CN104531035B - A kind of flocking injection moulding two group part two liquid type polyurethane caking agent and its preparation method - Google Patents
A kind of flocking injection moulding two group part two liquid type polyurethane caking agent and its preparation method Download PDFInfo
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- CN104531035B CN104531035B CN201410836830.8A CN201410836830A CN104531035B CN 104531035 B CN104531035 B CN 104531035B CN 201410836830 A CN201410836830 A CN 201410836830A CN 104531035 B CN104531035 B CN 104531035B
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Abstract
The present invention relates to one and it is applicable to the injection molding two group part two liquid type polyurethane caking agent of flocking and its preparation method. The component A of this polyurethane adhesive is made up of the component of following mass content: tolylene diisocyanate 3.5%-5.0%; Poly-hexanodioic acid system polyester polyol 33%-42%; Diol chain-extension agent 0.3%-0.5%; N, dinethylformamide 10%-10%, toluene 50%-30%; Chlorine vinegar multipolymer 7.5%-9.5%; Ethylene vinyl acetate 3.5%-5.0%; The B component of this polyurethane adhesive is made up of the component of following mass content: tolylene diisocyanate 52%-55%; Ditan-4,4 ��-vulcabond 5.5%-6.5%; TriMethylolPropane(TMP) 14.5%-15.0%; Vinyl acetic monomer 25%-27%. The polyurethane adhesive component A of the present invention and B component with the use of, there is good flocking injection moulding effect. Can be used for the flocking of the fine hair of all length, it is applicable to PU shoe last surface and the injection moulding of TPR, PVC and MD sole material, injection moulding fastness height, effective.
Description
Technical field
The present invention relates to a kind of urethane resin, specifically, it relates to one is applicable to flocking injection moulding two group part two liquid type polyurethane caking agent and its preparation method.
Background technology
So-called flocking by specific technique, fine hair (also claiming staple fibre, length is between 0.03-0.5cm) is knitted on the surface of the fabric, increases the thickness of cloth and magnificent sense. At present, the method for synthetic leather industry many employings static flocking. So-called static flocking refers to the fabric face planted by the method for electrostatic attraction by fine hair and scribble caking agent; Therefore the cashmere density of flocking and effect are bigger by the characteristics influence of caking agent (also claiming tackiness agent, solid). The tack of caking agent and bonding force are more good, and the effect of static flocking is more good, and flocking density is more big. The length of fine hair is different also different for the requirement of caking agent, and fine hair is more short, more difficult flocking, it is desired to the tack of caking agent is more good.
Conventional polyurethane adhesive can be divided into single component adhesive and two group part caking agent, and industry is also commonly called as single-component one liquid type and two group part binary liquid shape caking agent. Single-component one liquid type caking agent relies on the effect of Van der Waals force and contact surface generation physical action and provides bonding force; Two groups of part binary liquid shape caking agents provide bonding force by the chemical reaction of NCO group with-OH group or other group. Therefore, it will be apparent that the caking agent of two groups of part binary liquid shapes has better bonding force. Meanwhile, the tack of two groups of part binary liquid shape caking agents is also good than the tack of single-component one liquid type caking agent.
Based on above-mentioned principle, synthetic leather industry, when carrying out flocking, according to the length of the fine hair of flocking, selects different caking agents. Single-component one liquid type caking agent can only plant long fine hair due to the restriction of tack and bonding force, and when planting short suede, flocking density is low, does not reach requirement; Two groups of part binary liquid shape caking agents are then owing to tack and bonding force are good, and when planting short suede, flocking density also can reach requirement, therefore can plant the fine hair of all length.
The so-called flocking injection moulding in synthetic leather footwear field, the one layer of caking agent covered with paint, lacquer, colour wash, etc. on PU shoe last surface when being rely on flocking, through the method for overheated laminating after flocking so that the sole bondings such as PU shoe last surface after flocking and TPR, PVC and MD are got up. This kind of technique first requirement for injection moulding caking agent be adhesive fastness height, simultaneously from the sole of different footwear material, namely TPR, PVC and MD etc. have good consistency; Next has requirement for the condition of injection moulding, and the temperature of general requirement injection moulding is low, easy construction, it is easy to processing, energy consumption is little.
Single-component one liquid type caking agent commercially available at present is general due to tack and bonding force, during for flocking, can only plant long fine hair, and when planting down, flocking density is low, does not reach requirement. Although commercially available two group part binary liquid shape caking agent tacks are good at present, bonding force is big, firmness height, it is possible to plant down, but is cross-linked due to NCO group in resin and hydroxyl reaction, intensity become high while, the softening temperature of resin becomes high, and melt temperature becomes height; Therefore, commercially available at present two group part binary liquid shape caking agents are not suitable for requiring low Shooting Technique for injection temperature.
Summary of the invention
It is an object of the invention to provide a kind of satisfied two group part binary liquid shape caking agents planting all length fine hair and injection moulding requirement simultaneously.
One of technical problem to be solved by this invention is to provide two group part binary liquid shape caking agents of a kind of planted all length fine hair with better tack and adhesive fastness, this kind of binary liquid shape caking agent simultaneously can injection moulding at a lower temperature (injection temperature is generally between 180 DEG C-190 DEG C), that is, organize the requirement that part binary liquid shape caking agent can meet flocking and injection moulding simultaneously for this kind pair.
The two of technical problem to be solved by this invention are the preparation method providing above-mentioned flocking injection moulding with two group part two liquid type polyurethane caking agent.
A kind of flocking injection moulding as first aspect present invention organizes part two liquid type polyurethane caking agent with two, comprises A, B two kinds of components, and component A wherein is prepared from by the raw material of following weight percent:
B component is the raw material composition of following mass percent:
Described component A and B component quality proportioning are 100:10-100:12.
In a preferred embodiment of the invention, the poly-hexanodioic acid system polyester polyol in described component A is one or both in poly-hexanodioic acid system ethylene glycol-DOPCP dibasic alcohol, poly-hexanodioic acid system 1,4-butyleneglycol-DOPCP dibasic alcohol.
In a preferred embodiment of the invention, the described diol chain-extension agent in component A is the one in 1,4-butyleneglycol and ethylene glycol.
In a preferred embodiment of the invention, the described N in component A, the weight sum of dinethylformamide and toluene accounts for the 40%-50% of component A weight content.
In a preferred embodiment of the invention, the chlorine vinegar multipolymer in described component A is vinyl acetate content in 10%-16%, K value at 49%-60%, and second-order transition temperature is lower than the benzene molten property vinyl chloride-vinyl acetate resin of 80 DEG C.
In the preferred embodiment of the present invention, described chlorine vinegar multipolymer is vinyl acetate content in 12%-16%, K value at 49%-54%, and second-order transition temperature is lower than the benzene molten property vinyl chloride-vinyl acetate resin of 70 DEG C.
In a preferred embodiment of the invention, the described ethylene vinyl acetate in component A is that vinyl acetate content is at 20%-40%, the molten hot melt type EVA of the benzene that melting means (MI) is 6-65.
In the preferred embodiment of the present invention, described ethylene vinyl acetate be vinyl acetate content at 28%-40%, melting means is at the molten hot melt level EVA of benzene of 6-65.
In the preferred embodiment of the present invention, described poly-hexanodioic acid system ethylene glycol-DOPCP dibasic alcohol is in building-up process, and the mol ratio of ethylene glycol and neopentyl glycol is 5:5-3:7; The number-average molecular weight of the poly-hexanodioic acid system ethylene glycol-DOPCP dibasic alcohol of synthesis is 2000.
In the preferred embodiment of the present invention, described poly-hexanodioic acid system 1,4-butyleneglycol-DOPCP dibasic alcohol is in building-up process, and the mol ratio of 1,4-butyleneglycol and neopentyl glycol is 5:5-3:7. The number-average molecular weight of the poly-hexanodioic acid system 1,4-butyleneglycol-DOPCP dibasic alcohol of synthesis is 2000.
In the preferred embodiment of the present invention, the mass ratio of described chlorine vinegar multipolymer and ethylene vinyl acetate is 2:1.
In the preferred embodiment of the present invention, the described tolylene diisocyanate in B component and the mol ratio of TriMethylolPropane(TMP) are 3:1;
In the preferred embodiment of the present invention, the described tolylene diisocyanate in B component and the mass ratio of ditan-4,4 ��-vulcabond are 9:1.
In the preferred embodiment of the present invention, needs according to practical situation when flocking injection moulding uses with two group part two liquid type polyurethane caking agent, when being diluted to 25 DEG C with vinyl acetic monomer or N-BUTYL ACETATE, viscosity is between 3000-10000CPS.
A kind of flocking injection moulding of the present invention organizes part two liquid type polyurethane caking agent with two, pass through A, the composite use of B component, the polyurethane adhesive obtained is made to have better tack and adhesive fastness, simultaneously this kind of binary liquid shape caking agent can injection moulding at a lower temperature (injection temperature is generally between 180 DEG C-190 DEG C), therefore, while flocking, injection moulding requirement can met again.
The researchist of the industry knows, polyurethane adhesive is due to containing groups such as ammonia ester bond, ester, ethers, and these groups can form hydrogen bond with the polar group on the footwear material surface such as PVC used, TPR, MD, is formed with the sticky object of certain bonding strength; In addition, the NCO group in two groups of part two liquid type polyurethane caking agents can also form chemical adhesive power with the hydroxyl reaction of substrate surface, and therefore, the bonding force of two groups of part binary liquid shape caking agents is better, and firmness is higher. Before curing, owing to molecular chain is short, molecular weight is little, therefore has good tack, it is possible to meet the requirement of all length fine hair planted, and flocking density height, effective simultaneously for two group part binary liquid shape caking agent simultaneously.
A kind of flocking injection moulding of the present invention organizes part two liquid type polyurethane caking agent with two, particularly in component A, the common use of chlorine vinegar multipolymer and ethylene vinyl acetate, make component chlorine vinegar multipolymer that two group part two liquid type polyurethane caking agent still still has second-order transition temperature low in guarantee system after cross-linking and the existence of the low ethylene vinyl acetate of melting means, therefore the melt temperature of resin system is low, it is possible to injection moulding at a lower temperature. Meanwhile, the adding of chlorine vinegar multipolymer and ethylene vinyl acetate so that their consistencies in urethane resin greatly exceed independent a kind of consistency when using, and the mobility of resin improves, and is more prone to processing; This is a unexpected result.
In addition, due to the existence in two groups of part two liquid type polyurethane caking agents of chlorine vinegar multipolymer and ethylene vinyl acetate, due to the principle of similar compatibility, make in injection moulding process, better with the injection moulding effect of the footwear materials such as other footwear materials, particularly PVC, adhesive fastness is more increased.
As a kind of flocking injection moulding preparation method of two group part two liquid type polyurethane caking agent of second aspect present invention, the preparation of component A wherein is specifically made up of following step:
(1) by poly-hexanodioic acid system polyester polyol, diol chain-extension agent and the toluene calculated according to reaction solid content drop into after being uniformly mixed in reactor, drop into tolylene diisocyanate again, start reaction, temperature of reaction is 70 DEG C-80 DEG C, and reaction solid content is 70%-80%, NCO/OH=0.80-0.85, in 2 hours reaction times, when remaining without NCO when hydrogen peroxide test does not turn yellow, start (2) step;
(2) adding tolylene diisocyanate rises sticky, and each additional amount is the 0.5%-1% of tolylene diisocyanate Theoretical Mass, and when viscosity reaches 50 DEG C, 200pa.s-300pa.s, carries out (3) step;
(3) when viscosity reaches 50 DEG C, 200pa.s-300pa.s, remaining toluene is added; When final viscosity reaches 50 DEG C, during 25pa.s-45pa.s, termination reaction, finally adds chlorine vinegar multipolymer and ethylene vinyl acetate, stirs evenly at 60 DEG C-70 DEG C;
The preparation of described B component is specifically made up of following step:
(1) by tolylene diisocyanate, ditan-4,4 ��-vulcabond and the vinyl acetic monomer calculated according to reaction solid content drop into after being uniformly mixed in reactor, temperature drops into the TriMethylolPropane(TMP) of 1/3 Theoretical Mass when being 40 DEG C-45 DEG C, solid content is 75%-80%; Naturally after heating up, temperature controls to react between 70 DEG C-75 DEG C, 1 hour reaction times;
(2) after test NCO reaches theoretical value, then dropping into remaining vinyl acetic monomer, be cooled to 40 DEG C-45 DEG C, drop into the TriMethylolPropane(TMP) of 1/3 Theoretical Mass, after naturally heating up, temperature controls to react between 70 DEG C-75 DEG C, 1 hour reaction times;
(3) after test NCO reaches theoretical value again, being cooled to 40 DEG C-45 DEG C, drop into remaining TriMethylolPropane(TMP), after naturally heating up, temperature controls to react between 70 DEG C-75 DEG C, 1 hour reaction times, when final NCO reaches theoretical value, and termination reaction.
In a preferred embodiment of the invention, in step (2) prepared by component A, when viscosity reaches 50 DEG C, 200pa.s-300pa.s, adds N, dinethylformamide, carries out (3) step.
A kind of flocking injection moulding of the present invention, with two group part two liquid type polyurethane caking agent, is applicable to the footwear leather flocking injection moulding industry of synthetic leather industry, has good flocking injection moulding effect, it is possible to plant the fine hair of all length, and flocked pile is fine and smooth, and stereoscopic sensation is strong. Can injection moulding (between 180 DEG C-190 DEG C) at a lower temperature, be applicable to PU shoe last surface and the injection moulding of TPR, PVC and MD sole material, injection moulding fastness height, effective.
Embodiment
Below by specific embodiment, the present invention is described further.
Embodiment 1
Component A proportioning
Chlorine vinegar multipolymer wherein is vinyl acetate content in 12%-16%, K value at 49%-54%, and second-order transition temperature is lower than the molten property vinyl chloride-vinyl acetate resin CP450 of benzene of 70 DEG C.
Ethylene vinyl acetate wherein be vinyl acetate content 40%, melting means is the EVA40W of 65.
B component proportioning
The preparation method of component A, comprises the following steps:
(1) (number-average molecular weight is 2000g/mol to drop into poly-hexanodioic acid system ethylene glycol/neopentyl glycol esterdiol 2000 in a kettle., ethylene glycol and neopentyl glycol mol ratio are 5:5) 355g, 1,4-butyleneglycol 5.66g, toluene 170g, after being uniformly mixed, drop into tolylene diisocyanate 35.56g again, start reaction, temperature of reaction is 70-80 DEG C, and reaction solid content is 70%, NCO/OH=0.85, in 2-3 hour reaction times, when remaining without NCO when hydrogen peroxide test does not turn yellow, start the 2nd step;
(2) adding 3g tolylene diisocyanate rises sticky, when viscosity reaches 50 DEG C, during 200-300pa.s, adds N, dinethylformamide 105g.
(3) add tolylene diisocyanate 2.5g again, when viscosity reaches 50 DEG C, during 200-300pa.s, add toluene 249g; When viscosity reaches 50 DEG C, during 25-45pa.s, termination reaction; Add CP45080.53g and EVA40W40.26g, stir evenly.
The preparation method of B component, comprises the following steps:
(1) dropping into tolylene diisocyanate 484.5g, ditan-4,4 ��-vulcabond 53.84g, TriMethylolPropane(TMP) 44.7g, vinyl acetic monomer 146g in a kettle., solid content is 80%. Naturally after heating up, temperature controls to react between 70 DEG C-75 DEG C, 1 hour reaction times;
(2), after test NCO reaches theoretical value, residue vinyl acetic monomer 78g is dropped into; When being cooled to 40 DEG C-45 DEG C, add TriMethylolPropane(TMP) 44.7g. Naturally after heating up, temperature controls to react between 70 DEG C-75 DEG C, 1 hour reaction times;
(3), after test NCO reaches theoretical value again, it is cooled to 40 DEG C-45 DEG C, drops into remaining TriMethylolPropane(TMP) 44.6g, naturally after heating up, temperature controls to react between 70 DEG C-75 DEG C, 1 hour reaction times, when final NCO reaches theoretical value, termination reaction.
Embodiment 2
Component A proportioning
Chlorine vinegar multipolymer wherein is vinyl acetate content in 12%-16%, K value at 49%-54%, and second-order transition temperature is lower than the molten property vinyl chloride-vinyl acetate resin CP430 of benzene of 70 DEG C.
Ethylene vinyl acetate wherein be vinyl acetate content 28%, melting means is the EVA260 of 6.
B component proportioning
With the proportioning of B component in embodiment 1.
The preparation method of component A, comprises the following steps:
(1) (number-average molecular weight is 2000g/mol to drop into poly-hexanodioic acid system ethylene glycol/neopentyl glycol esterdiol 2000 in a kettle., ethylene glycol and neopentyl glycol mol ratio are 3:7) 425g, ethylene glycol 4..58g, toluene 117g, after being uniformly mixed, drop into tolylene diisocyanate 39.86g again, start reaction, temperature of reaction is 70-80 DEG C, reaction solid content is 80%, NCO/OH=0.80, in 2-3 hour reaction times, starts (2) step when remaining without NCO when hydrogen peroxide test does not turn yellow;
(2) adding 2.5g tolylene diisocyanate rises sticky, when viscosity reaches 50 DEG C, during 200-300pa.s, adds N, dinethylformamide 83g.
(3) add tolylene diisocyanate 2.5g, when viscosity reaches 50 DEG C, during 200-300pa.s, add toluene 205g; When viscosity reaches 50 DEG C, during 25-45pa.s, termination reaction; Add CP43095.88g and EVA26047.94g, stir evenly.
The preparation method of B component: with the B component preparation method in embodiment 1.
Embodiment 3
Component A proportioning
Chlorine vinegar multipolymer wherein is vinyl acetate content in 12%-16%, K value at 49%-54%, and second-order transition temperature is lower than the molten property vinyl chloride-vinyl acetate resin CP450 of benzene of 70 DEG C.
Ethylene vinyl acetate wherein be vinyl acetate content 33%, melting means is the EVA150 of 30.
B component proportioning
The preparation method of component A, comprises the following steps:
(1) poly-hexanodioic acid system 1 is dropped in a kettle., (number-average molecular weight is 2000g/mol to 4-butyleneglycol/neopentyl glycol esterdiol 2000, ethylene glycol and neopentyl glycol mol ratio are 5:5) 425g, 1,4-butyleneglycol 6.78g, toluene 157g, after being uniformly mixed, dropping into tolylene diisocyanate 40.06g again, start reaction, temperature of reaction is 70-80 DEG C, reaction solid content is 75%, NCO/OH=0.80, in 2-3 hour reaction times, starts (2) step when remaining without NCO when hydrogen peroxide test does not turn yellow;
(2) adding 3.5g tolylene diisocyanate rises sticky, when viscosity reaches 50 DEG C, during 200-300pa.s, adds toluene 261g, when viscosity reaches 50 DEG C, during 25-45pa.s, and termination reaction; Add CP45096.37g and EVA15048.19g, stir evenly.
The preparation method of B component, comprises the following steps:
(1) dropping into tolylene diisocyanate 484.5g, ditan-4,4 ��-vulcabond 53.84g, TriMethylolPropane(TMP) 44.7g, vinyl acetic monomer 146g in a kettle., solid content is 80%. Naturally after heating up, temperature controls to react between 70 DEG C-75 DEG C, 1 hour reaction times;
(2), after test NCO reaches theoretical value, residue vinyl acetic monomer 103g is dropped into; When being cooled to 40 DEG C-45 DEG C, add TriMethylolPropane(TMP) 44.7g. Naturally after heating up, temperature controls to react between 70 DEG C-75 DEG C, 1 hour reaction times;
(3), after test NCO reaches theoretical value again, it is cooled to 40 DEG C-45 DEG C, drops into remaining TriMethylolPropane(TMP) 44.6g, naturally after heating up, temperature controls to react between 70 DEG C-75 DEG C, 1 hour reaction times, when final NCO reaches theoretical value, termination reaction.
Embodiment 4
Component A proportioning
Chlorine vinegar multipolymer wherein is vinyl acetate content in 12%-16%, K value at 49%-54%, and second-order transition temperature is lower than the molten property vinyl chloride-vinyl acetate resin CP430 of benzene of 70 DEG C.
Ethylene vinyl acetate wherein be vinyl acetate content 28%, melting means is the EVA260 of 6.
B component proportioning
With the B component proportioning in embodiment 3
The preparation method of component A, comprises the following steps:
(1) poly-hexanodioic acid system 1 is dropped in a kettle., (number-average molecular weight is 2000g/mol to 4-butyleneglycol/neopentyl glycol esterdiol 2000, ethylene glycol and neopentyl glycol mol ratio are 3:7) 355g, ethylene glycol 3.83g, toluene 169g, after being uniformly mixed, drop into tolylene diisocyanate 35.38g again, start reaction, temperature of reaction is 70-80 DEG C, and reaction solid content is 70%, NCO/OH=0.85, in 2-3 hour reaction times, when remaining without NCO when hydrogen peroxide test does not turn yellow, start (2) step;
(2) adding 2.5g tolylene diisocyanate rises sticky, and when viscosity reaches 50 DEG C, 200-300pa.s, adds N, dinethylformamide 104g.
(3) add tolylene diisocyanate 2.5g again, when viscosity reaches 50 DEG C, during 200-300pa.s, add toluene 248g; When viscosity reaches 50 DEG C, during 25-45pa.s, termination reaction; Add CP43080.1g and EVA26040.05g, stir evenly.
The preparation method of B component: with the preparation method of B component in embodiment 3.
Embodiment 5
Component A proportioning
Chlorine vinegar multipolymer wherein is vinyl acetate content in 10%-16%, K value at 49%-54%, and second-order transition temperature is lower than the molten property vinyl chloride-vinyl acetate resin CP710 of benzene of 80 DEG C.
Ethylene vinyl acetate wherein be vinyl acetate content 20%, melting means is the EVA633 of 20.
B component proportioning
With the B component proportioning in embodiment 1.
The preparation method of component A, comprises the following steps:
(1) (number-average molecular weight is 2000g/mol to drop into poly-hexanodioic acid system ethylene glycol/neopentyl glycol esterdiol 2000 in a kettle., ethylene glycol and neopentyl glycol mol ratio are 5:5) 177.5g, poly-hexanodioic acid system 1, (number-average molecular weight is 2000g/mol to 4-butyleneglycol/neopentyl glycol esterdiol 2000, ethylene glycol and neopentyl glycol mol ratio are 5:5) 177.5g, 1, 4-butyleneglycol 5.66g, toluene 170g, after being uniformly mixed, drop into tolylene diisocyanate 35.56g again, start reaction, temperature of reaction is 70-80 DEG C, reaction solid content is 70%, NCO/OH=0.85, 2-3 hour reaction times, (2) step is started when remaining without NCO when hydrogen peroxide test does not turn yellow,
(2) adding 3g tolylene diisocyanate rises sticky, and when viscosity reaches 50 DEG C, 200-300pa.s, adds N, dinethylformamide 105g.
(3) add tolylene diisocyanate 2.5g again, when viscosity reaches 50 DEG C, during 200-300pa.s, add toluene 249g; When viscosity reaches 50 DEG C, during 25-45pa.s, termination reaction; Add CP71080.53g and EVA63340.26g, stir evenly.
The preparation method of B component: with the B component preparation method in embodiment 1.
In order to prove the superiority of the present invention, respectively the component A in embodiment 1-5 is mixed with the mass ratio of 100 parts of ratios 10 parts with B component, add vinyl acetic monomer adjusting viscosity and be corresponding in turn to as embodiment sample 1-5 at 4000cps/25 DEG C of label; Component A in embodiment 1-5 is mixed with the mass ratio of 100 parts of ratios 12 parts with B component, adds vinyl acetic monomer adjusting viscosity and be corresponding in turn to as embodiment sample 6-10 at 4000cps/25 DEG C of label.
Two group part two liquid type polyurethane caking agent DA-60A and matching used solidifying agent DAC-77 by commercially available at present) mix with the mass ratio of 100 parts of ratios 10 parts, add vinyl acetic monomer adjusting viscosity at 4000cps/25 DEG C, label is comparative example 6;
By single-component one liquid type caking agent SA-50 vinyl acetic monomer adjusting viscosity commercially available at present at 4000cps/25 DEG C, label is comparative example 7, and 1-7 is used for flocking and injection moulding, fine hair specification is 1.5D*0.03mm, and injection temperature is 180 DEG C, is respectively PVC at the bottom of injection moulded shoes, TPR, MD sole. Flocking result and injection molding result are as follows:
The flocking injection moulding of sample and PVC sole material tested by table 1
| Flocking density | Injection moulding good article rate | |
| Embodiment sample 1 | Density height | 97% |
| Embodiment sample 2 | Density height | 98% |
| Embodiment sample 3 | Density height | 98% |
| Embodiment sample 4 | Density height | 97% |
| Embodiment sample 5 | Density height | 97% |
| Embodiment sample 6 | Density height | 98% |
| Embodiment sample 7 | Density height | 98% |
| Embodiment sample 8 | Density height | 98% |
| Embodiment sample 9 | Density height | 97% |
| Embodiment sample 10 | Density height | 98% |
| Comparative example 6 | Density height | Can not injection moulding, then loosely |
| Comparative example 7 | Density is low, leakage base cloth | 90% |
The flocking injection moulding of sample and TPR sole material tested by table 2
| Flocking density | Injection moulding good article rate | |
| Embodiment sample 1 | Density height | 97% |
| Embodiment sample 2 | Density height | 95% |
| Embodiment sample 3 | Density height | 96% |
| Embodiment sample 4 | Density height | 96% |
| Embodiment sample 5 | Density height | 95% |
| Embodiment sample 6 | Density height | 97% |
| Embodiment sample 7 | Density height | 96% |
| Embodiment sample 8 | Density height | 96% |
| Embodiment sample 9 | Density height | 96% |
| Embodiment sample 10 | Density height | 95% |
| Comparative example 6 | Density height | Can not injection moulding, then loosely 9--> |
| Comparative example 7 | Density is low, leakage base cloth | 88% |
The flocking injection moulding of sample and MD sole material tested by table 3
| Flocking density | Injection moulding good article rate | |
| Embodiment sample 1 | Density height | 96% |
| Embodiment sample 2 | Density height | 95% |
| Embodiment sample 3 | Density height | 95% |
| Embodiment sample 4 | Density height | 96% |
| Embodiment sample 5 | Density height | 98% |
| Embodiment sample 6 | Density height | 96% |
| Embodiment sample 7 | Density height | 96% |
| Embodiment sample 8 | Density height | 95% |
| Embodiment sample 9 | Density height | 96% |
| Embodiment sample 10 | Density height | 98% |
| Comparative example 6 | Density height | Can not injection moulding, then loosely |
| Comparative example 7 | Density is low, leakage base cloth | 85% |
Thus the result in table is it may be seen that embodiment sample 1-10 is compared with comparative example 6,7, and not only flocking density height, the more important thing is, for different types of sole material, all has good injection moulding effect, good article rate height. Although and two group part two liquid type polyurethane caking agent flocking density height that comparative example 6 is that is commercially available, but injection moulding can not be used for completely; Although comparative example 7 i.e. single-component one fluid polyurethane caking agent can injection moulding, but the injection moulding good article rate of different sole material is had difference, and a good article rate height not as embodiment 1-10, the most important thing is, during comparative example 7 flocking, flocking density is low, leakage base cloth, can not meet flocking requirement.
Claims (14)
1. flocking injection moulding is with two group part two liquid type polyurethane caking agent, comprises A, B two kinds of components, and component A wherein is prepared from by the raw material of following weight percent:
B component is the raw material composition of following mass percent:
Described component A and B component quality proportioning are 100:10-100:12;
Chlorine vinegar multipolymer in described component A is vinyl acetate content in 10%-16%, K value at 49%-60%, and second-order transition temperature is lower than the benzene molten property vinyl chloride-vinyl acetate resin of 80 DEG C;
The described ethylene vinyl acetate in component A is that vinyl acetate content is at 20%-40%, the molten hot melt type EVA of the benzene that melting means (MI) is 6-65;
2. a kind of flocking injection moulding as claimed in claim 1 organizes part two liquid type polyurethane caking agent with two, it is characterized in that, poly-hexanodioic acid system polyester polyol in described component A is one or both in poly-hexanodioic acid system ethylene glycol-DOPCP dibasic alcohol, poly-hexanodioic acid system 1,4-butyleneglycol-DOPCP dibasic alcohol.
3. a kind of flocking injection moulding as claimed in claim 2 organizes part two liquid type polyurethane caking agent with two, it is characterised in that, described poly-hexanodioic acid system ethylene glycol-DOPCP dibasic alcohol is in building-up process, and the mol ratio of ethylene glycol and neopentyl glycol is 5:5-3:7; The number-average molecular weight of the poly-hexanodioic acid system ethylene glycol-DOPCP dibasic alcohol of synthesis is 2000.
4. a kind of flocking injection moulding as claimed in claim 2 organizes part two liquid type polyurethane caking agent with two, it is characterized in that, described poly-hexanodioic acid system 1,4-butyleneglycol-DOPCP dibasic alcohol is in building-up process, 1, the mol ratio of 4-butyleneglycol and neopentyl glycol is 5:5-3:7, and the number-average molecular weight of the poly-hexanodioic acid system 1,4-butyleneglycol-DOPCP dibasic alcohol of synthesis is 2000.
5. flocking injection moulding as claimed in claim 1 a kind of is with two group part two liquid type polyurethane caking agent, it is characterised in that, the described diol chain-extension agent in component A is the one in 1,4-butyleneglycol and ethylene glycol.
6. a kind of flocking injection moulding as claimed in claim 1 organizes part two liquid type polyurethane caking agent with two, it is characterised in that, the described N in component A, the weight sum of dinethylformamide and toluene accounts for the 40%-50% of component A weight content.
7. a kind of flocking injection moulding as claimed in claim 1 organizes part two liquid type polyurethane caking agent with two, it is characterized in that, described chlorine vinegar multipolymer is vinyl acetate content in 12%-16%, K value at 49%-54%, and second-order transition temperature is lower than the benzene molten property vinyl chloride-vinyl acetate resin of 70 DEG C.
8. a kind of flocking injection moulding as claimed in claim 1 organizes part two liquid type polyurethane caking agent with two, it is characterised in that, described ethylene vinyl acetate is vinyl acetate content 28%-40%, and melting means is at the molten hot melt level EVA of benzene of 6-65.
9. a kind of flocking injection moulding as claimed in claim 1 organizes part two liquid type polyurethane caking agent with two, it is characterised in that, the mass ratio of described chlorine vinegar multipolymer and ethylene vinyl acetate is 2:1.
10. a kind of flocking injection moulding as claimed in claim 1 organizes part two liquid type polyurethane caking agent with two, it is characterised in that, the described tolylene diisocyanate in B component and the mol ratio of TriMethylolPropane(TMP) are 3:1.
11. a kind of flocking injection mouldings as claimed in claim 1 organize part two liquid type polyurethane caking agent with two, it is characterised in that, the described tolylene diisocyanate in B component and the mass ratio of ditan-4,4 ��-vulcabond are 9:1.
12. a kind of flocking injection mouldings as claimed in claim 1 organize part two liquid type polyurethane caking agent with two, it is characterized in that, needs according to practical situation when flocking injection moulding uses with two group part two liquid type polyurethane caking agent, when being diluted to 25 DEG C with vinyl acetic monomer or N-BUTYL ACETATE, viscosity is between 3000-10000CPS.
The 13. a kind of flocking injection mouldings as described in claim 1 to 12 arbitrary claim preparation method of two group part two liquid type polyurethane caking agent, the preparation of component A wherein is specifically made up of following step:
(1) by poly-hexanodioic acid system polyester polyol, diol chain-extension agent and the toluene calculated according to reaction solid content drop into after being uniformly mixed in reactor, drop into tolylene diisocyanate again, start reaction, temperature of reaction is 70 DEG C-80 DEG C, and reaction solid content is 70%-80%, NCO/OH=0.80-0.85, in 2 hours reaction times, when remaining without NCO when hydrogen peroxide test does not turn yellow, start (2) step;
(2) adding tolylene diisocyanate rises sticky, and each additional amount is the 0.5%-1% of tolylene diisocyanate Theoretical Mass, and when viscosity reaches 50 DEG C, 200pa.s-300pa.s, carries out (3) step;
(3) when viscosity reaches 50 DEG C, 200pa.s-300pa.s, remaining toluene is added; When final viscosity reaches 50 DEG C, during 25pa.s-45pa.s, termination reaction, finally adds chlorine vinegar multipolymer and ethylene vinyl acetate, stirs evenly at 60 DEG C-70 DEG C;
The preparation of described B component is specifically made up of following step:
(1) by tolylene diisocyanate, ditan-4,4 ��-vulcabond and the vinyl acetic monomer calculated according to reaction solid content drop into after being uniformly mixed in reactor, temperature drops into the TriMethylolPropane(TMP) of 1/3 Theoretical Mass when being 40 DEG C-45 DEG C, solid content is 75%-80%; Naturally after heating up, temperature controls to react between 70 DEG C-75 DEG C, 1 hour reaction times;
(2) after test NCO reaches theoretical value, then dropping into remaining vinyl acetic monomer, be cooled to 40 DEG C-45 DEG C, drop into the TriMethylolPropane(TMP) of 1/3 Theoretical Mass, after naturally heating up, temperature controls to react between 70 DEG C-75 DEG C, 1 hour reaction times;
(3) after test NCO reaches theoretical value again, being cooled to 40 DEG C-45 DEG C, drop into remaining TriMethylolPropane(TMP), after naturally heating up, temperature controls to react between 70 DEG C-75 DEG C, 1 hour reaction times, when final NCO reaches theoretical value, and termination reaction.
14. preparation methods as claimed in claim 13, it is characterised in that, in step (2) prepared by component A, when viscosity reaches 50 DEG C, 200pa.s-300pa.s, adds N, dinethylformamide, carries out (3) step.
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| CN106753161A (en) * | 2016-12-02 | 2017-05-31 | 嘉兴禾欣化学工业有限公司 | Compound dual-component polyurethane adhesives of heat resistant type PVC and preparation method thereof |
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| CN110699030B (en) * | 2019-10-11 | 2022-03-15 | 汕头市鑫源化工科技有限公司 | Electrostatic flocking adhesive and preparation method thereof |
| CN111234161A (en) * | 2020-03-09 | 2020-06-05 | 江苏东邦科技有限公司 | Preparation method of wear-resistant polyurethane primer two-liquid type adhesive for sanding |
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