CN103554425A - Polyurethane resin for raincoat leather and preparation method thereof - Google Patents
Polyurethane resin for raincoat leather and preparation method thereof Download PDFInfo
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- CN103554425A CN103554425A CN201310526585.6A CN201310526585A CN103554425A CN 103554425 A CN103554425 A CN 103554425A CN 201310526585 A CN201310526585 A CN 201310526585A CN 103554425 A CN103554425 A CN 103554425A
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention relates to a polyurethane resin for high-cycle wave fitting and a preparation method thereof. The polyurethane resin comprises the following raw materials in percentage by weight on the basis of the total mass of raw materials: 9.9%-11.6% of diphenylmethane-4,4'-diisocyanate, 15%-18% of polyadipate/1,2-bis(propylene glycol ester), 0.5%-1.2% of glycol chain extender A, 0.9-2.9% of glycol chain extender B, 0.08%-0.15% of silane coupling agent, 46.6%-52.5% of solvent C, and 17.5-23.3% of solvent D. The polyurethane resin has the advantages of low high-cycle wave fitting current, short fitting time and high fitting firmness, and can be applied to the preparation of raincoat leather in the synthetic leather industry.
Description
Technical field
The present invention relates to a kind of urethane resin, specifically, relate to a kind of raincoat leather urethane resin and preparation method thereof that is applicable to.
Background technology
Raincoat leather belongs to a kind of of clothing leather, general PVC and the PU material used of conventional raincoat leather.And these two kinds of material comparisons, PVC raincoat leather is relatively cheap, but fastness is poor, and ventilation property is poor, and weight is heavier, light not; PU raincoat leather (urethane raincoat leather) has ventilation property, and fastness is good simultaneously.The another one feature of PU raincoat leather is according to customer group for demand functional and fashion aesthetic property, to derive the raincoat of various performance purposes.Such as: labour protection raincoat, windproof cold-proof raincoat, reflective raincoat etc.
PU raincoat is removed from office conventional working method hot melt adhesive laminating method, high frequency laminating method.So-called high frequency is high frequency waves.High frequency is to utilize higher frequency electromagnetic field to make mutual fierce collision between material interior molecules produce the object that high temperature reaches welding and welding, therefore compare with indirect heating, no matter at heat seal strength, on welding speed and face of weld aesthetic measure, all than indirect heating, has superiority.Therefore current synthetic leather industry is this part of raincoat leather processing particularly, and many producers adopt all applying methods of this height to replace traditional hot melt adhesive laminating method.Compare hot melt adhesive laminating, this method laminating fastness is high, and speed is fast, and aesthetic property is good.
During high frequency laminating, for laminating electric current and the length of laminating time, have strict requirement, the electric current of fitting is in general higher, and the laminating time is longer, larger for the damage of instrument itself.Therefore, it is low that the raincoat leather of fitting for high frequency preferably meets the following requirements with urethane resin the electric current that just can make to fit, and the laminating time is short.First, require resin itself to have lower glass transition temperature Tg, namely require the Intermolecular Forces between molecular radical as far as possible little, chain density is little, is embodied in the test of synthetic leather industry, requires exactly resin itself to have lower thermotolerance; Meanwhile, must guarantee that resin is the same also low for the thermotolerance that is processed into the finished product after raincoat leather, uses alap electric current when guarantee high frequency is fitted like this.Secondly, require under lower laminating electric current, resin has higher laminating fastness.
Analyze in theory, in the raincoat leather preparation course of processing, when resin is when being used in conjunction with other adhesive linkages, particularly primer is used namely usually said two liquid type polyurethane resin of two components, primer inevitably has a process of dissolving again for surface layer resin, be penetrated in surface layer resin and then make surface layer resin generation bridge formation cross-linking reaction, the thermotolerance of the finished product raincoat leather therefore machining can increase.This just claims with the raw-material selection of urethane resin to raincoat leather, raw-material use should guarantee that the thermotolerance of resin itself is low, guarantee again relatively low (also can the saying of finished product thermotolerance after generation is cross-linked, after crosslinked, thermotolerance rising amplitude is relatively little), electric current used when guarantee is used high frequency laminating is like this low as far as possible.
The raincoat leather urethane resin using in the market, common aromatic urethane resin is due to after being processed into raincoat leather finished product, thermotolerance raises more, can not guarantee the low current requirement of high frequency laminating, therefore current, common aromatic urethane resin can only be used on hot melt adhesive applying method.Although and aliphatic polyurethane resin can meet the low current requirement of high frequency laminating, because price is high, can not meet synthetic leather producer for the requirement of cost.
Summary of the invention
The object of this invention is to provide aromatic urethane resin a kind of low price, common, be used as high frequency laminating raincoat leather, make it can meet the low current requirement of high frequency laminating, there is higher laminating fastness simultaneously.
One of technical problem to be solved by this invention is, a kind of raincoat leather urethane resin that can be used for high frequency laminating of low heat resistant is provided, its thermotolerance when as resin is low, after particularly two component binary liquid shape caking agents uses are built bridge with tack coat again, thermotolerance raises few, still keep lower thermotolerance, so just can guarantee the low current requirement of high frequency laminating.
Researchist of the present invention is analyzed from polyurethane structural design, in the selection of segmented polyurethane, consider to use the diol chain-extension agent that contains side chain diol chain-extension agent how or long-chain to reduce the second-order transition temperature of system, but consider the intensity of hard section simultaneously, also need to coordinate the unbranched diol chain-extension agent of short chain to be used in conjunction with, such design can guarantee that urethane resin itself has lower thermotolerance.
In the selection of polyester polyol, consider to use the polyvalent alcohol that contains secondary hydroxyl, the secondary hydroxyl reactive behavior of this polyvalent alcohol is low, therefore last synthetic resin system substantially can be with secondary hydroxyl end-blocking, make it finally with bridging agent, the activity decreased of building bridge and reacting to occur, therefore after building bridge, finished product thermotolerance rising amplitude is relatively little, such design can guarantee in preparing the process of raincoat leather finished product, there is relatively low (also can the saying of finished product thermotolerance after being cross-linked, after crosslinked, thermotolerance rising amplitude is relatively little), thereby electric current used while guaranteeing to use high frequency laminating is low as far as possible.
Two of technical problem to be solved by this invention, is to provide to meet the raincoat leather urethane resin that the low current of high frequency laminating requires, and will guarantee the laminating fastness that high frequency is fitted simultaneously.
Said structure design has guaranteed the low heat resistant of raincoat leather, but the existence due to side chain or long-chain polyhydric alcohol, the polarity of the hard segment base group of resin is reduced, therefore Intermolecular Forces is little, be embodied on the physical index of resin, be exactly the poor properties of resin, the laminating fastness of raincoat leather does not reach standard, and this is actually the conflict body that structure design causes.
In order to solve the poor problem of above-mentioned laminating fastness, guarantee that resin has higher laminating fastness, researchist has carried out a large amount of experiments.Finally, the way that researchist adds silane coupling agent in filling a prescription by synthetic resins, has improved the adhesive property of urethane resin, has improved the laminating fastness of resin.
Silane coupling agent is in fact the silane that a class has organo-functional group, has energy and the reactive group of inorganic material chemistry combination and the reactive group of being combined with organic materials chemistry in its molecule simultaneously.So the common usage of silane coupling agent is for strengthening the adhesive fastness between organism and inorganics.
Allow people is beyond thought is, adding of silane coupling agent, finally improved the laminating fastness of raincoat leather with urethane resin, in fact, researchist finds unexpectedly, the use of silane coupling agent, has equally also increased the adhesive fastness between organism and organism, has namely improved the laminating intensity of raincoat leather.Analyze reason, may be in the course of processing of raincoat leather, the again dissolution process of primer resin to surface layer resin, make coupling agent see through primer and base cloth effect, strengthened the adhesive fastness with base cloth, namely during final physical property application testing, strengthened the stripping strength of raincoat leather, when having guaranteed raincoat leather low heat resistant, there is again good laminating fastness, solved the contradiction that structure design is brought.
Three of technical problem to be solved by this invention is to provide the preparation method of above-mentioned high frequency laminating raincoat leather with urethane resin.
As a kind of raincoat leather urethane resin of first aspect present invention (technical problem one) and second aspect (technical problem two), wherein, by the component of following mass content, formed:
Described solvent C is DMF, and described solvent D is a kind of in toluene, butanone, vinyl acetic monomer; Described diol chain-extension agent A is ethylene glycol; Described diol chain-extension agent B is neopentyl glycol, 3-methyl isophthalic acid, 5-pentanediol, 1, and 6-hexylene glycol, 1, a kind of in 9-nonanediol, wherein the mol ratio of diol chain-extension agent A and diol chain-extension agent B is 1:1.
In a preferred embodiment of the present invention, the mass ratio of solvent C and solvent D is 2:1-3:1.
In a preferred embodiment of the present invention, the quality sum of solvent C and solvent D accounts for raincoat leather 70% of urethane resin total mass.
In a preferred embodiment of the present invention, described poly-hexanodioic acid/1,2 propylene glycol ester glycol are synthetic by hexanodioic acid and 1,2-PD polycondensation, and number-average molecular weight is 700-2000g/mol.
In a preferred embodiment of the present invention, described silane coupling agent is to contain amino organo-silicon coupling agent GP1863.
The preparation method who uses urethane resin as a kind of raincoat leather of third aspect present invention (technical problem three), the method is specifically comprised of following steps:
(1) will gather hexanodioic acid/1,2 propylene glycol ester glycol, diol chain-extension agent A, after being uniformly mixed in diol chain-extension agent B and a part of solvent C input reactor, drop into again ditan-4,4 ＇-vulcabond, starts reaction, and temperature of reaction is 70-90 ℃, reaction solid content is 40-50%, NCO/OH=0.9-0.92, reaction times 2-3 hour, starts second step when residual without NCO when hydrogen peroxide is tested not flavescence;
(2) add ditan-4 of residual content, 4 ‵-vulcabond rise sticky, when viscosity reaches in the situation of 50 ℃ of room temperatures that viscosity number is 500-600pa.s, add remaining solvent C; Sticky when continue rising, when viscosity reaches in the situation of 50 ℃ of room temperatures that viscosity number is 500-600pa.s, add solvent D; When final viscosity reaches in the situation of 25 ℃ of room temperatures that viscosity number is 120-160pa.s, termination reaction; Finally add silane coupling agent to stir.
Raincoat leather urethane resin of the present invention, by structure design, has guaranteed the low heat resistant of resin itself; By selecting SA polyols that carry secondary oh, make resin with secondary hydroxyl end-blocking, guaranteed that resin is when processed and applied, low with the reactive behavior of bridging agent, after building bridge, raincoat leather finished product thermotolerance raises few; While guaranteeing the laminating of resin high frequency by above 2 designs, use lower electric current.By the use of silane coupling agent, make resin there is higher laminating fastness, meet the requirement that raincoat leather is used.This resin is applied to the raincoat leather field that synthetic leather is capable, is applicable to applying method high-frequency, and laminating fastness is good, and evenly, product aesthetic property is good in laminating.
Embodiment
Below by specific embodiment, further illustrate the present invention.
Below poly-hexanodioic acid/1 selected of each embodiment, 2 propylene glycol ester glycol Shi Wo companies oneself synthesize, and by hexanodioic acid and 1,2-PD polycondensation, are synthesized, number-average molecular weight is 700-2000g/mol, and silane coupling agent GP1863 marque is TOPCO GP1863.
Table 1 is the proportioning of urethane resin for the raincoat leather of the present embodiment.
Table 1
| Component | Weight part |
| Poly-hexanodioic acid/1,2 propylene glycol ester glycol 2000 | 185 |
| Ethylene glycol | 10.31 |
| Neopentyl glycol | 17.30 |
| Ditan-4,4 ＇-vulcabond | 106.3 |
| DMF | 561 |
| Toluene | 187 |
| Silane coupling agent GP1863 | 1.59 |
The preparation method of this resin, comprises the following steps:
(1) in reactor, drop into poly-hexanodioic acid/1,2 propylene glycol ester glycol 2000(number-average molecular weights are 2000g/mol) 185 parts, 10.31 parts of ethylene glycol, 17.30 parts of neopentyl glycol, N, 377 parts of N dimethyl formamides, after being uniformly mixed, then drop into ditan-4,95.7 parts of 4 ＇-vulcabond, start reaction, temperature of reaction is 70-90 ℃, and reaction solid content is 45%, NCO/OH=0.9, reaction times 2-3 hour starts second step when residual without NCO without the characteristic peak of NCO group with examination of infrared spectrum;
(2) add ditan-4 of residual content, 4 ＇-vulcabond rises sticky, when viscosity reaches viscosity number in the situation of 50 ℃ of room temperatures, be 500-600pa.s, add remaining N, 184 parts of dinethylformamides, continue to rise stickyly, when viscosity reaches in the situation of 50 ℃ of room temperatures that viscosity number is 500-600pa.s, add 187 parts of toluene; When final viscosity reaches in the situation of 25 ℃ of room temperatures that viscosity number is 120-160pa.s, termination reaction; Finally add 1.59 parts of silane coupling agent GP1863 to stir.
Embodiment 2
Table 2 is the proportioning of urethane resin for the raincoat leather of the present embodiment.
Table 2
| Component | Weight part |
| Poly-hexanodioic acid/1,2 propylene glycol ester glycol 2000 | 180 |
| Ethylene glycol | 10.21 |
| 1,6-ethylene glycol | 19.43 |
| Ditan-4,4 ＇-vulcabond | 104.8 |
| DMF | 553 |
| Butanone | 184 |
| Silane coupling agent GP1863 | 1.57 |
The preparation method of this resin, comprises the following steps:
(1) in reactor, drop into poly-hexanodioic acid/1,2 propylene glycol ester glycol 2000(number-average molecular weights are 2000g/mol) 180 parts, 10.21 parts of ethylene glycol, 1,6 19.43 parts of hexylene glycols, 459 parts of DMFs, after being uniformly mixed, drop into again ditan-4,96.4 parts of 4 ＇-vulcabond, start reaction, and temperature of reaction is 70-90 ℃, reaction solid content is 40%, NCO/OH=0.92, reaction times 2-3 hour starts second step when residual without NCO without the characteristic peak of NCO group with examination of infrared spectrum;
(2) add ditan-4 of residual content, 4 ‵-vulcabond rises sticky, when viscosity reaches viscosity number in the situation of 50 ℃ of room temperatures, be 500-600pa.s, add remaining N, 94 parts of dinethylformamides, continue to rise stickyly, when viscosity reaches in the situation of 50 ℃ of room temperatures that viscosity number is 500-600pa.s, add 184 parts of butanone; When final viscosity reaches in the situation of 25 ℃ of room temperatures that viscosity number is 120-160pa.s, termination reaction; Finally add 1.57 parts of silane coupling agent GP1863 to stir.
Embodiment 3
Table 3 is the proportioning of urethane resin for the raincoat leather of the present embodiment.
Table 3
| Component | Weight part |
| Poly-hexanodioic acid/1,2 propylene glycol ester glycol 2000 | 180 |
| Ethylene glycol | 10.21 |
| 3-methyl isophthalic acid, 5-pentanediol | 19.43 |
| Ditan-4,4 ＇-vulcabond | 104.8 |
| DMF | 553 |
| Vinyl acetic monomer | 184 |
| Silane coupling agent GP1863 | 1.57 |
The preparation method of this resin, comprises the following steps:
(1) in reactor, drop into poly-hexanodioic acid/1,2 propylene glycol ester glycol 2000(number-average molecular weights are 2000g/mol) 180 parts, 10.21 parts of ethylene glycol, 3-methyl isophthalic acid, 19.43 parts of 5-pentanediols, 459 parts of DMFs, after being uniformly mixed, drop into again ditan-4,96.4 parts of 4 ＇-vulcabond, start reaction, and temperature of reaction is 70-90 ℃, reaction solid content is 40%, NCO/OH=0.92, reaction times 2-3 hour starts second step when residual without NCO without the characteristic peak of NCO group with examination of infrared spectrum;
(2) add ditan-4 of residual content, 4 ‵-vulcabond rises sticky, when viscosity reaches viscosity number in the situation of 50 ℃ of room temperatures, be 500-600pa.s, add remaining N, 94 parts of dinethylformamides, continue to rise stickyly, when viscosity reaches in the situation of 50 ℃ of room temperatures that viscosity number is 500-600pa.s, add 184 parts of vinyl acetic monomers; When final viscosity reaches in the situation of 25 ℃ of room temperatures that viscosity number is 120-160pa.s, termination reaction; Finally add 1.57 parts of silane coupling agent GP1863 to stir.
Embodiment 4
Table 4 is the proportioning of urethane resin for the raincoat leather of the present embodiment.
Table 4
| Component | Weight part |
| Poly-hexanodioic acid/1,2 propylene glycol ester glycol 700 | 180 |
| Ethylene glycol | 5.43 |
| Neopentyl glycol | 9.11 |
| Ditan-4,4 ＇-vulcabond | 108.1 |
| DMF | 472 |
| Toluene | 236 |
| Silane coupling agent GP1863 | 0.91 |
The preparation method of this resin, comprises the following steps:
(1) in reactor, drop into poly-hexanodioic acid/1,2 propylene glycol ester glycol 700(number-average molecular weights are 700g/mol) 180 parts, 5.43 parts of ethylene glycol, 9.11 parts of neopentyl glycol, N, 294 parts of N dimethyl formamides, after being uniformly mixed, then drop into ditan-4,99.4 parts of 4 ＇-vulcabond, start reaction, temperature of reaction is 70-90 ℃, and reaction solid content is 50%, NCO/OH=0.92, reaction times 2-3 hour starts second step when residual without NCO without the characteristic peak of NCO group with examination of infrared spectrum;
(2) add ditan-4 of residual content, 4 ‵-vulcabond rises sticky, when viscosity reaches viscosity number in the situation of 50 ℃ of room temperatures, be 500-600pa.s, add remaining N, 178 parts of dinethylformamides, continue to rise stickyly, when viscosity reaches in the situation of 50 ℃ of room temperatures that viscosity number is 500-600pa.s, add 236 parts of toluene; When final viscosity reaches in the situation of 25 ℃ of room temperatures that viscosity number is 120-160pa.s, termination reaction; Finally add 0.91 part of silane coupling agent GP1863 to stir.
Embodiment 5
Table 5 is the proportioning of urethane resin for the raincoat leather of the present embodiment.
Table 5
| Component | Weight part |
| Poly-hexanodioic acid/1,2 propylene glycol ester glycol 2000 | 180 |
| Ethylene glycol | 10.21 |
| 3-methyl isophthalic acid, 5-pentanediol | 19.43 |
| Ditan-4,4 ＇-vulcabond | 104.8 |
| DMF | 552 |
| Vinyl acetic monomer | 184 |
| Silane coupling agent GP1863 | 0.94 |
The preparation method of this resin, comprises the following steps:
(1) in reactor, drop into poly-hexanodioic acid/1,2 propylene glycol ester glycol 2000(number-average molecular weights are 2000g/mol) 180 parts, 10.21 parts of ethylene glycol, 3-methyl isophthalic acid, 19.43 parts of 5-pentanediols, 459 parts of DMFs, after being uniformly mixed, drop into again ditan-4,96.4 parts of 4 ＇-vulcabond, start reaction, and temperature of reaction is 70-90 ℃, reaction solid content is 40%, NCO/OH=0.92, reaction times 2-3 hour starts second step when residual without NCO without the characteristic peak of NCO group with examination of infrared spectrum;
(2) add ditan-4 of residual content, 4 ‵-vulcabond rises sticky, when viscosity reaches viscosity number in the situation of 50 ℃ of room temperatures, be 500-600pa.s, add remaining N, 93 parts of dinethylformamides, continue to rise stickyly, when viscosity reaches in the situation of 50 ℃ of room temperatures that viscosity number is 500-600pa.s, add 184 parts of vinyl acetic monomers; When final viscosity reaches in the situation of 25 ℃ of room temperatures that viscosity number is 120-160pa.s, termination reaction; Finally add 0.94 part of silane coupling agent GP1863 to stir.
Embodiment 6
Table 6 is the proportioning of urethane resin for the raincoat leather of the present embodiment.
Table 6
| Component | Weight part |
| Poly-hexanodioic acid/1,2 propylene glycol ester glycol 2000 | 160 |
| Ethylene glycol | 11.34 |
| 1,9 nonanediol | 29.26 |
| Ditan-4,4 ＇-vulcabond | 111.4 |
| DMF | 548 |
| Toluene | 183 |
| Silane coupling agent GP1863 | 0.94 |
The preparation method of this resin, comprises the following steps:
(1) in reactor, drop into poly-hexanodioic acid/1,2 propylene glycol ester glycol 2000(number-average molecular weights are 2000g/mol) 180 parts, 11.34 parts of ethylene glycol, 1,29.26 parts of 9-nonanediols, 303 parts of DMFs, after being uniformly mixed, drop into again ditan-4,102.4 parts of 4 ＇-vulcabond, start reaction, and temperature of reaction is 70-90 ℃, reaction solid content is 50%, NCO/OH=0.92, reaction times 2-3 hour starts second step when residual without NCO without the characteristic peak of NCO group with examination of infrared spectrum;
(2) add ditan-4 of residual content, 4 ‵-vulcabond rises sticky, when viscosity reaches 50 ℃, 500-600pa.s, add 245 parts of remaining DMFs, continue to rise sticky, when viscosity reaches in the situation of 50 ℃ of room temperatures that viscosity number is 500-600pa.s, add 183 parts of toluene; When final viscosity reaches in the situation of 25 ℃ of room temperatures that viscosity number is 120-160pa.s, termination reaction; Finally add 0.94 part of silane coupling agent GP1863 to stir.
Embodiment 7
Table 7 is the proportioning of urethane resin for the raincoat leather of the present embodiment.
Table 7
| Component | Weight part |
| Poly-hexanodioic acid/1,2 propylene glycol ester glycol 700 | 170 |
| Ethylene glycol | 7.82 |
| 1,9 nonanediol | 20.17 |
| Ditan-4,4 ＇-vulcabond | 123.8 |
| DMF | 351 |
| Toluene | 176 |
| Silane coupling agent GP1863 | 0.97 |
The preparation method of this resin, comprises the following steps:
(1) in reactor, drop into poly-hexanodioic acid/1,2 propylene glycol ester glycol 700(number-average molecular weights are 700g/mol) 170 parts, 7.82 parts of ethylene glycol, 1,20.17 parts of 9-nonanediols, 311 parts of DMFs, after being uniformly mixed, drop into again ditan-4,113.8 parts of 4 ＇-vulcabond, start reaction, and temperature of reaction is 70-90 ℃, reaction solid content is 50%, NCO/OH=0.92, reaction times 2-3 hour starts second step when residual without NCO without the characteristic peak of NCO group with examination of infrared spectrum;
(2) add ditan-4 of residual content, 4 ‵-vulcabond rises sticky, when viscosity reaches viscosity number in the situation of 50 ℃ of room temperatures, be 500-600pa.s, add remaining N, 40 parts of dinethylformamides, continue to rise stickyly, when viscosity reaches in the situation of 50 ℃ of room temperatures that viscosity number is 500-600pa.s, add 176 parts of toluene; When final viscosity reaches in the situation of 25 ℃ of room temperatures that viscosity number is 120-160pa.s, termination reaction; Finally add 0.97 part of silane coupling agent GP1863 to stir.
By the synthetic urethane resin of embodiment 1-7, with following 1, be that resin thermotolerance test formulations and the technique of drawing a design are drawn a design, the thermotolerance of test resin itself; With 2, it is the thermotolerance that raincoat leather finished product thermotolerance is tested draw a design formula and the process test raincoat leather finished product of drawing a design; With 3 being draw a design formula and the technique of drawing a design of raincoat leather finished product high frequency laminating fastness (peel strength test), with the attaching process of high frequency plastic rubber heat sealing machine, fit, the test laminating fastness under electric current of fitting.
1, it is as follows that resin thermotolerance is tested the formula of drawing a design:
The technique of drawing a design:
R/P: super mist separate-type paper
Surface layer coating: 0.15mm (120 ℃ of * 2min are dry)
Surface layer coating: 0.15mm(110 ℃ of * 20 second half dry doubling)
Laminating: black looped fabric BASE (120 ℃ of * 3min are dry)
Thermotolerance testing method: batten to be measured is cut into the sample of 3cm*3cm, sticks on setup test on white hard paper plate; Baking oven is warming up to 80 ℃, after homo(io)thermism, batten to be measured and fiber board is put into baking oven, keep 5 minutes, then take out batten, observe surperficial changing conditions; As unchanged in surface, according to the intervals of 10 ℃, continue to heat up and append test, put into again batten after all needing waiting temperature constant after each intensification, and in baking oven, keep 5 minutes; Test is always shinny to surface, and test completes.Shinny temperature deducts 10 ℃ of the temperature intervals thermotolerance that is resin.(remarks: have plenty of gradually and brighten due to the surface situation of brightening, have plenty of quickly and brighten, so the thermotolerance of resin has plenty of single numerical value, have plenty of two scopes between numerical value.Explanation simultaneously, stable on heating testing method is to know in synthetic leather industry.）
2, the raincoat leather finished product thermotolerance test formula of drawing a design is as follows:
The technique of drawing a design:
R/P: super mist separate-type paper
Surface layer coating: 0.15mm (120 ℃ of * 2min are dry)
Tack coat coating: 0.15mm(110 ℃ of * 20 second half dry doubling)
Laminating: black looped fabric BASE (120 ℃ of * 3min are dry)
Bridge formation slaking: room temperature cure 7 days
Thermotolerance testing method: batten to be measured is cut into the sample of 3cm*3cm, sticks on setup test on white hard paper plate; Baking oven is warming up to 80 ℃, after homo(io)thermism, batten to be measured and fiber board is put into baking oven, keep 5 minutes, then take out batten, observe surperficial changing conditions; As unchanged in surface, according to the intervals of 10 ℃, continue to heat up and append test, put into again batten after all needing waiting temperature constant after each intensification, and in baking oven, keep 5 minutes; Test is always shinny to surface, and test completes.Shinny temperature deducts 10 ℃ of the temperature intervals thermotolerance that is resin.(remarks: because the surface situation of brightening has plenty of gradually and brightens, have plenty of quickly and brighten, so the thermotolerance of resin has plenty of single numerical value, have plenty of two scopes between numerical value, it should be noted that, stable on heating testing method is that synthetic leather industry is known simultaneously.）
3, raincoat leather finished product high frequency laminating fastness (peel strength test) formula of drawing a design is as follows:
The technique of drawing a design:
R/P: super mist separate-type paper
Surface layer coating: 0.10mm (120 ℃ of * 2min are dry)
Tack coat coating: 0.20mm(110 ℃ of * 20 second half dry doubling)
Laminating: black looped fabric BASE (120 ℃ of * 3min are dry)
Bridge formation slaking: room temperature cure 7 days.
High frequency plastic rubber heat sealing machine attaching process:
Electric current: 0.3A-0.5A
Pressure: 7kg
Temperature: 250 ℃
The voltage-frequency time: 5 seconds
The finished product raincoat leather finished product doubling that formula according to 3 and technique are drawn a design, fits with the attaching process of high frequency plastic rubber heat sealing machine, after having fitted, carries out peel strength test.
In order to prove superiority of the present invention, the urethane resin that Example formulations 1-7 is synthetic is drawn a design according to the method for above-mentioned 1-3, corresponding by the sequence number of 1-7; By common aromatic urethane resin HDS-30A as a comparison case, carry out respectively thermotolerance, the test of high frequency laminating fastness, test result is in Table 8.
Table 8
| Sequence number | The thermotolerance of resin own | Raincoat leather finished product thermotolerance after bridge formation slaking | Laminating electric current | The laminating time | Laminating fastness |
| Embodiment 1 | 170℃ | 180-190℃ | 0.3A | 5S | 6.0kg/3cm |
| Embodiment 2 | 170℃ | 180-190℃ | 0.3A | 5S | 5.8kg/3cm |
| Embodiment 3 | 160-170℃ | 180℃ | 0.3A | 5S | 6.3kg/3cm |
| Embodiment 4 | 160-170℃ | 180℃ | 0.3A | 5S | 6.2kg/3cm |
| Embodiment 5 | 160-170℃ | 180℃ | 0.3A | 5S | 5.9kg/3cm |
| Embodiment 6 | 170℃ | 180-190℃ | 0.3A | 5S | 6.1kg/3cm |
| Embodiment 7 | 160-170℃ | 180℃ | 0.3A | 5S | 6.0kg/3cm |
| Comparative example HDS-30A | 170℃ | 210℃ | 0.3A | 5S | Do not paste, do not have intensity |
| Comparative example 2 | 170℃ | 210℃ | 0.5A | 5S | 1kg/3cm |
As can be seen from Table 8, embodiment compares with comparative example, and under identical high frequency laminating condition, comparative example is not pasted, the fastness of not fitting; And the laminating fastness of embodiment is all very good; Although comparative example is improved to laminating electric current to 0.5A, and laminating fastness is still very poor.Can reach a conclusion thus; The method of high frequency laminating for the resin of the present embodiment, has higher laminating fastness, can meet the requirement of high frequency laminating.
Claims (6)
1. a raincoat leather urethane resin, is characterized in that, is made the total mass of described weight percentage based on raw material by the raw material that comprises following weight percentage:
Described solvent C is DMF, and described solvent D is a kind of in toluene, butanone, vinyl acetic monomer;
Described diol chain-extension agent A is ethylene glycol, and described diol chain-extension agent B is neopentyl glycol, 3-methyl isophthalic acid, 5-pentanediol, 1, and 6-hexylene glycol, 1, a kind of in 9-nonanediol, wherein the mol ratio of diol chain-extension agent A and diol chain-extension agent B is 1:1.
2. raincoat leather urethane resin according to claim 1, is characterized in that, the mass ratio of solvent C and solvent D is 2:1-3:1.
3. raincoat leather urethane resin according to claim 2, is characterized in that, the quality sum of solvent C and solvent D accounts for raincoat leather 70% of urethane resin total mass.
4. raincoat leather urethane resin according to claim 3, is characterized in that, described poly-hexanodioic acid/1, and 2 propylene glycol ester glycol are synthetic by hexanodioic acid and 1,2-PD polycondensation, and number-average molecular weight is 700-2000g/mol.
5. raincoat leather urethane resin according to claim 4, is characterized in that, described silane coupling agent is to contain amino organo-silicon coupling agent GP1863.
6. the preparation method of urethane resin for the arbitrary described a kind of raincoat leather of claim 1 to 5, is characterized in that, specifically following steps, consists of:
(1) will gather hexanodioic acid/1,2 propylene glycol ester glycol, diol chain-extension agent A, after being uniformly mixed in diol chain-extension agent B and a part of solvent C input reactor, drop into again ditan-4,4 ＇-vulcabond, starts reaction, and temperature of reaction is 70-90 ℃, reaction solid content is 40-50%, NCO/OH=0.9-0.92, reaction times 2-3 hour, starts second step when residual without NCO when hydrogen peroxide is tested not flavescence;
(2) add ditan-4 of residual content, 4 ＇-vulcabond rise sticky, when viscosity reaches in the situation of 50 ℃ of room temperatures that viscosity number is 500-600pa.s, add remaining solvent C; Continue to rise stickyly, when viscosity reaches in the situation of 50 ℃ of room temperatures that viscosity number is 500-600pa.s, add solvent D; When final viscosity reaches in the situation of 25 ℃ of room temperatures that viscosity number is 120-160pa.s, termination reaction; Finally add silane coupling agent GP1863 to stir.
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| CN111154061A (en) * | 2020-02-20 | 2020-05-15 | 上海华峰超纤科技股份有限公司 | Silicon-containing polyurethane resin and preparation method and application thereof |
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| US20080223255A1 (en) * | 2007-03-13 | 2008-09-18 | Basf Corporation | Film-forming material containing silane |
| CN102010497A (en) * | 2010-09-29 | 2011-04-13 | 上海汇得树脂有限公司 | Polyurethane resin as well as preparation method and application thereof |
| CN102453223A (en) * | 2010-10-20 | 2012-05-16 | 上海汇得化工有限公司 | Polyurethane resin for high-glossiness coating |
| CN102558486A (en) * | 2011-12-23 | 2012-07-11 | 上海汇得化工有限公司 | Dry-process polyurethane synthetic leather resin material for hot attaching, preparation method and uses |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20080223255A1 (en) * | 2007-03-13 | 2008-09-18 | Basf Corporation | Film-forming material containing silane |
| CN102010497A (en) * | 2010-09-29 | 2011-04-13 | 上海汇得树脂有限公司 | Polyurethane resin as well as preparation method and application thereof |
| CN102453223A (en) * | 2010-10-20 | 2012-05-16 | 上海汇得化工有限公司 | Polyurethane resin for high-glossiness coating |
| CN102558486A (en) * | 2011-12-23 | 2012-07-11 | 上海汇得化工有限公司 | Dry-process polyurethane synthetic leather resin material for hot attaching, preparation method and uses |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111154061A (en) * | 2020-02-20 | 2020-05-15 | 上海华峰超纤科技股份有限公司 | Silicon-containing polyurethane resin and preparation method and application thereof |
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