CN103554425B - A kind of Polyurethane resin for raincoat leather and preparation method thereof - Google Patents
A kind of Polyurethane resin for raincoat leather and preparation method thereof Download PDFInfo
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- CN103554425B CN103554425B CN201310526585.6A CN201310526585A CN103554425B CN 103554425 B CN103554425 B CN 103554425B CN 201310526585 A CN201310526585 A CN 201310526585A CN 103554425 B CN103554425 B CN 103554425B
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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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- C—CHEMISTRY; METALLURGY
- 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 present invention relates to a kind of high frequency laminating urethane resin and preparation method thereof, this urethane resin is made up of the raw material comprising following weight percentage, described weight percentage is based on the total mass of raw material: ditan-4,4 ＇-vulcabond 9.9%-11.6%; Poly-hexanodioic acid/1,2 propylene glycol ester glycol 15%-18%; Diol chain-extension agent A0.5%-1.2%; Diol chain-extension agent B0.9-2.9%; Silane coupling agent 0.08%-0.15%; Solvent C 46.6%-52.5%; Solvent D17.5%-23.3%; It is low that urethane resin of the present invention has high frequency laminating electric current, and the laminating time is short, the advantage that laminating fastness is high, can be applicable to the preparation that in synthetic leather industry, raincoat is removed from office.
Description
Technical field
The present invention relates to a kind of urethane resin, specifically, relate to one and be applicable to Polyurethane resin for raincoat leather and preparation method thereof.
Background technology
Raincoat leather belongs to the one of clothing leather, and conventional raincoat leather is general uses PVC and PU material.And these two kinds of materials compare, PVC raincoat leather is relatively cheap, but fastness is poor, poor air permeability, heavier-weight, light not; PU raincoat leather (urethane raincoat leather) then has ventilation property, and fastness is good simultaneously.The another one feature of PU raincoat leather according to customer group for demand that is functional and fashion aesthetic property, can derive the raincoat of various performance purposes.Such as: labour protection raincoat, windproof cold-proof raincoat, reflective raincoat etc.
The working method that PU raincoat leather is conventional has Hot melt adhesive plaster legal, high frequency laminating method.So-called high frequency and high frequency waves.High frequency utilizes higher frequency electromagnetic field to make the intermolecular mutual fierceness collision of internal batch produce high temperature to reach welding and the object of welding, therefore compared with indirect heating, no matter at heat seal strength, on welding speed and face of weld aesthetic measure, all has superiority than indirect heating.Therefore current synthetic leather industry particularly this part of raincoat leather processing, it is legal that many producers adopt all applying methods of this height to replace traditional Hot melt adhesive plaster.Compare hot melt adhesive laminating, this method laminating fastness is high, and speed is fast, and aesthetic property is good.
Have strict requirement for laminating electric current and the length of laminating time during high frequency laminating, electric current of fitting in general is higher, and the laminating time is longer, and the damage for instrument itself is larger.Therefore, the Polyurethane resin for raincoat leather for high frequency laminating preferably meets the following requirements and laminating electric current just can be made low, and the laminating time is short.First, require that resin itself has lower glass transition temperature Tg, namely require that the Intermolecular Forces between molecular radical is little as far as possible, chain density is little, is embodied in the test of synthetic leather industry, requires that resin itself has lower thermotolerance exactly; Meanwhile, must ensure that resin-made is the same also low for the thermotolerance of the finished product be processed into after raincoat leather, during such guarantee high frequency laminating, use alap electric current.Secondly, require that, under lower laminating electric current, resin has higher laminating fastness.
Analyze in theory, in the raincoat leather preparation course of processing, when resin with other adhesive linkages with the use of time, particularly primer uses two components i.e. usually said two liquid type polyurethane resin, primer inevitably has a process of dissolving again for surface layer resin, penetrate in surface layer resin and then make surface layer resin generation bridge formation cross-linking reaction, the thermotolerance of the finished product raincoat therefore machined leather can increase.This just claims to the raw-material selection of Polyurethane resin for raincoat leather, raw-material use should ensure that the thermotolerance of resin itself is low, ensure that the finished product thermotolerance after being cross-linked occurs again relatively low (alternatively, after crosslinked, thermotolerance elevation amplitude is relatively little), electric current used when such guarantee uses high frequency to fit is low as far as possible.
The Polyurethane resin for raincoat leather used in the market, common aromatic polyurethane resins is due to after being processed into raincoat leather finished product, thermotolerance raises more, the low current requirement that high frequency is fitted can not be ensured, therefore current, common aromatic polyurethane resins 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, the requirement of synthetic leather producer for cost can not be met.
Summary of the invention
That the object of this invention is to provide a kind of low price, common aromatic polyurethane resins, is used as high frequency laminating raincoat leather, makes it can meet the low current requirement of high frequency laminating, have higher laminating fastness simultaneously.
One of technical problem to be solved by this invention is, a kind of Polyurethane resin for raincoat leather that can be used for high frequency laminating of low heat resistant is provided, it is low as thermotolerance during resin, after particularly two component binary liquid shape caking agent uses and builds bridge with tack coat again, thermotolerance raises few, still keep lower thermotolerance, so just can guarantee the low current requirement that high frequency is fitted.
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 containing the many diol chain-extension agents of side chain or long-chain to reduce the second-order transition temperature of system, but consider the intensity of hard section simultaneously, also need to coordinate short chain unbranched diol chain-extension agent with the use of, such design can ensure that urethane resin itself has lower thermotolerance.
In the selection of polyester polyol, consider to use the polyvalent alcohol containing secondary hydroxyl, the secondary hydroxyl reactive behavior of this polyvalent alcohol is low, therefore the resin system of last synthesis substantially can with secondary hydroxyl end-blocking, make it last and the bridging agent activity of reacting that occurs to build bridge reduces, therefore after building bridge, finished product thermotolerance elevation amplitude is relatively little, such design can ensure in the process preparing raincoat leather finished product, there is the finished product thermotolerance after being cross-linked relatively low (alternatively, after crosslinked, thermotolerance elevation amplitude is relatively little), thus electric current used when ensureing to use high frequency laminating is low as far as possible.
Technical problem two to be solved by this invention, the Polyurethane resin for raincoat leather being to provide the low current that can meet high frequency laminating to require, will ensure the laminating fastness that high frequency is fitted simultaneously.
Said structure design ensure that the low heat resistant that raincoat is removed from office, but due to the existence of 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 problem of above-mentioned laminating fastness difference, ensure that resin has higher laminating fastness, researchist has carried out a large amount of experiments.Finally, researchist adds the way of silane coupling agent in being filled a prescription by synthetic resins, improve the adhesive property of urethane resin, improves the laminating fastness of resin.
Silane coupling agent is in fact the silane that a class has organo-functional group, the reactive group simultaneously in the molecule thereof with energy and inorganic material chemistry combination and the reactive group be combined with organic materials chemistry.So the usual usage of silane coupling agent is the adhesive fastness for strengthening between organism and inorganics.
Allow people surprisingly, adding of silane coupling agent, finally improve the laminating fastness of Polyurethane resin for raincoat leather, in fact, researchist finds unexpectedly, the use of silane coupling agent, too increases the adhesive fastness between organism and organism equally, namely improves the laminating intensity of raincoat leather.Analyze reason, may be in the course of processing of raincoat leather, primer resin is to the dissolution process again of surface layer resin, make coupling agent through primer and the effect of base cloth, enhance the adhesive fastness with base cloth, namely during final physical property application testing, enhance the stripping strength of raincoat leather, while ensure that raincoat leather low heat resistant, there is again fastness of fitting preferably, solve the contradiction that structure design is brought.
Three of technical problem to be solved by this invention is the preparation method providing above-mentioned high frequency laminating Polyurethane resin for raincoat leather.
As a kind of Polyurethane resin for raincoat leather of first aspect present invention (technical problem one) and second aspect (technical problem two), wherein, be made up of the component of following mass content:
Described solvent C is DMF, and described solvent D is the one 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, the one in 5-pentanediol, 1,6-hexylene glycol, 1,9-nonanediol, and wherein the mol ratio of diol chain-extension agent A and diol chain-extension agent B is 1:1.
In the preferred embodiment of the present invention, the mass ratio of solvent C and solvent D is 2:1-3:1.
In the preferred embodiment of the present invention, the quality sum of solvent C and solvent D accounts for 70% of Polyurethane resin for raincoat leather total mass.
In the preferred embodiment of the present invention, described poly-hexanodioic acid/1,2 propylene glycol ester glycol are synthesized by hexanodioic acid and 1,2-PD polycondensation, and number-average molecular weight is 700-2000g/mol.
In the preferred embodiment of the present invention, described silane coupling agent is containing amino organo-silicon coupling agent GP1863.
As the preparation method of a kind of Polyurethane resin for raincoat leather of third aspect present invention (technical problem three), the method is specifically made up of following steps:
(1) hexanodioic acid/1 will be gathered, 2 propylene glycol ester glycol, after diol chain-extension agent A, diol chain-extension agent B and a part of solvent C drop into and are uniformly mixed in reactor, drop into ditan-4 again, 4 ＇-vulcabond, start reaction, temperature of reaction is 70-90 DEG C, reaction solid content is 40-50%, NCO/OH=0.9-0.92, reaction times 2-3 hour, start second step when remaining without NCO when hydrogen peroxide test does not turn yellow;
(2) ditan-4, the 4 ‵-vulcabond adding residual content rises sticky, when viscosity number is 500-600pa.s when viscosity reaches room temperature 50 DEG C, adds remaining solvent C; When continuation rises sticky, when viscosity number is 500-600pa.s when viscosity reaches room temperature 50 DEG C, add solvent D; When final viscosity reaches room temperature 25 DEG C, viscosity number is 120-160pa.s, termination reaction; Finally add silane coupling agent to stir.
Polyurethane resin for raincoat leather of the present invention, by structure design, ensure that the low heat resistant of resin itself; By selecting SA polyols that carry secondary oh, making resin with secondary hydroxyl end-blocking, ensure 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; When ensureing the laminating of resin high frequency by above 2 designs, use lower electric current.By the use of silane coupling agent, make resin have higher laminating fastness, meet the requirement that raincoat leather uses.This resin is applied to the capable raincoat leather field of synthetic leather, and be applicable to applying method high-frequency, laminating fastness is good, and evenly, product aesthetic property is good in laminating.
Embodiment
The present invention is further illustrated below by specific embodiment.
Poly-hexanodioic acid/1 selected of each embodiment below, 2 propylene glycol ester glycol are that my company oneself synthesizes, and are synthesized by hexanodioic acid and 1,2-PD polycondensation, number-average molecular weight is 700-2000g/mol, and silane coupling agent GP1863 marque is TOPCOGP1863.
Table 1 is the proportioning of the Polyurethane resin for 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) poly-hexanodioic acid/1 is dropped in a kettle., 2 propylene glycol ester glycol 2000(number-average molecular weights are 2000g/mol) 185 parts, ethylene glycol 10.31 parts, neopentyl glycol 17.30 parts, N, N-dimethylformamide 377 parts, after being uniformly mixed, then drop into ditan-4,4 ＇-vulcabond 95.7 parts, start reaction, temperature of reaction is 70-90 DEG C, and reaction solid content is 45%, NCO/OH=0.9, reaction times 2-3 hour, starts second step when namely remaining without NCO without the characteristic peak of NCO group with examination of infrared spectrum;
(2) ditan-4 of residual content is added, 4 ＇-vulcabond rises sticky, when viscosity reaches room temperature 50 DEG C, viscosity number is 500-600pa.s, add remaining N, dinethylformamide 184 parts, continue to rise and glue, when viscosity number is 500-600pa.s when viscosity reaches room temperature 50 DEG C, add toluene 187 parts; When final viscosity reaches room temperature 25 DEG C, 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 the Polyurethane resin for 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) poly-hexanodioic acid/1 is dropped in a kettle., 2 propylene glycol ester glycol 2000(number-average molecular weights are 2000g/mol) 180 parts, ethylene glycol 10.21 parts, 1,6 hexylene glycols 19.43 parts, DMF 459 parts, after being uniformly mixed, drop into ditan-4 again, 4 ＇-vulcabond 96.4 parts, start reaction, temperature of reaction is 70-90 DEG C, reaction solid content is 40%, NCO/OH=0.92, reaction times 2-3 hour, start second step when namely remaining without NCO without the characteristic peak of NCO group with examination of infrared spectrum;
(2) ditan-4 of residual content is added, 4 ‵-vulcabond rises sticky, when viscosity reaches room temperature 50 DEG C, viscosity number is 500-600pa.s, add remaining N, dinethylformamide 94 parts, continue to rise and glue, when viscosity number is 500-600pa.s when viscosity reaches room temperature 50 DEG C, add butanone 184 parts; When final viscosity reaches room temperature 25 DEG C, 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 the Polyurethane resin for 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) poly-hexanodioic acid/1 is dropped in a kettle., 2 propylene glycol ester glycol 2000(number-average molecular weights are 2000g/mol) 180 parts, ethylene glycol 10.21 parts, 3-methyl isophthalic acid, 5-pentanediol 19.43 parts, DMF 459 parts, after being uniformly mixed, drop into ditan-4 again, 4 ＇-vulcabond 96.4 parts, start reaction, temperature of reaction is 70-90 DEG C, reaction solid content is 40%, NCO/OH=0.92, reaction times 2-3 hour, start second step when namely remaining without NCO without the characteristic peak of NCO group with examination of infrared spectrum;
(2) ditan-4 of residual content is added, 4 ‵-vulcabond rises sticky, when viscosity reaches room temperature 50 DEG C, viscosity number is 500-600pa.s, add remaining N, dinethylformamide 94 parts, continue to rise and glue, when viscosity number is 500-600pa.s when viscosity reaches room temperature 50 DEG C, add vinyl acetic monomer 184 parts; When final viscosity reaches room temperature 25 DEG C, 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 the Polyurethane resin for 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) poly-hexanodioic acid/1 is dropped in a kettle., 2 propylene glycol ester glycol 700(number-average molecular weights are 700g/mol) 180 parts, ethylene glycol 5.43 parts, neopentyl glycol 9.11 parts, N, N-dimethylformamide 294 parts, after being uniformly mixed, then drop into ditan-4,4 ＇-vulcabond 99.4 parts, start reaction, temperature of reaction is 70-90 DEG C, and reaction solid content is 50%, NCO/OH=0.92, reaction times 2-3 hour, starts second step when namely remaining without NCO without the characteristic peak of NCO group with examination of infrared spectrum;
(2) ditan-4 of residual content is added, 4 ‵-vulcabond rises sticky, when viscosity reaches room temperature 50 DEG C, viscosity number is 500-600pa.s, add remaining N, dinethylformamide 178 parts, continue to rise and glue, when viscosity number is 500-600pa.s when viscosity reaches room temperature 50 DEG C, add toluene 236 parts; When final viscosity reaches room temperature 25 DEG C, 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 the Polyurethane resin for 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) poly-hexanodioic acid/1 is dropped in a kettle., 2 propylene glycol ester glycol 2000(number-average molecular weights are 2000g/mol) 180 parts, ethylene glycol 10.21 parts, 3-methyl isophthalic acid, 5-pentanediol 19.43 parts, DMF 459 parts, after being uniformly mixed, drop into ditan-4 again, 4 ＇-vulcabond 96.4 parts, start reaction, temperature of reaction is 70-90 DEG C, reaction solid content is 40%, NCO/OH=0.92, reaction times 2-3 hour, start second step when namely remaining without NCO without the characteristic peak of NCO group with examination of infrared spectrum;
(2) ditan-4 of residual content is added, 4 ‵-vulcabond rises sticky, when viscosity reaches room temperature 50 DEG C, viscosity number is 500-600pa.s, add remaining N, dinethylformamide 93 parts, continue to rise and glue, when viscosity number is 500-600pa.s when viscosity reaches room temperature 50 DEG C, add vinyl acetic monomer 184 parts; When final viscosity reaches room temperature 25 DEG C, 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 the Polyurethane resin for 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 nonanediols | 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) poly-hexanodioic acid/1 is dropped in a kettle., 2 propylene glycol ester glycol 2000(number-average molecular weights are 2000g/mol) 180 parts, ethylene glycol 11.34 parts, 1,9-nonanediol 29.26 parts, DMF 303 parts, after being uniformly mixed, drop into ditan-4 again, 4 ＇-vulcabond 102.4 parts, start reaction, temperature of reaction is 70-90 DEG C, reaction solid content is 50%, NCO/OH=0.92, reaction times 2-3 hour, start second step when namely remaining without NCO without the characteristic peak of NCO group with examination of infrared spectrum;
(2) ditan-4 of residual content is added, 4 ‵-vulcabond rises sticky, when viscosity reaches 50 DEG C, 500-600pa.s, add remaining DMF 245 parts, continue to rise and glue, when viscosity number is 500-600pa.s when viscosity reaches room temperature 50 DEG C, add toluene 183 parts; When final viscosity reaches room temperature 25 DEG C, 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 the Polyurethane resin for 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 nonanediols | 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) poly-hexanodioic acid/1 is dropped in a kettle., 2 propylene glycol ester glycol 700(number-average molecular weights are 700g/mol) 170 parts, ethylene glycol 7.82 parts, 1,9-nonanediol 20.17 parts, DMF 311 parts, after being uniformly mixed, drop into ditan-4 again, 4 ＇-vulcabond 113.8 parts, start reaction, temperature of reaction is 70-90 DEG C, reaction solid content is 50%, NCO/OH=0.92, reaction times 2-3 hour, start second step when namely remaining without NCO without the characteristic peak of NCO group with examination of infrared spectrum;
(2) ditan-4 of residual content is added, 4 ‵-vulcabond rises sticky, when viscosity reaches room temperature 50 DEG C, viscosity number is 500-600pa.s, add remaining N, dinethylformamide 40 parts, continue to rise and glue, when viscosity number is 500-600pa.s when viscosity reaches room temperature 50 DEG C, add toluene 176 parts; When final viscosity reaches room temperature 25 DEG C, viscosity number is 120-160pa.s, termination reaction; Finally add 0.97 part of silane coupling agent GP1863 to stir.
By embodiment 1-7 synthesize urethane resin with following 1 that is resin thermotolerance test formulations and technique of drawing a design draw a design, test resin itself thermotolerance; With 2 that is the test of raincoat leather finished product thermotolerance to draw a design the thermotolerance of formula and process test raincoat leather finished product of drawing a design; With 3 that is raincoat leather finished product high frequency laminating fastness (peel strength test) to draw a design formula and technique of drawing a design, fit with the attaching process of high frequency plastic rubber heat sealing machine, the laminating fastness under test laminating electric current.
1, resin thermotolerance test draw a design formula as follows:
To draw a design technique:
R/P: super mist separate-type paper
Surface layer is coated with: 0.15mm (120 DEG C of * 2min are dry)
Surface layer is coated with: 0.15mm(110 DEG C of * 20 second half dry doubling)
Laminating: black looped fabric BASE (120 DEG C of * 3min are dry)
Thermotolerance testing method: sample batten to be measured being cut into 3cm*3cm, is pasted onto setup test on white hard paper plate; Baking oven is warming up to 80 DEG C, when 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 surface is unchanged, continuing to heat up according to the intervals of 10 DEG C adds test, puts into batten more at every turn, and keep 5 minutes in an oven after heating up after all needing waiting temperature constant; Test is shinny to surface always, and test completes.Shinny temperature deducts the thermotolerance that 10 DEG C, temperature interval is resin.(remarks: have plenty of due to the surface situation of brightening and brighten gradually, have plenty of and brighten quickly, therefore the thermotolerance of resin has plenty of single numerical value, has plenty of the scope between two numerical value.Illustrate, the testing method of thermotolerance knows in synthetic leather industry simultaneously.）
2, raincoat leather finished product thermotolerance test formula of drawing a design is as follows:
To draw a design technique:
R/P: super mist separate-type paper
Surface layer is coated with: 0.15mm (120 DEG C of * 2min are dry)
Tack coat is coated with: 0.15mm(110 DEG C of * 20 second half dry doubling)
Laminating: black looped fabric BASE (120 DEG C of * 3min are dry)
Bridge formation slaking: room temperature cure 7 days
Thermotolerance testing method: sample batten to be measured being cut into 3cm*3cm, is pasted onto setup test on white hard paper plate; Baking oven is warming up to 80 DEG C, when 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 surface is unchanged, continuing to heat up according to the intervals of 10 DEG C adds test, puts into batten more at every turn, and keep 5 minutes in an oven after heating up after all needing waiting temperature constant; Test is shinny to surface always, and test completes.Shinny temperature deducts the thermotolerance that 10 DEG C, temperature interval is resin.(remarks: have plenty of due to the surface situation of brightening and brighten gradually, have plenty of and brighten quickly, therefore the thermotolerance of resin has plenty of single numerical value, has plenty of the scope between two numerical value, it should be noted that, the testing method of thermotolerance 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:
To draw a design technique:
R/P: super mist separate-type paper
Surface layer is coated with: 0.10mm (120 DEG C of * 2min are dry)
Tack coat is coated with: 0.20mm(110 DEG C of * 20 second half dry doubling)
Laminating: black looped fabric BASE (120 DEG C 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 DEG C
The voltage-frequency time: 5 seconds
By according to 3 formula and the technique finished product raincoat leather finished product doubling of drawing a design, fit with the attaching process of high frequency plastic rubber heat sealing machine, after having fitted, carry out peel strength test.
In order to prove superiority of the present invention, the urethane resin that Example formulations 1-7 synthesizes is drawn a design according to the method for above-mentioned 1-3, corresponding by the sequence number of 1-7; By common aromatic polyurethane resins HDS-30A as a comparison case, carry out thermotolerance respectively, 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 is compared with comparative example, and under identical high frequency laminating condition, comparative example is not pasted, fastness of not fitting; And the laminating fastness of embodiment is all very good; Although comparative example is improved laminating electric current to 0.5A, laminating fastness is still very poor.Can reach a conclusion thus; The method that the resin of the present embodiment is fitted with high frequency, has higher laminating fastness, can meet the requirement of high frequency laminating.
Claims (2)
1. a Polyurethane resin for raincoat leather, is characterized in that, is made up of the raw material comprising following weight percentage, and described weight percentage is based on the total mass of raw material:
Described solvent C is DMF, and described solvent D is the one 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, the one in 5-pentanediol, 1,6-hexylene glycol, 1,9-nonanediol, and wherein the mol ratio of diol chain-extension agent A and diol chain-extension agent B is 1:1;
The preparation method of described Polyurethane resin for raincoat leather, is specifically made up of following steps:
(1) hexanodioic acid/1 will be gathered, 2 propylene glycol ester glycol, after diol chain-extension agent A, diol chain-extension agent B and a part of solvent C drop into and are uniformly mixed in reactor, drop into ditan-4 again, 4 ＇-vulcabond, start reaction, temperature of reaction is 70-90 DEG C, reaction solid content is 40-50%, NCO/OH=0.9-0.92, reaction times 2-3 hour, start second step when remaining without NCO when hydrogen peroxide test does not turn yellow;
(2) ditan-4, the 4 ＇-vulcabond adding residual content rises sticky, when viscosity number is 500-600pa.s when viscosity reaches room temperature 50 DEG C, adds remaining solvent C; Continue to rise and glue, when viscosity number is 500-600pa.s when viscosity reaches room temperature 50 DEG C, add solvent D; When final viscosity reaches room temperature 25 DEG C, viscosity number is 120-160pa.s, termination reaction; Finally add silane coupling agent GP1863 to stir;
The mass ratio of described solvent C and solvent D is 2:1-3:1; The quality sum of described solvent C and solvent D accounts for 70% of Polyurethane resin for raincoat leather total mass;
Described poly-hexanodioic acid/1,2 propylene glycol ester glycol are synthesized by hexanodioic acid and 1,2-PD polycondensation, and number-average molecular weight is 700-2000g/mol.
2. Polyurethane resin for raincoat leather according to claim 1, is characterized in that, described silane coupling agent is containing amino organo-silicon coupling agent GP1863.
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| 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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| 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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