CN107353762A - Silicone-modified polyacrylate leather finishing agent, its preparation method and leather composite bed - Google Patents
Silicone-modified polyacrylate leather finishing agent, its preparation method and leather composite bed Download PDFInfo
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- CN107353762A CN107353762A CN201710719667.0A CN201710719667A CN107353762A CN 107353762 A CN107353762 A CN 107353762A CN 201710719667 A CN201710719667 A CN 201710719667A CN 107353762 A CN107353762 A CN 107353762A
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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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C09D151/085—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds on to polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
- C14C11/003—Surface finishing of leather using macromolecular compounds
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- Life Sciences & Earth Sciences (AREA)
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- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention provides a kind of silicone-modified polyacrylate leather finishing agent, and it is obtained by crylic acid ester mixture monomer, initiator, organosilicone copolymer, acrylic acid, hydroxypropyl acrylate, emulsifying agent and deionized water through emulsion polymerization.The present invention passes through emulsion polymerization synthesizing organo-silicon modified polyacrylate finishing agent using the organosilicone copolymer of the end-blocking containing single-ended double bond with function monomer and acrylate monomer；Because organosilicone copolymer contains the long-chain of polymerization degree n=10~20, therefore its softness, water resistance, resistance to blocking are more preferable than conventional double bond containing organic silicon monomer, the silicone-modified polyacrylate finishing agent that then present invention synthesizes is used for leather finish, make leather that there is firmly crisp etc. performance of excellent feel, pliability, resistance to blocking, smooth, water resistance and low temperature, soft and smooth sense positive effect, hence it is evident that improve the hot sticky cold crisp of acrylic emulsion；Film elongation percentage is especially set to be more than 20, coating not tacky without modeling sense.
Description
Technical field
The present invention relates to leather technology field, more particularly to silicone-modified polyacrylate leather finishing agent, its preparation
Method and leather composite bed.
Background technology
Leather finishing agent is a kind of important leather chemistry lifted to the outward appearance, performance and economic value of leather
Product.Finishing agent in leather surface forms one layer of uniform thinfilm protective coating after covering with paint, lacquer, colour wash, etc. leather, assigns that leather is excellent makes
With performance, such as solvent resistant, flex endurant, Bearable dry and wet wipe, impact resistance and water proofing property performance.
In all kinds of finishing agents, polyacrylate finishing agent due to color it is shallow, protect color, protect light, corrosion-resistant and anti-pollution
The advantages that and be widely used in leather industry.But, the coating after conventional polyacrylate leather finishing agent covering with paint product is normal
Often with there is stronger modeling sense, also easily there is tacky phenomenon in priming coat, in, top coat also not abrasion-resistant, it is non-watertight etc..Acrylic acid tree
The study on the modification of fat leather finishing agent obtains the concern of people.Such as：(the skins such as Gao Futang, Zhang Xiaolei, Feng Jianyan, Wang Zhaowen
Remove from office scientific and engineering, 2006, Vol.16, No.1) it is condensed by silane coupler KH570 hydrolysate and hydroxy silicon oil
The introducing C=C double bonds into hydroxy silicon oil molecule are reacted, under ammonium persulfate initiation, condensation product is sent out with acrylate monomer again
Raw emulsion polymerization has synthesized hydroxyl silicon oil modified acrylic resin leather finishing agent；As a result show：The introducing of organosilicon, effectively
The defects of improving acrylic resin " hot sticky cold crisp ", Leather Finishing has the superiority such as hydrophobic, soft, smooth and Bearable dry and wet wipe
Energy.Publication No. CN1498930A Chinese patent discloses a kind of functional resin finishing agent, and it is from two containing terminal double bond
Methylsiloxane, function monomer (acrylic acid, acrylonitrile) and acrylate monomer polymerization synthesis modification polyacrylate finishing agent,
The finishing agent film forming levelling is good, and the film after covering with paint has extremely comfortable lubricious feel, and coating is soft, not tacky, and with preferable
Water proofing property and resistance to wet rubbing ability.Above-mentioned silicone-modified polyacrylate finishing agent is all to use silane coupler and acrylic acid
Ester monomer polymeric modification, although the defects of effectively improving " hot sticky cold crisp " known to polyacrylate, there is Leather Finishing soft
The excellent properties such as soft, smooth, waterproof and Bearable dry and wet wipe, but the extension of the film of these leathers is bad, coating has modeling to feel.
The content of the invention
Present invention solves the technical problem that it is to provide a kind of leather finishing agent, the leather finishing agent application that the application provides
In leather, the elongation percentage of obtained coating is more than 20, and coating is not tacky without modeling sense.
In view of this, this application provides a kind of silicone-modified polyacrylate leather finishing agent, passed through by following components
Emulsion polymerization obtains：
The organosilicone copolymer has the structure as shown in formula (I)：
Wherein, m is the integer more than or equal to 1；
N is the degree of polymerization, n=10~20.
Preferably, nertralizer is also included in the silicone-modified polyacrylate leather finishing agent, the nertralizer is
Ammoniacal liquor, the dosage of the nertralizer is so that the pH of the silicone-modified polyacrylate leather finishing agent is 7~9.
Preferably, the crylic acid ester mixture monomer be selected from methyl methacrylate, methyl acrylate, butyl acrylate and
Two or more in ethyl acrylate.
Preferably, the emulsifying agent is that mass ratio is (1.5~2.5)：1 anion emulsifier and nonionic emulsifier
Mixture；The anion emulsifier is in lauryl sodium sulfate, dodecyl sodium sulfate and neopelex
One or more, the nonionic emulsifier in SA-9, DIPONIL, Emulsogen LCN407 and paregal O one
Kind is a variety of.
Preferably, the content of the organosilicone copolymer is 1~1.5 parts by weight.
Present invention also provides the preparation method of described silicone-modified polyacrylate leather finishing agent, including it is following
Step：
By emulsifying agent, acrylic acid, hydroxypropyl acrylate, organosilicone copolymer, crylic acid ester mixture monomer and deionized water
Mixing, obtains pre-emulsion；
After the pre-emulsion, initiator are mixed with deionized water, heating response, polyacrylate leather finish is obtained
Agent.
Preferably, ammoniacal liquor is added after the reaction, so that the pH of reaction solution is 7.5~8.5.
Preferably, described the step of obtaining polyacrylate leather finishing agent, is specially：
Initiator is mixed with deionized water, obtains initiator solution；Deionized water is heated to after 70~90 DEG C adding again
Enter the initiator solution of 2~5wt% pre-emulsion and 25~50wt%, 8~12min of heating response, in 1.5~2h
Remaining pre-emulsion and initiator solution are added, continue 1~1.5h of insulation reaction, then be cooled to 40~60 DEG C.
Present invention also provides a kind of leather composite bed, including leather is with being compound in the organic-silicon-modified of the leather surface
Polyacrylate leather finishing agent, the silicone-modified polyacrylate leather finishing agent are the organosilicon described in such scheme
The silicone-modified polyacrylate prepared by preparation method described in modified polyacrylate leather finishing agent or such scheme
Leather finishing agent.
This application provides a kind of silicone-modified polyacrylate leather finishing agent, its by crylic acid ester mixture monomer,
Initiator, organosilicone copolymer, acrylic acid, hydroxypropyl acrylate, emulsifying agent and deionized water obtain through emulsion polymerization；The present invention
Using the organosilicon polymer blocked containing single-ended double bond and function monomer (acrylic acid, hydroxypropyl acrylate) and acrylate monomer
Pass through emulsion polymerization synthesizing organo-silicon modified polyacrylate finishing agent；Because the organosilicone copolymer of single-ended double bond end-blocking contains
The long-chain of polymerization degree n=10~20, therefore its softness, water resistance, resistance to blocking are more preferable, then the application provides organic-silicon-modified
Polyacrylate finishing agent is used for leather finish, leather is had excellent feel, pliability, resistance to blocking, smooth, water resistance
With firmly crisp etc. performance of low temperature, soft and smooth sense positive effect, hence it is evident that improve the hot sticky cold crisp of acrylic emulsion；Especially make prolonging for film
Rate is stretched more than 20, and coating is not tacky without modeling sense.
Embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, still
It should be appreciated that these descriptions are simply further explanation the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
For the short chain organic silicon monomer of terminal double bond, it has the silane coupler used for leather finishing agent in the prior art
There is certain crosslinked action, finally make the extension of film that is formed by leather finishing agent bad, coating has the shortcomings that modeling sense, the present invention
A kind of silicone-modified polyacrylate leather finishing agent is disclosed, is obtained by following components through emulsion polymerization：
The organosilicone copolymer has the structure as shown in formula (I)：
Wherein, m is the integer more than or equal to 1；
N is the degree of polymerization, n=10~20.
The organosilicone copolymer used in the silicone-modified polyacrylate leather finishing agent that the application provides contains poly-
The long-chain of right n=10~20, its softness, water resistance and resistance to blocking are more preferable, therefore, provided by the invention organic-silicon-modified poly-
Acrylate leather coating agent is applied to leather finish, and the elongation percentage of obtained film is more than 20, and coating is not tacky without modeling sense.
Specifically, herein described silicone-modified polyacrylate leather finishing agent obtains by emulsion polymerization,
The emulsion polymerization is reaction means well known to those skilled in the art, and this application is had no particular limits.
In silicone-modified polyacrylate leather finishing agent, raw material includes acrylic ester mixed zoarium, the acrylic acid
Ester mixture two kinds or two kinds in methyl methacrylate, methyl acrylate, butyl acrylate and ethyl acrylate with
On；In a particular embodiment, the acrylic ester mixed fit mixture selected from methyl methacrylate and ethyl acrylate, third
The mixture or butyl methacrylate of e pioic acid methyl ester and ethyl acrylate and the mixture of ethyl acrylate.The acrylate
The content of mixture is 50~100 parts by weight, in some specific embodiments, the acrylic ester mixed fit content be 65~
90 parts by weight.
The initiator is initiator well known to those skilled in the art, the initiator to promote the progress of reaction,
In the application, the initiator is selected from ammonium persulfate.The content of the initiator is 0.1~1 parts by weight.
Function monomer in herein described silicone-modified polyacrylate leather finishing agent is acrylic acid and acrylic acid
Hydroxypropyl acrylate, the content of the acrylic acid is 1~3 parts by weight, and the content of the hydroxypropyl acrylate is 0.5~1 parts by weight.
Emulsifying agent is that mass ratio is (1.5~2.5)：1 anion emulsifier and the mixture of nonionic emulsifier, are having
In body embodiment, the mass ratio of the anion emulsifier and nonionic emulsifier is (1.6~2)：1.It is described anionic emulsifying
One or more of the agent in lauryl sodium sulfate, dodecyl sodium sulfate and neopelex, it is described it is non-from
One or more of the sub- emulsifying agent in SA-9, DIPONIL, Emulsogen LCN407 and paregal O；In specific embodiment
In, the emulsifying agent is lauryl sodium sulfate and SA-9 mixture or lauryl sodium sulfate and Emulsogen LCN407
Mixture.The content of the emulsifying agent is 1~3 parts by weight.
Also include ammoniacal liquor in the raw material of the silicone-modified polyacrylate leather finishing agent, the purpose of the ammoniacal liquor exists
In the pH of adjustment polyacrylate leather finishing agent, so that its pH value is 7~9.
Herein described silicone-modified polyacrylate leather finishing agent is obtained by polymerizable organosilicon is modifies, by
In the attribute of organosilicone copolymer in itself, while the cooperation of other components, finally it is applied to polyacrylate leather finishing agent
Leather finish, there is preferable effect.The outward appearance of the polyacrylate leather finishing agent is the milky white emulsion with blue light, and it is
Anionic property, pH value is 7~9, and solid content is 29%~31%.
Present invention also offers the preparation method of the silicone-modified polyacrylate leather finishing agent, including following step
Suddenly：
By emulsifying agent, acrylic acid, hydroxypropyl acrylate, organosilicone copolymer and crylic acid ester mixture monomer and deionized water
Mixing, obtains pre-emulsion；
After the pre-emulsion, initiator are mixed with deionized water, heating response, organic-silicon-modified polyacrylic acid is obtained
Ester leather finishing agent.
In the preparation process of above-mentioned silicone-modified polyacrylate leather finishing agent, pre-emulsion is prepared for first,
In order that above-mentioned each component is well mixed, the detailed process of the pre-emulsion is：
Emulsifying agent is mixed with deionized water, adds acrylic acid, hydroxypropyl acrylate, organosilicone copolymer and acrylic acid
Ester mix monomer, 20~30min is emulsified, obtains pre-emulsion.
The application and then the emulsion polymerization process for carrying out silicone-modified polyacrylate leather finishing agent, specifically：
Initiator is mixed with deionized water, obtains initiator solution；Deionized water is heated to after 70~90 DEG C adding again
Enter the initiator solution of 2~5wt% pre-emulsion and 25~50wt%, 8~12min of heating response, in 1.5~2h
Remaining pre-emulsion and initiator solution are added, continue 1~1.5h of insulation reaction, then be cooled to 40~60 DEG C.
According to the present invention, ammoniacal liquor is finally added, the pH for making reaction solution is 7.5~8.5, obtains organic-silicon-modified polypropylene
Acid esters leather finishing agent.
The detailed process of above-mentioned reaction is well known to those skilled in the art, and this application is had no particular limits.
Present invention also offers a kind of leather composite bed, and it includes leather and changed with the organosilicon for being compound in the leather surface
Property polyacrylate leather finishing agent, the silicone-modified polyacrylate leather finishing agent be such scheme described in it is organic
Si modification polyacrylate leather finishing agent.Described compound mode the application has no particular limits, according to art technology
Mode known to personnel.
For a further understanding of the present invention, with reference to embodiment to silicone-modified polyacrylate provided by the invention
Leather finishing agent is described in detail, and protection scope of the present invention is not limited by the following examples.
Embodiment 1
20 grams of deionized water, 4 grams of emulsifying agent (wherein 2.5 grams of lauryl sodium sulfate, SA- are put into 500ml emulsifies bottle
9 1.5 grams), after stirring, by esters of acrylic acid 75 grams (wherein 10 grams of methyl methacrylate, 65 grams of ethyl acrylates),
2 grams of the organosilicone copolymer (SPS) that 1 gram of hydroxypropyl acrylate, 3 grams of acrylic acid and the single-ended double bond with formula (I) structure block
Add, emulsify 15min, obtain monomer pre-emulsion；
120 grams of deionized water is added in 500ml four-hole boiling flasks, is warming up to 80 DEG C；0.40 gram of ammonium persulfate is dissolved in 40
Initiator is made into gram deionized water, then 5 grams of monomer pre-emulsions, 15 grams of initiators are put into four-hole boiling flask together, heating is anti-
5min is answered, treats that micro emulsion blue light occurs in emulsion, residual monomer pre-emulsion and initiator are uniformly added drop-wise in four-hole boiling flask by 2h；It is added dropwise
After be further continued for be incubated 1h；40 DEG C are cooled to, adds 3 grams of ammoniacal liquor, regulation pH is 7.5-8.5, solid content 30 ± 1%, is filtered,
Silicone-modified polyacrylate leather finishing agent is made, elongation percentage is 12 times.Above-mentioned polyacrylate leather finishing agent is applied
Leather surface is overlying on, coating does not mould sense, and feel is soft and smooth.
Embodiment 2
500ml emulsify bottle in put into 20 grams of deionized water, 3 grams of emulsifying agent (wherein 2 grams of lauryl sodium sulfate,
407 1 grams of Emulsogen LCN), after stirring, by esters of acrylic acid 75 grams of (wherein 10 grams of methyl acrylate, acrylic acid
65 grams of ethyl ester), 1 gram of hydroxypropyl acrylate, 3 grams of acrylic acid and with formula (I) structure single-ended double bond block polymerizable organosilicon
1 gram of addition of body (SPS), emulsifies 15min, obtains monomer pre-emulsion；
120 grams of deionized water is added in 500ml four-hole boiling flasks, is warming up to 80 DEG C；0.40 gram of ammonium persulfate is dissolved in 40
Initiator is made into gram deionized water；5 grams of monomer pre-emulsions, 15 grams of initiators are put into four-hole boiling flask together again, heating is anti-
5min is answered, treats that micro emulsion blue light occurs in emulsion, residual monomer mixture and initiator are uniformly added drop-wise in four-hole boiling flask by 2h；It is added dropwise
After be further continued for be incubated 1h；40 DEG C are cooled to, adds 3 grams of ammoniacal liquor, regulation pH is 7.5-8.5, solid content 30 ± 1%, is filtered,
Silicone-modified polyacrylate leather finishing agent is made, elongation percentage is 15 times.Above-mentioned polyacrylate leather finishing agent is applied
Leather surface is overlying on, coating does not mould sense, and feel is soft and smooth.
Embodiment 3
20 grams of deionized water, 4 grams of emulsifying agent (wherein 2.5 grams of lauryl sodium sulfate, SA- are put into 500ml emulsifies bottle
9 1.5 grams), after stirring, by esters of acrylic acid 75 grams of (wherein 40 grams of base butyl acrylate, 35 grams of ethyl acrylate), third
0.5 gram of the organosilicone copolymer (SPS) that 1 gram of olefin(e) acid hydroxypropyl acrylate, 3 grams of acrylic acid and the single-ended double bond with formula (I) structure block
Add, emulsify 15min, obtain monomer pre-emulsion；
120 grams of deionized water is added in 500ml four-hole boiling flasks, is warming up to 80 DEG C；0.40 gram of ammonium persulfate is dissolved in 40
Initiator is made into gram deionized water；5 grams of monomer pre-emulsions, 15 grams of initiators are put into four-hole boiling flask together again, heating is anti-
5min is answered, treats that micro emulsion blue light occurs in emulsion, residual monomer mixture and initiator are uniformly added drop-wise in four-hole boiling flask by 2h；It is added dropwise
After be further continued for be incubated 1h；40 DEG C are cooled to, adds 3 grams of ammoniacal liquor, regulation pH is 7.5-8.5, solid content 30 ± 1%, is filtered,
Silicone-modified polyacrylate leather finishing agent is made, elongation percentage is 20 times.Above-mentioned polyacrylate leather finishing agent is applied
Leather surface is overlying on, coating does not mould sense, and feel is soft and smooth.
Embodiment 4
20 grams of deionized water, 4 grams of emulsifying agent (wherein 2.5 grams of lauryl sodium sulfate, SA- are put into 500ml emulsifies bottle
9 1.5 grams), after stirring, by esters of acrylic acid 75 grams of (wherein 40 grams of base butyl acrylate, 35 grams of ethyl acrylate), third
1 gram of the organosilicone copolymer (SPS) that 1 gram of olefin(e) acid hydroxypropyl acrylate, 3 grams of acrylic acid and the single-ended double bond with formula (I) structure block adds
Enter, emulsify 15min, obtain monomer pre-emulsion；
120 grams of deionized water is added in 500ml four-hole boiling flasks, is warming up to 80 DEG C；0.40 gram of ammonium persulfate is dissolved in 40
Initiator is made into gram deionized water；5 grams of monomer pre-emulsions, 15 grams of initiators are put into four-hole boiling flask together again, heating is anti-
5min is answered, treats that micro emulsion blue light occurs in emulsion, residual monomer mixture and initiator are uniformly added drop-wise in four-hole boiling flask by 2h；It is added dropwise
After be further continued for be incubated 1h；40 DEG C are cooled to, adds 3 grams of ammoniacal liquor, regulation pH is 7.5-8.5, solid content 30 ± 1%, is filtered,
Silicone-modified polyacrylate leather finishing agent is made, elongation percentage is 22 times.Above-mentioned polyacrylate leather finishing agent is applied
Leather surface is overlying on, coating does not mould sense, and feel is soft and smooth.
Comparative example 1
20 grams of deionized water, 4 grams of emulsifying agent (wherein 2.5 grams of lauryl sodium sulfate, SA- are put into 500ml emulsifies bottle
9 1.5 grams), after stirring, by esters of acrylic acid 75 grams (wherein 10 grams of methyl methacrylate, 65 grams of ethyl acrylates),
The 3 grams of additions of 1 gram of hydroxypropyl acrylate and acrylic acid, emulsify 15min, obtain monomer pre-emulsion；
120 grams of deionized water is added in 500ml four-hole boiling flasks, is warming up to 80 DEG C；0.40 gram of ammonium persulfate is dissolved in 40
Initiator is made into gram deionized water；5 grams of monomer pre-emulsions, 15 grams of initiators are put into four-hole boiling flask together again, heating is anti-
5min is answered, treats that micro emulsion blue light occurs in emulsion, residual monomer mixture and initiator are uniformly added drop-wise in four-hole boiling flask by 2h；It is added dropwise
After be further continued for be incubated 1h；40 DEG C are cooled to, adds 3 grams of ammoniacal liquor, regulation pH is 7.5-8.5, solid content 30 ± 1%, is filtered,
Silicone-modified polyacrylate leather finishing agent is made, elongation percentage is 8 times.Above-mentioned polyacrylate leather finishing agent is coated
In leather surface, coating has modeling to feel, and feel is coarse without sliding sense.
The explanation of above example is only intended to help the method and its core concept for understanding the present invention.It should be pointed out that pair
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
The foregoing description of the disclosed embodiments, professional and technical personnel in the field are enable to realize or using the present invention.
A variety of modifications to these embodiments will be apparent for those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, it is of the invention
The embodiments shown herein is not intended to be limited to, and is to fit to and principles disclosed herein and features of novelty phase one
The most wide scope caused.
Claims (9)
1. a kind of silicone-modified polyacrylate leather finishing agent, obtained by following components through emulsion polymerization：
The organosilicone copolymer has the structure as shown in formula (I)：
Wherein, m is the integer more than or equal to 1；
N is the degree of polymerization, n=10~20.
2. silicone-modified polyacrylate leather finishing agent according to claim 1, it is characterised in that the organosilicon
Also include nertralizer in modified polyacrylate leather finishing agent, the nertralizer is ammoniacal liquor, the dosage of the nertralizer so that
The pH of the silicone-modified polyacrylate leather finishing agent is 7~9.
3. silicone-modified polyacrylate leather finishing agent according to claim 1, it is characterised in that the acrylic acid
Two kind or two kind of the ester mix monomer in methyl methacrylate, methyl acrylate, butyl acrylate and ethyl acrylate
More than.
4. silicone-modified polyacrylate leather finishing agent according to claim 1, it is characterised in that the emulsifying agent
It is (1.5~2.5) for mass ratio：1 anion emulsifier and the mixture of nonionic emulsifier；The anion emulsifier choosing
One or more from lauryl sodium sulfate, dodecyl sodium sulfate and neopelex, the nonionic Emulsion
One or more of the agent in SA-9, DIPONIL, Emulsogen LCN407 and paregal O.
5. silicone-modified polyacrylate leather finishing agent according to claim 1, it is characterised in that the organosilicon
Polymeric content is 1~1.5 parts by weight.
6. the preparation method of the silicone-modified polyacrylate leather finishing agent described in claim 1, comprises the following steps：
Emulsifying agent, acrylic acid, hydroxypropyl acrylate, organosilicone copolymer, crylic acid ester mixture monomer are mixed with deionized water,
Obtain pre-emulsion；
After the pre-emulsion, initiator are mixed with deionized water, heating response, polyacrylate leather finishing agent is obtained.
7. preparation method according to claim 6, it is characterised in that ammoniacal liquor is added after the reaction, so that reaction solution
PH be 7.5~8.5.
8. preparation method according to claim 6, it is characterised in that described to obtain the step of polyacrylate leather finishing agent
It is rapid to be specially：
Initiator is mixed with deionized water, obtains initiator solution；Deionized water is heated to adding 2 after 70~90 DEG C~
The initiator solution of the 5wt% pre-emulsion and 25~50wt%, 8~12min of heating response will be surplus in 1.5~2h
Remaining pre-emulsion adds with initiator solution, continues 1~1.5h of insulation reaction, then be cooled to 40~60 DEG C.
9. a kind of leather composite bed, including leather and the silicone-modified polyacrylate leather painting for being compound in the leather surface
Agent is adornd, the silicone-modified polyacrylate leather finishing agent is organic-silicon-modified poly- described in any one of Claims 1 to 5
The organic-silicon-modified polypropylene prepared by preparation method described in acrylate leather coating agent or any one of claim 6~8
Acid esters leather finishing agent.
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| CN108442141A (en) * | 2018-03-20 | 2018-08-24 | 东莞长联新材料科技股份有限公司 | A kind of environment-friendly type printing and dyeing special-purpose high temperature foaming slurry and preparation method thereof |
| CN110862737A (en) * | 2018-08-28 | 2020-03-06 | 郑州珊瑚纳米科技有限公司 | Polyacrylate super-hydrophobic leather brightener containing organic silicon long side chains and preparation method of coating thereof |
| CN111410720A (en) * | 2019-01-08 | 2020-07-14 | 广州市俊达手套有限公司 | Powder-free glove finishing agent containing organic silicon modified acrylate copolymer |
| CN111410722A (en) * | 2019-01-08 | 2020-07-14 | 广州市俊达手套有限公司 | Powder-free glove offline coating agent containing modified acrylate and modified acrylate |
| CN111809003A (en) * | 2020-07-14 | 2020-10-23 | 温州珍瑾服装有限公司 | Mildew-proof leather garment and processing technology thereof |
| CN112920349A (en) * | 2021-01-26 | 2021-06-08 | 嘉兴学院 | Silicon-containing polymer additive and preparation method thereof |
| CN115433790A (en) * | 2021-10-14 | 2022-12-06 | 武汉市祥运鞋业有限责任公司 | Application of breathable soft leather to shoemaking |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1498930A (en) * | 2002-11-05 | 2004-05-26 | 中国科学院成都有机化学研究所 | Method for synthesizing and preparing functional resin coating agent |
-
2017
- 2017-08-21 CN CN201710719667.0A patent/CN107353762A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1498930A (en) * | 2002-11-05 | 2004-05-26 | 中国科学院成都有机化学研究所 | Method for synthesizing and preparing functional resin coating agent |
Non-Patent Citations (2)
| Title |
|---|
| 不明: "丙烯酸滑爽改性单体SPS", 《百度文库》 * |
| 王锡娇: "《涂料与颜料标准应用手册 上册》", 30 April 2005, 军事谊文出版社 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108442141A (en) * | 2018-03-20 | 2018-08-24 | 东莞长联新材料科技股份有限公司 | A kind of environment-friendly type printing and dyeing special-purpose high temperature foaming slurry and preparation method thereof |
| CN110862737A (en) * | 2018-08-28 | 2020-03-06 | 郑州珊瑚纳米科技有限公司 | Polyacrylate super-hydrophobic leather brightener containing organic silicon long side chains and preparation method of coating thereof |
| CN111410720A (en) * | 2019-01-08 | 2020-07-14 | 广州市俊达手套有限公司 | Powder-free glove finishing agent containing organic silicon modified acrylate copolymer |
| CN111410722A (en) * | 2019-01-08 | 2020-07-14 | 广州市俊达手套有限公司 | Powder-free glove offline coating agent containing modified acrylate and modified acrylate |
| CN111809003A (en) * | 2020-07-14 | 2020-10-23 | 温州珍瑾服装有限公司 | Mildew-proof leather garment and processing technology thereof |
| CN112920349A (en) * | 2021-01-26 | 2021-06-08 | 嘉兴学院 | Silicon-containing polymer additive and preparation method thereof |
| CN115433790A (en) * | 2021-10-14 | 2022-12-06 | 武汉市祥运鞋业有限责任公司 | Application of breathable soft leather to shoemaking |
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