JPH08294668A - Precoat metal - Google Patents

Abstract

PURPOSE: To take the balance of bending processability, antistaining properties and hardness and to enhance other coating film properties by applying a specific one-pack type thermosetting resin compsn. CONSTITUTION: A first component is composed of polyester polyol having at three functional groups and a second component is composed of a compd. obtained by adding a lactone compd. or alkylene oxide to an epoxy resin having at least one secondary hydroxyl group and a third component is composed of org. blocked polyisocyanate or a blocked prepolymer having a NCO terminal group obtained by reacting org. polyisocyanate and active hydride. An one-pack type thermosetting resin compsn. containing the first - third components is prepared. This compsn. is applied to a metal panel and heated and cured to form precoat metal.

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention
Pleco with good hardness balance and excellent stain resistance
Regarding metal. [0002] In general, precoated metal is a zinc iron plate.
Paint the other metal plate in advance and then make it into any shape
It is molded and provided for final use. For example,
Home appliances such as refrigerators, washing machines, electric stoves, vending
Furniture including vending machines, office equipment, food display cases, etc.
Used for metal products. Such precoated gold
The metal plate is formed into a complex shape by molding a metal plate first.
Compared to the post-coating method in which painting is added later, the painting process is
Streamlined, uniform quality, paint consumption
In the future, there are advantages such as savings in volume
Its use is expected to expand. Pre-coated metal
The paint applied to the board, according to the above application after the coating film formation
Since it is molded into a shape, the coating film is bent and
Resistance to molding processes such as metal molding, embossing press, drawing
Maintain sufficient extensibility and adhesion to metal surfaces
Is required. On the other hand, the products after molding
Performance suitable for end use, for example, for building exterior materials
High weather resistance and strong corrosion resistance including processed parts are required
Household appliances, such as refrigerators,
Contamination is required. Besides these performances, gloss and water resistance
Durability, such as chemical resistance, chemical resistance, and moisture resistance,
Required. In applications such as the home appliances mentioned above,
Amino alkyd resin, melamine cured acrylic poly
All or epoxy resin was used. By the way
However, with these resins, the bending workability of the coating film is poor, and
Defects that cause cracks in the coating when bent at an angle of more than °
There is a point. Bis (isocyanatomethyl) cyclohexa
Blocker of adduct or its adduct and polyol resin
Is applied to a metal plate and cured by heating.
A method of manufacturing a pre-coated metal is also known (Japanese Unexamined Patent Application Publication No.
No. 56-89548) obtained by this method.
Pre-coated metal is not always
Not all satisfied. In addition, ethyleneimid
Blocked isocyanate compound and poly
Applying a composition containing an all-resin to a metal plate,
Also known is the method of manufacturing pre-coated metal by heat curing
(JP-A-57-10375), this method
The pre-coated metal obtained by
I was not satisfied with all my sexuality. [0003] The folding as described above
Paint with balance of processability, stain resistance and hardness
Improving membrane performance has been a very difficult task.
The present invention relates to bending workability, stain resistance and hardness.
It is well-balanced and also in other coating performance.
To provide a pre-coated metal with a stray coating
To aim. [0006] The present inventors
No cracks will occur in the coating film even after bending after coating
Diligently study which resin composition has excellent coating performance
As a result, the number of functional groups was low as a polyol component.
Reduce at least 3 polyester polyols and secondary hydroxyl groups
At least one epoxy resin has a lactone compound or
Is a combination with the one with alkylene oxide added
By using it, bending resistance is good and hardness is high,
In addition, chemical and stain resistance, especially magic stain resistance
And found that a coating film with excellent stain resistance can be obtained.
However, based on these findings, the present invention was completed.
It was That is, in the present invention, (1) the number of functional groups is at least
Polyester polyol (3), secondary hydroxyl groups (2)
At least one epoxy resin has a lactone compound or
Is an alkylene oxide-added product and (3) yes
Of organic polyisocyanate or organic polyisocyanate
Obtained by the reaction of a socyanate with an active hydrogen compound
A blocked product of a prepolymer having an NCO group at the terminal,
A one-pack thermosetting resin composition containing
A pre-coated film characterized by being clothed and heat-cured.
It is tall. DETAILED DESCRIPTION OF THE INVENTION (1) Functionality used in the present invention
Polyester polyols with at least 3 groups are
Rubonic acid, glycol and at least three OH groups
Obtained by esterifying a polyol having
It Zical used in the production of polyester polyols
Examples of boric acid include succinic acid, succinic anhydride,
Dipic acid, azelaic acid, sebacic acid, dodecane diacid,
Maleic acid, maleic anhydride, fumaric acid, itacone
Aliphatics such as acid, dimer acid, etc., eg phthal
Acid, phthalic anhydride, isophthalic acid, isophthalic acid
Dimethyl ester, terephthalic acid, terephthalic acid di
Methyl ester, 2,6 naphthalenedicarboxylic acid, hex
Sahydrophthalic anhydride, tetrahydrophthalic anhydride
Acid, cyclohexanedicarboxylic acid dimethyl ester,
Tyl hexahydrophthalic anhydride, hymic anhydride,
Of aromatic and alicyclic systems such as methylhymic anhydride
I can give you something. As glycol, for example, ethylene
Len glycol, diethylene glycol, propylene glycol
Recall, 1,3-butylene glycol, 1,4-butyl
Len glycol, dipropylene glycol, 1,5-pe
Pentanediol, 1,6-hexanediol, neopen
Neopentyl of tyl glycol and hydroxypivalic acid
Glycol ester, triethylene glycol, 1,9
-Nonanediol, 3-methyl-1,5 pentanedio
Le, 2,2,4-trimethyl-1,3-pentanedio
, 2-ethyl-1,3-hexanediol, polycap
Lactone diol, polypropylene glycol, poly
Tetramethylene ether glycol, polycarbonate
Diol, 2-n-butyl 2-ethyl 1,3-propane
Diol, 2,2-diethyl-1,3-propanedio
Aliphatic compounds such as cyclohexane dime
Tanol, cyclohexanediol, xylylene glyco
, Bishydroxyethyl terephthalate, 1,4-bi
(2-hydroxyethoxy) benzene, hydrogenated bisphene
Ethylene oxide addition of Nole A and Bisphenol A
Is a propylene oxide adduct of bisphenol A
Any alicyclic or aromatic one can be mentioned. Polyol having at least 3 OH groups
For example, glycerin and trimethylol pro
Bread, trimethylolethane, 1,2,6-hexanetri
Oat, pentaerythritol, diglycerin and this
With ethylene oxide using these polyols as initiators
Additive, propylene oxide adduct or ε-capro
Lactone adducts and the like. The esterification reaction is
It is carried out by distilling off the condensate by a conventional method.
However, since the product is polyfunctional, the reaction proceeds too much.
If the acid value is 0.1 to 50, it may cause gelation.
It is preferable to stop in the range of 1 to 20. Concrete made
As a manufacturing method, for example, dicarboxylic acid is
At a temperature of 180 to 260 ° C.
Condensed water is distilled off while blowing gas, and the
Polyester having COOH groups at both ends by reacting up to the valence
Obtain the telluride. Then the end of this polyester compound
PO with at least three OH groups to become OH groups
Charge liol, distill off the condensed water in the same manner, and
Is stopped at 50 or less, preferably in the range of 1 to 20
Law. In addition, the dimethyl ester of dicarboxylic acid
In case of using alcohol, prepare more than the number of moles of glycol.
Then, the condensate was distilled off under the same conditions as above, and both ends were
To obtain a polyester having a polyester ester group
Charge a polyol with at least 3 OH groups,
Transesterification is carried out under the same conditions as
To obtain rupolyol. When using an acid anhydride together,
Charge the acid less than the number of moles of glycol, as above
The condensate is distilled off under the following conditions, and first, OH groups are present at both ends.
To obtain a polyester compound, and then dicarboxylic anhydride is obtained.
To have COOH groups at both ends by this ring opening reaction
To obtain a polyester compound. Then at least three O
A polyol having an H group was charged and the same method as described above was used.
There is a method to obtain polyester polyol by reacting.
You can Polyester polyol used in the present invention
Has a number of functional groups of 3 to 7, especially 4 to 6, and a number average molecular weight of
600 to 3500 and a hydroxyl value of 80 to 460
It is particularly preferable that when the number of functional groups is less than 3
The hardness of the coating film decreases, and the chemical resistance deteriorates. Further, when the number of functionalities exceeds 7, the coating film is resistant to bending.
May deteriorate. Number average molecular weight less than 600
Then the gloss of the cured coating becomes worse, and when it exceeds 3500
High viscosity, causing problems in painting workability,
Pollution may worsen. When the hydroxyl value is less than 80
In this case, the chemical resistance and stain resistance of the cured coating may deteriorate.
It If the hydroxyl value exceeds 460, the coating film will not bend.
Performance may worsen. Polio used in the present invention
(2) secondary hydroxyl group which is the other component
Epoxy resin having at least one lactone compound
Or as a product to which an alkylene oxide is added,
Lactone compounds and epoxy resins represented by the following general formula
Or alkylene oxide added by means known per se
What was done is given. Embedded image [Wherein X is phenylene optionally substituted with halogen]
And n is 0.5 to 12.0.
Indicates. [0009] Lactone compound or alkylene oxide
The added amount of the resin is about 95 to 60 parts by weight of the epoxy resin.
About 5 to 40 parts by weight. In particular, the epoxy resin
About 90 to 70 parts by weight of the lactone compound or
The xylene oxide is preferably about 10 to 30 parts by weight. Up
Among the epoxy resins represented by the general formula, X is p-f
N is preferably an enylene group, and n is preferably 2 to 9. Ha
Examples of logens include bromine and chlorine.
It The number of this substituent is usually about 1 to 3 and its position
Is a phenylene group or a cyclohexylene group
It may be a position. As the lactone compound, for example, β-
Propiolactone, butyrolactone, γ-valerolactone
, Γ-caprolactone, δ-valerolactone, δ-capro
Prolactone, ε-caprolactone, etc.
However, among these, ε-caprolactone is particularly preferred.
Yes. As the alkylene oxide, for example, ethylene
Oxide, propylene oxide, styrene oxide
Glycidyl methacrylate, epichlorohydrin
But ethylene oxide is particularly preferred.
Yes. Epoxy resin having at least one secondary hydroxyl group
To the lactone compound or alkylene oxide
The blending ratio of the dried product is about 10 to 70
%, But especially in the range of about 10 to 60% by weight.
It is preferably used. Less than 10% by weight
Of the contamination properties, especially mustard resistance may deteriorate.
It If it exceeds 70% by weight, the stain resistance is good.
However, the hardness may be extremely reduced. Blocked compound (3) used in the present invention
Is a compound having at least two NCO groups,
For example, trimethylene diisocyanate, tetramethyl
Range isocyanate, hexamethylene diisocyanate
G, pentamethylene diisocyanate, 1,2-propyl
Diisocyanate, 2,3-butylene diisocyanate
1,3-butylene diisocyanate, 2,4,4-
Or 2,2,4-trimethylhexamethylene diisocyanate
Nate, dodecamethylene diisocyanate, 2,6-di
Aliphatic diisomers such as isocyanate methyl caproate
Cyanates such as 1,3-cyclopentanediisocy
Anate, 1,4-cyclohexane diisocyanate,
1,3-cyclohexane diisocyanate, 3-isocyanate
Anatomethyl-3,5,5-trimethylcyclohexyl
Isocyanate, 4,4'-methylenebis (cyclohexene
Silisocyanate), methyl-2,4-cyclohexa
Diisocyanate, methyl-2,6-cyclohexane
Diisocyanate, 1,2-bis (isocyanatomethyi)
) Cyclohexane, 1,4-bis (isocyanatome)
Tyl) cyclohexane, 1.3-bis (isocyanate
Methyl) cyclohexane, trans-cyclohexane-
Cycloalkylene-based diene such as 1,4-diisocyanate
Isocyanates such as m-phenylenediisocyanate
, P-phenylene diisocyanate, 4,4'-di
Phenyl diisocyanate, 1,5-naphthalenediiso
Cyanate, 4,4'-diphenylmethane diisocyanate
2,4- or 2,6-tolylene diisocyanate
G, 4,4'-toluidine diisocyanate, dianisium
Gin isocyanate, 4,4'-diphenyl ether di
Aromatic diisocyanates such as isocyanates
Ω, ω'-Diisocyanate-1,3-dimethylbenze
, Ω, ω'-Diisocyanate 1,4-dimethylbenze
, Ω, ω'-Diisocyanate-1,4-diethylben
Zen, α, α, α ', α' tetramethylmetaxylylene
Isocyanate, α, α, α ', α' tetramethylparaxyl
Aromatic diisocyanates such as silylene diisocyanate
Nate, for example triphenylmethane-4,4 ', 4 "-
Triisocyanate, 1,3,5-triisocyanate
Benzene, 2,4,6-triisocyanate toluene, ω-
Isocyanate ethyl-2,6-diisocyanate cap
Triisocyanates such as roate, for example, 4,4 '
-Diphenyldimethylmethane-2,2 ', 5,5'-teto
Blocks of tetraisocyanate such as laisocyanate
Reaction of hydrides or these with active hydrogen compounds
The block of the prepolymer having an NCO group at the end obtained is obtained.
I can give you some of these. When used as a pre-coated metal, weather resistance
Is required for the compound having an NCO group.
Hexamethylene diisocyanate, 3-isocyanate
Natomethyl-3,5,5-trimethylcyclohexylyl
Socyanate, 1,4-bis (isocyanatomethyl)
Cyclohexane, 1,3-bis (isocyanatomethyl
) Cyclohexane, 4,4'-methylenebis (cyclo
Hexyl isocyanate), α, α, α ', α'tetrame
Isocyanes such as tilmetaxylylene diisocyanate
It is preferable to use a salt compound. These isocyanes
Terminal obtained by the reaction of a salt compound with active hydrogen activity
The prepolymer having an NCO group in the isocyanate is
Excess isocyanate group between monomer and active hydrogen compound
It is obtained by reacting in a state. This prepolymer
As active hydrogen compounds used to produce
For example, ethylene glycol, propylene glycol
1,2-butylene glycol, 1,3-butylene glycol
Coal, 1,6-hexanediol, diethylene glyco
, Dipropylene glycol, neopentyl glycol
, Neopentyl glycol hydroxypivalate S
Tellurium, triethylene glycol, hydrogenated bisphenol
A, xylylene glycol, 1,4-butylene glyco
Dihydric alcohol such as glycerin, trime
Tyrolethane, trimethylolpropane, 1,2,6-
Trihydric alcohols such as hexanetriol, such as
Low molecular weight compounds such as tetrahydric alcohols such as nantaerythritol
Amount of polyol, propylene oxide of the above polyol
Or polyether such as ethylene oxide adduct
Polyol, the aforementioned low molecular weight polyol and dicarboxylic acid
Polyester polyol or poly obtained by reacting with
Those modified with fatty acids when producing ester polyols
And high molecular weight polyols. These poly
All may be used alone or in combination. The prepolymer is generally an NCO group / OH
The equivalent ratio with the group is about 2.0 to 15, preferably about 4 to 8
At 40 to 140 ° C., preferably 70 to 100 ° C.
After the reaction, if necessary, unreacted isocyanate
The usual thin film distillation or extraction methods
It can be obtained by removing with a method. This anti
In particular, organometallic catalysts such as tin, lead, zinc, and iron
May be used. In addition, as the prepolymer, water,
Or lower amine such as ethylenediamine and excess
Bullet obtained by reacting isocyanate monomer
Compound or low molecular weight polyol or high molecular weight
By reacting riol with excess isocyanate monomer
The resulting allophanate compound, and the organic diisocyanate
Catalysts known as dimerization and trimerization catalysts for anates
By reacting the isocyanate monomer with a medium.
Dimerized compounds and trimer compounds obtained
Be done. The aforementioned isocyanate monomers or their prepolymers
Blocked polymer is isocyanate monomer or
These prepolymers are used as a blocking agent by a known method.
It is obtained by reacting. Used in this reaction
Blocking agent for isocyanate blocking
Blocking agents known to be used, such as
Phenol, lactam, active methylene, alcohol
, Mercaptan, acid amide, imide, amine
System, imidazole system, urea system, carbamate system, imid
Or oxime-based or sulfite-based blocks
Any of the agents can be used, especially phenolic,
Oxime-based, lactam-based, imine-based blocking agents
Used to advantage. The following are specific examples of the blocking agent.
I can give you something. Phenolic blocking agent: phenol, phenol
Resol, xylenol, nitrophenol, chloroph
Phenol, ethylphenol, p-hydroxydiphenyl
Ru, t-butylphenol, o-isopropylphenol
, O-sec-butylphenol, p-nonylpheno
, Pt-octylphenol, hydroxybenzoate
Acid, hydroxybenzoic acid ester, etc. Lactam blocking agent: ε-caprolactam, δ-vale
Loractam, γ-butyrolactam, β-propiolacta
Etc. Active methylene block agents: diethyl malonate, malon
Dimethyl acid, ethyl acetoacetate, methyl acetoacetate,
Cetylacetone etc. Alcohol blocking agent: methanol, ethanol, n
-Propyl alcohol, isopropyl alcohol, n-
Butyl alcohol, isobutyl alcohol, t-butyl
Alcohol, n-amyl alcohol, t-amyl alcohol
, Lauryl alcohol, ethylene glycol monomer
Tyl ether, ethylene glycol monoethyl ether
, Ethylene glycol monobutyl ether, diethyl
Glycol glycol methyl ether, diethylene glycol
Lumonoethyl ether, propylene glycol monomethyl
Ruether, benzyl alcohol, methoxy methanol
L, glycolic acid, methyl glycolate, glycolic acid
Ester such as ethyl and butyl glycolate
Lactic acid, methyl lactate, ethyl lactate, butyl lactate, etc.
Lactate ester, methylol urea, methylol melamine,
Diacetone alcohol, ethylene chlorohydrin, ethi
Lenbromhydrin, 1,3-dichloro-2-propano
, Ω-hydroperfluoroalcohol, acetoxy
Anhydrin etc. [0014] Mercaptan-based blocking agent: butyl merca
Ptan, hexyl mercaptan, t-butyl mercapta
, T-dodecyl mercaptan, 2-mercaptobenzo
Thiazole, thiophenol, methylthiophenol,
Ethylthiophenol and the like. Acid amide block agents: acetanilide, acetaniishi
Zide, acetoloid, acrylamide, methacrylure
Mid, acetic acid amide, stearic acid amide, benzamide
Such. Imide-based blocking agents: succinimide, phthalic acid
And maleic imide. Amine-based blocking agent: diphenylamine, phenylnaphth
Cylamine, xylidine, N-phenylxylidine, mosquito
Lubazole, aniline, naphthylamine, butylami
, Dibutylamine, butylphenylamine and the like. Imidazole blocking agent: imidazole, 2-ethyl
Such as imidazole. Urea blocking agents: urea, thiourea, ethylene urea, d
Tylene thiourea, 1,3-diphenyl urea, etc. Carbamate-based blocking agent: N-phenylcarbamine
Phenyl acid, 2-oxazolidone and the like. Imine blocking agents: ethyleneimine, propyleneimine
And so on. Oxime blocking agents: formamidoxime, acetoa
Rudoxime, acetoxime, methyl ethyl ketoxime,
Diacetyl monooxime, benzophenone oxime, shi
Clohexanone oxime and the like. Sulfite blocking agent: sodium bisulfite,
Potassium bisulfite, etc. The aforementioned isocyanate monomers or their prepolymers
As a specific method of reacting the blocking agent with the
Isocyanate monomers or their prepolymers
And blocking agent with NCO group / active hydrogen group in blocking agent
Equivalent ratio of about 0.9 to 1.0, preferably about 0.95
1.0, reaction with isocyanate monomer and bromine
NCO group / Equivalent of active hydrogen group in blocking agent
Ratio = about 1.1-3.0, preferably about 1.2-2.0
After reacting, it is used for the production of the prepolymer described above.
Low molecular weight polyols, high molecular weight polyols
Method of reacting with water, water or lower amine, or
Is isocyanate monomer and low molecular weight polyol, polymer
Amount of polyol, water or lower amine NCO group / active
Equivalent ratio of hydrogen groups = about 1.5 to 10.0, preferably about 2.
After reacting at 0 to 7.0, the blocking agent was reacted with this.
And the like. Each of the above reactions is an active hydrogen group
Solvent (eg, benzene, toluene, xylene
Aromatic systems such as, Solvesso 100, Solvesso 20
Petroleum-based solvents such as ethyl acetate, butyl acetate, etc.
Steroids such as acetone, methyl ethyl ketone,
Ketones such as chill isobutyl ketone and cyclohexanone
System, for example, ether system such as tetrahydrofuran
Etc. or in the absence of such a solvent by known methods.
Done. In the reaction, for example, tertiary amine, organic
A known catalyst such as a metal may be used. Used in the present invention
The one-component thermosetting resin composition used is the above-mentioned polyol.
Containing (1) and (2) and blocked product (3)
Is a composition. Mixing ratio of polyol and blocked product
When the equivalent ratio of OH group / regenerated NCO group is about 1/2 to 2 /
1, especially 1 / 0.8 to 1 / 1.2. The composition of the present invention can be used as a clear paint or
Can be used as an adhesive, etc.
In addition to all and blocked products, for example, ethyl acetate
Butyl acetate, methyl acetoacetate, 2-ethoxyethyl
Ester type such as ru-acetate, xylene, toluene
Aromatics such as methyl ethyl ketone, methyl isobuty
Ketones such as luketone and cyclohexanone,
Ether type such as glycol glycol dimethyl ether, sol
Petroleum-based, such as Vesso 100 and Solvesso 200
Organic solvents, such as coloring pigments, extender pigments, silicon
System, amine system, polyether system, polyester system, castor
Dispersion of oil, synthetic wax, bentonite, etc.
Agent, antifoaming agent, leveling agent, thixotropic agent, benzotriazo
, Hindered amine, hindered phenol
Which stabilizer, tin-based, lead-based, zinc-based, iron-based reaction catalyst, etc.
Etc. may be added as needed. Obtained in this way
The one-part thermosetting resin composition is applied to a metal plate and
Blocking agent contained in the blocked product by heating
Dissociates to regenerate NCO groups, and the regenerated NCO groups
It reacts with the OH groups in the oar to give a cured coating. [0017] Used for producing the pre-coated metal of the present invention.
Metal plates are usually used as pre-coated metal
Anything can be used, but even if
Cold rolled steel sheet, galvanized steel sheet, alloyed galvanized steel sheet,
Tin plated steel plate, chrome plated steel plate, aluminum plating
Steel sheet, lead-plated steel sheet, nickel-plated steel sheet, aluminum
Plate, titanium plate, stainless plate, and the like. Book
The resin composition used in the invention may be applied directly or by an ordinary coating.
Painted after pre-mounting treatment. Also, in any case
After applying the primer paint and drying if necessary
Alternatively, the resin composition can be applied without drying. Paint
Chromate conversion treatment or phosphate conversion treatment
Processing, complex oxide film treatment, etc. Chromate conversion treatment
Include electrolytic chromate, coating chromate, and reactive chromate
Coating treatment, zinc phosphate treatment and phosphate treatment
The iron oxide treatment is nickel and cobalt for the composite oxide film treatment.
There is a treatment that contains Primer paint is epoxy tree
Commonly used such as fat type and high molecular weight polyester type
Can be used. As the shape of the metal plate, for example, a flat plate
Shape, cylindrical shape, etc. In the present invention,
The resin composition to be used is applied. Limited amount of coating
It can be freely decided, but dry film thickness 10
The amount is preferably 30 μm. As a means of applying
For example, spray gun, roll coater, flow
Coaters and the like. Next, remove the coated metal plate
Heat cure. The heating temperature depends on the type of blocking agent, etc.
About 150 to 350 ° C. for about 20 hours.
It is preferably about 120 seconds. This heating operation
The blocking agent contained in the compound dissociates to form the NCO group
It is regenerated, and the regenerated NCO groups react with the OH groups in the polyol.
Correspondingly, crosslinking occurs and a tough coating film is obtained. The one-component thermosetting resin used in the present invention
The coating film obtained by curing the composition is burned by heating.
No heat deterioration was observed. Moreover, it has high hardness and can be bent
In terms of buffing workability, stain resistance, and above all resistance to mustard stain
It is excellent. Therefore, the precoat coated with this composition
Coated metal can be used advantageously for home appliances.
it can. EXAMPLES The present invention will be described below with reference examples and examples.
This will be described more specifically. In the examples, part or% is that
Each part by weight or% by weight is shown. Production Example 1 of Polyol Hydrogenated bisphenol A 364.9 parts (1.52 mol),
Adipic acid 441.6 parts (3.02 mol) was prepared in a reaction vessel.
To 220 ° C and blow nitrogen gas to generate
The reaction is carried out while distilling off the condensed water to give an acid value of 250.0.
Where trimethylolpropane (hereinafter referred to as TMP)
304.1 parts (2.27 mol) were charged, and
The reaction was carried out while distilling off the combined water, and the acid value was 2.6 and the hydroxyl value was 18
7.2, 5 functional groups, number average molecular weight 1478
A terpolyol was obtained. This polyester polyol 6
With respect to 00 parts and 80 parts by weight of the epoxy resin of the following formula,
A product with 20 parts by weight of caprolactone added (Plaxel
G-402 (manufactured by Daicel Chemical Industries, Ltd.), hydroxyl value 1
19, epoxy equivalent 1250) 400 parts
Dissolved in 1500 parts of Sanon to make a 40% solids solution
It was The properties of this solution are shown in [Table 1]. Embedded image Reference Example 2 800 parts of the polyester polyol obtained in Reference Example 1
Epsilon-caprola to 80 parts by weight of epoxy resin of the following formula
With 20 parts by weight of lactone (Placcel G-70)
2 (manufactured by Daicel Chemical Industries, Ltd.), hydroxyl value 140, d
200 parts of poxy equivalent 2710) is cyclohexanone 1
It was dissolved in 500 parts to obtain a solution having a solid content of 40%. This melt
The properties of the liquid are shown in [Table 1]. Embedded image Reference Example 3 205.8 parts of 1,6-hexanediol (1.74 moles)
), 670.1 parts of dimethyl isophthalate (3.45
) And 0.1 g of zinc acetate in a reaction vessel,
Into the furnace and blow nitrogen gas to generate methanol.
Reaction was carried out while distilling off, and 121 ml of methanol was distilled off.
Charge TMP347.2 parts (2.59 moles)
Then, the acid value is 1.
4, hydroxyl value 193.6, number of functional groups 5, number average molecular weight 1
438 polyester polyols were obtained. This Poles
600 parts of terpolyol and Praxel G-4 of Reference Example 1
02 Dissolve 400 parts in 1500 parts of cyclohexanone
Then, a solution having a solid content of 40% was obtained. The properties of this solution
1]. Reference Example 4 24-Methyl-1,5-pentanediol 245.3 parts (2.
08 mol) and 541.6 parts (3.71 mol) of adipic acid
Charge to a reaction vessel, heat to 220 ° C and blow nitrogen gas.
Acid, the reaction is carried out while distilling off the condensation water generated, and the acid value is 2
When it reached 80.0, TMP 372.9 copy (2.7
8 mol) and 0.1 part of dibutyltin dilaurate are charged.
Similarly, the reaction was carried out while distilling off the condensed water, and the acid value was 1.6.
Hydroxyl value 216.0, number of functional groups 5, number average molecular weight 128
Thus, 9 polyester polyols were obtained. This polyester
800 parts of polyol and Praxel G-402 of Reference Example 1
Dissolve 200 parts in 1500 parts of cyclohexanone,
A 40% solution was obtained. The properties of this solution are shown in [Table 1].
Indicated. Reference Example 5 151.8 parts (2.45 mol) of ethylene glycol, amber
550.0 parts (4.66 mol) of citric acid were charged.
When the reaction was performed under the same conditions and the acid value reached 420.0,
159.3 parts (1.17 mol) of pentaerythritol
, The esterification reaction continued, and the acid value became 165.0.
By the way, further pentaerythritol 159.3 parts
(1.17 mol) and 157.0 parts (1.17 mol) of TMP
Was added and the condensation water was distilled off to give an acid value of 3.8 and a hydroxyl value of 44.
Polyester with 7.8, 7 functional groups and 870 number average molecular weight
A rupolyol was obtained. This polyester polyol 80
0 parts and 200 parts of Praxel G-402 of Reference Example 1
Dissolved in 1500 parts of clohexanone and dissolved at a solid content of 40%
It was a liquid. The properties of this solution are shown in [Table 1]. Reference Example 6 325.9 parts of bishydroxyethyl terephthalate (1.
28 mol), 513.8 parts (2.54 mol) of sebacic acid
The reaction was carried out under the same conditions as in Reference Example 1, and the acid value was 18
When it became 4.4, TMP256.7 part (1.91 model)
), And condensed water is distilled off.
With a base number of 168.3, a functional group number of 5, and a number average molecular weight of 1591
A polyester polyol was obtained. This polyester poly
All 800 parts and Praxel G-402 2 of Reference Example 1
00 parts was dissolved in 1500 parts of cyclohexanone.
A 40% solution was obtained. The properties of this solution are shown in [Table 1].
It was Reference Example 7 183.4 parts of ethylene glycol (2.95 mol), amber
664.7 parts of citric acid (5.63 mol) were charged,
When the reaction was performed under the same conditions and the acid value reached 420.0,
189.4 parts of TMP (1.41 mol) were charged,
When the acid value reached 170.0,
183.4 parts of ethylene glycol (2.95 mol)
The condensed water of condensation was distilled off to obtain an acid value of 1.5 and a hydroxyl value of 215.5.
Polyester polyol having 3 functional groups and a number average molecular weight of 776
I got it. 800 parts of this polyester polyol
200 parts of Praxel G-702 of Example 2 was
Dissolved in 1500 parts of Sanon to make a 40% solids solution
It was The properties of this solution are shown in [Table 1]. Preparation of Blocked Product Reference Example 8 1,3-Bis (isocyanatomethyl) cyclohexane
241.6 parts dissolved in 400.0 parts Solvesso 100
Then, add 180.6 parts of methyl ethyl ketoxime in 1 hour.
Down. After dropping, heat to 75-80 ° C for another hour
It Next, 0.6 parts of dibutyltin dilaurate and polyester
Lupolyol (876.6 parts of adipic acid, ethylene glycol
186.3 parts of Cole, 201.2 parts of TMP, dipropylene
Obtained by condensing 402.3 parts of glycol glycol by a conventional method.
Acid value 3.5, hydroxyl value 172.0, solid content 100%)
Add 177.0 parts and react at 75-80 ° C for 6 hours.
Thus, the regenerated isocyanate group content is 8.5% and the solid content is 6
0%, foam viscosity (25 ° C.)
Obtained. The properties of this solution are shown in [Table 2]. Reference Example 9 TMP-3-isocyanate was placed in a 2-liter 4-diameter flask.
Tomethyl-3,5,5-trimethylcyclohexyl isocyanato
Anate adduct solution (Takenate D-140N, (Takenate
75% solid content, including isocyanate
Amount of 10.78%, ethyl acetate solution) 801.2 parts and
Charge 316.1 parts of cellosolve acetate, and add nitrogen gas
Under an atmosphere, maintain the internal temperature at 60-70 ° C
182.7 parts of tilketoxime was slowly dropped, and the addition was completed.
After that, if the temperature is maintained for about 4 hours, the solid content is 60%,
A blocked solution having a isocyanate group content of 6.64% was obtained.
It was The properties of this solution are shown in [Table 2]. Reference Example 10 ω, ω'-Diisocyanate-1,3-dimethylbenze
307.5 parts to 519.1 parts of Solvesso 100
And methyl ethyl ketone dissolved in 129.7 parts, methyl
237.2 parts of ethyl ketoxime are added dropwise in about 2 hours.
After completion of the dropping, the mixture is heated at 75 to 80 ° C. for another hour. next
0.3 parts of dibutyltin dilaurate and the polyester used in Reference Example 8
Add 752.4 parts of reester polyol to 75-80
React at 6 ° C for 6 hours. Thus regenerated isocyanate groups
A blocked product solution having a content of 8.02% and a solid content of 55% was obtained.
It was The properties of this solution are shown in [Table 2]. Reference Example 11 TMP-hexamethylenediene was added to a 2-liter 4-diameter flask.
Isocyanate adducts (Takenate D-160N, (Take
75% solid content, including isocyanate
Amount 13.2%, foam viscosity (25 ° C) J to K) 760.7
And 325.6 parts of cellosolve acetate,
Keep the internal temperature at 60-70 ℃ under nitrogen gas atmosphere.
Slowly add 213.7 parts of methyl ethyl ketoxime.
After the addition is completed, the temperature is maintained at the above-mentioned temperature for about 2 hours to obtain a solid content of 60%.
%, Regenerated isocyanate group content 7.77%, foam viscosity
(25 ° C.) Blocked solutions of QR were obtained. This solution
The properties are shown in [Table 2]. Reference Example 12 4,4'-methylenebis (cyclohexyl isocyanate)
G) 228.6 parts of toluene 160.0 parts and cyclo
Hexanone dissolved in 160.0 parts, methyl ethyl ketoki
126.5 parts of shim are added dropwise in about 1 hour. After dropping
Then heat to 75-80 ° C for 1 hour. Next, 1,1,3,3
-Tetra-n-butyl-1,3-diacetoxydistannoki
Sun 0.48 parts and polyester polyol (Refer to Example 8)
Same as polyester polyol used) 123.92 parts
And react at 75-80 ° C. for 8 hours. Thus play
Block with isocyanate group content of 7.6% and solid content of 60%
A chloride solution was obtained. Table 2 shows the properties of this solution.
It was Reference Example 13 A 2-liter 4-diameter flask was placed in a stirrer, a thermometer, and nitrogen gas.
Attach the inlet pipe and condenser for reflux cooling,
α, α, α ', α' Tetramethylmethacrylylene diisocyanate
Adduct with anate (solid at room temperature, isocyanate
500 parts, ethyl acetate 427.1 parts
And 1,1,3,3-tetra-n-butyl-1,3-dia
0.19 parts of cetoxydistannoxane was charged and nitrogen gas was added.
Under an atmosphere, maintain methyl-ethyl
Add 140.5 parts of luxetoxime gradually and add
After completion of the addition, if the temperature is maintained for about 4 hours, the solid content is 60%,
Raw isocyanate group content 6.20%, foam viscosity (25
C) Blocked solutions of QR were obtained. Properties of this solution
Are shown in [Table 2]. Example 1 43.4 parts of the polyol solution obtained in Reference Example 1 and Reference Example
24.5 parts of block 8 (NCO / OH equivalent)
Quantity ratio = 1.0), PWC (pigment weight concealment)
(Translation) = 50%.
Ipaque R-820; Ishihara Sangyo Co., Ltd. 32.1 parts
Put in. Further, 1,1,3,3-tetra-n-butyl is used as a catalyst.
Add 1,024 diacetoxy distannoxane 0.024 parts
And knead well with a paint conditioner.
A namel solution was obtained. This solution was added to 0.6 mm thick electrolytic zinc.
After subjecting the plated steel sheet to electrolytic chromate treatment,
Apply resin-based primer paint to a dry film thickness of 5μ.
On the baked product so that the dry film thickness becomes 20μ.
Paint with a bar coater and bake at 260 ° C for 60 seconds
A glossy white coating was obtained on application. White enamel
The composition and coating film performance are shown in [Table 3]. Examples 2 to 10 The blocked products of Reference Examples 8 to 13 are used and shown in [Table 3].
Thus, the total amount of the white enamel solution having a PWC = 50% is 100%.
About the composition which is to be a part, baking under the same conditions as in Example 1.
Injured. [Table 1] [Table 2] [Table 3] Evaluation method * ¹ Pencil hardness scratch mark method: Clean the paint film with a pencil according to the method of JIS-K-5400.
Lead, wipe the swept surface with absorbent cotton, and leave no scratch marks
Expressed by the hardness of the brush. JIS method: According to the method of JIS-K-5400. * ² Bending resistance: sandwich an iron plate of the same thickness as the test piece
And hand press 50kgG / cm ² Pressure of 180 degrees
Observe the bends and bends with a 30x loupe
Expressed by the minimum number of sandwiched steel plates that cannot fit in the rack. * ³ Stain resistance: Draw on the painted surface with magic ink,
After leaving it for 24 hours, wipe the absorbent cotton with ethanol.
And evaluate after the line. ：: No residue left. ◯: A slight mark remains. Δ: A slight mark remains. X: The rest remains clear. * ^Four Solvent resistance: Cloth is impregnated with xylene and fixed load
Scrape the coated surface with heavy weight, make 1 round trip and break the coated surface 50 times.
It is determined whether this occurs. * ^Five Mustard stain resistance: 60 parts of commercially available paste must be water 10
It is sufficiently dispersed in 0 part and the coated plate is immersed in this at room temperature.
Take it out after 24 hours, wash it thoroughly with water and visually check the state of the painted surface
evaluate. A: No yellow residue remains. ○: The yellow color remains slightly. Δ: The yellow color remains. ×: A clear yellow color remains.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Oka             Kimitsuichi, Chiba Prefecture, Japan Kimitsuichi Nippon Steel Corporation             Within (72) Inventor Yoshikatsu Matsuura             45, 655 Aoyu-Shinke, Minoh-shi, Osaka

Claims (1)

Claims (1) Polyester polyol having at least 3 functional groups, (2) Epoxy resin having at least one secondary hydroxyl group, to which a lactone compound or alkylene oxide has been added, and (3) organic polyisocyanate. A one-part thermosetting resin composition containing a blocked product of a prepolymer having an NCO group at the terminal obtained by the reaction of the blocked product or an organic polyisocyanate with an active hydrogen compound, and coating it on a metal plate, Pre-coated metal characterized by being heat-cured.