CN107849230A - Copolyester and profit use the metal primer coating of the copolyester - Google Patents
Copolyester and profit use the metal primer coating of the copolyester Download PDFInfo
- Publication number
- CN107849230A CN107849230A CN201680040100.4A CN201680040100A CN107849230A CN 107849230 A CN107849230 A CN 107849230A CN 201680040100 A CN201680040100 A CN 201680040100A CN 107849230 A CN107849230 A CN 107849230A
- Authority
- CN
- China
- Prior art keywords
- copolyester
- moles
- acid
- composition
- acid composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C09D167/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/002—Priming paints
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
- Paints Or Removers (AREA)
Abstract
The application provides a kind of copolyester, and it is effective as the adhesive component of the metal primer coating for coil coating.Furthermore, there is provided a kind of metal primer coating, is the coating composition for having used the copolyester, excellent in case hardness, bendability and corrosion resistance, chemical-resistant.A kind of copolyester (A), it is the copolyester using polybasic carboxylic acid composition and polyol component as copolymer composition, when setting whole polybasic carboxylic acid compositions as 100 moles of %, aromatic dicarboxylic acid composition is 95~100 moles of %, and aliphatic dicarboxylic acid composition is 0~5 mole of %；And when setting whole polyol components as 100 moles of %, the diol component with specific structure is 1~30 mole of %；The glass transition temperature of copolyester (A) is 25~50 DEG C of scope.
Description
Technical field
Metal primer coating the present invention relates to copolyester and using this copolyester.In more detail, the present invention relates to
And the resin and coating composition of corrosion resistance and excellent in workability.
Background technology
Copolyester as in smears, ink and bonding agent etc. the raw material that uses of resin combination and made extensively
With being typically made up of polybasic carboxylic acid and polyalcohol.Due to can freely be controlled by the selection and combination of polybasic carboxylic acid and polyalcohol
The height of flexibility processed or molecular weight, therefore the quilt in the miscellaneous purposes based on smears purposes or bonding agent purposes
Widely use.
Wherein, the coating of resinous composition is coated with the pre-coated metal formed on sheet metal, and normal use employs
The coating (such as patent document 1) of the excellent HMW copolyester of film bendability.However, using in terms of health effect
Have the polyalcohol of bisphenol-A main chain of doubt as neccessary composition, and if the polyester of HMW when coating is made solid constituent it is dense
Degree is high, then solution viscosity becomes very high, and operation becomes difficult.On the other hand, if reducing solid component concentration, it is difficult to improve
Coating thickness, it is also necessary to largely using solvent, therefore economically, environmentally have problem.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 5-295239 publications
The content of the invention
Invent problem to be solved
The present invention is completed using above-mentioned problem of the prior art as background.That is, it is an object of the invention to provide a kind of conduct
The adhesive component that is mixed in metal primer coating (metal bottom-coating) and effective copolyester, it is further provided even if
Higher-solid still maintain maneuverable low solution viscosity and with the high bendability that is equal with high molecular weight polyesters and
Can be formed high rigidity, corrosion resistance, good chemical resistance film coating composition.
To the means to solve the problem
The result that the present inventor attentively studies, discovery can be solved the above problems by means as shown below, reach this hair
It is bright.
That is, the present invention is made up of following.
A kind of copolyester (A), it is the copolyester using polybasic carboxylic acid composition and polyol component as copolymer composition, when
If whole polybasic carboxylic acid compositions are 100 moles of %, aromatic dicarboxylic acid composition is 95~100 moles of %, aliphatic dicarboxylic acid
Composition is 0~5 mole of %；And when setting whole polyol components as 100 moles of %, the diol component represented by formula (1)
For 1~30 mole of %；Scope of the glass transition temperature of the copolyester (A) at 25~50 DEG C,
[changing 1]
In formula (1), n is more than 3 integer.
Above-mentioned copolyester (A), preferred number average molecular weight are 4000~9000 scope.Furthermore it is preferred that it is free from fat
Race dicarboxylic acid component.
Above-mentioned formula (1) is preferably triethylene glycol.
A kind of metal primer coating, comprising the copolyester (A) described in any of the above-described, crosslinking agent (B), pigment (C), add
Add agent (D) and organic solvent (E).
A kind of metal coated panel, it has above-mentioned metal primer coating as prime coat.
Invention effect
Metal primer coating using the copolyester of the present invention is higher-solid and low solution viscosity, and is played high hard
Degree, high bendability, highly corrosion resistant and excellent chemical-resistant.Therefore, it is suitable for the coil coating of household electrical appliances or building materials
Prime coat.
Embodiment
The present invention described below.
＜ copolyesters (A) ＞
Excellent bendability, hardness, corrosion resistance and resistance toization are played using the metal primer coating of the copolyester (A) of the present invention
Learn moral character.Therefore, it is suitable as needing the primary coat of the metal foil of deformation processing after being coated with.Use the copolyester of the present invention
(A) product manufactured can be obtained with high rigidity and high working property, the film of highly corrosion resistant.
The present invention copolyester (A) as can by the condensation polymer of polybasic carboxylic acid composition and polyol component obtained by chemistry
Structure is formed, and polybasic carboxylic acid composition and the one kind or two or more selected composition of each freedom of polyol component are formed.
In the copolyester (A) of the present invention, polybasic carboxylic acid composition is preferably dicarboxylic acids, more preferably aromatic dicarboxylic acid.
Relative to all dicarboxylic acid components, the copolymerization amount of aromatic dicarboxylic acid is necessary for 95 moles of %~100 mole %.Preferably 98 rub
You are more than %, more preferably 100 moles of %.If containing the dicarboxylic acids beyond the aromatic dicarboxylic acid composition for having more than 5 moles of % into
It is allocated as copolymer composition, then the chemical-resistant that film be present reduces.
As the aromatic dicarboxylic acid for the copolyester (A) for forming the present invention, it is not particularly limited, but terephthaldehyde can be used
Acid, M-phthalic acid, phthalic acid, naphthalenedicarboxylic acid, 4,4 '-biphenyl dicarboxylic acid, 5- sulfoisophthalic acid sodium etc..It is wherein excellent
Select terephthalic acid (TPA), M-phthalic acid.
As the aliphatic dicarboxylic acid for the copolyester (A) for forming the present invention, it is not particularly limited, but usable butanedioic acid,
Adipic acid, azelaic acid, decanedioic acid, cyclohexyl dicarboxylic acid, tetrahydrochysene phthalandione etc..Wherein preferred decanedioic acid.Relative to whole dicarboxylic acids, fat
The copolymerization amount of fat race dicarboxylic acids is preferably 5 moles of below %, more preferably 2 moles of below %, more preferably 0 mole of %.
If more than 5 moles %, the chemical-resistant that film be present reduces.
In the copolyester (A) of the present invention, relative to whole polyol components, the diol component represented with formula (1)
It must be copolymerized with 1~30 mole of %.
[changing 1]
In formula (1), n is more than 3 integer.Preferably less than 23 integer, more preferably less than 15 integer are further excellent
Elect less than 5 integer, particularly preferably less than 4 integer, most preferably 3 as.If n is less than 3, the bendability of film has reduction
Tendency.On the other hand, if n is excessive, corrosion resistance can reduce sometimes.
As the diol component represented with formula (1), it is not particularly limited, but triethylene glycol, tetraethylene glycol, five second can be enumerated
Glycol, polyethylene glycol (number-average molecular weight 650), polyethylene glycol (number-average molecular weight 1000) etc..Wherein, consider to contribute to and be coated with
The ester bond amount of adherence between steel plate and the well balanced viewpoint of ehter bond amount, preferably triethylene glycol.
When setting whole polyol components as 100 moles of %, the copolymerization amount of the diol component represented by formula (1) is preferably
3 moles of more than %, more preferably 5 moles of more than %.Furthermore it is preferred that be 28 moles of below %, more preferably 25 moles of below %,
More preferably 20 moles of below %.If very few, the glass transition temperature of copolyester (A) can uprise sometimes, and bendability (adds
Work) decline.On the other hand, if excessively, the glass transition temperature of copolyester (A) can become too low sometimes, hardness or corrosion resistant
Corrosion can reduce.
As the polyalcohol for the copolyester (A) for forming the present invention, beyond the diol component preferably represented with formula (1)
Diol component.As the diol component beyond formula (1), it is not particularly limited, but such as ethylene glycol, 1,2- the third two can be used
Alcohol, 1,3- propane diols, 1,3 butylene glycol, 1,2- butanediols, 1,4- butanediols, 2- methyl-1,3-propanediols, neopentyl glycol, 1,
5- pentanediols, 3- methyl isophthalic acids, 5- pentanediols, 1,6-HD, 1- methyl isophthalic acids, 8- ethohexadiols, 2,2- dimethyl -1,3- the third two
The aliphatic diol compositions such as alcohol, 2- ethyls -2- butyl -1,3-PD, can be from these materials using one kind or two or more.
In addition, it is possible to use the alicyclic diol composition, polytetramethylene two of 1,4-CHDM, Tricyclodecane Dimethanol etc.
The polyalkylene ether glycols composition of alcohol, polypropylene glycol etc..Preferably ethylene glycol, 1,2- propane diols, 2- methyl-1,3-propanediols,
Neopentyl glycol, 3- methyl isophthalic acids, 5- pentanediols, 1,6-HD, 2- ethyl -2- butyl -1,3- propane diols, 1,4- hexamethylene diformazans
Alcohol.
When setting all polyol components as 100 moles of %, aliphatic diol composition, alicyclic ring beyond above-mentioned formula (1)
The copolymerization amount of race's diol component and polyalkylene ether glycols composition is preferably 70~99 moles of %.If very few, copolymerization is poly- sometimes
The glass transition temperature of ester (A) can become too low, and hardness or corrosion resistance can reduce.On the other hand, if excessively, copolymerization is poly- sometimes
The glass transition temperature of ester (A) can uprise, and bendability (processability) can decline.
In addition, the diol component with bisphenol backbone of bisphenol-A, Bisphenol F etc., because there is doubting as endocrine disruptor
Consider, therefore to be preferred less.When setting whole polyol components as 100 moles of %, there is the copolymerization amount of the diol component of bisphenol backbone
Preferably 5 moles of below %, more preferably 1 mole of below %, more preferably 0 mole of %.
The glass transition temperature of the copolyester (A) of the present invention is necessary for 25~50 DEG C of scope.By making glass transition temperature
In 25~50 DEG C of scope, corrosion resistance and bendability can be taken into account.Preferably 30~48 DEG C of scope, more preferably 35~45 DEG C
Scope.If glass transition temperature is less than 25 DEG C, corrosion resistance can reduce sometimes.In addition, if glass transition temperature is more than 50 DEG C,
The bendability of film has the tendency of reduction, unsatisfactory.
More than the polybasic carboxylic acid composition and/or trivalent of more than trivalent can also be copolymerized in the copolyester (A) of the present invention
Polyol component.As polybasic carboxylic acid composition more than trivalent, such as trimellitic acid, Pyromellitic Acid, benzophenone can be enumerated
Aliphatic carboxylic acids such as the aromatic carboxylic acid of tetracarboxylic acid, trimesic acid etc., 1,2,3,4- ethylene-dimalonic acids etc..More than trivalent
Polyol component, can enumerate for example glycerine, trimethylolpropane, trimethylolethane, new penta tetrol, methyl glucose,
Mannitol, D-sorbite, can be from these materials using one kind or two or more.Rubbed when setting whole polybasic carboxylic acid compositions as 100
During your %, the copolymerization amount of polybasic carboxylic acid composition more than trivalent is preferably 5 moles of below %, more preferably 2 moles of below %, is entered
One step is preferably 1 mole of below % or 0 mole of %.In addition, when setting whole polyol components as 100 moles of %, 3
The copolymerization amount of polyol component more than valency is preferably 2 moles of below %, and more preferably 1 mole of below % or 0 rubs
You are %.If excessive, copolyester (A) can gelation during polymerization sometimes.
The number-average molecular weight of the copolyester (A) of the present invention is preferably more than 2000, and more preferably more than 4000.In addition,
Preferably less than 9000, more preferably less than 8000, especially preferably less than 7400.If number-average molecular weight is less than 2000, have
When film bendability can reduce, it is therefore unsatisfactory.On the other hand, if more than 9000, viscosity when making coating is high, behaviour
Work becomes difficult, unsatisfactory.
The reduced viscosity of the copolyester (A) of the present invention is preferably more than 0.15dl/g, more preferably more than 0.18dl/g.
Furthermore it is preferred that it is below 0.35dl/g, more preferably below 0.32dl/g.If reduced viscosity is too small, the bending of film sometimes
Property can reduce, if excessive, viscosity when being dissolved in organic solvent becomes too high, and operation becomes difficult.
As the method for the polycondensation reaction of the copolyester (A) of the manufacture present invention, such as have：1) in arbitrary catalyst
In the presence of heat polybasic carboxylic acid and polyalcohol, by dehydration esterification process, carry out the method for de- polyhydric alcohol reaction, 2) exist
The alcohol ester body and polyalcohol of polybasic carboxylic acid are heated in the presence of arbitrary catalyst, by ester exchange reaction, carries out de- polyalcohol
Method of polycondensation reaction etc..In above-mentioned method 1), 2), part or all of sour composition can be replaced with acid anhydrides.
In copolyester (A) of the manufacture present invention, known polymerization catalyst, such as four positive fourth of metatitanic acid can be used
The antimonial such as the titanium compounds such as ester, tetraisopropyl titanate, epoxide pentanedione titanium, antimony trioxide, three butoxy antimony, oxidation
Germanium compound, the in addition acetates of magnesium, iron, zinc, manganese, cobalt, aluminium etc. etc. such as germanium, four n-butoxy germanium.These catalyst can be used 1
Kind and uses two or more.
Manufacture the present invention copolyester (A) when, be alternatively lifting base material adherence, bridging property and improve copolyesters
(A) resinous acid value.Resinous acid value is preferably leq/106More than g, more preferably 3eq/106More than g, especially preferably 5eq/
106More than g.Furthermore it is preferred that it is 200eq/106Below g, more preferably 100eq/106Below g, especially preferably 50eq/106g
Hereinafter, particularly preferably 40eq/106Below g, most preferably 30eq/106Below g.By making resinous acid value within the above range,
These effects can be expected.If resinous acid value is too small, it is difficult to the lifting for obtaining base material adherence or bridging property sometimes, if excessive,
Then although base material adherence or bridging property lifting, chemical-resistant decline sometimes, therefore for requiring the purposes of durability
It is not appropriate for.
As the method for the acid number for the copolyester (A) for improving the present invention, such as have：(1) after polycondensation reaction terminates, add
Add polybasic carboxylic acid and/or polybasic acid anhydride and make its reaction, (2) heat, oxygen, water etc. is played a role, intentionally in polycondensation reaction
Ground carries out the methods of resin is rotten, can arbitrarily carry out these methods.
The copolyester (A) of the present invention can use in the state of known organic solvent is dissolved in.As workable
Known organic solvent, the fragrant family hydro carbons such as toluene, dimethylbenzene, Solvesso (registration mark), ethyl acetate, second can be enumerated
The esters such as acid butyl ester, propylene glycol methyl ether acetate, dibasic ester (DBE), MEK, methyl iso-butyl ketone (MIBK), cyclohexanone, different Fo Er
Ethers such as the ketones such as ketone, normal-butyl cellosolve, tert-butyl group cellosolve etc., it may be considered that dissolubility, evaporation rate (drying property) etc.
And arbitrarily select, mix.Wherein, the preferably mixed solvent of fragrant family hydro carbons and ketone, preferably Solvesso and hexamethylene
The mixed solvent of ketone.
The polyester (A) of the present invention is preferably dissolved in above-mentioned organic solvent in 25 DEG C of concentration with more than 40 mass %, more
Preferably dissolved with more than 50 mass % concentration, be further preferred that the concentration dissolving with more than 60 mass %.By to be upper
The solubility stated, can improve the solid component concentration as metal primer coating, and operation becomes easy.
＜ crosslinking agents (B) ＞
The copolyester (A) of the present invention can be used together with crosslinking agent (B).Known crosslinking agent can be used in crosslinking agent (B).Crosslinking
Agent (B) can be enumerated different as long as the material that relative copolyester (A) crosslinks reaction is just not particularly limited as preference
Cyanate esters, epoxy resin, amino resins (the usual title of alkyl etherified formaldehyde resin), phenolic resin etc., Ke Yicong
In arbitrarily from one kind or two or more.
It is not particularly limited as isocyanate compound, can is aromatic series, alicyclic, aliphatic polyisocyanate esterification
Compound, low molecule amount type or HMW type.It is different that such as tetramethylene diisocyanate, hexa-methylene two can be enumerated
Cyanate, toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, hydrogenated diphenyl methane diisocyanate, sub- dimethylbenzene
Group diisocyanate, hydrogenation eylylene diisocyanate, IPDI or these isocyanate compounds
Trimer, and make above-mentioned isocyanate compound and ethylene glycol, trimethylolpropane, propane diols, glycerine, D-sorbite,
The reactive hydrogen of ethylenediamine, monoethanolamine, diethanol amine, triethanolamine, polyester polyols alcohols, polyether polyols alcohols, polyamide-based etc.
Compound is reacted obtained terminal isocyanate compound.These compounds can be used a kind, or and use two or more.
In addition, if end-blockingization isocyanate compound is used to extend metal primer painting as isocyanate compound
The useful life of material.As the end-capping reagent of end-blockingization isocyanate compound, such as phenol, benzenethiol, thiocresol, first can be enumerated
The oximes such as the phenols such as phenol, xylenols, resorcinol, nitrophenols, chlorophenol, acetoxime, methyl ethyl ketoxime, cyclohexanone oxime, methanol, second
The lactams such as the alcohols such as alcohol, propyl alcohol, butanol, the tert-butyl alcohol, tert-pentyl alcohol, epsilon-caprolactams, other aromatic amines, acid imide
Class, acetylacetone,2,4-pentanedione, acetoacetic ester, malonic ester isoreactivity methylene compound, thio-alcohol, imines, ureas etc..End-blocking
It is above-mentioned isocyanate compound is reacted and is obtained according to known method with end-capping reagent to change isocyanate compound, can be made
With a kind, or and use two or more.
As epoxy resin, can enumerate for example：Glycidol ether and its oligomer, the phthalic acid two of bisphenol-A shrink
Glyceride, Diglycidyl M-phthalate, terephthalic acid diglycidyl ester, P-hydroxybenzoic acid 2-glycidyl
Ester, tetrahydrophthalic acid 2-glycidyl ester, hexahydrophthalic acid 2-glycidyl ester, butanedioic acid 2-glycidyl ester,
Adipic acid 2-glycidyl ester, Diglycidyl Sebacate, ethylene glycol diglycidyl ester, propane diols 2-glycidyl ester,
1,4- butanediols 2-glycidyl ester, 1,6-HD 2-glycidyl ester and PAG 2-glycidyl esters, partially
Benzenetricarboxylic acid three-glycidyl ester, triglycidyl isocyanurate, 1,4- glycidoxypropyls benzene, diglycidyl propylene
Base urea, T 55, trimethylolethane glycidol ether, trihydroxymethylpropanyltri diglycidyl ether, Ji Wusi
The triglycidyl ether etc. of the glycidol ether of alcohol four, glycerine alkylene oxide adduct.These materials can be used a kind, or and with 2 kinds with
On.
It is not particularly limited, can be enumerated by melamine, urea, benzoguanamine, methyl guanamines, steroidal guanamines as amino resins
(steroguanamine), the amino component such as spiral shell guanamines (spiroguanamine), dicyandiamide and formaldehyde, metaformaldehyde, acetaldehyde,
Methylolation amino resins obtained from the reaction of the aldehyde composition such as benzaldehyde.By the alcohol of 1~6 carbon atom by this methylolation
Material after the methylol of amino resins is etherified is also contained in the amino resins.These materials can be used alone, or simultaneously
Use two or more.
As phenolic resin, resol type phenol resin can be used.As resol type phenol resin, can enumerate with such as benzene
Phenol, metacresol, a sylvan, 3,5- xylenols, meta-methoxy phenol, orthoresol, paracresol, p-tert-butylphenol, to ethyl
Phenol, 2,3- xylenols, 2,5- xylenols, bisphenol-A, Bisphenol F etc. are the phenolic resin of raw material, and these resins can individually make
With, or and use two or more.
Relative to the mass parts of copolyester (A) 100, crosslinking agent (B) is preferably more than 1 mass parts more preferably 5 mass parts
More than, more preferably more than 10 mass parts.Furthermore it is preferred that below 50 mass parts, more preferably below 40 mass parts, to enter
One step is preferably below 30 mass parts.If very few, the crosslinking of the film obtained by metal primer coating becomes insufficient, whether there is
Method obtains the situation of the flintiness of necessary film, firmness or bonding strength.If excessive, the bendability for the film being necessary
The situation of reduction.
In the present invention, can be further using the catalysis for contributing to the cross-linking reaction of copolyester (A) and crosslinking agent (B)
Agent.For example, as acid catalyst, the organic sulfonic acid chemical combination such as p-methyl benzenesulfonic acid, DBSA, camphorsulfonic acid can be used
The amine corrective of thing, phosphate cpd and these compounds.As base catalyst, amines can be used.As metal catalytic
Agent, the acylates of various metals, halide salt, nitrate, sulfate, organic coordination compounds etc. can be used.These catalyst
The curing action of crosslinking agent (B) can be coordinated and using a kind or and use two or more.
＜ pigment (C) ＞
The copolyester (A) of the present invention can be used together with pigment (C).As pigment (C) concrete example, it is not particularly limited,
Titanium oxide, zinc oxide, zirconium oxide, calcium carbonate, barium sulfate, aluminum oxide, chromium oxide, chromate, kaolin, carbon black, oxygen can be enumerated
Change iron, talcum, mica, trbasic zinc phosphate, ferric phosphate, aluminum phosphate, zinc phosphite, aluminium triphosphate, calcium molybdate, molybdic acid aluminium, barium molybdate,
The inorganic pigments such as vanadium oxide, chromic acid fine linen, zinc chromate, calcium silicates, water dispersed silicon dioxide, aerosil, or phthalocyanine indigo plant,
The organic pigment such as phthalocyanine green, carbazole dioxazine violet, anthracene pyrimidine Huang, isoindoline Huang, indanthrene blue.By a kind or 2 of addition
Kind the above material, can expect coloring, anticorrosion, the effect of the lifting of durability.
Relative to the mass parts of copolyester (A) 100, pigment (C) is preferably more than 5 mass parts more preferably 50 mass parts
More than, more preferably more than 100 mass parts.Furthermore it is preferred that for below 300 mass parts, more preferably 250 mass parts with
Under, more preferably below 200 mass parts.If pigment (C) is very few, there are the coloring or anticorrosion that can not be obtained as purpose
And other effects situation.If in addition, excessively, have the situation that the bendability of film reduces.
＜ additives (D) ＞
The copolyester (A) of the present invention can use additive (D) as needed.Concrete example as additive (D) does not limit especially
It is fixed, but the acid catalysts such as p-methyl benzenesulfonic acid, DBSA, camphorsulfonic acid, phosphate cpd, amines etc. can be enumerated
Base catalyst, defoamer, levelling agent, heat ageing inhibitor, ultra-violet absorber, viscosity modifier, wax etc..These materials can make
With one kind or two or more.Additive (D) is not as long as to influence the degree of Physical properties of coating film, so that it may freely mixes.Preferably relative to
The mass parts of copolyester (A) 100, it is more than 0.1 mass parts, below 5 mass parts.
＜ organic solvents (E) ＞
The organic solvent (E) used in the present invention, as long as the solvent of dissolving copolyester (A) is just not particularly limited.Specifically
For, the fragrant family hydro carbons such as toluene, dimethylbenzene, Solvesso (registration mark), ethyl acetate, butyl acetate, third can be enumerated
The ketone such as the esters such as glycol methyl ether acetate, dibasic acid ester, MEK, methyl iso-butyl ketone (MIBK), cyclohexanone, isophorone, positive fourth
Ethers such as base cellosolve, tert-butyl group cellosolve etc., it is contemplated that dissolubility, evaporation rate (drying property) etc. and arbitrarily select, mix.
Wherein it is preferably the mixed solvent of the mixed solvent of fragrant family hydro carbons and ketone, preferably Solvesso and cyclohexanone.
Relative to the mass parts of copolyester (A) 100, organic solvent (E) is preferably more than 50 mass parts more preferably 100
More than mass parts, more preferably more than 150 mass parts.Furthermore it is preferred that it is more preferably 400 mass below 500 mass parts
Below part, more preferably below 300 mass parts.If very few, storage stability can reduce sometimes, if excessively, sometimes
Become Expenses Cost etc. and do not conform to reality.
＜ metal primer coating ＞
The metal primer coating of the present invention is comprising copolyester (A), crosslinking agent (B), pigment (C), additive (D) and organic molten
The coating of agent (E).
＜ metal coated panels ＞
The metal coated panel of the present invention is as prime coat in metal primer coating of at least one side of metallic plate with the present invention
Plate.Be not particularly limited on coating method, can use roll coater coating, curtain apply machine coating, aerial spraying, electrostatic spraying,
Silk-screen printing etc..
In addition, be not particularly limited as metallic plate, such as preferred hot rolled steel plate, plated steel sheet, alloy plating steel plate, aluminum-zinc alloy
Alloy-steel plate, aluminium sheet, tin plate, stainless steel plate, copper coin, copper plated steel, tin-free steel, nickel-clad steel plate, very thin tin plate, chromium
Handle the metallic plates such as steel plate.
Embodiment
Hereinafter, embodiment is enumerated to illustrate the present invention.In addition, in the present embodiment and comparative example, part represents quality
Part.
(1) measure of the composition of copolyester (A)
Use 400MHz's1H- NMR spectrums device (hereinafter sometimes referred to simply as NMR), carries out composition copolyester (A)
Polybasic carboxylic acid composition, the mol ratio of polyol component quantify.Solvent has used deuterochloroform.In addition, passing through rear addition of acid (day
Language：Sour Hou pay plus) to improve the acid number of copolyester when, if the sum total of the sour composition beyond sour composition used during rear addition of acid
For 100 moles of %, to calculate the mol ratio of each composition.
(2) measure of the number-average molecular weight of copolyester (A)
After sample (copolyester (A)) 4mg is dissolved in into 4mL tetrahydrofuran, with 0.2 μm of the polytetrafluoroethylene (PTFE) filter membrane in aperture
Filtering.In this, as sample solution, analyzed with gel permeation chromatography (GPC).Device is TOSOH HLC-8220, detection
Device is differential refraction rate detector, and mobile phase uses tetrahydrofuran, is measured at 1mL/ points of flow velocity, 40 DEG C of tubing string temperature.
Tubing string uses Showa electrician KF-802,804L, 806L.Molecular weight standards use monodisperse polystyrene, number-average molecular weight
It is to be saved equivalent to part of the molecular weight less than 1000 and calculated using polystyrene standard scaled value.
(3) measure of glass transition temperature
Determined using differential scanning sweat instrument (SII companies, DSC-200).Sample (copolyester (A)) 5mg is put into aluminium to push
Cap-type container is sealed, and -50 DEG C are cooled to using liquid nitrogen.Then, 150 DEG C are warming up to 20 DEG C/minute of programming rate, heated up
In the endothermic curve that process obtains, the extended line of the baseline before endothermic peak is occurred (below glass transition temperature) with towards endothermic peak
The temperature of intersection point of tangent line (showing the tangent line from the rising part at peak to the maximum slope between the summit at peak) be set to glass
Change temperature (Tg, unit：℃)
(4) measure of acid number
Accurate weighing 0.2g samples (copolyester (A)), are dissolved in chloroform 40mL.Then, with the second of 0.01N potassium hydroxide
Alcoholic solution is titrated.Indicator is to use phenolphthalein.For sample, potassium hydroxide equivalent is asked for, measured value is converted into often
106The equivalent of g samples, unit are equivalent/106g。
(5) reduced viscosity η sp/c (dl/g) measure
Sample (copolyester (A)) 0.10g is dissolved in the mixed solvent 25cc of phenol/tetrachloroethanes (weight is than 6/4), uses crow
Formula viscosity tube is measured in 30 DEG C.
Hereinafter, the copolyester (A) of the present invention and the Production Example of the copolyester as comparative example are shown.
The Production Example of copolyester (a1)
By 809 parts of dimethyl terephthalate (DMT), 793 parts of DMIP, 19 parts of trimellitic anhydride, ethylene glycol 407
Part, 540 parts of neopentyl glycol, 287 parts of triethylene glycol and as catalyst tetra-butyl orthotitanate relative to all sour compositions 0.03
Mole % is fitted into the reaction vessel for having mixer, condenser, thermometer, lasts 4 hours and is warming up to 220 DEG C by 160 DEG C,
While pass through separating methanol process, while carrying out ester exchange reaction.Then, polycondensation reaction process is that 20 points are lasted in reaction system
Clock is decompressed to 5mmHg, then is warming up to 250 DEG C.Then, below 0.3mmHg is decompressed to, the polycondensation reaction of 60 minutes is carried out, by it
Take out.By the result of NMR composition analysis, the mol ratio of obtained copolyester (a1) is：Terephthalic acid (TPA)/isophthalic diformazan
Acid/trimellitic acid/ethylene glycol/neopentyl glycol/triethylene glycol=50/49/1/40/40/20 [mol ratio].In addition, number is divided equally
Son amount is 7000, and glass transition temperature is 40 DEG C, acid number 20eq/106g.As a result remember in table 1.
Copolyester (a2)~(a10) Production Example
According to copolyester (a1) Production Example, the species and blending ratio of feed change, copolyester of the invention is manufactured
(a2)~(a11).As a result remember in table 1.
[table 1]
Embodiment 1
The preparation of metal primer coating (A1)
By the in the mixed solvent of 80 parts of cyclohexanone for being dissolved in 100 parts of copolyester (a1), 100 parts of Solvesso 150.
50 parts of calcium silicates, 13 parts of aluminium triphosphate, 37 parts of titanium oxide are wherein added, is disperseed 6 hours using vibrating machine.Then, add and make
For 20 parts of CYMEL 303 (Allnex company systems, melamine cured dose), the dodecyl as curing catalysts of crosslinking agent
0.2 part of benzene sulfonic acid, the metal primer coating (Al) of the present invention is made.
Embodiment 2~10, comparative example 1~3
Metal primer coating (A2)~(Kl) preparation
With with metal primer coating (Al) identical method, obtain as the metal primer of embodiments of the invention or comparative example apply
Expect (A2)~(Kl).Blending ratio is shown in table 2.
[table 2]
The evaluation of metal coated panel
The making of test film
Prepare thick 0.5mm hot-dip galvanized steel sheet, the metal primer coating described in above-described embodiment is coated with to it, make after drying
Thickness turn into 5 μm, 210 DEG C dry 45 seconds.Then, it is 15000 and glass transition temperature to be coated with thereon by number-average molecular weight
For 38 DEG C of the mass parts of copolymer polyester resin 16, the mass parts of melmac 4, the mass parts of titanium oxide 20 and the mass of cyclohexanone 60
The topcoat paint that part is made, dried thickness is turned into 15 μm, dried 60 seconds at 250 DEG C, obtain metal coated panel
Test film.
(hardness of film)
Pencil-lead is against to the coated face of above-mentioned metal coated panel test film with 45 degree of angle, it is made forward with 1kg load
Slide side.The flintiness of pencil-lead is that H, F, HB, B, 2B are used by harder person, and evaluation does not cause the maximum hardness of scar.Firmly
Degree is higher, and the hardness of film is higher, is more difficult to cause scar.
Metewand
○：More than H
△：F~B
×：Below 2B
(flexibility)
Above-mentioned metal coated panel test film is subjected to 180 ° of bend tests at 25 DEG C.By visual observation, the crackle of film is confirmed.2T
It is that film does not crack when the metallic plate for clamping 2 pieces and experiment metallic plate same thickness is bent.Numeral is smaller, bends
Qu Xingyue is good.
○：0~2T
△：3~4T
×：More than 5T
(corrosion resistance)
The end of above-mentioned metal coated panel test film is protected with adhesive tape, imposes the horizontal stroke until arriving at base material on the surface with cut-off knife
After cutting (cross cut), the method recorded with J1S Z2371-2015 implements the neutral salt spray test of 500 hours.Survey
The protuberance size in the crosscutting portion of the fixed coated panel from after testing.Protuberance size is smaller, and corrosion resistance is better.
Metewand
○：Below diameter 3mm
△：Diameter is less than 7mm more than 3mm
×：More than diameter 7mm
(higher-solid adaptive (solution viscosity))
Obtained copolyester (A) is dissolved in the identical of cyclohexanone and Solvesso l50 with the weight % of solid component concentration 60
In the mixed solution of weight rate, using Type B rotation viscometer (Tokyo Keiki Inc.'s system, EM types, rotor No.4,
12rpm), solution viscosity is determined under the conditions of 25 DEG C.If solution viscosity, more than 200 pools, operation when manufacturing coating can become
It is difficult.
Metewand
○：Less than 130 pools
△：More than 130 pools, below 200 pools
×：More than 200 pools
(chemical-resistant)
The end of above-mentioned metal coated panel test film is protected with adhesive tape, in the environment of 25 DEG C, in 5 weight % sodium hydroxide
After being soaked 48 hours in the aqueous solution, visual appearance is evaluated.Protuberance etc. is fewer, and chemical-resistant is better.
○：It is less than 1mm small protuberance without protuberance~diameter
△：There is big protuberance more than diameter 1mm
×：Film is peeled off
Usability in industry
The copolyester of the present invention and processability, corrosion resistance, the good chemical resistance of coating composition, as metal
The priming paint resin of plate is useful.It is useful especially as the composition that uses of coil coating in household electrical appliances.
Claims (6)
1. a kind of copolyester A, it is the copolyester using polybasic carboxylic acid composition and polyol component as copolymer composition, complete when setting
When portion's polybasic carboxylic acid composition is 100 moles of %, aromatic dicarboxylic acid composition is 95~100 moles of %, aliphatic dicarboxylic acid composition
For 0~5 mole of %；And when setting whole polyol components as 100 moles of %, diol component represented by formula (1) for 1~
30 moles of %；Scope of the copolyester A glass transition temperature at 25~50 DEG C,
[changing 1]
In formula (1), n is more than 3 integer.
2. copolyester A as claimed in claim 1, the copolyester A number-average molecular weight are 4000~9000 scope.
3. the copolyester A as described in claim 1~2, copolyester A are free of aliphatic dicarboxylic acid composition.
4. the copolyester A as described in any one of claims 1 to 3, the formula (1) is triethylene glycol.
5. a kind of metal primer coating, comprising the copolyester A described in any one of Claims 1 to 4, crosslinking agent B, pigment C,
Additive D and organic solvent E.
6. a kind of metal coated panel, it has the metal primer coating described in claim 5 as prime coat.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015182806 | 2015-09-16 | ||
| JP2015-182806 | 2015-09-16 | ||
| PCT/JP2016/069141 WO2017047197A1 (en) | 2015-09-16 | 2016-06-28 | Copolymerized polyester and metal primer coating material using same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107849230A true CN107849230A (en) | 2018-03-27 |
| CN107849230B CN107849230B (en) | 2021-02-05 |
Family
ID=58288707
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680040100.4A Active CN107849230B (en) | 2015-09-16 | 2016-06-28 | Copolyester and metal primer coating using the same |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6724921B2 (en) |
| KR (1) | KR20180055758A (en) |
| CN (1) | CN107849230B (en) |
| TW (1) | TWI719998B (en) |
| WO (1) | WO2017047197A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113227198A (en) * | 2019-01-17 | 2021-08-06 | 东洋纺株式会社 | Copolyester and aqueous dispersion thereof |
| CN115066452A (en) * | 2020-02-17 | 2022-09-16 | 东洋纺株式会社 | Aromatic polyester and process for producing the same |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018084064A1 (en) * | 2016-11-04 | 2018-05-11 | Dic株式会社 | Polyester polyol resin and coating |
| WO2018084065A1 (en) * | 2016-11-04 | 2018-05-11 | Dic株式会社 | Polyester polyol resin and coating |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11121270A (en) * | 1997-10-17 | 1999-04-30 | Toyo Metallizing Co Ltd | Dielectric polyester film for capacitor and plastic film capacitor |
| CN1503730A (en) * | 2001-03-21 | 2004-06-09 | 东洋钢钣株式会社 | Metal sheet coated with thermoplastic resin and can obtained therefrom |
| JP2004339446A (en) * | 2003-05-19 | 2004-12-02 | Mitsubishi Rayon Co Ltd | Acrylic syrup composition, resin mortar and method for laying laminate |
| JP2010235647A (en) * | 2009-03-30 | 2010-10-21 | Unitika Ltd | Polyether-ester block copolymer, and adhesive and laminate comprising the same |
| JP2011184642A (en) * | 2010-03-11 | 2011-09-22 | Unitika Ltd | Polyester resin aqueous dispersion, method for producing the same, and resin film obtained from the same |
| CN104220483A (en) * | 2012-03-28 | 2014-12-17 | 东洋纺株式会社 | Polyester resin, resin composition for can paint, painted metal plate for can, and can |
| JP2015160875A (en) * | 2014-02-26 | 2015-09-07 | ユニチカ株式会社 | Polyester resin composition and laminate |
-
2016
- 2016-06-28 KR KR1020177034247A patent/KR20180055758A/en not_active Application Discontinuation
- 2016-06-28 WO PCT/JP2016/069141 patent/WO2017047197A1/en active Application Filing
- 2016-06-28 JP JP2017539723A patent/JP6724921B2/en active Active
- 2016-06-28 CN CN201680040100.4A patent/CN107849230B/en active Active
- 2016-07-11 TW TW105121689A patent/TWI719998B/en active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11121270A (en) * | 1997-10-17 | 1999-04-30 | Toyo Metallizing Co Ltd | Dielectric polyester film for capacitor and plastic film capacitor |
| CN1503730A (en) * | 2001-03-21 | 2004-06-09 | 东洋钢钣株式会社 | Metal sheet coated with thermoplastic resin and can obtained therefrom |
| JP2004339446A (en) * | 2003-05-19 | 2004-12-02 | Mitsubishi Rayon Co Ltd | Acrylic syrup composition, resin mortar and method for laying laminate |
| JP2010235647A (en) * | 2009-03-30 | 2010-10-21 | Unitika Ltd | Polyether-ester block copolymer, and adhesive and laminate comprising the same |
| JP2011184642A (en) * | 2010-03-11 | 2011-09-22 | Unitika Ltd | Polyester resin aqueous dispersion, method for producing the same, and resin film obtained from the same |
| CN104220483A (en) * | 2012-03-28 | 2014-12-17 | 东洋纺株式会社 | Polyester resin, resin composition for can paint, painted metal plate for can, and can |
| JP2015160875A (en) * | 2014-02-26 | 2015-09-07 | ユニチカ株式会社 | Polyester resin composition and laminate |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113227198A (en) * | 2019-01-17 | 2021-08-06 | 东洋纺株式会社 | Copolyester and aqueous dispersion thereof |
| TWI818144B (en) * | 2019-01-17 | 2023-10-11 | 日商東洋紡Ｍｃ股份有限公司 | Copolyester and aqueous dispersions |
| CN113227198B (en) * | 2019-01-17 | 2024-01-23 | 东洋纺Mc株式会社 | Copolyester and aqueous dispersion thereof |
| CN115066452A (en) * | 2020-02-17 | 2022-09-16 | 东洋纺株式会社 | Aromatic polyester and process for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI719998B (en) | 2021-03-01 |
| KR20180055758A (en) | 2018-05-25 |
| JP6724921B2 (en) | 2020-07-15 |
| CN107849230B (en) | 2021-02-05 |
| TW201712051A (en) | 2017-04-01 |
| WO2017047197A1 (en) | 2017-03-23 |
| JPWO2017047197A1 (en) | 2018-07-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2832763B1 (en) | Polyester resin, resin composition for can paint, painted metal plate for can, and can | |
| CN107849230A (en) | Copolyester and profit use the metal primer coating of the copolyester | |
| JPH083297A (en) | Coating resin composition | |
| JP5316426B2 (en) | Resin composition for paint and painted metal plate | |
| CN111971324B (en) | Copolyester, aqueous dispersion and aqueous coating using the same | |
| JPH0258532A (en) | Modified polyester resin composition and coating using same | |
| JPS6132351B2 (en) | ||
| EP4223827A1 (en) | Copolymerized polyester and water dispersion | |
| JPS625467B2 (en) | ||
| JPH09302075A (en) | Copolyester resin for coating material | |
| CN106103541B (en) | Copolymer resin and coating composition | |
| JP6547549B2 (en) | Painted metal plate and food can | |
| JP5003930B2 (en) | Polyester resin for overcoat clear paint and overcoat clear paint resin composition using the same | |
| JPH10176135A (en) | Copolymer saturated polyester resin for coating | |
| JP2008019420A (en) | Resin composition for coating, and the coating | |
| WO2022093614A1 (en) | Polyester compositions for metal packaging coatings | |
| JPH03296580A (en) | Coating composition | |
| JPH05179198A (en) | Polyester coating composition and coated steel sheet | |
| JPS6221830B2 (en) | ||
| WO2022093615A1 (en) | Polyester polyol compositions for metal packaging coatings | |
| JPH09165439A (en) | Copolyester resin for coating material | |
| JPH05179197A (en) | Polyester coating composition and coated steel sheet | |
| JP2000119359A (en) | Water-based dispersion and water-based coating resin composition using the same | |
| JPH05171106A (en) | Production of polyester resin for coating and coating | |
| JPH02142871A (en) | Coating composition for coated steel sheet |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP02 | Change in the address of a patent holder |
Address after: No. 1, No. 13, meitian-1, Shibei District, Osaka, Osaka, Japan Patentee after: TOYOBO Co.,Ltd. Address before: Japan's Osaka Osaka North Doushima Haji chome 2 times 8 Patentee before: TOYOBO Co.,Ltd. |
|
| CP02 | Change in the address of a patent holder | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230814 Address after: South Building, Meitian Twin Towers, No. 13-1, Meitian 1-chome, Kita ku, Osaka City, Osaka Prefecture, Japan Patentee after: Dongyang Textile MC Co.,Ltd. Address before: No. 1, No. 13, meitian-1, Shibei District, Osaka, Osaka, Japan Patentee before: TOYOBO Co.,Ltd. |
|
| TR01 | Transfer of patent right |