JPH0366721A - New amino compound, new amino resin, preparation of the same resin and resin composition for aqueous coating - Google Patents

Abstract

NEW MATERIAL:A compound of the formula [R1 to R8 are H, CH2OH, CH2OR9 (R9 is 1-3C alkyl)]. EXAMPLE:o-Phthaloguanamine. USE:A raw material for preparing amino resins, aqueous coating resins, etc. PREPARATION:For example, o-phthalonitrile is reacted with dicyanodiamide in the presence of potassium hydroxide, methylcellosolve, etc., at 130-140 deg.C for 7hr, and white crystals deposited just after the beginning of the reaction and increased with time are filtered out, washed with the methylcellosolve, etc., and subsequently dried at 50 deg.C for 24hr in vacuo to provide the o- phthaloguanamine of the formula. The compound of the formula is reacted with paraformaldehyde in the presence of sodium hydroxide in methanol at 60 deg.C for 5hr and subsequently neutralized to provide an o-phthaloguanamine resin.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a new amino compound, a new amino resin, a method for producing the resin, and a resin composition for water-based paints.

(Prior Art) In recent years, m-based materials are shifting from conventional organic solvent-based ones to water-based ones from the viewpoint of saving resources and energy, as well as from the viewpoint of solvent regulations to prevent air pollution. Conventionally, methylated melamine resins have been used as amino resins for water-based paints.

(Problems to be Solved by the Invention) However, paints containing melamine resin have the drawback of poor boiling resistance and removability.

On the other hand, organic solvent-based paints containing methylated benzoguanamine resin, which is a typical oil-soluble amino resin, are 1!1
Although it shows excellent performance in terms of film flexibility and water boiling resistance, it cannot be used for water-based paints because it does not dissolve or disperse in water.

Kinei gA is a new amino compound, a new amino resin, suitable for water-based paints with excellent boiling resistance and flexibility.
#Provides a resin manufacturing method and a resin assembly for water-based paints.

(Means for Solving the Problems) The present invention relates to a novel amino compound represented by -Monken [I].

(In the formula #Rie Rz #Rs * R4e R
sp Rs m Ry and Rs are each independently -H
, -CHsOI (or -CH20Rs (however, R9 represents an alkyl group having 1 to 1 carbon atoms)) The present invention is applicable to the present invention. The present invention relates to a novel amino resin containing a novel amino compound represented by the above general formula [1) as a main component and a multimer of the compound as a subcomponent.

The present invention also provides methylolization of 7-taguanamine represented by -Momonena [H] (in the formula, the substitution position of the benzene ring is the ortho, meta or para position), and then the carbon atom number is 1 to 3. The present invention relates to a method for producing a novel amino resin, which is characterized by etherification using an alcohol.

The present invention also provides a method for methylolizing a phthaloguanamine represented by the formula ID (in the formula, the substitution position of the benzene ring is the ortho, meta or para position), and then The present invention relates to a resin composition for water-based paints containing a novel amino resin obtained by etherification using alcohol and (B) a resin that reacts with the amino resin.

In the present invention, the phthaloguanamine represented by the general formula [■] is 2, for example, Fui Ifukura, Kei Uno, Nis Shiradashi. Pal Chem Society Japan, 38th
Vol. 11, p. 1820 (1965) [Y, Iwaku
ra, K, Uno, S, 8hirashi,
BullChem, 8oc, Japan, 38
．． ) kkl 1. 1820 (1965)). That is, o +
, m- or p-17 talonitrile and dicyandiamide using potassium hydroxide as a solvent, methyl cellosolve,
υ can be obtained by reaction in a solvent such as dimethyl sulfoxide.

In the present invention, the methylolation of phthaloguanamine represented by - Monana [■] is carried out under alkaline conditions of pH 10 to 12 in water and/or alcohol solvent, for example,
, m+, or Fip-7 can be carried out by reacting Taguanamine with formaldehyde at a temperature of about 60 to 75° C. for 1 to 8 hours. Examples of alcohols that are solvents for methylolation include methyl alcohol, ethyl alcohol, and propyl alcohol.

Diethylene glycol, mixtures thereof, and the like can be used. Methanol is preferred as a solvent for methylolation. To make the reaction system alkaline, 1. For example,
Hydroxide) IJum, potassium hydroxide, etc. at pH 1o
Just add enough amount to make it ~12. -Monka [■]
The phthaloguanamine/formaldehyde (mole ratio) Fi expressed by the formula can be carried out in the range of approximately 1/8 to 1/30. Paraformaldehyde can also be used instead of formaldehyde.

The methylolated product of phthaloguanamine represented by the general formula [■] obtained above according to the present invention has 1 to 3 carbon atoms.
etherification using alcohol.

For example, it can be carried out by reacting the methylolated product with an alcohol having 1 to 3 carbon atoms at a temperature of about 60 to 75°C under acidic conditions of pH 2 to 4 for 1 to 8 hours.

Alcohols having 1 to 3 carbon atoms include methanol,
There are ethanol, propanol and inpropanol. Methanol is preferred because it has excellent compatibility with water. The molar ratio of methylol compound/alcohol having 1 to 3 carbon atoms can be approximately 1/20 to 1/60. To make the reaction system acidic9 For example, nitric acid etc. to pH2
Just add enough amount to make ~4.

In etherification, ethylene glycol has 1 carbon atom
It can also be used in combination with the alcohols listed in ~3.

As described above, the novel phthaloguanamine of general formula (II) was methylolated according to a known method.

The novel amino resin of the present invention can then be obtained by etherification.

The novel amino resin has a main component which is the novel amino compound of the present invention represented by the following formula [1] and also contains a multimer of the amino compound as a subcomponent.

(In the formula HR1g R2g R31R4g R8@R@
p R7 and Rs are each independently -H, -CHI
OH or -CHxOR* (however, R9 has 1 to 1 carbon atom
(indicates an alkyl group of ヰ)) Among them, the isolation of the novel amino compound represented by -Momona [I] can be easily carried out by appropriately setting the conditions by a known fractional precipitation method. .

The novel amino resin of the present invention has an -N-CHz- structure per be/zene nucleus calculated from the integrated intensity ratio of the proton of the N-CTb- structure on the proton of the benzene nucleus in the NMFL spectrum of the axillary resin. The average number is 6 or more, and the average number of methoxy groups per benzene nucleus calculated from the integrated intensity ratio of the protons of the benzene nucleus and the protons of the methoxy group (-0CHs) is 4 or more. It is a good choice because of its excellent water and boiling resistance.

In the resin composition for water-based paints of the present invention, (1) CB used with the new amino resin) [Resins that react with the amino resin include conventionally known hydroxy group-containing polyester resins and alkyd resins.

Acrylic resin, acrylic modified Borier, Stell resin, etc. 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, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, maleic acid, fumaric acid, succinic acid, adipic acid, sebacic 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, and neopentyl glycol.

1,4-butanediol, 1,6-hexanediol.

These include trimethylene glycol, glycerin, trimethylolpropane, trimethylolethane, and pentaerythritol. For example, oil.

Tung oil, linseed oil, soybean oil, dehydrated castor oil, safflower oil,
These include castor oil, coconut oil, and tall oil.

The alkyd resin can be produced by a known method, and when oil is used, the oil and polyhydric alcohol are mixed in the presence of a transesterification catalyst such as lithium hydroxide at 20 to 26
After reacting at 0°C, add 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, etc. There is.

For example, α,β-monoethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and 2-hydroxyethyl cetacrylate. Preferred examples include acrylic resins obtained by copolymerizing α, β-ethylenically unsaturated monomers having hydroxy groups such as 2-hydroxyethyl methacrylate and other unsaturated monomers by a known method. Can be used. Other unsaturated monomers include 1, for example, methyl acrylate, ethyl acrylate, loobyl acrylate,
2-ethylhexyl acrylate, methyl methacrylate,
Alkyl esters of α,β-monoethylenically unsaturated A-bonic acids such as n-butyl methacrylate, acrylamide derivatives such as acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, diacetone acrylamide, acrylic Glycidyl esters of α,β-monoethylenically unsaturated carboxylic acids such as glycidyl acid and glycidyl methacrylate, 61
Examples include vinyl esters of saturated carboxylic acids such as vinyl and vinyl propionate, and aromatic unsaturated monomers such as styrene, α-methylstyrene, and vinyltoluene. The above copolymerization can be carried out by heating to 130 to 160° C. in the presence of a radical polymerization catalyst such as 2 azobisisobutyronitrile, benzoyl peroxide, dibutyl oxide, or cumene hydroperoxide.

The above alkyd resin and acrylic resin have an acid value of 20 to 10.
It is preferable to use one having a hydroxyl value of 0 and a hydroxyl value of 15 to 200. If the acid value is too low, the water solubility or water dispersibility will be poor after neutralization, and if the acid value is too high, the coating film properties will tend to deteriorate. Moreover, 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.

In order to make such alkyd resins and acrylic resins water-soluble or water-dispersible, the acid groups of the resins can be neutralized with volatile bases such as ammonia or amines. , monoglobilamine, monobutylamine, diethylamine, dibutylamine, triethylamine, tributylamine, monoethanolamine,
Primary, secondary and tertiary aliphatic or alicyclic amines such as ethyl monoethanolamine, monocyclohexylamine, formalin and piperidine can be used.

It is preferable to use ammonia and amine in an amount of 0.3 to 1.2 equivalents per equivalent of acid group.Blending ratio of (A) new amino resin and (B) resin that reacts with the resin. (X amount ratio) varies depending on the resin to be combined and the purpose, but (4) new amino resin/(B) resin that reacts with the resin (solid content weight ratio) is approximately 5/ 95~
It is preferably in the range of 50150.

−. Outside this range, water boiling resistance etc. tend to deteriorate.

The resin composition for water-based paints may contain a diluent solvent, but such dilutable solvents include water-soluble organic solvents such as alcohols, ethylene, and 1-call monoethers. Can be used mixed with water. Examples of such water-soluble organic solvents include 2, for example, isopro, Sol) n-butyl alcohol,
t-"jf Luato:l:'I-,lt,, methyl cellosolve, ethyl cellosolve.

Budilceronlube or the like can be used.

The resin composition for water-based paints of the present invention contains Ginoni/1. ．． −;
, 17 talenesulfone Lp-) luenesulfonic acid.

It is preferred to add a conventionally known acid catalyst such as phthalic anhydride as a curing accelerator. The amount added is preferably 1% by weight or less based on the new amino resin.

Depending on the purpose, pigments and other additives may be added to the resin composition for water-based paints of the present invention.

The resin composition for water-based paints of the present invention is applied onto a predetermined base material (such as a tin plate) by a known method.

It can be cured by baking at a temperature range of 170 to 200° C. for 1 to 30 minutes to form a coating film with good properties.

Hereinafter, the present invention will be explained in detail with reference to two examples.

(Example) Synthesis example 1 Synthesis of 0-7 Taguanamine Wai Iwakura, Kei Uno, Nis Shiraishi.

Pal Chem Nsaiatei Japan, Volume 38, No. 11
No. 1820 (1965) (Y, Iwakura.

K, Uno, S, 8hirashi, Bull, Ch
em, Soc.

Japan, 38. &11, 1820 (1965)), 0-7 Taguanamine was synthesized.

7 at 130-140 °C in the presence of a cooling tube, a stirring device and a thermoelectric and methyl cellosolve 600W1t for temperature control.
Allowed time to react. Immediately after the start of the reaction, 9 reactive white crystals were precipitated and the amount increased over time. After the reaction was completed, the white crystals were separated from P, washed with methyl cellosolve, and dried under reduced pressure (10 mmHg) at 50° C. for 24 hours.

Example 1 Synthesis of 0-7 Taguanamine Resin A
0-Separable flask, paraformaldehyde (manufactured by Mitsui Toatsu, paraformaldehyde content 80%) 56.
39 (1.5 mop in terms of formaldehyde!)
, 40 g of methanol (1,3 moI),
Add 0 weight aqueous sodium hydroxide solution to pH 10.4
Adjusted to. The o-7 Taguanamine obtained in Synthesis Example 1 was added at 14.8% when the temperature was raised while stirring and the mixture became a uniform solution.
g (0.05 moI) was added and reacted at 60°C for 5 hours. Next, 40 g (1,3 moI) was added to the above reaction solution in methanol.
After adding nitric acid to adjust the pH to 3.1, the mixture was reacted at 60° C. for 3 hours. After cooling the reaction solution, a 30 weight polysodium hydroxide aqueous solution was added to adjust the pH to 9.5 or higher, and methanol, water, etc. were removed by vacuum distillation.
The precipitated salt (sodium nitrate) was removed by filtration, and 4) o-7 Taguanamine Resin A as a novel amino resin was obtained.

Infrared absorption spectrum, 'H-NMR spectrum and gel permeation spectrum of the above O-phthaloguanamine resin.
Figure 2 shows the chromatograms.

It is shown in FIGS. 3 and 4.

The analysis was conducted under the following conditions.

IH-NMR spectrum measurement method ■Newly manufactured by Hitachi, model R, -250 nuclear magnetic resonance instrument Infrared absorption spectrometry method ■Newly manufactured by Hitachi, model 260-30 infrared spectrophotometer Gel permeation chromatography measurement method Column: Ge1pack R420, R430 and 几4
40 (manufactured by Hitachi Chemical Co., Ltd., trade name) connected in series Column size: Internal diameter 10.7 mm 5 Length 30 cm Carrier: Tetrahydrofuran Flow rate: 1.7 mj/min Detector: Differential refractometer The conditions for the above analysis are the same for the following. It is.

The average number of -N-CHh- structures per benzene nucleus determined from the absorption ratio of each proton in the IH-NMR spectrum is 8.0 (-N-CHz-(4,6-5.2p
pm) and Cs H4 (7,3-8.0 ppm
)), the average number of methoxy groups (-0CHs) C+ per benzene nucleus Fi5
．． 9 (calculated from the integrated intensity ratio of the beams of -0CHs (3.0 to 3.4 ppm > and C6H4, (4.3 to 8.0 ppm)). From the gel permeation chromatography method. The number average molecular weight calculated in terms of standard polystyrene was 541.The content i of the main component attributed to the monomer by the cutout weight method was 86% by weight.

The above 0-7 Taguanamine Resin A was dissolved in butyl cellosolve to prepare a resin solution with a nonvolatile content (108° C., 73 hours) of 75% by weight. Gardner viscosity (2
5°C) was Y-, and the Gardner color number was 1 or less.

Example 2 Synthesis of 0-7 Taguanamine Resin B 50 equipped with a cooling tube, a stirring device and a thermocouple for temperature control
In a 0d separable flask, add rose formaldehyde (manufactured by Mitsui Toatsu, contains rose formaldehyde *80%>56.
39 (formaldehyde equivalent 1.5 mat) water 4o
g was prepared and the pH was adjusted to 10.3 by adding 30 weight aqueous sodium hydroxide solution.

Raise the temperature while stirring, and when it becomes a homogeneous solution, O-7
14.8 g (0.05 mol) of taguanamine was added and reacted at 60°C for 5 hours. Next, 80 g (2-5 mol) of methanol was added to the reaction solution, and nitric acid was added to adjust the pH to 3.6, followed by reaction at 60° C. for 3 hours. After cooling the reaction solution, adjust the pH to 9.5 or higher with a 30 weight aqueous sodium hydroxide solution, remove methanol, water, etc. by vacuum distillation, and remove precipitated salt (sodium nitrate) by filtration. 4) O-phthaloguanamine resin B as a new amino resin was obtained.

The above O-7 Taguanamine Resin B was subjected to IR analysis, H-NMRfNIT and gel permeation chromatography analysis in the same manner as in Example 1.The IR spectrum was almost the same as that in Figure 1. It was confirmed that the average number of -N-C)b- structures per one pentene nucleus determined from the H-NMR spectrum was:
8. The average number of methoxy groups per O, benzene nucleus was 5.5. The number average molecular weight in terms of standard polystyrene determined by gel permeation chromatography is 535. The content of the main component attributed to the monomer by the cutout weight method was 87]i.

The above 0-7 Taguanamine Resin B was dissolved in butyl cellosolve to prepare a resin solution with a nonvolatile content (108° C./3 hours) of 75 weight is. Gardner viscosity (2
5°C) was Y-Z, and the Gardner color number was 1 or less.

Example 3.4 and Comparative Example 1 The phthaloguanamine resin-containing resin solution prepared in Example 1 and Example 2 and the butyl cellosolve resin solution of B (non-volatile content: 75% by weight) and the methylated melamine resin (Hitachi Chemical Co., Ltd.) Manufactured by Melan 523, non-volatile content 96% by weight
) to a water-soluble acrylic resin with a hydroxyl value of 22 and an acid value of 33 (manufactured by Hitachi Chemical Co., Ltd., trade name: Hitaloid 7200,
Non-volatile content: 50% by weight, solvent water/impropanol = 1/
1 (weight ratio)) and combinations shown in Table 1, a water-based paint was prepared. It was coated on a tin plate using a bar coater φ18 so that the dry thickness was 7 μm.

It was cured at 170° C. for 10 minutes to obtain a test piece. The pencil hardness, Elixir value, impact value, and ice boiling resistance of each test piece were examined, and the results are shown in Table 2.

The test method for the coating film is as follows.

(1) Pencil hardness 2 Determined using Mitsubishi Pencil Uni.

(2) Erichsen value: Tested according to JIS K 5400.

(3) Impact value: DuPont impactor 1/2″-5009
It was determined in centimeters.

(4) Water boiling resistance: After being immersed in boiling water for 1 hour, it was taken out and the condition of the coating surface was visually judged.

○ No change △ Slightly attacked × Severely attacked Table 2 It is clear that the amino resin with good coating film performance is superior to the amino resin of Comparative Example 1 in water dilutability.

Comparative Example 2 A butylated phthaloguanamine resin was obtained in the same manner as in Example 1, except that all methanol was replaced with n-butyl alcohol.

Measurement of water dilutability The amino resins obtained in Example 1 and Comparative Example 1 were evaluated for water dilutability, and the results are shown in Table 3.

To determine water dilutability, each resin solution (butyl cellosolve solution, nonvolatile content 75% by weight) was diluted little by little with water, and the transmittance at 600 nm was measured using an absorption photometer.
Evaluation was made based on the amount of water at which the transmittance was 50%. From this table, it can be seen that the novel amino resin of the present invention has excellent water dilutability and is suitable as an amino resin for water-based paints. It has superior hardness compared to the melamine resin that was previously used,
In particular, flexibility (Erichsen values in Table 2).

It is shown that it has excellent impact value (substituted by impact value) and water boiling resistance.

(Effects of the Invention) A resin composition for water-based paints with excellent water dilutability, hardness, flexibility, and water boiling resistance is obtained by using a new amino resin containing the novel amino compound of the present invention as a main component. be able to.

[Brief explanation of drawings]

Figure 1 shows the infrared absorption spectrum of 0-7 taguanamine obtained in Synthesis Example 1, Figure 92 shows the infrared absorption spectrum of the phthaloguanamine resin-containing product obtained in Example 1, and Figure 3 shows the infrared absorption spectrum of 0-7 taguanamine obtained in Synthesis Example 1. IH- containing phthaloguanamine resin obtained in Example 1
The NMR spectrum and FIG. 4 are gel permeation chromatograms containing phthaloguanamine resin obtained in Example 1. secret thinking

Claims (1)

[Claims] 1. A novel amino compound represented by the general formula [I]. ▲There are mathematical 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_2OR_9 (however, R_9 represents an alkyl group having 1 to 3 carbon atoms)) 2. The main component is a novel amino compound represented by the above general formula [I], and other components of the compound A new amino resin containing a multimer as a subcomponent. 3. General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] (In the formula, the substitution position of the benzene ring is the ortho, meta or para position) Phthaloguanamine is methylolated, A novel method for producing an amino resin, which is then etherified using an alcohol having 1 to 3 carbon atoms. 4. (A) General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] (In the formula, the substitution position of the benzene ring is the ortho, meta or para position) Phthaloguanamine A resin composition for water-based paints, comprising a novel amino resin obtained by methylolization and then etherification using an alcohol having 1 to 3 carbon atoms, and (B) a resin that reacts with the amino resin.