CN103497429A - Low-smell TPV (thermoplastic vulcanizate) formed by secondary coating with ABS (acrylonitrile-butadiene-styrene) substrate and preparation method thereof - Google Patents
Low-smell TPV (thermoplastic vulcanizate) formed by secondary coating with ABS (acrylonitrile-butadiene-styrene) substrate and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of thermoplastic elastomer modification and discloses low-smell TPV (thermoplastic vulcanizate) formed by secondary coating with an ABS (acrylonitrile-butadiene-styrene) substrate and a preparation method and application thereof. The low-smell TPV formed by secondary coating with an ABS substrate comprises the following components in percentage by mass: 0.02-4% of deodorant, 10-30% of polyolefin, 20-40% of rubber component, 20-40% of rubber plasticizer, 5-30% of polyester thermoplastic elastomer, 0-20% of filler, 0.02-2% of peroxide crosslinking initiator, 0.02-2% of assistant crosslinking agent and 0.01-2% of antioxidant. In the invention, the material prepared by taking a peroxide as the crosslinking initiator and a substance containing a polyunsaturated bond as the assistant crosslinking agent and by adding the deodorant to remove low-molecular volatiles has the advantages of good heat resistance, weather resistance, fatigue resistance, oil resistance, low smell and the like, and also has a good secondary coating effect with ABS.
Description
Technical field
The invention belongs to thermoplastic elastomer modified field, particularly Overmolded low smell TPV of a kind of and ABS base material secondary and its preparation method and application.
Background technology
The ABS(acrylonitrile-butadiene-styrene terpolymer) resin has the excellent properties such as HI high impact, high rigidity, oil resistant, good stability of the dimension, molding shrinkage be little, is a kind of thermoplastics be widely used.Adopt the product surface rigidity that ABS resin is base material higher and smooth, lack texture and sense of touch in the application of some product.Utilization is penetrated sticky Overmolded technology (double injection molding) (Overmolding) by thermoplastic elastomer, as thermoplastic polyurethane (TPU), thermoplastic polyester (TPEE), styrene-ethylene/butylene-styrene polymkeric substance (SEBS), copolyesters, copolyamide, thermoplastic rubber (TPR) and Thermoplastic Vulcanizate (TPV) etc. are coated on the ABS product, make the product surface be full of soft feeling, can also increase product functionality and added value, as noise abatement, damping, waterproof, crashproof, anti-skidding, comfort etc.
Utilize TPV prepared by dynamic vulcanization technology to there is unique island structure, make its feature performance benefit that had both there is rubber (performance such as weather-proof as excellence, anti-ozone, heat-resisting, cold-resistant, oil resistant), also given its good antifatigue, anti-subduing and incompressible permanentset performance, be widely used in the every field of daily life simultaneously.TPV is due to the characteristic with vulcanized rubber, its apparent sense of touch and people's skin is close, there is good feel and skidproof effect with the product of its coating, raising along with people's living standard, people's aesthetic conceptions are also changing, sample more and more higher, so at secondary, the application aspect Overmolded also more and more is subject to people's concern and attention to TPV.
TPV itself belongs to the weak Thermoplastic Vulcanizate of nonpolar or polarity, poor with the intermiscibility of ABS, utilizes above-mentioned bi-material to carry out secondary Overmolded very difficult, and serious restricted T PV is in the use in this field.In order to improve the surface adhesion of TPV and polar substrates, method comparatively commonly used is directly in system, to add compatilizer now; As United States Patent (USP) 4,957,968 and the issued patents CN 101356228A of Advanced Elastomer Systems, L.P. in mention the graft resin contained with the olefin type unsaturation (comprising acid, alcohol, acid anhydrides, imide and derivative thereof) of carbonyl conjugation joined in the TPV system, thereby improve the adhesive effect on material and polar substrates surface.Checking is learnt by experiment, although add above-mentioned grafts can improve to a certain extent the adhesive effect of TPV and ABS base material, also makes the smell of material increase the weight of, and product hardness rises very fast, is unfavorable for producing odorlessness soft product.In Chinese patent CN 103045149A, mention to adding in the TPV system poly maleimide class response type compatilizer to improve the adhesiveproperties with the polarity hard substrate.But the toxicity of this type of response type compatilizer is larger, serious to production environment and human health risk, be not suitable for being applied in actual production.Except the method for adding compatilizer, the issued patents CN 1331724A of Advanced Elastomer Systems, L.P. and United States Patent (USP) 6, in 503,984, select polyolefine and the functionalised polyolefin of low modulus in flexure and low-crystallinity to be used in combination, obtain thering is excellent adhesion modification TPV with polar polymer; But show from experimental result, utilize the bounding force of product that aforesaid method learns and ABS base material poor, can not meet service requirements.United States Patent (USP) 5,397,839,5,637,407 and the issued patents CN1281484A of Advanced Elastomer Systems, L.P. all mention the polyester for external phase of non-polar polyolefinic in TPV, polyethers, polyamide-based isopolarity polymkeric substance replaced, prepare the thermoplasticity cross-linked rubber that polarity is higher, improve the cementability with polar substrates.Because this type of method of modifying still rests on the experimental phase and production difficulty is high, realize in the short period of time that industrialization is unrealistic.Therefore by a kind of simple and easy effective method of modifying, developing a kind ofly has the high-performance TPV material of bonds well effect to have important practical significance with the ABS material.
Summary of the invention
For the shortcoming and deficiency that overcomes above-mentioned prior art, primary and foremost purpose of the present invention is to provide a kind of low smell TPV Overmolded with ABS base material secondary.This vulcanized rubber possesses good over-all properties, low smell, with ABS, the characteristics such as good thermal caking effect, surface touch be good is arranged.
Another purpose of the present invention is to provide the preparation method of the Overmolded low smell TPV of a kind of above-mentioned and ABS base material secondary.The method is to add the master batch (deodovization agent) that is rich in the lower boiling fugitive constituent in the dynamic vulcanization process of TPV, thereby produces a large amount of volatile gas in material melt blending process; The small molecules volatile matter consistency produced in this gas and dynamic vulcanization process is fabulous, plays obvious extraction, finally by vacuumizing, both is together taken away, thereby obtains the TPV product that hangs down smell.
Still a further object of the present invention is to provide the above-mentioned low smell TPV application in ABS secondary Overmolded Overmolded with ABS base material secondary.
Purpose of the present invention realizes by following proposal:
A kind of low smell TPV Overmolded with ABS base material secondary, the component that comprises following massfraction:
Described deodovization agent is the masterbatch that is rich in the lower boiling fugitive constituent, carrier and volatile components, consists of.
Described carrier has the Spatial Multi-Dimensional vesicular structure, and its micropore is half opening or open structure, and pore size is 1～100nm.
Described volatile components refers to that boiling point under the room temperature normal pressure is lower than the organic or inorganic liquid of 180 ℃.
Preferably, described carrier refers at least one in zeolite, molecular sieve, hollow glass micropearl, carbon black, cinder powder, diatomite, porous alumina, expanded polyolefin, expanded polyester and foamed thermoplastic elastomers, foamed thermoplastic cross-linked rubber.
Preferably, described volatile components refers at least one in alcohols, ketone, alkanes, cycloalkane, water, white oil, rubber filling oil, fluidizer, solvent oil and silicone oil.
Described deodovization agent is prepared by following methods: carrier is placed in to the negative pressure encloses container, injects volatile components, standing 10～30min, make deodovization agent.
The weight ratio of used carrier and volatile components is 1:(0.01～10); Preferred 1:(1～3).
Described deodovization agent produces a large amount of volatile gas in material melt blending process, the small molecules volatile matter consistency produced in this gas and dynamic vulcanization process is fabulous, play obvious extraction, finally by vacuumizing, both are together taken away, effectively reduce the smell of product.
Described polyolefine refers at least one in Co-polypropylene, homo-polypropylene, high density polyethylene(HDPE), Low Density Polyethylene, LLDPE and POE (POE).
Preferably, described polyolefinic melt flow rate (MFR) is 0.5～20g/10min.
Described rubber components refers at least one in ethylene propylene rubber (EPR), terpolymer EP rubber (EPDM), natural rubber (NR), paracril (NBR) and acrylic elastomer (ACM).
Described rubber plastic agent refers at least one in paraffin oil, naphthenic oil and hydrocarbon oil.
Described polyester thermoplastic elastomer refers at least one in thermoplastic polyurethane (TPU) and thermoplastic polyester (TPEE).
Described peroxide crosslinking initiator refers to the material that contains peroxy-radical.
Preferably, described peroxide crosslinking initiator refers to 2,5-dimethyl-2,5-bis(t-butylperoxy) hexin, 2,5-dimethyl-2, at least one in 5-bis(t-butylperoxy) hexane (claiming again two 2 5) and dicumyl peroxide.
More preferably, described peroxide crosslinking initiator refers to 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane (two 2 5).Two 25 is oily liquids, and the premix be conducive in material disperses, and can more effectively cause the dynamic vulcanization reaction of TPV system.
Described additional crosslinker claims again adjuvant grafting branch cross-linked evocating agent, is the material that contains many unsaturated link(age)s.
Preferably, described additional crosslinker refers at least one in polyester material, polybutadiene material, cyanate material, isocyanates material and esters of acrylic acid material.Additional crosslinker add the cross-linking density that not only can improve the TPV material, make material there is better elasticity and sense of touch; And can make the polyester thermoplastic elastomer be grafted to better in the TPV system, also alleviate the polyolefinic degraded that peroxide radical causes simultaneously.
Described filler refers at least one in wollastonite, kaolin, diatomite, calcium carbonate, talcum powder, barium sulfate and mica.
Described oxidation inhibitor is comprised of primary antioxidant and auxiliary antioxidant.
Described primary antioxidant refers to Hinered phenols antioxidant.
Described auxiliary antioxidant refers at least one in phosphite oxidation inhibitor and ester kind antioxidant.
Preferably, described oxidation inhibitor refers at least one in 2,6 di tert butyl 4 methyl phenol (BHT), antioxidant 1010, antioxidant 1076, oxidation inhibitor 1790, irgasfos 168 and oxidation inhibitor 626.
Adding of oxidation inhibitor can improve the stability of alloy in processing and use procedure, avoids the product variable color.
The preparation method of the low smell TPV that above-mentioned and ABS base material secondary is Overmolded comprises following concrete steps:
First that polyolefine, rubber components, rubber plastic agent, polyester thermoplastic elastomer, filler and oxidation inhibitor is mixing, obtain a step material; A step material, peroxide crosslinking initiator, additional crosslinker and deodovization agent blend, extrude, obtain the low smell TPV Overmolded with ABS base material secondary.
Wherein, each constituent mass mark is as follows:
Described mixing finger is at 150～180 ℃ of mixing 10～30min.
Described extruding can be carried out in single screw extrusion machine, twin screw extruder, Banbury mixer or Double-rotor continuous mixing equipment.
Preferably, described extruding in twin screw extruder carried out.
Described each section temperature of extruding is 180～230 ℃, and rotating speed is 200～500rpm.
It in the time of described extruding, is the dynamic vulcanization process.
The low smell TPV that utilizes aforesaid way to prepare can be in dynamic vulcanization, by polarity, higher polyester thermoplastic elastomer is connected in the TPV system effectively by the mode of grafting, thereby the generation layering of polyester thermoplastic elastomer component and inconsistent problem that the weakly polar component while avoiding utilizing common blending and modifying in the TPV material (polyolefine, rubber components, rubber plastic agent) is higher with polarity, prepare the TPV that has the bonds well effect with the ABS base material.
Add deodovization agent in the process of TPV raw material extrusion reaction, by vacuumizing, the small molecules volatile matter produced in the dynamic vulcanization process is together taken away, can obtain low smell TPV, solve the larger problem of response type thermoplastic elastomer smell.
Overmolded low smell TPV and the ABS of above-mentioned and ABS base material secondary has good thermal caking effect, is suitable for secondary Overmolded.
Mechanism of the present invention is:
Utilization of the present invention melt extrudes in process, the vulcanization crosslinking (being commonly called as dynamic vulcanization) of rubber components in peroxide crosslinking initiator initiator system, also by consistency, not good polar compound polyester thermoplastic elastomer is grafted in the TPV system effectively simultaneously, thereby makes the Thermoplastic Vulcanizate that has the bonds well effect with the ABS base material.And add deodovization agent, and by vacuumizing, the small molecules volatile matter produced in the dynamic vulcanization process is together taken away, can obtain low smell TPV, solve the larger problem of response type thermoplastic elastomer smell.
The present invention, with respect to prior art, has following advantage and beneficial effect:
1, to adopt superoxide be cross-linked evocating agent in the present invention, the material that contains many unsaturated link(age)s of take is additional crosslinker, extrude or mixing facilities in carry out the TPV raw material simultaneously in crosslinked, the In Situ Compatibilization graft reaction that shear to become broken, dispersed and polyester thermoplastic elastomer component of rubber components.The modification TPV material that utilizes this method to prepare not only has the advantages such as good thermotolerance, weathering resistance, resistance to fatigue, agent of low hygroscopicity, oil resistant, low smell, also with ABS, has good secondary covered effect.
2, the present invention adds deodovization agent in the preparation process of TPV, can effectively remove the low molecular weight volatile thing produced because of extrusion reaction, reduces the smell problem of even eliminating product.
3, the preparation method of modification TPV of the present invention is simple to operate, and materials procurement is easy, is convenient to implement industrialization.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Raw-material melt flow index (MI) in embodiment and Comparative Examples records under 230 ℃, load 2.16Kg condition.
Embodiment 1: with the preparation of the Overmolded low-odor thermoplastic vulcanized rubber of ABS base material secondary
(1) massfraction of each component is as follows:
(2) its preparation method is:
The preparation method of deodovization agent: by the carrier expanded polyolefin be placed in pressure for-0.06MPa～-encloses container of 0.1MPa, then with syringe, the metering of hexanaphthene volatile components is injected in encloses container, wherein the weight ratio of carrier and volatile components is 1:2, standing 10～30min, make deodovization agent.
First polyolefine, rubber components, rubber plastic agent, polyester thermoplastic elastomer, filler, oxidation inhibitor and processing aid are put in Banbury mixer, mixing 10～30min under 150～180 ℃, then extruding pelletization, prepare TPV raw material one step material; One step material premix together with peroxide crosslinking initiator, additional crosslinker, deodovization agent that will make again is even, finally puts in twin-screw extrusion equipment, and 190～230 ℃ of lower extrusion reactions obtain the low smell TPV Overmolded with ABS base material secondary.The correlated performance of this material is in Table 1, and in table, smell experiment and smell are judged the PV3900 standard of grade execution Volkswagen.Below the smell of all embodiment and Comparative Examples judge this standard of all carrying out.
Embodiment 2: with the preparation of the Overmolded low-odor thermoplastic vulcanized rubber of ABS base material secondary
(1) massfraction of each component is as follows:
(2) its preparation method is:
The preparation method of deodovization agent: by the carrier hollow glass micropearl be placed in pressure for-0.06MPa～-encloses container of 0.1MPa, then with syringe, the metering of 5# white oil volatile components is injected in encloses container, wherein the weight ratio of carrier and volatile components is 1:1, standing 10～30min, make deodovization agent.
First polyolefine, rubber components, rubber plastic agent, polyester thermoplastic elastomer, filler, oxidation inhibitor and processing aid are put in Banbury mixer, mixing 10～30min under 150～180 ℃, then extruding pelletization, prepare TPV raw material one step material; One step material premix together with peroxide crosslinking initiator, additional crosslinker, deodovization agent that will make again is even, finally put in twin-screw extrusion equipment, 190～230 ℃ of lower extrusion reactions obtain the low smell TPV Overmolded with ABS base material secondary, and the correlated performance of this material is in Table 1.
Embodiment 3: with the preparation of the Overmolded low-odor thermoplastic vulcanized rubber of ABS base material secondary
(1) massfraction of each component is as follows:
(2) its preparation method is:
The preparation method of deodovization agent: by carrier foamed thermoplastic vulcanized rubber be placed in pressure for-0.06MPa～-encloses container of 0.1MPa, then with syringe, the metering of acetone volatile components is injected in encloses container, wherein the weight ratio of carrier and volatile components is 1:3, standing 10～30min, make deodovization agent.
First polyolefine, rubber components, rubber plastic agent, polyester thermoplastic elastomer, filler, oxidation inhibitor and processing aid are put in Banbury mixer, mixing 10～30min under 150～180 ℃, then extruding pelletization, prepare TPV raw material one step material; One step material premix together with peroxide crosslinking initiator, additional crosslinker, deodovization agent that will make again is even, finally put in twin-screw extrusion equipment, 190～230 ℃ of lower extrusion reactions obtain the low smell TPV Overmolded with ABS base material secondary, and the correlated performance of this material is in Table 1.
Embodiment 4: with the preparation of the Overmolded low-odor thermoplastic vulcanized rubber of ABS base material secondary
The massfraction of each component is as follows:
Its preparation method is with embodiment 3, and the correlated performance of resulting TPV is in Table 1.
Embodiment 5: with the preparation of the Overmolded low-odor thermoplastic vulcanized rubber of ABS base material secondary
The massfraction of each component is as follows:
Its preparation method is with embodiment 3, and the correlated performance of resulting TPV is in Table 1.
Embodiment 6: Comparative Examples 1
(1) massfraction of each component is as follows:
(2) its preparation method is: will first polyolefine, rubber components, rubber plastic agent, filler, oxidation inhibitor and processing aid be put in mixing facilities, mixing 10～30min under 150～180 ℃, prepare TPV raw material one step material; Again that step material premix together with peroxide crosslinking initiator, additional crosslinker is even, then put into and melt extrude in equipment, extrusion reaction occurs under 190～230 ℃ obtain general purpose grade TPV.The correlated performance of this material is in Table 1.
Embodiment 7: Comparative Examples 2
(1) massfraction of each component is as follows:
General purpose grade TPV 69.8%
Thermoplastic polyester elastomer 20%
Maleic anhydride graft PP 10%
Oxidation inhibitor (1010/168=1:1; Weight ratio) 0.2%
(2) its preparation method is: general purpose grade TPV obtains by feed composition mass percent and the preparation technology of Comparative Examples 1.And then TPV is mixed with maleic anhydride inoculated polypropylene, thermoplastic polyester elastomer, oxidation inhibitor, extruding pelletization in twin screw extruder, finally obtain product; The processing temperature of material in forcing machine is 190～230 ℃.Resulting modification TPV correlated performance is in Table 1.
Embodiment 8: Comparative Examples 3
(1) massfraction of each component is as follows:
General purpose grade TPV 69.8%
Polyurethane Thermoplastic Elastomer 20%
Maleic anhydride graft PP(BONDYRAM1001CN, Puli is bright) 10%
Oxidation inhibitor (1010/168=1:1; Weight ratio) 0.2%
Its preparation method is with Comparative Examples 2, and resulting modification TPV correlated performance is in Table 1.
Embodiment 9: Comparative Examples 4
(1) massfraction of each component is as follows:
General purpose grade TPV 69.8%
SEBS grafted maleic anhydride (M1913, Asahi Chemical Industry) 20%
Maleic anhydride graft PP 10%
Oxidation inhibitor (1010/168=1:1; Weight ratio) 0.2%
Its preparation method is with Comparative Examples 2, and resulting modification TPV correlated performance is in Table 1.
The performance index of table 1 low-odor thermoplastic vulcanized rubber
As can be seen from Table 1, the general T PV in Comparative Examples 1 and ABS matrix polarity, consistency differ greatly, and between bi-material, the interface bonding strength is very weak; Added respectively 20% thermoplastic polyester elastomer, Polyurethane Thermoplastic Elastomer, the SEBS grafted maleic anhydride compatilizer as TPV and base material ABS in Comparative Examples 2,3,4.Although add above-mentioned compatilizer can improve to a certain extent the interface cohesive force of TPV and ABS base material; But because polarity and the consistency of itself and TPV differs greatly, the material that two kinds of simple melt blendings of process prepare can the serious demixing phenomenons of product, affect mechanical property and the bonding strength of TPV material.
With each Comparative Examples, compare, low smell TPV of the present invention, owing to having added deodovization agent in preparation process, can effectively alleviate the low molecular weight volatile thing of TPV, makes the thermoplasticity cross-linked rubber be more suitable for being applied to Voc is had the field of strict demand.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (10)
1. a low smell TPV Overmolded with ABS base material secondary is characterized in that the component that comprises following massfraction:
2. the Overmolded low smell TPV of according to claim 1 and ABS base material secondary, it is characterized in that: described deodovization agent is the masterbatch that is rich in the lower boiling fugitive constituent, carrier and volatile components, consists of.
3. the Overmolded low smell TPV of according to claim 2 and ABS base material secondary, it is characterized in that: described carrier has the Spatial Multi-Dimensional vesicular structure, and its micropore is half opening or open structure, and pore size is 1～100nm; Described volatile components refers to that boiling point under the room temperature normal pressure is lower than the organic or inorganic liquid of 180 ℃.
4. the Overmolded low smell TPV of according to claim 2 and ABS base material secondary, it is characterized in that: described carrier refers at least one in zeolite, molecular sieve, hollow glass micropearl, carbon black, cinder powder, diatomite, porous alumina, expanded polyolefin, expanded polyester and foamed thermoplastic elastomers, foamed thermoplastic vulcanized rubber; Described volatile components refers at least one in alcohols, ketone, alkanes, cycloalkane, water, white oil, rubber filling oil, fluidizer, solvent oil and silicone oil.
5. the Overmolded low smell TPV of according to claim 1 and ABS base material secondary, it is characterized in that: described deodovization agent is prepared by following methods: carrier is placed in to the negative pressure encloses container, inject volatile components, standing 10～30min, make deodovization agent; The weight ratio of used carrier and volatile components is 1:(0.01～10).
6. the Overmolded low smell TPV of according to claim 1 and ABS base material secondary, it is characterized in that: described polyolefine refers at least one in Co-polypropylene, homo-polypropylene, high density polyethylene(HDPE), Low Density Polyethylene, LLDPE and POE; Described rubber components refers at least one in ethylene propylene rubber, terpolymer EP rubber, natural rubber, paracril and acrylic elastomer; Described rubber plastic agent refers at least one in paraffin oil, naphthenic oil and hydrocarbon oil; Described polyester thermoplastic elastomer refers at least one in thermoplastic polyurethane and thermoplastic polyester; Described peroxide crosslinking initiator refers to the material that contains peroxy-radical; Described additional crosslinker refers to the material that contains many unsaturated link(age)s; Described filler refers at least one in wollastonite, kaolin, diatomite, calcium carbonate, talcum powder, barium sulfate and mica; Described oxidation inhibitor is comprised of primary antioxidant and auxiliary antioxidant.
7. the Overmolded low smell TPV of according to claim 1 and ABS base material secondary, it is characterized in that: described polyolefinic melt flow rate (MFR) is 0.5～20g/10min; Described peroxide crosslinking initiator refers to 2,5-dimethyl-2,5-bis(t-butylperoxy) hexin, 2,5-dimethyl-2, at least one in 5-bis(t-butylperoxy) hexane and dicumyl peroxide; Described additional crosslinker refers at least one in polyester material, polybutadiene material, cyanate material, isocyanates material and esters of acrylic acid material; Described oxidation inhibitor refers at least one in 2,6 di tert butyl 4 methyl phenol, antioxidant 1010, antioxidant 1076, oxidation inhibitor 1790, irgasfos 168 and oxidation inhibitor 626.
8. the preparation method of and ABS base material secondary Overmolded low smell TPV described according to claim 1～7 any one is characterized in that comprising following concrete steps:
First that polyolefine, rubber components, rubber plastic agent, polyester thermoplastic elastomer, filler and oxidation inhibitor is mixing, obtain a step material; A step material, peroxide crosslinking initiator, additional crosslinker and deodovization agent blend, extrude, obtain the low smell TPV Overmolded with ABS base material secondary;
Wherein, each constituent mass mark is as follows:
9. the preparation method of the Overmolded low smell TPV of according to claim 8 and ABS base material secondary, it is characterized in that: described mixing finger is at 150～180 ℃ of mixing 10～30min; Described extruding can be carried out in single screw extrusion machine, twin screw extruder, Banbury mixer or Double-rotor continuous mixing equipment; Described each section temperature of extruding is 180～230 ℃, and rotating speed is 200～500rpm.
10. according to the described application in Overmolded with the Overmolded low smell TPV of ABS base material secondary and ABS secondary of claim 1～7 any one.
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