CN109320705A - Low gloss TGIC system polyester resin for powder coating and preparation method and application - Google Patents
Low gloss TGIC system polyester resin for powder coating and preparation method and application Download PDFInfo
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- CN109320705A CN109320705A CN201811320241.9A CN201811320241A CN109320705A CN 109320705 A CN109320705 A CN 109320705A CN 201811320241 A CN201811320241 A CN 201811320241A CN 109320705 A CN109320705 A CN 109320705A
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- 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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
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- 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
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- 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
- C09D5/03—Powdery paints
Abstract
The invention belongs to production of resins technical fields, and in particular to a kind of low gloss TGIC system polyester resin for powder coating further relates to the preparation method of above-mentioned polyester resin and the application of the polyester resin.Polyester resin of the invention, it mainly include M-phthalic acid, pyridine -2,6- dioctyl phthalate, Acetaminocaproic Acid, 3- hydroxyl -4-Aminobutanoicacid, polyethyleneglycol diglycidylether, neopentyl glycol, 2,4,6- trihydroxybenzoic acids, N-hydroxyethyl-ethylenediamine triacetic acid, catalyst for esterification reaction, antioxidant.It is prepared in obtained polyester resin molecule by means of the present invention simultaneous with active amido, hydroxyl and carboxyl, difference using the epoxy group curing reaction rate in these three groups and TGIC molecule can be used for preparing low gloss powder coating (glossiness < 20%), and film performance fully achieves the requirements of powdery paints.
Description
Technical field
The invention belongs to production of resins technical fields, and in particular to a kind of TGIC system powdery paints polyester of low gloss
Resin further relates to the preparation method of above-mentioned polyester resin and the application of the polyester resin.
Background technique
Since last century the seventies come out, for powdery paints because it is free of organic solvent, 100% is solid component, phase
Than conventional coating, have it is pollution-free, save the energy and resource, coating machinery intensity are high and that excess coating material can recycle completely etc. is excellent
Point is just applied to the painting of the shells such as household electrical appliance, auto industry, office accommodation, metal material, outdoor building more and more widely
Dress.
Common TGIC system is current maximum one kind of outdoor weathe resistance powdery paints dosage with powdery paints, by institute
With polyester resin since molecular structure is relatively uniform and single, the active function groups in strand only have carboxyl, and activity is more equal
One, the glossiness of film is higher, and the powdery paints of preparation low gloss (< 20%) has biggish difficulty.
CN106752765A discloses a kind of toughening modifying low-temperature setting low-luster powdery paints, including following parts by weight
Component: 28-35 parts of polyester resin；28-35 parts of epoxy resin；3-5 parts of delustering agent；3-5 parts of toughener；1-10 parts of pigment；It fills out
15-27.5 parts of material；1-5 parts of levelling agent；0.3-0.5 parts of styrax.The toughening modifying low-temperature setting low-luster powder of the invention
Coating concurrently sets suitable amount ranges by the suitable raw material of selection, resistance to low-temperature setting low gloss high-flexibility is made
The powdery paints of impact, hence it is evident that improve the resistance to bend(ing) energy and impact resistance of low-temperature setting low gloss product.
Polyester resin P5980 used in CN106752765A is that the indoor powdery paints used is matched with E-12 epoxy resin
With polyester resin, indoor powder coating systems are only used for, and be only suitable for low-temperature setting such as 160 DEG C/15min to obtain
Must be compared with the film of low gloss, the extinction effect that 180 DEG C/15min of hot setting can not have been played since melt viscosity is too low, and
And the P5980 polyester resin is that solidification can not be matched with TGIC, is not suitable for the outdoor weather-proof system of TGIC.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of low gloss TGIC system powdery paints with polyester tree
Rouge；
Additionally provide the preparation method of the polyester resin and the application in powdery paints and paint coatings of the polyester；
It is prepared in its polyester chain of obtained polyester resin by means of the present invention with active different carboxyl, hydroxyl
And amino, they react precedence with the epoxy group in TGIC molecule and differ greatly, may be implemented be heating and curing when
It waits the difference of functional group and TGIC solidification rate different in polyester molecule and leads to film coated surface slight shrinkage, to obtain low
The film of gloss.
Low gloss TGIC system polyester resin for powder coating provided by the present invention, comprising:
Raw material A and raw material B；
(1) in raw material A, the molar content of each component is as follows:
(2) in raw material B, the content of each component is as follows:
Catalyst for esterification reaction: dioctyltin dichloride, dosage are the 0.1-0.3% of the integral molar quantity of raw material A；
Antioxidant: antioxidant four [methyl-β-(3,5- di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester,
Dosage is the 0.2-0.4% of raw material A integral molar quantity.
The preparation method of above-mentioned low gloss TGIC system polyester resin for powder coating, its step are as follows:
S1: preparing raw material A, and the molar content of raw material A component is as follows:
Prepare raw material B: the content of raw material B each component is as follows:
Catalyst for esterification reaction: dioctyltin dichloride, dosage are the 0.1-0.3% of the integral molar quantity of raw material A；
Antioxidant: pentaerythritol ester is (i.e. for antioxidant four [methyl-β-(3,5- di-tert-butyl-hydroxy phenyl) propionic ester]
Antioxidant 1010), dosage is the 0.2-0.4% of raw material A integral molar quantity；
It is taken in following steps by the dosage prepared in S1；
S2: neopentyl glycol, polyethyleneglycol diglycidylether, 3- hydroxyl -4-Aminobutanoicacid prepared in S1 is taken to be added
In reaction kettle, and the heating melting at 120-130 DEG C, obtain mixed material；
S3: M-phthalic acid, pyridine -2,6- dioctyl phthalate, Acetaminocaproic Acid are added in the mixed material obtained by S2, together
When catalyst for esterification reaction is added, under nitrogen protection gradually temperature reaction to 220 DEG C, keep the temperature esterification 2-8h, to acid value
Be added 2,4,6- trihydroxybenzoic acids when being reduced to 30-45mgKOH/g, slow temperature reaction to being steamed without obvious distillate and
Until the acid value of reactant reaches 25-30mgKOH/g；Slow temperature reaction temperature is about 245 DEG C；
S4: being added antioxidant four [methyl-β-(3,5- di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester,
2-6h is kept under the vacuum degree of 50mmHg, facilitates the formation of polyester resin, stops taking out when acid value is reduced to 15-16mgKOH/g
Vacuum；
S5: when being cooled to 200 DEG C, being added N-hydroxyethyl-ethylenediamine triacetic acid, and be to slowly warm up to 240 DEG C of reaction 2-8h,
Stop reaction when the acid value of reactant is 28-36mgKOH/g, discharge immediately, and is cooling, be crushed and be granulated, obtains polyester resin.
Preferably, cooling using the steel band with condensed water in S5.
Polyester resin acid value obtained in S5 is 28-36mgKOH/g, and 108-120 DEG C of softening point, appearance is colorless and transparent
Grain.
Adopt application of the polyester resin prepared with the aforedescribed process in paint coatings, and the claimed model of the present invention
It encloses.
It is used to prepare powdery paints by above-mentioned method polyester resin obtained, specifically includes following step:
(1) for example each raw material of following weight fraction ratio is pressed:
(2) by (1) each raw material be uniformly mixed, then extrusions, tabletting, be crushed, obtain sheet stock, then sheet stock crushed
Sieve, obtains powdery paints.
Paint coatings are used to prepare by above-mentioned method polyester resin obtained, specifically include following step:
(1) for example each raw material of following weight fraction ratio is pressed:
(2) by (1) each raw material be uniformly mixed, then extrusions, tabletting, be crushed, obtain sheet stock, then sheet stock crushed
Sieve, obtains powdery paints；
(3) by powder paint on the tinplate substrate after surface treatment, under conditions of 180 DEG C/15min
Solidification, obtains paint coatings.
In step (2), using the uniform raw material of double screw extruder extrusion mixing.
In step (3), using electrostatic gun by powder paint on tinplate substrate after surface treated.
Resin employed in background technique is polyester resin P5980, and the resin that the present invention uses is that have specifically
It is formulated and prepares resin obtained by specific technique, maximum feature is, from the raw material of selection, to make raw material
Amino, carboxyl, hydroxyl and epoxy group itself are had, the activity of itself of the polyester resin caused is different, final polyester chain
The active different carboxyl of middle band, hydroxyl and amino, they reacted with the epoxy group in TGIC molecule precedence difference compared with
Greatly, the difference of functional group different in polyester molecule when being heating and curing and TGIC solidification rate may be implemented and cause to apply
Film surface slight shrinkage, to obtain the film of low gloss.
The beneficial effects of the present invention are prepared resulting poly- using raw material provided by the present invention and specific technique
Ester resin is compared with common commercially available polyester resin, and significant advantage is, the polyester resin of acquisition to produce coating or
When paint coatings, planarization flatness is excellent, and after boiling water boiling 2 hours, the stability of coating is good, unchanged, will not
There is the phenomenon that bubble produced by commercially available coating.
Specific embodiment
The present invention will be further explained combined with specific embodiments below, so that those skilled in the art knows more about
The present invention, but be not intended to limit the present invention.
Raw material of the present invention is purchased from producer below:
M-phthalic acid: Foshan Xin Hang Biotechnology Co., Ltd；
Pyridine -2,6- dioctyl phthalate: one base Industrial Co., Ltd. of Shanghai；
Acetaminocaproic Acid: Wuhan Sheng Baoxiang development in science and technology Co., Ltd
3- hydroxyl -4-Aminobutanoicacid: Wuhan Yi Xinghe development in science and technology Co., Ltd；
Polyethyleneglycol diglycidylether: Suzhou Fu Lu Biotechnology Co., Ltd；
Neopentyl glycol: Jinan Lian Ying Chemical Co., Ltd.；
2,4,6- trihydroxybenzoic acid: Wuhan Hezhong Bio-chemical Manufature Co., Ltd.
N-hydroxyethyl-ethylenediamine triacetic acid: Hubei Heng Jingrui Chemical Co., Ltd.；
Antioxidant 1010: antioxidant four [methyl-β-(3,5- di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythrite
Ester；Kunshan century dragon Chemical Co., Ltd.；Model: Irganox 1010；
Dioctyltin dichloride: Nantong Ai Dewang Chemical Co., Ltd.；
TGIC: triglycidyl isocyanurate；Huangshan Huahui Technology Co., Ltd.；
Titanium dioxide: Guangzhou Jia Liang mineral products Co., Ltd；
Delustring barium sulfate: Yuan Lei powder Co., Ltd of Foshan City；
Levelling agent: the auxiliary reagent factory Laiyang City Hao Run；
Physics delustering agent: DY-315, Zhongshan city reach mattress resin material Co., Ltd；
Styrax: Guangzhou national strength and prestige Biotechnology Co., Ltd.
Embodiment 1
The preparation method of low gloss TGIC system polyester resin, its step are as follows:
S1: preparing raw material A, and the molar content of raw material A component is as follows:
Prepare raw material B: the content of raw material B each component is as follows:
Catalyst for esterification reaction: dioctyltin dichloride, dosage are the 0.2mol% of the integral molar quantity of raw material A；
Antioxidant: i.e. antioxidant 1010, dosage are the 0.3mol% or so of raw material A integral molar quantity；
It is taken in following steps by the dosage prepared in S1；
S2: neopentyl glycol, polyethyleneglycol diglycidylether, 3- hydroxyl -4-Aminobutanoicacid prepared in S1 is taken to be added
In mixer, and the heating melting at 125 DEG C, obtain mixed material；
S3: M-phthalic acid, pyridine -2,6- dioctyl phthalate, Acetaminocaproic Acid are added in the mixed material obtained by S2, together
When catalyst for esterification reaction (following but specified otherwise, catalyst refer both to dioctyltin dichloride) is added, protected in nitrogen
Gradually to 220 DEG C, heat preservation esterification 5h or so is added 2 when acid value is reduced to 40mgKOH/g or so for temperature reaction under shield,
4,6- trihydroxybenzoic acids, slow temperature reaction is extremely steamed without obvious distillate and the acid value of reactant reaches 28mgKOH/g
Until；The slow temperature reaction temperature highest temperature has reached 240 DEG C；
S4: being added antioxidant four [methyl-β-(3,5- di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester,
4h or so is kept under the vacuum degree of 50mmHg, facilitates the formation of polyester resin, stopping when acid value is reduced to 15mgKOH/g or so
It vacuumizes；
S5: when being cooled to 200 DEG C, being added N-hydroxyethyl-ethylenediamine triacetic acid, and be to slowly warm up to 240 DEG C of reaction 5h, to
Stop reaction when the acid value of reactant is 30mgKOH/g or so, discharge immediately, and is cooling with the steel band with condensed water, breaks
Broken granulation obtains polyester resin, gained polyester resin acid value are as follows: 33mgKOH/g, softening point are 115 DEG C.
Comparative example 1
Comparative example 1 and the difference of embodiment 1 are: not using M-phthalic acid, remaining Step By Condition and implementation in S3
Example 1 is identical；
S3 step specifically:
S3: pyridine -2,6- dioctyl phthalate, Acetaminocaproic Acid are added in the mixed material obtained by S2, while esterification is added
Catalysts, gradually to 220 DEG C, heat preservation esterification 5h or so is reduced to acid value for temperature reaction under nitrogen protection
2,4,6- trihydroxybenzoic acids are added when 40mgKOH/g or so, slow temperature reaction is extremely steamed and reacted without obvious distillate
Until the acid value of object reaches 28mgKOH/g；The slow temperature reaction temperature highest temperature has reached 240 DEG C.
Comparative example 2
Comparative example 2 and the difference of embodiment 1 are: in S3 do not use pyridine -2,6- dioctyl phthalate, remaining Step By Condition with
Embodiment 1 is identical；
S3 step specifically:
S3: M-phthalic acid, Acetaminocaproic Acid are added in the mixed material obtained by S2, while esterification is added and urges
Agent, gradually to 220 DEG C, heat preservation esterification 5h or so is reduced to 40mgKOH/g to acid value for temperature reaction under nitrogen protection
2,4,6- trihydroxybenzoic acids are added when left and right, slow temperature reaction is extremely steamed without obvious distillate and the acid value of reactant reaches
Until 28mgKOH/g；The slow temperature reaction temperature highest temperature has reached 240 DEG C.
Comparative example 3
Comparative example 3 and the difference of embodiment 1 are: in S3 do not use Acetaminocaproic Acid, remaining Step By Condition with
Embodiment 1 is identical；
S3 step specifically:
S3: M-phthalic acid, pyridine -2,6- dioctyl phthalate are added in the mixed material obtained by S2, while esterification is added
Catalyst, gradually to 220 DEG C, heat preservation esterification 5h or so is reduced to acid value for temperature reaction under nitrogen protection
2,4,6- trihydroxybenzoic acids are added when 40mgKOH/g or so, slow temperature reaction is extremely steamed and reacted without obvious distillate
Until the acid value of object reaches 28mgKOH/g；The slow temperature reaction temperature highest temperature has reached 240 DEG C.
Comparative example 4
Comparative example 4 and the difference of embodiment 1 are: not using 3- hydroxyl -4-Aminobutanoicacid, remaining Step By Condition in S2
It is identical with embodiment 1；
S2 step specifically:
S2: the neopentyl glycol prepared in S1, polyethyleneglycol diglycidylether is taken to be added in mixer, and at 125 DEG C
Lower heating melting, obtains mixed material.
Comparative example 5
Comparative example 4 and the difference of embodiment 1 are: in S2 do not use polyethyleneglycol diglycidylether, remaining step and
Condition is identical with embodiment 1；
S2 step specifically:
S2: taking the neopentyl glycol prepared in S1,3- hydroxyl -4-Aminobutanoicacid to be added in mixer, and adds at 125 DEG C
Heat fusing obtains mixed material.
Comparative example 6
Comparative example 4 and the difference of embodiment 1 are: not using neopentyl glycol, remaining Step By Condition and embodiment 1 in S2
It is identical；
S2 step specifically:
S2: taking the polyethyleneglycol diglycidylether prepared in S1,3- hydroxyl -4-Aminobutanoicacid to be added in mixer,
And the heating melting at 125 DEG C, obtain mixed material.
Comparative example 7
Comparative example 4 and the difference of embodiment 1 are: not using 2,4,6- trihydroxybenzoic acids, remaining step and item in S3
Part is identical with embodiment 1；
S3: M-phthalic acid, pyridine -2,6- dioctyl phthalate, Acetaminocaproic Acid are added in the mixed material obtained by S2, together
When catalyst for esterification reaction is added, gradually temperature reaction is to 220 DEG C under nitrogen protection, heat preservation esterification 5h or so, to acid
When value is reduced to 40mgKOH/g or so, slow temperature reaction is extremely steamed without obvious distillate and the acid value of reactant reaches
Until 28mgKOH/g；The slow temperature reaction temperature highest temperature has reached 240 DEG C.
Comparative example 8
Comparative example 4 and the difference of embodiment 1 are: in S5 do not use N-hydroxyethyl-ethylenediamine triacetic acid, remaining step and
Condition is identical with embodiment 1；
S5: when being cooled to 200 DEG C, discharging immediately, and cooling with the steel band with condensed water, is crushed and is granulated, is gathered
Ester resin.
Comparative example 9
Commercially available TGIC system powdery paints normal polyester resin.
1 embodiment 1 of table is compared with comparative example 1-9 polyester resin acid value obtained and softening point
The measuring method of polyester resin acid value (mgKOH/g): the GB 2895-82 " survey of unsaturated polyester resin acid value is pressed
It is fixed " it carries out；
The measuring method of polyester resin softening point: " epoxy resin softening point measurement method is global by GB/T12007.6-1989.
Method " it is measured.
Embodiment 2
The preparation method of low gloss TGIC system polyester resin, its step are as follows:
S1: preparing raw material A, and the molar content of raw material A component is as follows:
Prepare raw material B: the content of raw material B each component is as follows:
Catalyst for esterification reaction: dioctyltin dichloride, dosage 0.1mol%；
Antioxidant 1010, dosage are 0.2mol% or so；
It is taken in following steps by the dosage prepared in S1；
S2: neopentyl glycol, polyethyleneglycol diglycidylether, 3- hydroxyl -4-Aminobutanoicacid prepared in S1 is taken to be added
In mixer, and the heating melting at 128 DEG C, obtain mixed material；
S3: M-phthalic acid, pyridine -2,6- dioctyl phthalate, Acetaminocaproic Acid are added in the mixed material obtained by S2, together
When catalyst for esterification reaction is added, gradually temperature reaction is to 220 DEG C under nitrogen protection, heat preservation esterification 2h or so, to acid
2,4,6- trihydroxybenzoic acids are added in value when being reduced to 42mgKOH/g or so, slow temperature reaction is extremely steamed without obvious distillate
And until the acid value of reactant reaches 25mgKOH/g；The slow temperature reaction temperature highest temperature has reached 235 DEG C；
S4: being added antioxidant 1010, and 4h or so is kept under the vacuum degree of 50mmHg, facilitates the formation of polyester resin, to
Acid value, which is reduced to, to be stopped vacuumizing when 15mgKOH/g or so；
S5: when being cooled to 200 DEG C, being added N-hydroxyethyl-ethylenediamine triacetic acid, and be to slowly warm up to 240 DEG C of reaction 2h, to
Stop reaction when the acid value of reactant is 28mgKOH/g or so, discharge immediately, and is cooling with the steel band with condensed water, breaks
Broken granulation obtains polyester resin, gained polyester resin acid value are as follows: 30mgKOH/g, softening point are 114 DEG C.
Embodiment 3
The preparation method of low gloss TGIC system polyester resin, its step are as follows:
S1: preparing raw material A, and the molar content of raw material A component is as follows:
Prepare raw material B: the content of raw material B each component is as follows:
Catalyst for esterification reaction: dioctyltin dichloride, dosage are 0.3mol% or so；
Antioxidant: antioxidant 1010, dosage are 0.3mol% or so；
It is taken in following steps by the dosage prepared in S1；
S2: neopentyl glycol, polyethyleneglycol diglycidylether, 3- hydroxyl -4-Aminobutanoicacid prepared in S1 is taken to be added
In mixer, and the heating melting at 125 DEG C, obtain mixed material；
S3: M-phthalic acid, pyridine -2,6- dioctyl phthalate, Acetaminocaproic Acid are added in the mixed material obtained by S2, together
When be added catalyst for esterification reaction dioctyltin dichloride, under nitrogen protection gradually temperature reaction to 220 DEG C, keep the temperature ester
Change reaction 5h or so, 2,4,6- trihydroxybenzoic acids is added when acid value is reduced to 40mgKOH/g or so, slow temperature reaction is extremely
Until no obvious distillate steams and the acid value of reactant reaches 28mgKOH/g；The slow temperature reaction temperature highest temperature reaches
240 DEG C；
S4: being added antioxidant 1010, and 6h or so is kept under the vacuum degree of 50mmHg, facilitates the formation of polyester resin, to
Acid value, which is reduced to, to be stopped vacuumizing when 16mgKOH/g or so；
S5: when being cooled to 200 DEG C, being added N-hydroxyethyl-ethylenediamine triacetic acid, and be to slowly warm up to 240 DEG C of reaction 8h, to
Stop reaction when the acid value of reactant is 32mgKOH/g or so, discharge immediately, and is cooling with the steel band with condensed water, breaks
Broken granulation obtains polyester resin, gained polyester resin acid value are as follows: 28mgKOH/g, softening point are 118 DEG C.
Embodiment 4
Application of the polyester resin in paint coatings preparation in embodiment 1-3 and comparative example 1-9, method particularly includes:
Each raw material is taken by following weight proportion:
Paint coatings preparation:
Example 1, sample polyester resin obtained in comparative example 1-9 respectively, then respectively with TGIC, titanium dioxide, disappear
Light barium sulfate, levelling agent, physics delustering agent, styrax are uniformly mixed by above-mentioned weight proportion, squeezed out with double screw extruder,
It is tabletting, broken, then sheet stock is crushed and (180-200 mesh) acquisition powdery paints that is sieved.Powdery paints is sprayed using electrostatic gun
On tinplate substrate after being coated in surface treated, solidify through 180 DEG C/15min to get paint coatings.
It is detected by the method disclosed in GB/T 21776-2008 " the examination criteria guide of powdery paints and its coating ",
The data of resulting index are as follows:
The properties of product of table 2 embodiment 1-3 and comparative example 1-9 compare
Note: pin hole shape is from the appearance point of view, coating surface shows thickly dotted small pore-like；
Prepare paint coatings obtained by above method, film apparently, impact property, gloss, boiling water
Change after boiling and shows significant difference；
Embodiment 1, embodiment 2, the polyester resin in embodiment 3 are more smooth in film performance, and effect is preferable, nothing
Any pin-hole phenomena, impact property is excellent, the equal < 20% of gloss；It is after boiling water boiling 2 hours and unchanged；
And due to lacking related component in comparative example 2,4,5,7,8, be affected to curing performance, solidification effect compared with
Difference causes positive and negative impact that can not pass through, while water boiling resistance performance is also poor, and coating falls off after boiling, and gloss is also in
Reveal the case where can not being effectively reduced, gloss is substantially 35% or more.The 3- hydroxyl especially lacked in comparative example 4 and comparative example 7
Base -4-Aminobutanoicacid and 2,4,6- trihydroxybenzoic acids are to confer to the raw material that final polyester resin has a variety of different functional groups,
Lacking for these raw materials is especially apparent the influence of gloss, and the gloss of comparative example 4 and comparative example 7 is higher, and gloss is 40%
More than；And N-hydroxyethyl-ethylenediamine triacetic acid of the comparative example 8 due to lacking sealing end, cause polyester resin can not be with curing agent TGIC
It is cured, film can not be formed, and film coated surface can not solidify, and flowing time is long, cause gloss also higher, while N- ethoxy
Ethylenediamine triacetic acid contains hydroxyl and carboxyl simultaneously, is also to provide the raw material of different activities functional group, and missing inevitably results in
The reduction of activity hydroxy and carboxyl, unfavorable to delustring in molecule segment.
The component lacked in comparative example 1,3,6, is mainly affected to film comprehensive performance, is embodied in gloss, impact
The reduction of a variety of aspect performances such as property and water boiling resistance；
Commercially available TGIC system is lived with normal polyester resin due to being blocked using M-phthalic acid in comparative example 9
Property functional group be mainly M-phthalic acid provide carboxyl, activity it is more single, curing rate is also uniform, the problem of being primarily present
It is that extinction effect is bad, final coating film gloss is higher, simultaneously because the M-phthalic acid degree of functionality of sealing end is slightly lower, so water boiling resistance
Aspect also slightly has defect.
The present invention passes through the polyester tree that processing prepares by using suitable raw material type and with reasonable proportion
Rouge, amino, carboxyl, hydroxyl and epoxy group contained by raw material itself, so that by obtained by production technology preparation of the invention
Polyester resin its own activity it is active different with traditional commercial polyester resin, finally make in polyester chain with active difference
Carboxyl, hydroxyl and amino, they react precedence with the epoxy group in TGIC molecule and differ greatly, may be implemented adding
The difference of functional group different in polyester molecule and TGIC solidification rate when heat cure and lead to film coated surface slight shrinkage,
To obtain the film of low gloss.And the planarization flatness of the film is excellent, pin-free to occur without coarse phenomenon；Even if
After high temperature boiling 2 hours, coating is simultaneously unchanged, will not generate bubble or fall off and loss of gloss phenomenon.This explanation, the present invention
Method obtain polyester resin be applied to production powdery paints and paint coatings in after, smooth performance is excellent, glossiness
Lower, impact resistance is stronger, and stability is good, even if still unchanged in the case where long-time is by hot conditions.
But (certain raw material therein is reduced) after being adjusted to raw material proportioning of the invention, resulting polyester resin
For producing paint coatings, the performance of coating is impacted larger.As it can be seen that raw material itself used in even similarly has ammonia
Base, carboxyl, hydroxyl and epoxy group, but the polyester resin obtained also can make the performance difference of coating larger for producing coating.
Therefore, only using the painting of its TGIC system for being used to produce low low gloss of formula of the invention and the polyester resin of technique acquisition
Material or paint coatings, excellent effect.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (9)
1. low gloss TGIC system polyester resin for powder coating, comprising: raw material A and raw material B；
(1) in raw material A, the molar content of each component is as follows:
(2) in raw material B, the content of each component is as follows:
Catalyst for esterification reaction: dioctyltin dichloride, dosage are the 0.1-0.3% of the integral molar quantity of raw material A；
Antioxidant: antioxidant four [methyl-β-(3,5- di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, dosage
For the 0.2-0.4% of raw material A integral molar quantity.
2. the preparation method of low gloss TGIC system polyester resin for powder coating as described in claim 1, its step are as follows:
S1: preparing raw material A, and the molar content of raw material A component is as follows:
Prepare raw material B: the content of raw material B each component is as follows:
Catalyst for esterification reaction: dioctyltin dichloride, dosage are the 0.1-0.3% of the integral molar quantity of raw material A；
Antioxidant: antioxidant four [methyl-β-(3,5- di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, dosage
For the 0.2-0.4% of raw material A integral molar quantity；
It is taken in following steps by the dosage prepared in S1；
S2: take neopentyl glycol, polyethyleneglycol diglycidylether, 3- hydroxyl -4-Aminobutanoicacid prepared in S1 that reaction is added
In device, and the heating melting at 120-130 DEG C, obtain mixed material；
S3: being added M-phthalic acid, pyridine -2,6- dioctyl phthalate, Acetaminocaproic Acid in the mixed material obtained by S2, adds simultaneously
Enter catalyst for esterification reaction, gradually temperature reaction keeps the temperature esterification 2-8h to 220 DEG C under nitrogen protection, reduces to acid value
It is added 2,4,6- trihydroxybenzoic acids when to 30-45mgKOH/g, slow temperature reaction is to steaming and react without obvious distillate
Until the acid value of object reaches 25-30mgKOH/g；Slow temperature reaction temperature is less than or equal to 245 DEG C；
S4: being added antioxidant four [methyl-β-(3,5- di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester,
2-6h is kept under the vacuum degree of 50mmHg, to form polyester resin, stops vacuumizing when acid value is reduced to 15-16mgKOH/g；
S5: when being cooled to 200 DEG C, N-hydroxyethyl-ethylenediamine triacetic acid is added, and be to slowly warm up to 240 DEG C of reaction 2-8h, to anti-
Stop reaction when the acid value of object being answered to be 28-36mgKOH/g, discharges immediately, and cooling, be crushed and be granulated, obtain polyester resin.
3. the preparation method of low gloss TGIC system polyester resin for powder coating as claimed in claim 2, it is characterised in that:
It is cooling using the steel band with condensed water in S5.
4. the preparation method of low gloss TGIC system polyester resin for powder coating as claimed in claim 2, it is characterised in that:
Polyester resin acid value obtained in S5 be 28-36mgKOH/g, 108-120 DEG C of softening point.
5. using application of the polyester resin of method for claim 2 preparation in powdery paints and paint coatings.
6. the polyester resin in claim 1 is used to prepare powdery paints, following step is specifically included:
(1) prepare each raw material by following weight part ratio:
(2) by (1) each raw material be uniformly mixed, then extrusions, tabletting, be crushed, obtain sheet stock, then sheet stock is pulverized and sieved, obtain
Powdery paints.
7. the polyester resin in claim 1 is used to prepare paint coatings, following step is specifically included:
(1) prepare each raw material by following weight part ratio:
(2) by (1) each raw material be uniformly mixed, then extrusions, tabletting, be crushed, obtain sheet stock, then sheet stock is pulverized and sieved, obtain
Powdery paints；
(3) solid under conditions of 180 DEG C/15min by powder paint on the tinplate substrate after surface treatment
Change, obtains paint coatings.
8. polyester resin as claimed in claim 7 is used to prepare paint coatings, which is characterized in that squeezed out with double screw extruder
Uniformly mixed raw material.
9. polyester resin as claimed in claim 7 is used to prepare paint coatings, which is characterized in that use electrostatic gun by powder
Coating is sprayed on the tinplate substrate after surface treated.
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| CN201811320241.9A CN109320705A (en) | 2018-11-07 | 2018-11-07 | Low gloss TGIC system polyester resin for powder coating and preparation method and application |
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| CN201811320241.9A CN109320705A (en) | 2018-11-07 | 2018-11-07 | Low gloss TGIC system polyester resin for powder coating and preparation method and application |
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| CN110117355A (en) * | 2019-06-12 | 2019-08-13 | 黄山嘉恒科技有限公司 | The excellent TGIC polyester resin for powder coating of resistance to neutral salt spray and preparation method |
| CN110156973A (en) * | 2019-06-12 | 2019-08-23 | 黄山嘉恒科技有限公司 | The excellent PU cured powder paint polyester resin of cold resistance and preparation method |
| CN110283306A (en) * | 2019-07-01 | 2019-09-27 | 黄山正杰新材料有限公司 | A kind of semi-matte polyester resin for powder coating and the preparation method and application thereof |
| CN110655644A (en) * | 2019-10-12 | 2020-01-07 | 黄山市向荣新材料有限公司 | 60/40 polyester resin for low-gloss powder coating and three-kettle combined preparation method thereof |
| CN111647149A (en) * | 2020-07-07 | 2020-09-11 | 安徽永利新材料科技有限公司 | Polyester resin with excellent wear resistance and chemical resistance for powder and preparation method thereof |
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| CN110117355A (en) * | 2019-06-12 | 2019-08-13 | 黄山嘉恒科技有限公司 | The excellent TGIC polyester resin for powder coating of resistance to neutral salt spray and preparation method |
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| CN110283306A (en) * | 2019-07-01 | 2019-09-27 | 黄山正杰新材料有限公司 | A kind of semi-matte polyester resin for powder coating and the preparation method and application thereof |
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| CN110655644A (en) * | 2019-10-12 | 2020-01-07 | 黄山市向荣新材料有限公司 | 60/40 polyester resin for low-gloss powder coating and three-kettle combined preparation method thereof |
| CN110655644B (en) * | 2019-10-12 | 2021-09-07 | 黄山市向荣新材料有限公司 | 60/40 polyester resin for low-gloss powder coating and three-kettle combined preparation method thereof |
| CN111647149A (en) * | 2020-07-07 | 2020-09-11 | 安徽永利新材料科技有限公司 | Polyester resin with excellent wear resistance and chemical resistance for powder and preparation method thereof |
| CN111647149B (en) * | 2020-07-07 | 2022-08-02 | 安徽永利新材料科技有限公司 | Polyester resin with excellent wear resistance and chemical resistance for powder and preparation method thereof |
| CN111978527A (en) * | 2020-09-11 | 2020-11-24 | 安徽鑫友高分子新材料科技有限公司 | High-hardness powder coating with excellent fluorescence performance, preparation method and polyester resin used in preparation method |
| CN111978527B (en) * | 2020-09-11 | 2022-08-12 | 安徽鑫友高分子新材料科技有限公司 | High-hardness powder coating with excellent fluorescence performance, preparation method and polyester resin used in preparation method |
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Application publication date: 20190212 |