CN103540281A - Quickly-cured rubber-type hot melt adhesive - Google Patents

Quickly-cured rubber-type hot melt adhesive Download PDF

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Publication number
CN103540281A
CN103540281A CN201310494944.4A CN201310494944A CN103540281A CN 103540281 A CN103540281 A CN 103540281A CN 201310494944 A CN201310494944 A CN 201310494944A CN 103540281 A CN103540281 A CN 103540281A
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hot melt
melt adhesive
rubber
type hot
described
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CN201310494944.4A
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CN103540281B (en
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王学宪
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广东东方树脂有限公司
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Abstract

The invention discloses a quickly-cured rubber-type hot melt adhesive, comprising the following components by weight percent: 25-40% of thermoplastic rubber, 35-65% of tackifying resin, 5-20% of a plasticizer, greater than 0 and not greater than 10% of a curing speed regulator and 0-3% of an antioxidant. The prepared rubber-type hot melt adhesive not only has the curing speed which is the same as or close to those of universal polyamide folded edges in the prior art, but also has better adhesive property, and is wider in used base material, and more applicable to automatic folding of a machine. In addition, the quickly-solidified rubber-type hot melt adhesive also has good ageing resistance; energy consumption is saved; the service life of equipment is prolonged.

Description

A kind of quick-setting rubber-type hot melt adhesive

Technical field

The invention belongs to macromolecule product manufacture field, be specifically related to a kind of quick-setting rubber-type hot melt adhesive.

Background technology

In the manufacture production process of vamps of sport shoes, conventionally hot melt adhesive at high temperature (130 ℃ ~ 180 ℃) by heat seeling coating to spare and accessory parts, these spare and accessory parts are carried out to temporary transient fixing before sewing machine.Hot melt adhesive is generally applied to the following main position of vamps of sport shoes: 1, the combination of the repeatedly sewing machine spare and accessory parts before instep formation is fixed, and these spare and accessory parts materials are tNonwovens, synthetic leather, animal skin or EVA and PU foam material etc.; 2, middle base plate and shoe last is temporary transient fixing, and the general material at this position is fibre and plastic cement shoe last or aluminum last head; 3, the flanging before vamp spare and accessory parts sewing machine is fixed, and these spare and accessory parts materials are tNonwovens, synthetic leather, animal skin etc.For the 1st kind of above-mentioned application site, generally need pressure-sensitive type or half pressure-sensitive type hot melt adhesive, require the open hour long, solidify slow; For the 2nd kind of above-mentioned application site, generally need the EVA type hot melt adhesive of lower bonding force; For the 3rd kind of above-mentioned application site, require curing speed fast (open hour 3s or in), bonding force strong (after flanging, material does not flick) should there is certain snappiness simultaneously, some vamp also requires resistance to xanthochromia grade more than 3.8 grades.Therefore, for the flanging field before vamp spare and accessory parts sewing machine urgently a kind of be different from pressure-sensitive type or half pressure-sensitive type hot melt adhesive and base plate and shoe last temporarily fixedly EVA type hot melt adhesive can quick-setting rubber-type hot melt adhesive.

At present, being applied to the hot melt adhesive kind of flanging before vamp spare and accessory parts sewing machine, is main mainly with polyamide hot, and the feature of this hot melt adhesive is quick solidifying, good to leather bonding force, and shortcoming is that applicable material is more single, and poor in flexibility, yellowing resistance are poor; In addition, domestic also have report to carry out the flanging field of modification before for vamp spare and accessory parts sewing machine for polyolefins hot melt adhesive, but cannot reach all the time desirable curing speed (open hour 3s or in), thereby, this area needs a kind of deficiency that can quick-setting rubber-type hot melt adhesive makes up above-mentioned two types of hot melt adhesives, guaranteeing bonding force and flexible its curing speed that simultaneously improves, the coating performance in the time of also will guaranteeing it for flanging gumming machine.

Summary of the invention

Object of the present invention is overcoming above-mentioned deficiency of the prior art, a kind of quick-setting rubber-type hot melt adhesive is provided, described hot melt adhesive has good adhesiveproperties to tNonwovens and leather, and curing speed fast (open hour 3s or in) has good snappiness and coating performance simultaneously.

Above-mentioned purpose of the present invention is achieved by following technical solution:

A rubber-type hot melt adhesive, its component and weight percent are:

Thermoplastic elastomer: 25-40%, tackifying resin: 35-65%, softening agent: 5-20%, curing speed conditioning agent: be greater than 0 and be not more than 10%, oxidation inhibitor: 0-3%;

It is one or more mixtures in A-B-A triblock copolymer, A-B Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock, A-C-B-A Tetrablock copolymer, A-B-AB-A-B segmented copolymer, star block copolymer or its graft modification product that described thermoplastic elastomer is selected from structure formation, wherein A is vinylbenzene, C is ethene, and B is divinyl, isoprene or pentadiene; Described thermoplastic elastomer has at least a kind of melting index to be greater than 8g/10 minute when selecting;

Described curing speed conditioning agent is selected from aliphatic hydrocarbon, comprises one or more mixtures in paraffin, microcrystalline wax, synthetic paraffin, low molecular weight polyethylene wax, Fischer-Tropsch wax, Poly Propylene Wax; The molecular weight of described curing speed conditioning agent is greater than 350.

Preferably, the component of described rubber-type hot melt adhesive and weight percent are: thermoplastic elastomer: 25-35%, tackifying resin: 40-55%, softening agent: 5-12%, curing speed conditioning agent: 3-8%, oxidation inhibitor: 0.2-1.5%.

Preferred, described thermoplastic elastomer has at least a kind of melting index to be greater than 8g/10 minute when selecting.

Preferably, described thermoplastic elastomer is A-B-A triblock copolymer, and wherein A is vinylbenzene, and C is ethene, and B is divinyl, isoprene or pentadiene.

Described tackifying resin is selected from the rosin of the hydrocarbon resin of aliphatic hydrocarbon, clicyclic hydrocarbon, aromatic hydrocarbons, modification and hydrogenated derivatives, terpenes and hydrogenated derivatives thereof, rosin, modification and hydrogenated derivatives thereof etc., and the mixture of above-claimed cpd.

Tackifying resin of the present invention specifically can be selected from C5 petroleum resin, C9 petroleum resin, C5/C9 petroleum resin, terpine resin, rosin, rosin ester etc., and the hydrogenation of above-mentioned resin or modifier.Preferably, tackifying resin is hydrogenation or semihydrogenation C5 petroleum resin, C5/C9 petroleum resin, and melt Gardner colorimetric is less than terpine resin, Terpene styron and the rosin ester of No. 3 looks; Preferably, the ring and ball softening point of described tackifying resin is between 100 ℃-120 ℃, and the weight percent preferred amounts of described tackifying resin is 40%-55%.

Described softening agent is selected from mineral base hydrocarbon-type oil, petroleum base hydrocarbon-type oil, polybutene, polyisobutene liquid tackifiers resin, liquid elastomer, functionalized oil, fatty wet goods, and the mixture of above-claimed cpd.

Described softening agent comprises olefines oligopolymer and low-molecular(weight)polymer, also has vegetables oil and animal oil and derivative thereof, and adoptable petroleum derivative contains the very high boiling point material of small proportion aromatic hydrocarbon (preferably < 15% weight ratio).On the other hand, softening agent can be non-aromatic completely.Suitable oligopolymer comprises that molecular-weight average is 350 ~ 10000 polypropylene, polybutene, polyisoprene, polyhutadiene, polyisobutene or analogue, and liquid tackifying resin.Preferably, described softening agent weight percent preferred amounts is 5%-12%.Softening agent of the present invention specifically can be selected from KN4010, KN4008, KN4012 of Kelamayi company etc.

Preferably, described curing speed conditioning agent is one or more mixtures in synthetic paraffin, low molecular weight polyethylene wax or Fischer-Tropsch wax.As a kind of most preferably scheme, described curing speed conditioning agent most preferably is Fischer-Tropsch wax.

The hindered phenol that described oxidation inhibitor is selected from hindered phenol or is combined with aid anti-oxidants.

Preferably, described oxidation inhibitor weight percent preferred amounts is 0.2% ~ 1.5%, and oxidation inhibitor of the present invention specifically can be selected from the antioxidant 1010 and 1076 of Ciba company.Oxidation inhibitor of the present invention can be used separately, also can jointly use with the aid anti-oxidants such as phosphorous acid ester, sulfuration dipropionic acid SUNSOFT Q-182S.

Described thermoplastic elastomer comprises Kraton D and the G series polymer obtaining from U.S. shell chemical company, and described polymkeric substance can be used separately, or uses with the form of mixture.The molecular weight of described thermoplastic elastomer generally characterizes by testing its melting index, and the melting index of rubber is larger, shows that its molecular weight is less, and fluidity of molten is good, and vice versa.

According to actual needs, in hot melt adhesive of the present invention, can add other compounds that do not affect its physical and chemical performance.These compounds comprise compound, ultraviolet absorbers and the filler etc. that increase the pigment of color, fluorescent agent, any coverage smell.

The present invention select the thermoplastic elastomer of specific melting index and tackifying resin, softening agent, curing speed conditioning agent and oxidation inhibitor composite under specified weight per-cent condition, the hot melt adhesive preparing viscosity in the time of 175 ℃ is less than 13000 centipoises, guarantees the good coating performance at 150 ℃ of flanging temperature; And under this coating temperature, open hour≤3S, the flanging machine flanging that is applicable to automatization is used.The hot melt adhesive making under optimum ratio condition of the present invention viscosity in the time of 175 ℃ is less than 10000 centipoises, and about 2S of open hour, applicable to the flanging machine flanging use of more advanced automatization.Described hot melt adhesive curing speed is fast simultaneously, and adhesiveproperties is good, and applicable multiple base material, comprises leather, middle bottom edgefold, tNonwovens flanging, and above-mentioned base material analogue etc.

Compared with prior art, the present invention has following beneficial effect:

The invention discloses a kind of quick-setting rubber-type hot melt adhesive, not only have with polyamide-based flanging general in prior art and have identical or approaching curing speed, and there is better adhesiveproperties, the base material using is more extensive, be more suitable for the machine flanging of automatization, simultaneously good with ageing-resistant performance in addition, to save energy consumption and extension device work-ing life advantage.

Embodiment

Below in conjunction with specific embodiment, the present invention is further explained, but embodiments of the present invention is not limited in any way.Unless stated otherwise, in embodiment, related reagent, method is the conventional reagent in this area and method.

The present invention prepares sample with the following step:

Thermoplastic elastomer, oxidation inhibitor are joined together with softening agent in the paddle mixer of 160 ℃ of left and right of temperature control, each mixing of materials is stirred until evenly, then slowly add tackifying resin, add rear mix and blend 15-25 minute, add again curing speed conditioning agent, mix and blend 10-15 minute vacuumizes froth breaking simultaneously.Then the uniform hot melt adhesive of complete melting is poured in the box folding by separate-type paper, and cool to room temperature.

Selective thermoplastic elastomer is listed in table 1.

Table 1

Thermoplastic elastomer Melting index, g/10 minute Kind VectorD-4411 33 SIS KratonD-1155 14 SBS KratonG-1726 50 SEBS VectorG-1652 2 SEBS YH-792 1.5 SBS YH-1209 10 SIS

Selective tackifying resin is listed in table 2.

Table 2

Resin title Type Softening temperature ℃ Gardner's colorimetric Supplier SU-130 Hydrogenation C5 petroleum resin 130 <1﹟ Korea S Kolon company E-5600 Hydrogenation C5/C9 petroleum resin 100 <1﹟ Exxon Neftegas Limited PER-100L Pale rosin pentaerythritol ester 100 <2﹟ Wuzhou day becomes forest chemical

Curing speed conditioning agent is the Fischer-Tropsch wax PX-105 of Shell company.

Hot melt adhesive is carried out to the mensuration of following performance: brookfield viscosity, ring and ball softening point, open hour, to the stripping strength of tNonwovens, stripping strength to leather.

Brookfield viscosity: viscosity test carries out in 175 ℃ in Brookfield viscometer, unit cps(centipoise) represent.

Softening temperature: carry out with ring and ball softening point tester, control 5 ℃/min of heat-up rates.

Open hour: undertaken by HG/T 3716-2003 standard, use s(second) represent.

Stripping strength to tNonwovens and leather: at the melten gel temperature of 150 ℃, it is compound that the automatic edge folding that Yong Julong company provides carries out flanging by hot melt adhesive and tNonwovens or leather, controlling Amount of spread is 40g/ square meter, by the composite sample of above-mentioned preparation cooling approximately 30 minutes at normal temperatures, by GB2792-1998 standard, carry out peel strength test, take and reach material and break as standard.

embodiment 1

The present embodiment is prepared thermoplastic elastomer according to the formula of table 3, and test result is listed in table 3.

Table 3

Formula I-1 I-2 I-3 KN4010 8 8 8 YH792 15 ? 15 KratonD-1155 15 30 ? VectorD-4411 ? ? 15 PX-105 5 5 5 E-5600 56.5 56.5 56.5 Irganox1010 0.2 0.2 0.2 Irganox1076 0.3 0.3 0.3 Formula test result I-1 I-2 I-3 175 ℃ of viscosity, cps 13000 11500 11200 Softening temperature, ℃ 115 115 113 Open hour, S 2.5 2.5 3 To tNonwovens/leather stripping strength Material is broken Material is broken Material is broken

Above three formulas are all the fast setting rubber-type hot melt adhesives that go for automatic machinery flanging , I-1because the thermoplastic elastomer melting index of selecting is on the low side a little, viscosity is bigger than normal a little, and coating performance is general, i-2, i-3owing to having selected the more thermoplastic elastomer of high fusion index, viscosity drops to 11000 left and right, and coating performance improves obviously, and two indexs of crucial curing speed and adhesiveproperties change little simultaneously.

embodiment 2

The present embodiment is prepared thermoplastic elastomer according to the formula of table 4, and test result is listed in table 4.

Table 4

Formula Ⅱ-1 Ⅱ-2 White oil (as softening agent) 8 8 YH1209 20 ? KratonG-1726 10 20 VectorG-1652 ? 10 PX-105 5 5 SU-130 56.5 56.5 Irganox1010 0.2 0.2 Irganox1076 0.3 0.3 Formula test result Ⅱ-1 Ⅱ-2 175 ℃ of viscosity, cps 9000 10500 Softening temperature, ℃ 115 118 Open hour, S 3 2.5 To tNonwovens/leather stripping strength Material is broken Material is broken Yellowing resistance (UV xanthochromia grade) 3.8 4.0

Adopt VectorG-1652 to mix the anti-yellowing property that can improve product with KratonG-1726, but cost is higher, coating performance impact on product is little, two indexs of crucial curing speed and adhesiveproperties change not quite simultaneously, also can make the fast setting rubber-type hot melt adhesive that is applicable to automatic machinery flanging.

embodiment 3

The present embodiment is prepared thermoplastic elastomer according to the formula of table 5, and test result is listed in table 5.

Table 5

Formula Ⅲ-1 Ⅲ-2 KN4010 8 8 YH792 ? 10 Kraton D-1155 20 10 VectorD-4411 10 10 PX-105 5 5 PER-100L 56.5 56.5 Irganox1010 0.2 0.2 Irganox1076 0.3 0.3 Formula test result Ⅲ-1 Ⅲ-2 175 ℃ of viscosity, cps 9000 10500 Softening temperature, ℃ 105 106 Open hour, S 3 3 To tNonwovens/leather stripping strength Material is broken Material is broken Yellowing resistance (UV xanthochromia grade) 4.0 3.8

The product yellowing resistance that adopts YH792 to replace part Kraton D-1155 to obtain can be slightly poor, but cost is reduced, coating performance impact on product is little, two indexs of crucial curing speed and adhesiveproperties change not quite simultaneously, also can make the fast setting rubber-type hot melt adhesive that is applicable to automatic machinery flanging.

Claims (9)

1. a quick-setting rubber-type hot melt adhesive, is characterized in that, its component and weight percent are:
Thermoplastic elastomer: 25-40%, tackifying resin: 35-65%, softening agent: 5-20%, curing speed conditioning agent: be greater than 0 and be not more than 10%, oxidation inhibitor: 0-3%;
It is one or more mixtures in A-B-A triblock copolymer, A-B Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock, A-C-B-A Tetrablock copolymer, A-B-AB-A-B segmented copolymer, star block copolymer or its graft modification product that described thermoplastic elastomer is selected from structure formation, wherein A is vinylbenzene, C is ethene, and B is divinyl, isoprene or pentadiene; Described thermoplastic elastomer has at least a kind of melting index to be greater than 8g/10 minute when selecting;
Described curing speed conditioning agent is selected from aliphatic hydrocarbon, comprises one or more mixtures in paraffin, microcrystalline wax, synthetic paraffin, low molecular weight polyethylene wax, Fischer-Tropsch wax, Poly Propylene Wax; The molecular weight of described curing speed conditioning agent is greater than 350.
2. rubber-type hot melt adhesive according to claim 1, it is characterized in that, the component of described rubber-type hot melt adhesive and weight percent are: thermoplastic elastomer: 25-35%, tackifying resin: 40-55%, softening agent: 5-12%, curing speed conditioning agent: 3-8%, oxidation inhibitor: 0.2-1.5%.
3. rubber-type hot melt adhesive according to claim 1, is characterized in that, described thermoplastic elastomer has at least a kind of melting index to be greater than 12g/10 minute when selecting.
4. rubber-type hot melt adhesive according to claim 1, is characterized in that, described thermoplastic elastomer is A-B-A triblock copolymer, and wherein A is vinylbenzene, and C is ethene, and B is divinyl, isoprene or pentadiene.
5. rubber-type hot melt adhesive according to claim 1, it is characterized in that, described tackifying resin is selected from hydrocarbon resin or its hydrogenated derivatives, terpenes or its hydrogenated derivatives, rosin, the rosin of modification or one or more mixtures in its hydrogenated derivatives of aliphatic hydrocarbon, clicyclic hydrocarbon, aromatic hydrocarbons, modification.
6. rubber-type hot melt adhesive according to claim 5, is characterized in that, the ring and ball softening point of described tackifying resin is between 100 ℃ ~ 120 ℃.
7. rubber-type hot melt adhesive according to claim 1, it is characterized in that, described softening agent is selected from mineral base hydrocarbon-type oil, petroleum base hydrocarbon-type oil, polybutene, polyisobutene liquid tackifiers resin, liquid elastomer, functionalized oil, one or more mixtures in fatty oil; The molecular-weight average of described softening agent is 350 ~ 10000.
8. rubber-type hot melt adhesive according to claim 1, is characterized in that, described curing speed conditioning agent is one or more mixtures in synthetic paraffin, low molecular weight polyethylene wax or Fischer-Tropsch wax.
9. rubber-type hot melt adhesive according to claim 1, is characterized in that the hindered phenol that described oxidation inhibitor is selected from hindered phenol or is combined with aid anti-oxidants.
CN201310494944.4A 2013-10-21 2013-10-21 A kind of quick-setting rubber-type PUR CN103540281B (en)

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Cited By (8)

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CN106751359A (en) * 2016-12-02 2017-05-31 荆门金泰格电子材料有限公司 A kind of thermoplasticity cover strip
CN107033809A (en) * 2017-04-27 2017-08-11 安徽国登管业科技有限公司 Adhesive for steel-plastics composite pipe
CN107418459A (en) * 2017-07-24 2017-12-01 江苏和和新材料股份有限公司 A kind of new-type heat-melting glued membrane, preparation method and application
CN107496929A (en) * 2017-09-25 2017-12-22 上海朴方生物科技有限公司 Oleosin glue and preparation method thereof
CN107652928A (en) * 2016-07-23 2018-02-02 广东聚胶粘合剂有限公司 A kind of high viscous force hot-fusible pressure-sensitive adhesive gum of low spread
CN107760228A (en) * 2017-10-18 2018-03-06 广州市豪特粘接材料有限公司 A kind of case and bag PUR and preparation method thereof
CN108276940A (en) * 2018-01-23 2018-07-13 浙江精华科技有限公司 Hot-melt Pressure-sensitive Adhesive for Sanitary Napkins and its production method
CN108410399A (en) * 2018-03-28 2018-08-17 如皋市嘉好热熔胶有限公司 A kind of left and right waist patch special glue and preparation method thereof

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107652928A (en) * 2016-07-23 2018-02-02 广东聚胶粘合剂有限公司 A kind of high viscous force hot-fusible pressure-sensitive adhesive gum of low spread
CN106751359A (en) * 2016-12-02 2017-05-31 荆门金泰格电子材料有限公司 A kind of thermoplasticity cover strip
CN107033809A (en) * 2017-04-27 2017-08-11 安徽国登管业科技有限公司 Adhesive for steel-plastics composite pipe
CN107418459A (en) * 2017-07-24 2017-12-01 江苏和和新材料股份有限公司 A kind of new-type heat-melting glued membrane, preparation method and application
CN107496929A (en) * 2017-09-25 2017-12-22 上海朴方生物科技有限公司 Oleosin glue and preparation method thereof
CN107760228A (en) * 2017-10-18 2018-03-06 广州市豪特粘接材料有限公司 A kind of case and bag PUR and preparation method thereof
CN108276940A (en) * 2018-01-23 2018-07-13 浙江精华科技有限公司 Hot-melt Pressure-sensitive Adhesive for Sanitary Napkins and its production method
CN108410399A (en) * 2018-03-28 2018-08-17 如皋市嘉好热熔胶有限公司 A kind of left and right waist patch special glue and preparation method thereof
CN108410399B (en) * 2018-03-28 2019-10-11 江苏嘉好热熔胶股份有限公司 A kind of left and right waist patch special glue and preparation method thereof

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