invention) Since Shikashi and benzoguanamine resins contain a considerable amount of a low molecular weight volatile monomer having the following structure [■] t1, there is a problem that this volatilizes during baking hardening and contaminates the inside of the dryer. be.

The present invention provides a resin composition for paint that can solve this problem.

(In the formula, RlHa, Rs and R4 are each independently -
H1CH20H, or -CHzOCi&) (Means for Solving the Problems) The present invention is as follows.

(A) A novel amino compound represented by the general formula [■] is used as a product.

(In the formula, tal, R121R3y R4+ R5+
Kame, Tsuku and R8 each independently represent -H1-OH or -
The present invention also relates to a resin composition for coatings containing a novel amino resin containing a multimer of the compound as a subcomponent (B) a resin that reacts with the amine resin.

The novel amine resin (A) according to the present invention has the general formula [■]
Phthaloguanamine represented by is methylolized.

It is then obtained by butyl etherification.

Phthaloguanamine is 2 For example, Wai Iwakura, Kei Uno, Nis Shiraishi, Pultin Chemical Society Japan, Vol. 38, No. 11, p. 1820 (196
5) (Y, Iwakura, K, Uno.

S, 5hirashi, Bull, Chem,
Soc, Japan.

38, Fish 11, 1820 (1965)). That is, it can be obtained by reacting o-m- or p-phthalonitrile with dicyandiamide in a solvent such as methyl cellosolve or dimethyl sulfoxide using potassium hydroxide as a catalyst.

According to the present invention, methylolation of phthaloguanamine is carried out, for example, by combining o-, m-, or p-phthaloguanamine with formaldehyde in water and/or alcoholic solvent under alkaline conditions at pH 10-12 at a temperature of about 60-75°C. 1-8
This can be done by reacting for a period of time. Examples of alcohols that are solvents for methylolation include methyl alcohol, ethyl alcohol, and flobyl alcohol.

Butyl alcohol, mixtures thereof, and the like can be used. To make the reaction system alkaline, for example, sodium hydroxide, potassium hydroxide, etc. may be added in an amount sufficient to adjust the pH to 10 to 12.

The blending ratio (molar ratio) of phthaloguanamine/formaldehyde can be approximately in the range of 1/8 to 1/30. Paraformaldehyde can also be used instead of formaldehyde.

According to the present invention, the butyl etherification of the methylol compound of phthaloguanamine is carried out, for example, by combining the methylol compound with n-butyl alcohol under acidic conditions of pH 2-4 at a temperature of about 60-75° C. for 1-8 hours.

-Butyl alcohol, sec -Butyl alcohol.

This can be carried out by reacting with at least one selected from the group consisting of tert-butyl alcohol. The blending ratio (molar ratio) of methylol compound/alcohol can be approximately in the range of 1/20 to 1/60. To make the reaction system acidic, for example, nitric acid or the like may be added in an amount sufficient to adjust the pH to 2 to 4.

The novel amino resin of the present invention is a novel amino compound whose product component is represented by the following general formula [■], and also contains a multimer of the amino compound as a subcomponent. Among them, the amino compound is isolated by a known fractional precipitation method by appropriately setting conditions (in the formula, R+, E%t,
(R3, R4, 1%S, R4, Rt and Rs each independently represent -H, -CHzOH or -CH20C4H9) Resin that reacts with the novel amino resin of (B) (A) in the present invention These are conventionally known hydroxy group-containing polyester resins, alkyd resins, and acrylic resins.

Acrylic modified polyester resin or the like can be used. For example, an alkyd resin obtained by reacting a polyhydric carboxylic acid, a polyhydric alcohol, and optionally an oil or a fatty acid derived from these can be suitably used. Examples of polyvalent carboxylic acids include phthalic acid, inphthalic acid, terephthalic acid, tetrahydrophthalic acid, maleic acid, fumaric acid, succinic acid, adipic acid, sebannic acid, trimellitic acid, and pyromellitic acid. These may be used in the form of ester-forming derivatives such as acid anhydrides and methyl esters. Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol,
Dipropylene glycol, neopentyl glycol, x
, 4-phthanediol, 1,6-hexanediol, trimethylene glycol, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol and the like. Examples of the oil include tung oil, linseed oil, soybean oil, dehydrated castor oil, safflower oil, castor oil, coconut oil, and tall oil. The alkyd resin can be produced by known methods.

When using oil, heat the oil and polyhydric alcohol at 200 to 260°C in the presence of a transesterification catalyst such as lithium hydroxide.
After reacting at 180 to 250°C, add the polybasic acid and remaining polyhydric alcohol, and react at 180 to 250°C. If oil is not used, mix the raw materials and react at 180 to 250°C. .

In addition, 1 has a hydroxy group such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxybrobyl methacrylate, etc. -β-ethylene on t-, %α, βα An acrylic resin obtained by copolymerizing a Japanese monomer and other unsaturated monomers by a known method can be suitably used. Examples of other unsaturated monomers include 7.

α, β-monoethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, methacryl alpha,beta-monoethylenically unsaturated force-saturated carboxylic acid kill esters such as n-butyl acids, acrylamide, methacrylamide, N-methylolacrylamide.

Acrylamide derivatives such as N-methylolmethacrylamide and diacetone acrylamide, glycidyl esters of α,β-monoethylenically unsaturated carboxylic acids such as glycidyl acrylate and glycidyl methacrylate, and saturated carboxylic acids such as vinyl acetate and vinyl propionate. Examples include aromatic unsaturated monomers such as vinyl ester, styrene, α-methylstyrene, and vinyltoluene. Examples of the above copolymer include azobisisobutyronitrile, benzoyl peroxide, and dibutyl peroxide.

It can be carried out by heating to 130 to 160°C in the presence of a radical polymerization catalyst such as cumene hydroperoxide.

The above alkyd resin and acrylic resin have a hydroxyl value of 15 to
200 is preferably used.

If the hydroxyl value is too small, the curability may be poor, and if it is too large, the water resistance of the coating film may be poor.

The blending ratio (weight ratio) of (A) the new amino resin and (B) the resin that reacts with the resin varies depending on the resin used and the purpose, but (A)/(B) is approximately 5/95 to 501.
A range of 50 is preferable.

The coating resin composition of the present invention can contain a conventionally known coating solvent. Examples of such solvents include toluene, xylene, butanol, and Trupetz 100. Examples include Turupetz 150 (both trade names, manufactured by Ethane Standard Oil Company), ethyl cellosolve, butyl cellosolve, ethyl acetate, and butyl acetate.

Conventionally known pigments and other additives can be added to the coating resin composition of the present invention depending on the purpose.

The resin composition for paint of the present invention is coated on a predetermined base material by a known method, and then heated in a temperature range of 120 to 220°C.
It can be cured by baking for 240 minutes to provide a coating film with good properties.

The present invention will be explained below with reference to Examples.

(Example) Synthesis example 1 Synthesis of 0-phthaloguanamine Wai Iwakura, Kei Uno, Nis Shiraishi.

Pultin Chemical Society: Japan.

Vol. 38, No. 11, p. 1820 (1965) [Y.

Iwakura, K, Uno, S, 8hir
aishi, Bull.

Chem, Sac, Japan, 38. Nc
hl 1. 1820 (1965)], 0-phthaloguanamine was synthesized. In a 1E separable flask equipped with a cooling tube, a stirrer, and a thermocouple for temperature control, 26 g (0.2 mol) of 0-phthalonitrile, 349 (0.4 mol) of todicyandiamide, 49 hexagrams of potassium hydroxide and methyl 1 in the presence of Cellosolve 600-
It was made to react at 30-140 degreeC for 7 hours.

Immediately after the start of the reaction, white crystals were precipitated in one reaction system, and the amount thereof increased over time. After the reaction was completed, the white crystals were washed with methyl cellosolve and dried under reduced pressure at 50°C for 24 hours (
1 mmHg). The yield was 87%. The melting point of the compound determined by the DSC method was 345°C (literature value 340-3
59°C).

FIG. 1 shows the infrared absorption spectrum of O-phthaloguanamine, one of the compounds.

The analysis was conducted under the following conditions.

II (-NMR spectrum measurement method ■Newly manufactured by Hitachi, Model R-250 Nuclear magnetic resonance deviceInfrared absorption spectrum measurement method ■Newly manufactured by Hitachi, Model 260-30 Infrared spectrophotometerGel permeation chromatography substandard method Column: Ge1pack R420, R430 and R4
40 (manufactured by Hitachi Chemical Co., Ltd., trade name) connected in series Column size: 2 inner diameter: 10.7 mm, length: 30 cm Carrier: Tetrahydrofuran flow: 1.7 mZ/min Detector: Differential refractometer The conditions for the above analysis are as follows. The same goes for writing.

Synthesis Example 2 False) Synthesis of a new amino resin 50 equipped with a cooling tube, a stirring device, and a thermocouple for temperature control
0-In a separable flask, add rose formaldehyde (manufactured by Mitsui Toatsu Co., Ltd., containing rose formaldehyde 1t8 (1) 5
6.39 (1.5m0I in terms of formaldehyde,
n-Butyral-y-ol 4Qg (0.54mof)
was prepared and adjusted to p) 110.4 by adding 30% by weight aqueous sodium hydroxide solution. The temperature was raised while stirring, and when a homogeneous solution was obtained, 14.89 (0.05 mol) of 0-7 Taguanamine obtained in Synthesis 1 was added and reacted at 60°C for 5 hours.

Next, 148 g of n-butyl alcohol (Z
Oma! ) was added, nitric acid was added to adjust the pH to &1, and the mixture was reacted at 60° C. for 3 hours. After cooling the reaction solution, add 30% by weight aqueous sodium hydroxide solution to adjust the pH to 9.5 or higher, remove n-phthyl alcohol, water, etc. by vacuum distillation, and remove precipitated salt (sodium nitrate) by filtration. A) 0-7 Taguanamine resin as a new amine resin was obtained.

Infrared absorption spectrum of the above 0-phthaloguanamine resin,
The LH-NMR spectrum and gel permeation chromatogram are shown in FIGS. 2, 3 and 4, respectively.

Synthesis Example 3 (B) (A) Synthesis of a novel resin that reacts with an amino resin In a flask with a capacity of 500 cm3 using a cooling tube, a stirrer, a nitrogen blowing tube and a thermocouple for temperature control.

10g of xylene was charged. persimmon! Heat while stirring,
The temperature was increased to 130°C. Next, the following mixed solution was added dropwise over a period of 3 hours, and the mixture was reacted with stirring for an additional 3 hours.

Stine
209 2-ethylhexyl acrylate 54
9 2-Hydroxyethyl methacrylate 239 Methacrylic acid 3g Azobisisobutyronitrile 4g Xin
After cooling, the solvent was removed to obtain a xylene solution of styrene/acrylic resin with a non-volatile content of 70%. The number average molecular weight of this resin in terms of standard polystyrene determined by gel permeation chromatography was 2.ooo.

Example 1 Prepare a paint with the following formulation (non-volatile content: 52φ).

It was coated on a glass plate using a bar coater Φ18, baked at 200° C. for 5 minutes to harden, and the state of the coating film was examined.

As a result, a glossy, hard, and good coating film was obtained.

Total oog (Note) Product name: Elan Star/Aromatic solvent manufactured by Dart Oil ■ Coat the above o-7 Taguanamine resin solution with a bar coater ◆1
8 to a glass plate of known weight.

xii of the coating film after preheating at 160°C for 20 minutes: (w+
) was then further heated at 200° C. for 5 minutes to determine the final weight (w2) of the coating film. The amount of weight loss of the coating film was calculated from the formula below. As a result, the amount of weight loss was 1%.

Reduce weight i (%) = "" I looked into it. As a result, a glossy, hard, and good coating film was obtained.

Kishin
279 total 100 g (Note) Product name 2 Butylated benzoguanamine resin manufactured by Hitachi Chemical ■ The above Melan 362A was applied to a glass plate of known weight using a bar coater ◆18, and the coating was preheated at 160'C for 20 minutes. Membrane weight - 3t (WI), 5 at 200'C
The amount of weight loss of the coating film was calculated in the same manner as before from the final form f (W3) of the coating film after heating for a minute. the result.

The amount of decrease in M11 was 6%.

(Effects of the Invention) The coating resin composition of the present invention exhibits little volatilization during baking and curing, and is excellent in that it does not contaminate the interior of the dryer.

[Brief explanation of drawings]

FIG. 1 shows the infrared absorption spectrum of ○-phthaloguanamine in Synthesis Example 1, and FIG. 2 shows the infrared absorption spectrum. In Synthesis Example 2 of Examples. - Infrared absorption spectrum of phthaloguanamine resin, FIG. 3 shows Synthesis Example 2 of Examples. The IH-NMR spectrum of -7 Taguanamine resin and FIG. 4 are gel permeation chromatograms of 0-7 Taguanamine resin in Synthesis Example 2 of Examples.

Claims (1)

[Scope of Claims] 1. (A) Main component is a novel amino compound represented by the general formula [I], ▲There are numerical formulas, chemical formulas, tables, etc.▼[I] (In the formula, R_1, R_2, R_3, R_4, R_5, R
_6, R_7 and R_8 are each independently -H, -CH
_2OH or -CH_2OC_4H_9) A resin composition for a coating material, comprising a novel amino resin which also contains a multimer of the compound as a subcomponent, and (B) a resin that reacts with the amino resin.