CN109679436A - A kind of antifouling leather finishing agent and preparation method thereof - Google Patents
A kind of antifouling leather finishing agent and preparation method thereof Download PDFInfo
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- CN109679436A CN109679436A CN201811582243.5A CN201811582243A CN109679436A CN 109679436 A CN109679436 A CN 109679436A CN 201811582243 A CN201811582243 A CN 201811582243A CN 109679436 A CN109679436 A CN 109679436A
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/24—Homopolymers or copolymers of amides or imides
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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
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
A kind of antifouling leather finishing agent and preparation method thereof, is made of antifouling resin system, auxiliary agent and catalyst.The antifouling resin system is a kind of two-component system, and hydroxy acryl acid resin, hydroxyl value is between 50-130mgKOH/g；Curing agent is the amino resins of solid content 80%-98%.The Hydroxylated acrylic resin is high solid low viscosity resin, and solid content is 65% -85% or so, and viscosity is 1000cps -2500cps/25 DEG C, solvent-free, cooks reactive diluent using the acrylic ester monomer with space charge force.Simple process of the invention, conventional leather finishing agent construction drying process can solidify, and antifouling excellent effect after solidification, and cost is relatively low and environment-protecting and non-poisonous.
Description
Technical field
The present invention relates to a kind of macromolecule resin finishing agent, specially a kind of antifouling leather finishing agent and its preparation side
Method.
Background technique
The main function of antifouling paint is the antifouling property for improving coating or substrate, currently, either industrial coating, still
Family's coatings etc. all have the antifouling paint of high performance-price ratio in research and development energetically.Leather industry is especially true, in present leather row
Under the less prosperous overall situation of industry, developing, there is the leather antifouling paint of high sexual valence to seem especially urgent.
Main antifouling paint in the market mainly has using Organic fluoride, organosilicon and nano-oxide particles etc.
The coating system of low-surface-energy improves anti-pollution, on the one hand, these material costs are higher, need to be added to a certain amount
There can be antifouling effect；On the other hand, it synthesizes such coating system and needs higher technique requirement.And leather industry is whole now
Body profit is not high, and high cost and high technology require unsuitable leather industry.
Also there are the leather antifouling paint of document and Patent exploitation aqueous polyurethane system, from effect, water-based system
Anti-fouling effect cannot still reach the standard of solvent-based system, therefore, need to develop a kind of good antifouling effect, and cost performance is high
Leather antifouling paint.
Number of patent application 94111930.0；1055125C discloses one kind with acetylbutyrylcellulose and acrylic acid multielement
The compound of copolymer is the solvent type or aqueous emulsion type coating material for leather of main film-forming component.The acetate butyrate of the material is fine
It ties up and is crosslinked between plain molecule and acrylic-multipolymer molecule with aliphatic polyisocyante, and be crosslinked it
The carboxyl introduced on complexed macromolecules chain is reacted with organic polyamine compound and/or alcohol amine compound and has been connected containing polyamines
And/or the polar side chain of hydroxyl.Its object is to using with good physical mechanical performance and comfortable feel and fast light non yellowing
Performance, which occupies the acetylbutyrylcellulose first of coating cellulose, to have the acrylic resin of numerous good characteristics composite modified, with
Overcome its hot sticky cold crisp and the strong disadvantage of plastic sense, makes excellent white leathers surface layer coating material.
Number of patent application 201110039644.8 discloses a kind of Anti-graffito leather finishing agent and its application method, is related to
Leather surface process field solves the technical problem of current leather antigraffiti effect difference.The invention is characterised in that it is by separating
Two parts of storage are constituted, and the material composition and mass percentage of first part are as follows: hydroxy polyester resin 3%-30%, end
Hydroxyl polyurethane resin 3%-30%, polyurethane resin 0%-50%, organic-silicon-modified acrylic resin 1%-15%, catalysis
Agent 0.1%-1%, auxiliary agent 0.5%-5%, remaining be solvent, second part is polyisocyanate curing agent, solid in second part
The NCO mole of agent is 1-1.05 times of hydroxyl mole in first part.After it handles leather surface, effectively subtract
Weak leather and fur products is polluted by scribble when in use, can also wipe scribble trace easily, restores the good appearance effect of leather
Fruit.Itself the problem is that: higher using the material costs such as organosilicon, antifouling effect can be had by needing to be added to a certain amount
Fruit；On the other hand, it synthesizes such coating system and needs higher technique requirement.And leather industry entirety profit is not high now, it is high
Cost and high technology require unsuitable leather industry.
Number of patent application 99115090.2 discloses a kind of preparation method of process hides bottom-closing coating and decorating agent.Its formula composition
Are as follows: sericin 0.4%~6.0%, cationic surfactant 0~5.0%, small molecule acid 0.04%~3.0%, acrylate list
It is small that body 5.0%~25%, nitrogen containing monomer 0.5%~10.0%, hydroxyl monomer 0~6.0% and water react 4~12 at 50~95 DEG C
Shi Hou adds alcohol compound 0~3.6%, and the reaction was continued 0.5 hour and obtains leather bottom-closing coating and decorating agent of the invention.This product cream
Liquid stability is good, and storage period is long, can save the usage amount of other leather chemicals, and finished leather is comfortably soft, and gloss is naturally bright,
Coating is strong adhesion, and Bearable dry and wet wipe, hiding rare is strong, has certain benefit wound property.Its object is to be replaced with silk sericin
Casein newly is formulated using one kind and technique prepares cationic leather back cover agent, to reduce the use of leather chemicals, is improved
Atom economy；Leather chemicals are produced using waste, save resource, production cost are reduced, to ecological environment and very
Friendly, but it does not have antipollution performance.
Summary of the invention
The purpose of the present invention is to provide a kind of antifouling leather finishing agent and preparation method thereof, have good antifouling effect,
The advantages that cost performance is high, to solve the problems mentioned in the above background technology.
To achieve the above object, the invention provides the following technical scheme: a kind of antifouling use the leather finishing agent, including hydroxyl value to be
Between 50-130mgKOH/g, the Hydroxylated acrylic resin of the acrylic ester monomer containing photolytic activity and the ammonia of solid content 80%-98%
Base resin and auxiliary agent appropriate, catalyst；Its resin+curing agent: auxiliary agent: catalyst=(90% -95%): (2% -5%):
(0% -2%).
Further, for the hydroxyl value of the Hydroxylated acrylic resin between 50-130mgKOH/g, solid content is 65%-
85%, viscosity is 1000cps -2500cps/25 DEG C；The monomer for synthesizing the Hydroxylated acrylic resin predominantly contains 3-18 carbon originals
The acrylic ester monomer of son may occur from the vinyl monomer within 8 carbon atoms being polymerize by base and contain unsaturation
The polyurethane prepolymer of key.
Further, the acrylic ester monomer of the synthesis of hydroxy acrylic resin is (methyl) acrylic acid -2- hydroxyl
Ethyl ester, (methyl) 2-hydroxypropyl acrylate, (methyl) acrylic acid, (methyl) methyl acrylate, (methyl) ethyl acrylate,
(methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) Isooctyl acrylate monomer, (first
Base) isobutyl acrylate, (methyl) lauryl acrylate, (methyl) aliphatic acrylate, (methyl) octadecyl
One or more of base ester, (methyl) isobornyl acrylate, dimethylaminoethyl methacrylate composition, the synthesis
The vinyl monomer of hydroxy acrylate is one in styrene, vinylacetate, maleic acid esters and fumaric acid esters
Kind or several compositions, the polyurethane prepolymer containing unsaturated bond by hydroxy acryl acid monomer, diisocyanate and
End-capping reagent, as ethylene glycol monobutyl ether is prepared under certain process conditions, applicable acrylate monomers include third
Olefin(e) acid -2- hydroxy methacrylate, 2-hydroxypropyl acrylate, methacrylic acid -2- hydroxy methacrylate, methacrylic acid -2- hydroxyl third
Ester；Applicable diisocyanate is mainly that the activity of two isocyanate group is discrepant, such as isophorone diisocyanate, is closed
Suitable end-capping reagent is mainly ethylene glycol monobutyl ether, propylene glycol monomethyl ether.
Further, the photolytic activity acrylic ester monomer of the synthesis of hydroxy acrylic resin is trimethylolpropane two
Acrylate, propylene glycol diacrylate, pentaerythritol triacrylate, N,N-DMAA, methacrylic acid are different
One of norbornene ester, isobornyl acrylate, polyoxyethylene glycol diacrylate, polyoxypropylene diols diacrylate or
Several compositions.
Further, the amino resins is the amino resins of solid content 80%-98%, specially profound new company
CYMEL385、CYMEL325。
Further, the catalyst is organic acid, such as benzene sulfonic acid, p-methyl benzenesulfonic acid and alkylsurfuric acid.
The present invention provides another technical solution are as follows: a kind of antifouling preparation method with leather finishing agent, including following step
It is rapid:
S1: acrylic ester monomer and/or vinyl monomer are subjected to bulk polymerization under the action of initiator；
S2: after detection hydroxyl value reaches 50-130mgKOH/g, the reaction was continued for stopping, being cooled within 50 DEG C；
S3: it is added and is diluted with photoactive acrylic acid reactive diluent, obtain hydroxy acryl acid resin；
S4: being down to room temperature, and amino resins is added, stirs, and suitable adjuvants are added and obtain resin Composition；
S5: catalytic component is added when use.
By the retrieval to the prior art, be related to the finishing agent containing acrylate patent and application it is more, but with this hair
The finishing agent of bright hydroxy acryl acid ester is compared, and discovery uses the formula of same materials, therefore by hydroxy acryl acid ester
As a kind of leather finishing agent, have constructive.Compared with prior art, the beneficial effects of the present invention are:
1, non-volatility solvent of the present invention is a kind of environmental friendly product.
2, the present invention is free of organosilicon and Organic fluoride with high costs, but can reach comparable anti-fouling effect, has very high
Cost performance.
3, the present invention has multiple cure mechanisms, has very high crosslink density, this makes it have good antifouling effect
Fruit, but it is harder and be not suitable for leather substrate to be unlikely to film forming matter again simultaneously.
Specific embodiment
It will be detailed below the embodiment of the present invention.However, based on the embodiments of the present invention, ordinary skill people
Member's every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.
The present invention provides a kind of antifouling leather finishing agents, including hydroxyl value to contain photolytic activity between 50-130mgKOH/g
The Hydroxylated acrylic resin of acrylic ester monomer and the amino resins of solid content 80%-98% and auxiliary agent appropriate, catalysis
Agent；Its resin+curing agent: auxiliary agent: catalyst=(90% -95%): (2% -5%): (0% -2%).
Wherein, for the hydroxyl value of Hydroxylated acrylic resin between 50-130mgKOH/g, solid content is 65% -85%, and viscosity is
1000cps—2500cps/25℃；The monomer for synthesizing the Hydroxylated acrylic resin is mainly the acrylic acid for containing 3-18 carbon atoms
Esters monomer may occur from the vinyl monomer within 8 carbon atoms being polymerize by base and the poly- ammonia containing unsaturated bond
Ester prepolymer；Wherein, the acrylic ester monomer of synthesis of hydroxy acrylic resin is (methyl) 2-Hydroxy ethyl acrylate, (first
Base) 2-hydroxypropyl acrylate, (methyl) acrylic acid, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) third
Olefin(e) acid propyl ester, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid
Isobutyl ester, (methyl) lauryl acrylate, (methyl) aliphatic acrylate, (methyl) octadecyl acrylate, (first
Base) isobornyl acrylate, one or more of dimethylaminoethyl methacrylate composition；Wherein, synthesis of hydroxy third
The vinyl monomer of olefin(e) acid ester is one of styrene, vinylacetate, maleic acid esters and fumaric acid esters or several
Kind composition；Wherein, the polyurethane prepolymer containing unsaturated bond is by hydroxy acryl acid monomer, diisocyanate and sealing end
Agent, as ethylene glycol monobutyl ether is prepared under certain process conditions, applicable acrylate monomers include acrylic acid-
2- hydroxy methacrylate, 2-hydroxypropyl acrylate, methacrylic acid -2- hydroxy methacrylate, methacrylic acid -2- hydroxy propyl ester；It is applicable in
Diisocyanate be mainly two isocyanate group activity it is discrepant, it is suitable to seal such as isophorone diisocyanate
Holding agent is mainly ethylene glycol monobutyl ether, propylene glycol monomethyl ether.
In the above-described embodiments, the photolytic activity acrylic ester monomer of synthesis of hydroxy acrylic resin is trimethylolpropane
Diacrylate, propylene glycol diacrylate, pentaerythritol triacrylate, N,N-DMAA, methacrylic acid
One of isobornyl thiocyanoacetate, isobornyl acrylate, polyoxyethylene glycol diacrylate, polyoxypropylene diols diacrylate
Or several compositions.
Amino resins is the amino resins of solid content 80%-98%, CYMEL385, CYMEL325 of specially profound new company.
Catalyst is organic acid, such as benzene sulfonic acid, p-methyl benzenesulfonic acid and alkylsurfuric acid.
Based on the above embodiment: a kind of antifouling preparation method with leather finishing agent is also provided, comprising the following steps:
Step 1: acrylic ester monomer and/or vinyl monomer are subjected to bulk polymerization under the action of initiator；
Step 2: after detection hydroxyl value reaches 50-130mgKOH/g, the reaction was continued for stopping, being cooled within 50 DEG C；
Step 3: it is added and is diluted with photoactive acrylic acid reactive diluent, obtain hydroxy acryl acid resin；
Step 4: being down to room temperature, and amino resins is added, stirs, and suitable adjuvants are added and obtain resin Composition；
Step 5: catalytic component is added when use.
It describes, in order to further preferably illustrate foregoing invention, comes below with reference to embodiment based on the above embodiment
The present invention is further illustrated:
Embodiment 1
Hydroxyethyl methacrylate 120g, methyl methacrylate 650g, butyl acrylate 600g are weighed, methacrylic acid is different pungent
Ester 357g, azo-bis-isobutyl cyanide 17g are uniformly mixed, and are taken out 1/4 in 3L four-hole boiling flask, are warming up to 75 DEG C of reaction 0.5h, later
Residual monomer mixture is dripped in 2h, hydroxyl value stops reaction after reaching 30mgKOH/g, is cooled to 45 DEG C, and three hydroxyl first are added
Base propane diacrylate 150g, isobornyl acrylate 155g, obtaining containing admittedly is 85%, the hydroxyl of cps/25 DEG C of viscosity 2500
Acrylic resin.
Above-mentioned resin 200g is taken, 327 50g of amino resins CYMEL, defoaming agent 3g, levelling agent 2.5g, catalyst pair is added
Toluenesulfonic acid 3.0g disperses 10min with the revolving speed of 1500r/min using dispersion machine to get antifouling leather finishing agent A is arrived.
Embodiment 2
Hydroxyethyl methacrylate 150g, ethyl acrylate 120g, styrene 100g, lauryl methacrylate 129g are weighed,
Azo-bis-isobutyl cyanide 5g is uniformly mixed, and is taken out 1/4 in 2L four-hole boiling flask, is warming up to 75 DEG C of reaction 0.5h, drips in 2h later
Residual monomer mixture is added, hydroxyl value stops reaction after reaching 130mgKOH/g, is cooled to 45 DEG C, and N, N- dimethyl allene is added
Amide 100g, polyoxyethylene glycol diacrylate 168g, obtaining containing admittedly is 65%, the hydroxy of cps/25 DEG C of viscosity 1050
Acid resin.
Above-mentioned resin 200g is taken, 325 50g of amino resins CYMEL, defoaming agent 5g, levelling agent 3g, p-methyl benzenesulfonic acid is added
5g disperses 10min with the revolving speed of 1500r/min using dispersion machine to get antifouling leather finishing agent B is arrived.
Embodiment 3
Weigh hydroxy-ethyl acrylate 120g, propyl methacrylate 300g, tetradecyl methylacrylate 309g, azo-bis-isobutyl cyanide
17g is uniformly mixed, and is taken out 1/4 in 2L four-hole boiling flask, is warming up to 75 DEG C of reaction 0.5h, is dripped in 2h later remaining single
Body mixture, hydroxyl value stop reaction after reaching 80mgKOH/g, are cooled to 45 DEG C, and pentaerythritol triacrylate 180g, first is added
Base isobornyl acrylate 63g, obtaining containing admittedly is 75%, the Hydroxylated acrylic resin of cps/25 DEG C of viscosity 1840.
Above-mentioned resin 200g is taken, 370 50g of amino resins CYMEL, defoaming agent 8g, levelling agent 6g, catalyst 12 is added
Alkylsurfuric acid 7g disperses 10min with the revolving speed of 1500r/min using dispersion machine to get antifouling leather finishing agent C is arrived.
Embodiment 4
Weigh hydroxypropyl acrylate 180g, 2-Propenoic acid, 2-methyl-, octyl ester 330g, octadecyl methacrylate 300g, vinylacetate
210g, azo-bis-isobutyl cyanide 11g are uniformly mixed, and are taken out 1/4 in 2L four-hole boiling flask, are warming up to 75 DEG C of reactions 0.5h, Zhi Hou
Residual monomer mixture is dripped in 2h, hydroxyl value stops reaction after reaching 55mgKOH/g, is cooled to 45 DEG C, and polyoxygenated third is added
Enediol diacrylate 300g, isobornyl methacrylate 137g, obtaining containing admittedly is 70%, cps/25 DEG C of viscosity 2200
Hydroxylated acrylic resin.
Above-mentioned resin 200g is taken, 323 50g of amino resins CYMEL, defoaming agent 3.2g, levelling agent 2.1g, catalyst is added
P-methyl benzenesulfonic acid 2.4g disperses 10min with the revolving speed of 1500r/min using dispersion machine to get antifouling leather finishing agent D is arrived.
Embodiment 5
Hydroxy propyl methacrylate 150g, butyl methacrylate 250g, dimethylaminoethyl methacrylate 119g are weighed, it is even
Two isobutyl cyanogen 11g of nitrogen is uniformly mixed, and is taken out 1/4 in 2L four-hole boiling flask, is warming up to 75 DEG C of reaction 0.5h, drips in 2h later
Residual monomer mixture is added, hydroxyl value stops reaction after reaching 105mgKOH/g, is cooled to 45 DEG C, and Polyoxyethylene glycol is added
Diacrylate 130g, obtaining containing admittedly is 80%, the Hydroxylated acrylic resin of cps/25 DEG C of viscosity 1400.
Above-mentioned resin 200g is taken, amino resins CYMEL 303ULF 50g is added, defoaming agent 3.5g, levelling agent 2.2g are urged
Agent p-methyl benzenesulfonic acid 3g disperses 10min with the revolving speed of 1500r/min using dispersion machine to get antifouling leather finishing agent E is arrived.
Embodiment 6
Weigh hydroxyethyl methacrylate 150g, ethyl acrylate 160g, isobutyl acrylate 139g, dimethyl maleate
200g, azo-bis-isobutyl cyanide 11g are uniformly mixed, and are taken out 1/4 in 2L four-hole boiling flask, are warming up to 75 DEG C of reactions 0.5h, Zhi Hou
Residual monomer mixture is dripped in 2h, hydroxyl value stops reaction after reaching 100mgKOH/g, is cooled to 45 DEG C, and polyoxyethylene is added
Enediol diacrylate 120g, propylene glycol diacrylate 62g, obtaining containing admittedly is 78%, the hydroxyl of cps/25 DEG C of viscosity 1650
Base acrylic resin.
Above-mentioned resin 200g is taken, 308 50g of amino resins CYMEL, defoaming agent 3.5g, levelling agent 2.2g, catalyst is added
P-methyl benzenesulfonic acid 3g disperses 10min with the revolving speed of 1500r/min using dispersion machine to get antifouling leather finishing agent F is arrived.
Embodiment 7
Isophorone diisocyanate 222g is first reached into reason in 75 DEG C of reaction assay NCO contents with ethylene glycol monobutyl ether 118g
By and then hydroxypropyl acrylate 130g is added dropwise, stop reaction until being warming up to 85 DEG C the reaction was continued measurement NCO without detection, it is cold
But discharging obtains unsaturated polyurethanes prepolymer；
Above-mentioned polyurethane prepolymer 150g, hydroxyethyl methacrylate 100g, Isooctyl acrylate monomer 250g, styrene 56g are weighed,
Azo-bis-isobutyl cyanide 5.6g is uniformly mixed, and is taken out 1/4 in 2L four-hole boiling flask, 75 DEG C of reaction 0.5h is warming up to, later in 2h
Residual monomer mixture is dripped, hydroxyl value stops reaction after reaching 110mgKOH/g, is cooled to 45 DEG C, and polyethylene glycol oxide two is added
Alcohol diacrylate 122g, obtaining containing admittedly is 82%, the Hydroxylated acrylic resin of cps/25 DEG C of viscosity 1250.
Above-mentioned resin 200g is taken, 1133 50g of amino resins CYMEL, defoaming agent 5g, levelling agent 2.8g, catalyst is added
P-methyl benzenesulfonic acid 4g disperses 10min with the revolving speed of 1500r/min using dispersion machine to get antifouling leather finishing agent G is arrived.
Embodiment 8
Isophorone diisocyanate 222g is first reached theoretical in 75 DEG C of reaction assay NCO contents with propylene glycol monomethyl ether 90g
And then hydroxyethyl methacrylate 130g is added dropwise, stop reaction until being warming up to 85 DEG C the reaction was continued measurement NCO without detection,
Cooling discharging obtains unsaturated polyurethanes prepolymer；
Above-mentioned polyurethane prepolymer 150g, hydroxyethyl methacrylate 100g, methyl acrylate 200g, styrene 282g are weighed,
Azo-bis-isobutyl cyanide 7.3g is uniformly mixed, and is taken out 1/4 in 2L four-hole boiling flask, 75 DEG C of reaction 0.5h is warming up to, later in 2h
Residual monomer mixture is dripped, hydroxyl value stops reaction after reaching 85mgKOH/g, is cooled to 45 DEG C, and polyethylene glycol oxide two is added
Alcohol diacrylate 100g, isobornyl acrylate 83g, obtaining containing admittedly is 80%, the hydroxy of cps/25 DEG C of viscosity 1530
Acid resin.
Above-mentioned resin 200g is taken, 1133 50g of amino resins CYMEL, defoaming agent 4g, levelling agent 3.8g, catalyst is added
P-methyl benzenesulfonic acid 3g disperses 10min with the revolving speed of 1500r/min using dispersion machine to get antifouling leather finishing agent H is arrived.
Based on the above embodiment one to eight, following Application Example is provided:
On the same leather that above-mentioned leather finishing agent A-H is applied respectively, dries and test film forming matter for oil pen, sauce
The contaminated resistance of oil, red wine and vinegar.As a result it see the table below:
| Oil pen | Soy sauce | Red wine | Vinegar | |
| Finishing agent A | It easily wipes, not trace | It easily wipes, not trace | It easily wipes, not trace | Slight trace |
| Finishing agent B | It easily wipes, not trace | It easily wipes, not trace | It easily wipes, not trace | It easily wipes, not trace |
| Finishing agent C | It easily wipes, not trace | It easily wipes, not trace | It easily wipes, not trace | It easily wipes, not trace |
| Finishing agent D | It easily wipes, not trace | It easily wipes, not trace | It easily wipes, not trace | It easily wipes, not trace |
| Finishing agent E | It easily wipes, not trace | It easily wipes, not trace | It easily wipes, not trace | Slight trace |
| Finishing agent F | It easily wipes, not trace | It easily wipes, not trace | It easily wipes, not trace | It easily wipes, not trace |
| Finishing agent G | It easily wipes, not trace | It easily wipes, not trace | It easily wipes, not trace | It easily wipes, not trace |
| Finishing agent H | It easily wipes, not trace | It easily wipes, not trace | It easily wipes, not trace | It easily wipes, not trace |
| Comparative example * | Slight trace | It easily wipes, not trace | It easily wipes, not trace | Slight trace |
Annotation: comparative example is commercial product.
In summary: the antifouling leather finishing agent and preparation method thereof of one kind provided by the invention, is by antifouling resin body
System, auxiliary agent and catalyst composition, antifouling resin system is a kind of two-component system, and resin system is hydroxy acryl acid tree
Rouge, hydroxyl value is between 50-130mgKOH/g；Curing agent is the amino resins of solid content 80%-98%, and Hydroxylated acrylic resin is
High solid low viscosity resin, solid content are 65% -85% or so, and viscosity is 1000cps -2500cps/25 DEG C, and non-volatility solvent is
A kind of environmental friendly product cooks reactive diluent using the acrylic ester monomer with space charge force, without with high costs
Organosilicon and Organic fluoride, but comparable anti-fouling effect can be reached, there is very high cost performance, and there are multiple cure mechanisms,
With very high crosslink density, this makes it with good anti-fouling effect, but it is harder and uncomfortable to be unlikely to film forming matter again simultaneously
For leather substrate.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (7)
1. a kind of antifouling leather finishing agent, which is characterized in that including hydroxyl value between 50-130mgKOH/g, contain photolytic activity third
The Hydroxylated acrylic resin of olefin(e) acid esters monomer and amino resins and auxiliary agent, the catalyst of solid content 80%-98%；Resin+
Curing agent: auxiliary agent: catalyst=90%-95%:2%-5%:0%-2%.
2. one kind according to claim 1 is antifouling to use leather finishing agent, which is characterized in that the Hydroxylated acrylic resin
Hydroxyl value is 50-130mgKOH/g, and solid content is 65% -85%, and viscosity is 1000cps -2500cps/25 DEG C；Synthesize the hydroxyl third
The monomer of olefin(e) acid resin be acrylic ester monomer containing 3-18 carbon atoms, may occur from 8 carbon atoms being polymerize by base with
Interior vinyl monomer and the polyurethane prepolymer containing unsaturated bond.
3. one kind according to claim 2 is antifouling to use leather finishing agent, which is characterized in that the synthesis of hydroxy acrylic acid tree
The acrylic ester monomer of rouge is (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) third
Olefin(e) acid, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) isopropyl acrylate,
(methyl) butyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) isobutyl acrylate, (methyl) lauryl acrylate, (first
Base) aliphatic acrylate, (methyl) octadecyl acrylate, (methyl) isobornyl acrylate, methacrylic acid two
One or more of methylamino ethyl ester composition；
The vinyl monomer of the synthesis of hydroxy acrylate is styrene, vinylacetate, maleic acid esters and rich horse
One or more of esters of gallic acid composition；
The polyurethane prepolymer containing unsaturated bond is by hydroxy acryl acid monomer, diisocyanate and end-capping reagent ethylene glycol
Monobutyl ether is prepared, and the acrylate monomers include 2-Hydroxy ethyl acrylate, 2-hydroxypropyl acrylate, methyl
2-Hydroxy ethyl acrylate, methacrylic acid -2- hydroxy propyl ester；
The diisocyanate is the discrepant isophorone diisocyanate of activity of two isocyanate group, the end-capping reagent
For ethylene glycol monobutyl ether, propylene glycol monomethyl ether.
4. one kind according to claim 1 is antifouling to use leather finishing agent, which is characterized in that the synthesis of hydroxy acrylic acid tree
The photolytic activity acrylic ester monomer of rouge is trimethylolpropane diacrylate, propylene glycol diacrylate, pentaerythrite three
Acrylate, N,N-DMAA, isobornyl methacrylate, isobornyl acrylate, polyoxyethylene glycol two
One or more of acrylate, polyoxypropylene diols diacrylate composition.
5. one kind according to claim 1 is antifouling to use leather finishing agent, which is characterized in that the amino resins is solid content
The amino resins of 80%-98%, the trade mark are CYMEL385, CYMEL325 of profound new company.
6. one kind according to claim 1 is antifouling to use leather finishing agent, which is characterized in that the catalyst is benzene sulphur
Acid, p-methyl benzenesulfonic acid and/or alkyl sulfide classes of organic acids.
7. a kind of antifouling preparation method with leather finishing agent according to claim 1, which is characterized in that including following step
It is rapid:
S1: acrylic ester monomer and/or vinyl monomer are subjected to bulk polymerization under the action of initiator；
S2: after detection hydroxyl value reaches 50-130mgKOH/g, the reaction was continued for stopping, being cooled within 50 DEG C；
S3: it is added and is diluted with photoactive acrylic acid reactive diluent, obtain hydroxy acryl acid resin；
S4: being down to room temperature, and amino resins is added, stirs, and suitable adjuvants are added and obtain resin Composition；
S5: catalytic component is added when use.
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Cited By (1)
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| CN115505285A (en) * | 2022-05-19 | 2022-12-23 | 东莞市科迪实业有限公司 | Easy-to-clean wear-resistant synthetic leather and preparation method thereof |
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