CN109535631A - Block copolymer composition - Google Patents

Block copolymer composition Download PDF

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Publication number
CN109535631A
CN109535631A CN201811050855.XA CN201811050855A CN109535631A CN 109535631 A CN109535631 A CN 109535631A CN 201811050855 A CN201811050855 A CN 201811050855A CN 109535631 A CN109535631 A CN 109535631A
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block copolymer
block
composition
weight
aromatic vinyl
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CN109535631B (en
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石井雄太
桥本贞治
小田亮二
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Zeon Corp
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Nippon Zeon Co Ltd
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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
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Adhesive Tapes (AREA)
  • Artificial Filaments (AREA)

Abstract

The present invention provides a kind of low viscosity and resistance to blocking and the excellent block copolymer composition of bonding characteristic.Block copolymer composition of the invention is characterized in that, contain block copolymer, above-mentioned block copolymer has at least one aromatic vinyl polymer block and at least one conjugated diolefin polymer block, the melt index of above-mentioned block copolymer is 20g/10 minutes or more, and above-mentioned block copolymer composition contains the water soluble surfactant active of 0.02~3.00 weight %.

Description

Block copolymer composition
Technical field
The present invention relates to the block copolymer composition comprising block copolymer, above-mentioned block copolymer has aromatic series second Alkenyl polymer block and conjugated diolefin polymer block, more particularly it relates to low viscosity and resistance to blocking and The excellent block copolymer composition of bonding characteristic.
Background technique
Styrene-isoprene-styrene block copolymer (SIS), Styrene-Butadiene-Styrene Block Copolymer (SBS) etc. the block copolymer with aromatic vinyl polymer block and conjugated diolefin polymer block is that have in all respects There is the thermoplastic elastomer (TPE) of characteristic properties, therefore can be used for various uses.
But the block copolymer with aromatic vinyl polymer block and conjugated diolefin polymer block is due to it Itself there is caking property, therefore exist and be easy to generate adhesion such problems.By block copolymer be molded into such as graininess, It is membranaceous and in the case where being processed, it becomes difficult to handled.
In order to overcome the problem, the technical solution of addition antiblocking agent is proposed.But the improvement of resistance to blocking is difficult to It is adequately, to need further to improve.
Moreover, being wanted for the block copolymer with aromatic vinyl polymer block and conjugated diolefin polymer block The bonding characteristics such as cohesive force, retentivity, initial bonding strength (tack) are sought, the various spies such as flexibility, processability, thermal stability are also required Property.In order to meet these requirements, the structure of block copolymer, composition are conducted extensive research.One of them be exactly make it is embedding Section copolymer becomes the means of the block copolymer of low viscosity.But in the case where block copolymer is low viscosity, especially The problem of adhesion, becomes significant.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2004-155851 bulletin；
Patent document 2: Japanese Unexamined Patent Publication 9-235316 bulletin.
Summary of the invention
Problems to be solved by the invention
Research is repeated in the inventors of the present invention to solve the above-mentioned problems, has been conceived to water soluble surfactant active.Separately Outside, water soluble surfactant active is known as documented by such as patent document 1 and 2, is used as when manufacturing block copolymer Dispersing agent.Moreover, the inventors of the present invention have further been repeated the study found that although water soluble surfactant active, which has, inhibits viscous Effect even, but when a large amount of additions, bonding characteristic decline.
The purpose of the present invention is to provide low viscosity and the excellent block copolymer combinations of resistance to blocking and bonding characteristic Object.
The solution to the problem
The inventors of the present invention have made intensive studies to achieve the goals above, as a result, it has been found that, with aromatic vinyl In the case that based polyalcohol block and the block copolymer of conjugated diolefin polymer block are low viscosity, cooperate the water-soluble of specified amount Property surfactant, can inhibit adhesion as a result, and can be well maintained bonding characteristic.In addition, though in such as patent document 1 Surfactant is added when manufacturing block copolymer as dispersing agent with disclosing in patent document 2, but is not prescribed by and is included Amount of surfactant in the block copolymer composition of block copolymer.The present invention is completed based on above-mentioned opinion.
Like this, according to the present invention, it is possible to provide a kind of block copolymer composition, which is characterized in that contain block copolymerization Object, above-mentioned block copolymer have at least one aromatic vinyl polymer block and at least one conjugated diolefin polymer embedding Section, the melt index of above-mentioned block copolymer are 20g/10 minutes or more, above-mentioned block copolymer composition contains 0.02~ The water soluble surfactant active of 3.00 weight %.
, according to the invention it is preferred to which the melt index of above-mentioned block copolymer is 30g/10 minutes or more.
Furthermore according to the present invention, it is preferred to the content of above-mentioned water soluble surfactant active is 0.10~2.50 weight %, it is more excellent It is selected as 0.12~2.00 weight %, further preferably 0.15~1.50 weight %.
According to the present invention, it is possible to provide the adhesive composite containing above-mentioned block copolymer composition.
According to the present invention, it is possible to provide the retractility film containing above-mentioned block copolymer composition.
According to the present invention, it is possible to provide the elastomer containing above-mentioned block copolymer composition.
According to the present invention, it is possible to provide the flexographic plate composition containing above-mentioned block copolymer composition.
Invention effect
In accordance with the invention it is possible to obtain low viscosity and resistance to blocking and the excellent block copolymer combinations of bonding characteristic Object.
Specific embodiment
Hereinafter, to block copolymer composition of the invention and using its adhesive composite, retractility film, bullet Property fiber and flexographic plate are illustrated with composition.
A. block copolymer composition
Block copolymer composition of the invention contains block copolymer, and above-mentioned block copolymer has at least one fragrance Race's polyvinyl block and at least one conjugated diolefin polymer block, the melt index of above-mentioned block copolymer are 20g/ 10 minutes or more, above-mentioned block copolymer composition contained the water soluble surfactant active of 0.02~3.00 weight %.
In the present invention, have at least one aromatic vinyl polymer block and at least one conjugated diolefin polymer embedding The melt index of the block copolymer of section is 20g/10 minutes or more, is low viscosity, it is therefore possible to be easy to cause adhesion, but It is, by so as to inhibit adhesion, also, passing through soluble surface containing water soluble surfactant active more than specified amount The content of activating agent is specified amount hereinafter, so as to be well maintained bonding characteristic.
1. block copolymer
Block copolymer used in the present invention is (hereinafter, sometimes referred to as " block copolymer (I) ".) there is at least one virtue Fragrant race's polyvinyl block and at least one conjugated diolefin polymer block, above-mentioned aromatic vinyl polymer block are It is constituted with the main repetitive unit of aromatic vinyl monomer unit obtained from polymerizeing aromatic vinyl monomer, It is main that above-mentioned conjugated diolefin polymer block, which is with conjugated diene monomeric unit obtained from polymerizeing conjugate diene monomer, Repetitive unit and constitute.Block copolymer (I) can be used as the component of polymer of block copolymer composition of the invention.
In addition, in the present specification, as long as no other explanation, " block copolymer " refer to comprising pure block copolymer, Any form in statistic copolymer and copolymer with tapered block structure.
(1) aromatic vinyl polymer block
Aromatic vinyl polymer block possessed by block copolymer (I) is so that aromatic vinyl monomer to polymerize Obtained from aromatic vinyl monomer unit be main repetitive unit and the polymer blocks that constitute.
Aromatic vinyl monomer used in formation as aromatic vinyl polymer block, as long as aromatic series Vinyl compound is not particularly limited.It can enumerate for example: styrene；α-methylstyrene, 2-methyl styrene, 3- methyl Styrene, 4- methyl styrene, 2- ethyl styrene, 3- ethyl styrene, 4- ethyl styrene, 2,4- diisopropyl benzene second Alkene, 2,4- dimethyl styrene, 4- t-butyl styrene, 5- tert-butyl -2-methyl styrene etc. have alkyl as substituent group Phenylethylene；2- chlorostyrene, 3- chlorostyrene, 4- chlorostyrene, 4- bromstyrol, 2,4- Dowspray 9 etc. have halogen Phenylethylene of the atom as substituent group；2- methyl -4,6- dichlorostyrene etc. has alkyl and halogen atom as substituent group Phenylethylene；Vinyl naphthalene etc..These aromatic vinyl monomers can be used alone a kind or two or more is applied in combination.? In these, from the viewpoint of accessibility, optimization styrene, the phenylethylene with alkyl as substituent group are especially excellent Choosing uses styrene.
As long as aromatic vinyl polymer block with aromatic vinyl monomer unit be main repetitive unit, It may include the monomeric unit in addition to it.Aromatic vinyl is removed as what composition aromatic vinyl polymer block may include The monomer of monomeric unit other than base monomeric unit can be enumerated: 1,3-butadiene, isoprene (2- methyl-1,3- butadiene) Equiconjugate diene monomers；The 'alpha ', ' bela '-unsaturated nitriles monomer such as acrylonitrile, methacrylonitrile；Acrylic acid, methacrylic acid, maleic acid, The unsaturated carboxylic acid monomers such as fumaric acid, itaconic acid；Maleic anhydride, butenylsuccinic anhydride, tetrabydrophthalic anhydride, citraconic acid The unsaturated carboxylic acid anhydrides such as acid anhydride；Methyl acrylate, ethyl acrylate, acrylic acid-2-ethyl caproite, methyl methacrylate, methyl The unsaturated carboxylic acids ester monomers such as ethyl acrylate, methacrylic acid -2- ethylhexyl；1,4- pentadiene, 1,4- hexadiene etc. are excellent Selecting carbon atom number is 5~12 non-conjugated diene monomers etc..
In addition, in the case where block copolymer (I) has multiple aromatic vinyl polymer blocks, multiple aromatic series Polyvinyl block may be the same or different each other.
Aromatic vinyl monomer unit does not limit especially relative to the content of whole monomeric units of block copolymer (I) It is fixed, it usually selects in the range of 10~70 weight %, is preferably selected in the range of 12~60 weight %.As block copolymer (I) In the content of aromatic vinyl monomer unit when being in such range, bonding characteristic and mouldability can be made excellent.Separately Outside, the content of the aromatic vinyl monomer unit in block copolymer is able to use1H NMR is measured.
(2) conjugated diolefin polymer block
Conjugated diolefin polymer block possessed by block copolymer (I) be conjugate diene monomer to be polymerize obtained from The polymer blocks that conjugated diene monomeric unit is constituted for main repetitive unit.
The content of conjugated diene monomeric unit in conjugated diolefin polymer block is preferably 80 weight % or more, more preferably For 90 weight % or more, particularly preferably substantial 100 weight %.When the conjugate diene monomer in conjugated diolefin polymer block When the content of unit is in such range, bonding characteristic can be made excellent.
Conjugate diene monomer used in the formation of conjugated diolefin polymer block does not have as long as conjugated diene compound It is particularly limited to.Such as 1,3- butadiene, isoprene, 2,3- dimethyl -1,3- butadiene, the chloro- 1,3- fourth of 2- can be illustrated Diene, 1,3- pentadiene, 1,3- hexadiene etc..These conjugate diene monomers can be used alone a kind or make two or more combination With., it is preferable to use 1,3-butadiene and/or isoprene, particularly preferably use isoprene in these.By with isoamyl two Alkene unit constitutes conjugated diolefin polymer block, so as to keep bonding characteristic and flexibility excellent.
As long as conjugated diolefin polymer block, for main repetitive unit, also may include with conjugated diene monomeric unit Monomeric unit in addition to it.As constitute conjugated diolefin polymer block may include in addition to conjugated diene monomeric unit The monomer of monomeric unit can illustrate: the aromatic vinyl monomers such as styrene, α-methylstyrene；'alpha ', ' bela '-unsaturated nitrile monomer； Unsaturated carboxylic acid monomer；Unsaturated carboxylic acid anhydrides；Unsaturated carboxylic acid ester monomer；Non-conjugated diene monomers etc..In addition, β-is no about α It is saturated nitrile monomer, unsaturated carboxylic acid monomer, unsaturated carboxylic acid anhydrides, unsaturated carboxylic acid ester monomer and non-conjugated diene monomers, energy The unit in addition to aromatic vinyl monomer unit that enough aromatic vinyl polymer blocks above-mentioned with composition may include The monomer of unit is similarly set.
In addition, in the case where block copolymer (I) has multiple conjugated diolefin polymer blocks, multiple conjugated-diolefin (co) polymers Close object block can be the same or different each other.In turn, a part of the unsaturated bond of conjugated diolefin polymer block can be with It is hydrogenated.
Vinyl bond content (whole conjugated dienes in conjugated diolefin polymer block of conjugated diolefin polymer block In monomeric unit, 1,2- vinyl bonds and 3, ratio shared by 4- vinyl bonds) it is not particularly limited, preferably 1~20 rubs You are %, more preferably 2~15 moles of %, particularly preferably 3~10 moles of %.When the vinyl bond content is excessively high, obtain The bonding characteristic of block copolymer composition is possible to be deteriorated.In addition, the vinyl bond content energy of conjugated diolefin polymer block It is enough to use1H NMR is measured.
(3) block copolymer
Block copolymer (I) is as long as have at least one aromatic vinyl polymer block and at least one conjugated-diolefin (co) polymer Object block is closed, then the number of respective polymer blocks, respective combination are just not particularly limited.
The specific example of form as block copolymer (I) indicates aromatic vinyl polymer block, D table in Ar In the case where showing the integer that conjugated diolefin polymer block, X indicate that the residue of singly-bound or coupling agent, n indicate 2 or more, Neng Gouju Aromatic ethenyl-conjugated diene block copolymer for being indicated out with Ar-D, with Ar-D-Ar or (Ar-D)nThe fragrance that-X is indicated Race's vinyl-conjugated diene-aromatic vinyl group block copolymer, with D-Ar-D or (D-Ar)nConjugated diene-virtue that-X is indicated Fragrant race's vinyl-conjugated diene block copolymer, the aromatic ethenyl-conjugated diene-aromatic series second indicated with Ar-D-Ar-D Alkenyl-conjugated diene block copolymer and by their two or more block copolymer mixed in any combination Mixture, but it is not limited to these.
In these, as present invention preferably uses block copolymer (I), the aromatic series indicated with Ar-D can be enumerated Vinyl-conjugated diene block copolymer, with Ar-D-Ar or (Ar-D)nAromatic ethenyl-conjugated diene-virtue that-X is indicated Fragrant race's vinyl block copolymer and their mixture.Particularly preferably use above-mentioned aromatic ethenyl-conjugated diene-virtue Fragrant race's vinyl block copolymer or above-mentioned aromatic ethenyl-conjugated diene-aromatic vinyl group block copolymer and above-mentioned Aromatic ethenyl-conjugated diene block copolymer mixture.
Aromatic ethenyl-conjugated diene-aromatic vinyl the group block copolymer indicated with Ar-D-Ar is with 2 The block copolymer of aromatic vinyl polymer block.In the block copolymer, 2 aromatic vinyl polymer blocks Weight average molecular weight may be the same or different.That is, can be with the block copolymer that Ar-D-Ar is indicated with defined The aromatic vinyl polymer block of weight average molecular weight, conjugated diolefin polymer block and there is defined weight average molecular weight Aromatic vinyl polymer block be sequentially connected and symmetrical aromatic ethenyl-conjugated diene-aromatic series second for constituting Alkenyl block copolymer is also possible to have the aromatic vinyl polymer block of lesser weight average molecular weight, conjugated diene Polymer blocks and aromatic vinyl polymer block with biggish weight average molecular weight are sequentially connected and constitute non- Symmetrical aromatic ethenyl-conjugated diene-aromatic vinyl group block copolymer.
In addition, with (Ar-D)nAromatic ethenyl-conjugated diene-aromatic vinyl group block copolymer that-X is indicated is 2 The diblock body that a above aromatic vinyl polymer block and conjugated diolefin polymer block are combined into directly passes through list Key or via coupling agent residue and combine to constitute block copolymer.In addition, the idol about the residue for constituting coupling agent It is as described later to join agent.In conjunction with diblock body (Ar-D) number (that is, n) as long as being not particularly limited for 2 or more, with difference The block copolymer of number combination diblock body can be mixed.As long as n is that 2 or more integers are not particularly limited, lead to It is often 2~8 integer, preferably 2~4 integer.
The weight average molecular weight of block copolymer (I) is not particularly limited, and usually 30000~500000, preferably 35000 ~400000, more preferably 40000~250000.
In addition, the weight average molecular weight of each polymer blocks of block copolymer (I) is not particularly limited, aromatic vinyl The weight average molecular weight of based polyalcohol block is usually 6000~400000, and preferably 6000~370000.Work as aromatic ethenyl When the weight average molecular weight of polymer blocks is too small, bonding characteristic is poor sometimes, when dividing equally for aromatic vinyl polymer block again When son amount is excessive, viscosity is got higher sometimes, and the manufacture of block copolymer (I) becomes difficult sometimes.
In addition, the weight average molecular weight of conjugated diolefin polymer block is usually 18000~400000, preferably 19000~ 350000.When the weight average molecular weight of conjugated diolefin polymer block is too small, bonding characteristic is poor sometimes, works as conjugated diolefin polymer When the weight average molecular weight of block is excessive, viscosity is got higher sometimes.
Block copolymer (I) and constitute block copolymer (I) each polymer blocks use weight average molecular weight (Mw) and The molecular weight distribution that the ratio (Mw/Mn) of number-average molecular weight (Mn) indicates is not particularly limited, be generally each 1.1 hereinafter, it is preferred that It is 1.05 or less.When the molecular weight distribution of block copolymer (I) and each polymer blocks for constituting block copolymer (I) is in When such range, bonding characteristic can be made excellent.
In addition, the weight average molecular weight and number-average molecular weight of block copolymer, polymer blocks are based on utilizing high-efficient liquid phase color Spectrometry measurement polystyrene conversion value and acquire.More specifically, the measurement of weight average molecular weight and number-average molecular weight can Using the tetrahydrofuran for being 0.35ml/ minutes using flow velocity as the high performance liquid chromatography of carrier as polystyrene convert molecular weight And it acquires.Device is able to use TOSOH CORPORATION HLC8320, column is able to use 3 Showa electrician's corporations Column that Shodex KF-404HQ links (column temperature is 40 DEG C), detector are able to use differential refractometer and UV detector, 12 of the standard polystyren (500 to 3,000,000) that the correction of molecular weight can be manufactured in Polymer Laboratory company Point is implemented.
Block copolymer (I) can be manufactured conventionally.As manufacturing method most commonly, it can enumerate: pass through Living anion polymerization method, respectively successively polymerizable aromatic race vinyl monomer and conjugate diene monomer and form polymer blocks, It is set to react the method being coupled with coupling agent as needed.
For example, block copolymer (I) can be manufactured by following process: being formed in a solvent using polymerization initiator The process (a) of block copolymer (I), and the process of the recycling of the solution obtained in the above-mentioned operation (a) block copolymer (I) (b).The details of reaction can be with reference to Japanese Unexamined Patent Publication 10-17611 bulletin etc..
In process (a), firstly, using polymerization initiator in a solvent, formed block copolymer (I).
As the polymerization initiator used, it is able to use usually to known to aromatic vinyl monomer and conjugate diene monomer There is Anionic Polymerization Living polymerization initiator, such as organic alkali metal compound can be enumerated, organic alkaline earth metal compound, had Machine group of the lanthanides column rare earth compound etc..Polymerization initiator can separately be applied in combination using or by two or more.
Polymerization reaction carries out in the hydrocarbon system solvent for not destroying polymerization initiator.As hydrocarbon system solvent appropriate, as long as Workable hydrocarbon system solvent is not particularly limited in common polymerisation in solution, can enumerate such as aliphatic hydrocarbon series solvent, rouge Ring type hydrocarbon system solvent, aromatic hydrocarbon series solvent etc..In addition it is also possible to the unsaturated hydrocarbons series solvent for using polymerism low as needed Deng.These hydrocarbon system solvents may be used alone or two or more is applied in combination.
In the present invention, in order to carry out conjugated diolefin polymer block microstructure adjusting and initiation reaction speed Degree, adjusting of polymerization rate etc., can add lewis base compound etc..As lewis base compound etc., can enumerate Such as ethers, amine, amides, alkali metal alcohol salt, thioether class etc..These lewis base compounds can separately make It is applied in combination with or by two or more.
Polymerization reaction can suitably be selected according to the purposes of block copolymer composition.For example, polymerization temperature is usually -20 DEG C In the range of~+150 DEG C, in the range of preferably 30 DEG C~120 DEG C.In addition, polymerization time according to conditions such as polymerization temperatures and Difference, usually in 24 hours, in the range of preferably 1~10 hour.Pressure is selected from the range solvent in above-mentioned polymerization temperature The range that liquid phase can be maintained with monomer, is not particularly limited.
Terminal-modified dose, coupling agent or the processing for adding hydrogen etc. can be carried out after above-mentioned polymerization reaction.
As terminal-modified dose, such as ketone, aldehydes, epoxies, carbodiimide class, Schiff (schiff) alkali can be enumerated Class, N- non-substituted aziridine cpd, N substituted amide class, N- substituted urea class, N- substituted-amino ketone, N- substituted-amino aldehyde Class etc..
It can be according to such as Japanese Unexamined Patent Application 58-162604 bulletin, Japanese Unexamined Patent Application using terminal-modified dose of processing Disclosed in 60-137913 bulletin, Japanese Unexamined Patent Application 62-86074 bulletin, Japanese Unexamined Patent Application 62-119257 bulletin etc. Method carries out.
As coupling agent, as long as multi-functional coupling agent, can enumerate for example: tin system coupling agent, silicon systems coupling Agent, metal halide system coupling agent, unsaturated nitrile system coupling agent, halogenation hydrocarbon system coupling agent, ester system coupling agent, halogenation coupling agent etc.. In addition, the compound with 2 or more radically polymerizable groups group in molecule also can be used as multi-functional coupling agent. As the compound with 2 or more radically polymerizable groups group in molecule, can enumerate for example: divinylbenzene, divinyl The aromatic diethylenes base chemical combination such as base toluene, divinylxylene, divinyl anthracene, divinyl naphthalene, divinyl durene Aromatic series tetravinyl compounds such as the aromatic series trivinyl such as object, trivinylbenzene compound, tetravinyl benzene etc. have 2 The free-radical polymerised aromatic compound of above radically polymerizable group group and aromatic ring；Pentaerythritol tetraacrylate etc. Free-radical polymerised aliphatic compound etc. with 2 or more radically polymerizable groups groups and aliphatic group.These couplings Agent can be used alone, two or more can also be applied in combination.
It can be according to Japanese Unexamined Patent Application 56-143209 bulletin, Japanese Unexamined Patent Application 56-17362 using the processing of coupling agent Number bulletin, Japanese Unexamined Patent Application 57-55912 bulletin, Japanese Unexamined Patent Application 58-162605 bulletin, Japanese Unexamined Patent Application 64-81844 Method disclosed in number No. 2017/057049 bulletin, International Publication No. separate edition etc. carries out.
As catalyst used in hydrogenation reaction, such as metal can be used to support the loaded heterogeneous catalysis in carrier Homogeneous catalysts such as agent, Ziegler-type catalyst, organic coordination compounds etc..
Hydrotreating can according to such as Japanese Patent Publication 42-8704 bulletin, Japanese Patent Publication 43-6636 bulletin, Method disclosed in Japanese Unexamined Patent Application 59-133203 bulletin, Japanese Unexamined Patent Application 60-220147 bulletin etc. carries out.
Furthermore it is possible to add polymerization terminator in the solution after above-mentioned polymerization reaction.As polymerization terminator, Neng Gouju Out for example: water；The alcohols such as methanol, ethyl alcohol, propyl alcohol, ethylene glycol, glycerol；The inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid；Acetic acid, third Organic acids such as acid, octanoic acid, capric acid, lauric acid, myristic acid, palmitinic acid, stearic acid, oleic acid, lactic acid, citric acid etc..These Polymerization terminator can use individually or two or more is applied in combination.
Then, in process (b), from the block copolymerization recycled by solution obtained from above-mentioned operation (a) as target Object (I).
As long as the method for recycling is conventionally, it is not particularly limited.For example, can be by obtained solution Using method well known to direct drying method, vaporizing extract process etc. to recycle block copolymer (I).It is further possible to by obtaining Solution the rear application direct drying method such as water soluble surfactant active, vaporizing extract process etc. is added as needed to as block copolymerization Object (I) recycling.
Such as when recycling block copolymer (I), in the case where adding water soluble surfactant active to obtained solution, The block copolymer composition containing block copolymer (I) and water soluble surfactant active can be efficiently obtained.In addition, about Water soluble surfactant active is as described later.
As steam stripped method is carried out in the presence of water soluble surfactant active, can enumerate for example: (1) in polymerization reaction Steam stripped method is carried out after addition water soluble surfactant active in solution afterwards, (2) dissolve water soluble surfactant active in advance In for steam stripped stripper aqueous solution, the method for contacting it with the solution after polymerization reaction etc..Usually carry out (2) makes water The method that soluble surfactants are dissolved in stripper aqueous solution.
Steam stripped method for example can for use arbitrary means the concentration of block copolymer (I) is adjusted to such as 10~ Temperature of the solution of the hydrocarbon system solvent of 50 weight % more than the boiling point of hydrocarbon system solvent or its azeotropic temperature with water is implemented.Pass through Stripping, block copolymer (I) are separated in the form of the granule for carrying out aqueous slurry, and aqueous granule uses vibrating screen first Net, centrifugal dehydrator etc. make moisture content become such as 30~60 weight % or so, and then squeeze out dewaterer etc. using screw and take off Water dispenser is dehydrated until moisture content is such as 5~30 weight % or so.Using heated air drier, squeeze out drying machine, expansion The drying machines such as type drying machine, make the granule through being dehydrated moisture content become be, for example, less than 5 weight %, preferably become 3 weight % with Under.
The method of convection drying concentration of defined block copolymer (I) as obtained from making to carry out as described above The solution of hydrocarbon system solvent is added dropwise on the roller of the temperature more than the boiling point for being heated to hydrocarbon system solvent and evaporates solvent or by making Drying machine etc. is squeezed out with the twin shaft with band and removes solvent, to obtain desolvated block copolymer (I).
In addition, (hereinafter referred to as embedding for the mixture of two or more block copolymer as described above in block copolymer (I) Section copolymer mixture.) in the case where, the method for obtaining block copolymer mixture is not particularly limited, can be according to existing The manufacturing method of block copolymer manufactured.
In addition, being such as 2 aromatic vinyl polymers comprising being indicated with Ar-D-Ar in block copolymer mixture The different asymmetrical aromatic ethenyl-conjugated diene-aromatic vinyl group block copolymer of the weight average molecular weight of block (with Under, referred to as block copolymer a.) and with the weight average molecular weight of the Ar-D-Ar 2 aromatic vinyl polymer blocks indicated Identical symmetrical aromatic ethenyl-conjugated diene-aromatic vinyl group block copolymer (hereinafter referred to as block copolymer b1.) mixture in the case where, in block copolymer mixture be comprising block copolymer a and with (Ar-D)nWhat-X was indicated Aromatic ethenyl-conjugated diene-aromatic vinyl group block copolymer (hereinafter referred to as block copolymer b2.) mixture In the case where, block copolymer mixture can also be manufactured by method described below.The details of reaction can refer to No. 2009/123089 separate edition of International Publication No., Japanese Unexamined Patent Publication 2012-77158 bulletin, International Publication No. 2015/099163 Number separate edition etc..
In the case where block copolymer mixture is the mixture comprising block copolymer a and block copolymer b1, tool For body, it can be manufactured by the process of following (la)~(6a).
(1a): the process in a solvent being polymerize aromatic vinyl monomer using polymerization initiator
(2a): containing above-mentioned (1a) process obtained in active end aromatic vinyl polymer it is molten The process of conjugate diene monomer is added in liquid
(3a): aromatic ethenyl-conjugated diene of the active end obtained in the process containing above-mentioned (2a) The process of aromatic vinyl monomer is added in the solution of block copolymer
(4a): aromatic ethenyl-conjugated diene-of the active end obtained in the process containing above-mentioned (3a) In the solution of aromatic vinyl group block copolymer, to become poly- less than the amount addition of 1 molar equivalent relative to the reactive terminal Terminator is closed, the process for forming block copolymer b1
(5a): the aromatic series second of block copolymer b1 and active end obtained in the process containing above-mentioned (4a) Aromatic vinyl monomer is added in alkenyl-conjugated diene-aromatic vinyl group block copolymer solution, forms block copolymerization The process of object a
(6a): the process of the recycling block copolymer mixture of solution obtained in the process from above-mentioned (5a)
In process (1a), firstly, aromatic vinyl monomer is polymerize using polymerization initiator in a solvent.About poly- Initiator is closed, and it is described above identical.
Then, in process (2a), in the aromatic vinyl containing active end obtained in above-mentioned operation (1a) Conjugate diene monomer is added in the solution of based polyalcohol.By the addition of the conjugate diene monomer, so as in reactive terminal shape At conjugated diolefin polymer chain, aromatic ethenyl-conjugated diene block copolymer containing active end can be obtained Solution.At this moment the amount of the conjugate diene monomer used is according to the conjugation of block copolymer a and block copolymer b1 as target The weight average molecular weight of diene polymer block determines.
Then, in process (3a), in the aromatic vinyl containing active end obtained in above-mentioned operation (2a) Aromatic vinyl monomer is added in base-conjugated diene block copolymer solution.Pass through adding for the aromatic vinyl monomer Add, so as to form aromatic vinyl polymer chain in reactive terminal, the aromatic series second containing active end can be obtained Alkenyl-conjugated diene-aromatic vinyl group block copolymer solution.Obtained aromatic vinyl polymer chain constitutes work For the aromatic vinyl polymer block with biggish weight average molecular weight of the block copolymer a of target a part and The aromatic vinyl polymer block of block copolymer b1.Therefore, the amount of the aromatic vinyl monomer at this moment used according to The weight average molecular weight of their aromatic vinyl polymer block determines.
Then, in process (4a), in the aromatic vinyl containing active end obtained in above-mentioned operation (3a) In base-conjugated diene-aromatic vinyl group block copolymer solution, to become relative to the reactive end functional group less than 1 The amount of molar equivalent adds polymerization terminator.It is and described above identical about polymerization terminator.
When adding polymerization terminator in the solution, aromatic ethenyl-conjugated diene-aromatic series of active end The reactive terminal of a part in vinyl block copolymer loses activity, as a result, the reactive terminal is deactivated poly- Closing object becomes block copolymer b1.Then, the aromatic ethenyl-conjugation for the active end that do not reacted with polymerization terminator Remaining a part directly residual of diene aromatic vinyl block copolymer is in the solution.
Then, in process (5a), containing block copolymer b1 and active end obtained in above-mentioned operation (4a) Aromatic vinyl monomer is added in aromatic ethenyl-conjugated diene-aromatic vinyl group block copolymer solution at end.
When adding aromatic vinyl monomer in the solution, do not reacted with polymerization terminator and remaining active The aromatic series second of the active end side of aromatic ethenyl-conjugated diene-aromatic vinyl group block copolymer of end Alkenyl polymer chain, further polymerizable aromatic race vinyl monomer and extend aromatic vinyl polymer chain, it is thus obtained Aromatic ethenyl-conjugated diene-aromatic vinyl based triblock copolymer becomes block copolymer a.At this moment, extended fragrance The aromatic vinyl polymer with biggish weight average molecular weight that race's polyvinyl chain constitutes block copolymer a is embedding Section.Therefore, the amount of the aromatic vinyl monomer at this moment used can be in the aromatic vinyl polymer block before considering to extend Weight average molecular weight on the basis of, determined according to the weight average molecular weight as target of aromatic vinyl polymer block.
By the process, to form the asymmetrical aromatic ethenyl-conjugated diene-virtue for constituting block copolymer a Fragrant race's ethylene based triblock copolymer, as a result, the solution containing block copolymer a and block copolymer b1 can be obtained.
Then, in process (6a), from containing by block copolymer a and block copolymer b1 obtained from above-mentioned operation Solution recycle block copolymer mixture as target.It is same as the above-mentioned method about the method for recycling.
In addition, block copolymer mixture be include the mixture of block copolymer a and block copolymer b2 the case where Under, specifically, can be manufactured by the process of following (lb)~(5b).
(1b): the process in a solvent being polymerize aromatic vinyl monomer using polymerization initiator
(2b): in the solution of the aromatic vinyl polymer containing active end obtained in above-mentioned operation (1b) The process of middle addition conjugate diene monomer
(3b): embedding in aromatic ethenyl-conjugated diene containing active end obtained in above-mentioned operation (2b) In the solution of section copolymer, the coupling agent for becoming the amount less than 1 molar equivalent relative to the reactive end functional group is added, is formed The process of block copolymer b2
(4b): in the aromatic vinyl containing block copolymer b2 and active end obtained in above-mentioned operation (3b) In base-conjugated diene block copolymer solution, aromatic vinyl monomer is added, the process for forming block copolymer a
(5b): the process of the recycling block copolymer mixture of the solution obtained in above-mentioned operation (4b)
About process (1b) and process (2b), can be set in the same manner with above-mentioned process (1a) and process (2a) respectively.
Then, in process (3b), in the aromatic vinyl containing active end obtained in above-mentioned operation (2b) In base-conjugated diene block copolymer solution, to add relative to the reactive end functional group as the amount less than 1 molar equivalent Add coupling agent.It is and described above identical about coupling agent.
The amount of the coupling agent of addition can be according to the block copolymer a and block copolymer b2 for constituting block copolymer mixture Ratio determine, as long as the reactive end functional group relative to polymer becomes the amount less than 1 molar equivalent then without special It limits, usually becomes the range of 0.15~0.90 molar equivalent relative to the functional group of the reactive terminal coupling agent of polymer, Preferably become the range of 0.20~0.70 molar equivalent relative to the functional group of the reactive terminal coupling agent of polymer.
In aromatic ethenyl-conjugated diene block copolymer solution containing active end, with opposite Aromatic series second when the reactive end functional group becomes the amount addition coupling agent less than 1 molar equivalent, in active end In a part of copolymer in alkenyl-conjugated diene block copolymer, conjugated diolefin polymer block is each other via coupling agent Residue and combine, as a result, formed block copolymer mixture block copolymer b2.Then, the tool not reacted with coupling agent The remaining a part of aromatic ethenyl-conjugated diene block copolymer of active end is remained in unreacted state In solution.
Then, in process (4b), containing block copolymer b2 and active end obtained in above-mentioned operation (3b) Aromatic vinyl monomer is added in aromatic ethenyl-conjugated diene block copolymer solution at end.
When adding aromatic vinyl monomer in the solution, do not reacted and remaining active end with coupling agent Aromatic vinyl-conjugated diene block copolymer end can form aromatic vinyl polymer chain.The aromatic vinyl The aromatic vinyl polymer block with biggish weight average molecular weight of based polyalcohol chain composition block copolymer a.Therefore, At this moment the amount of the aromatic vinyl monomer used is determined according to the weight average molecular weight as target of the polymer blocks.
Then, in process (5b), from containing by block copolymer a and block copolymer b2 obtained from above-mentioned operation Solution recycle block copolymer mixture as target.It is same as the above-mentioned method about the method for recycling.
Block copolymer obtained from carrying out as above and block copolymer mixture can be processed conventionally At after grain shape etc. for using.
In addition, in the present invention, being also able to use commercially available block copolymer.It is able to use such as " Quintac (registration Trade mark) " (Nippon Zeon Co., Ltd.'s manufacture), " JSR-SIS (registered trademark) " (manufacture of JSR company), " Vector (registered trademark) " (manufacture of DEXCO polymers company), " Asaprene (registered trademark) " " Tufprene (registered trademark) " " Tuftec (registered trademark) " (Asahi Kasei Chemicals Corporation manufacture), " SEPTON (registered trademark) " (Kuraray Co., Ltd. company manufactures) etc..
(4) characteristic
The melt index of block copolymer (I) in the present invention be 20g/10 minutes or more, preferably 30g/10 minutes with On.It is low viscosity in the case where the melt index of block copolymer (I) is above range, is easy to cause adhesion, but the present invention Block copolymer composition by containing surfactant more than specified amount, so as to inhibit adhesion.In addition, block is total The upper limit of the melt index of polymers (I) is not particularly limited, and usually 2000g/10 minutes hereinafter, preferably 1500g/10 minutes Hereinafter, more preferably 1000g/10 minutes or less.
In addition, melt index is the value that is measured according to ASTM D-1238 (G condition, 200 DEG C, 5kg).
In addition, the glass transition temperature of the block copolymer (I) in the present invention is not particularly limited, preferably smaller than -40 ℃.Glass transition temperature by block copolymer (I) is above range, thus become the material being more rich in flexibility, In the case where such as adhesive composite is made, adhesion properties are good.Bonding characteristic especially in low temperature is excellent.In addition, The lower limit of the glass transition temperature of block copolymer (I) is not particularly limited, and usually -62 DEG C or more.
It is surveyed in addition, glass transition temperature is able to use differential scanning calorimetry (DSC) (DSC) with 10 DEG C/min of heating It is fixed.
2. water soluble surfactant active
Block copolymer composition of the invention is other than containing above-mentioned block copolymer (I), also containing water solubility Surfactant.
Water soluble surfactant active used in the present invention can be anionic surfactant, cationic system Any one of surfactant, amphoteric surfactant and nonionic surfactants.
It as anionic surfactant, can enumerate for example: fatty acid salt (RCOONa), fatty alcohol sulfate salt class (ROSO3Na), liquid aliphatic oil sulfuric ester salt [R (OSO3Na) COOR], the sulfate of aliphatic amine and aliphatic amide (RCONHR’CH2CH3OSO3Na), aliphatic alcohol phosphates [ROP (ONa)2], the Sulfonates of di-fatty acid esters [ROCOCH2-CH(SO3Na) COCOR '], fatty acid amide sulfonate class (RCONR ' CH2CH2SO3Na), polyoxyethylene base sulfonic acid Salt (R-Ph-SO3Na) etc..In addition, they can be used in the form of free acid.
In addition, it is able to use the anionic surfactant of polymer electrolyte as anionic surfactant, it can It enumerates for example: polycarboxylic acids and its esters；Based high molecular containing sulfonic acid and its salt；Carboxymethyl cellulose, sodium alginate, rosin soap etc. Other anionic property macromolecules.As polycarboxylic acids and its esters, the polymer and its esters of such as (methyl) acrylic acid can be enumerated； The polymer of the unsaturated dibasic acids such as maleic anhydride, maleic acid, fumaric acid, itaconic acid or with the copolymer of other monomers etc. or Its esters etc..It as based high molecular containing sulfonic acid, can enumerate for example: the formalin of lignin sulfonic acid, naphthalene (or alkylnaphthalene) sulfonic acid Condensation product, the formaline condensates of benzene (or alkylbenzene) sulfonic acid, creasote the fragrance such as formaline condensates of sulfonated bodies The formaline condensates of race's sulfonic acid；The polymer etc. of vinyl sulfonic acid.
In these anionic surfactants, preferably fatty alcohol sulfate salt class, polycarboxylic acid and their salt Deng particularly preferred fatty alcohol sulfate salt class, polycarboxylic acid salt etc..
These anionic surfactants can separately be applied in combination using or by two or more.
As cationic system surfactant, can be used for example: aliphatic amine salt [N (R1R2R3)·X]；Lauryl three The quaternary ammoniums such as ammonio methacrylate, stearyl trimethyl ammonium chloride, hexadecyltrimethylammonium chloride, VARISOFT TA100 Salt [N (R1R2R3R4)·X]；Alkyl pyridine salt；Polyoxyethylene alkyl amine salt；Imidazolidine derivatives etc..It is excellent in these Select quaternary ammonium salt.It is further possible to use polyvinylpyridine system polysoap, acrylic ester cationic active agent, polyacrylamide The cationics macromolecule such as amine system cationic active agent.These cationic system surfactants can separately use or Two or more is applied in combination.
As nonionic surfactants, can enumerate for example: ethyleneoxide propylenenoxide block polymer etc. two or more The block polycondensate of epoxyalkane；Make the higher alcohols such as epoxyalkane and laruyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol；Octyl The alkyl phenols such as phenol, isooctylphenol, nonyl phenol；And polyoxy made of the polymerization addition such as alkyl naphthols such as butyl naphthols, octyl naphthols Ethylene laurel ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyl 10 oleyl ether, NONIN HS 240, The polyoxyalkylene ethers based compounds such as ethylene nonyl phenyl ether, polyoxyethylene higher alcohol (C12~C14) ether；Make epoxyalkane It polymerize polyoxyethylene glycol mono laurate made of addition with higher fatty acids such as lauric acid, palmitinic acid, stearic acid, oleic acid etc. Ester, polyoxyethylene glycol monopalmitate, polyethylene glycol mono stearate, polyglycol distearate, polyethyleneglycol oil The polyoxyalkylene diols fatty acid ester based compound such as acid esters；As glycerol, pentaerythrite, sorbitan, mannitol acid anhydride, hexose The intramoleculars such as alcohol acid anhydride and their condensation polymer have the polyalcohol of 3 or more hydroxyls and the ester compounds of higher fatty acids Glycerin monostearate, glyceryl monooleate, Span-20, sorbitan monopalmitate, sorbose Alcohol acid anhydride monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, Sorbitan dioleate, mannitol acid anhydride monolaurate, mannitol acid anhydride monostearate, mannitol acid anhydride distearate, Mannitol acid anhydride monoleate, hexitan monolaurate, hexitan monopalmitate, hexitan monostearate, oneself The polyalcohols such as sugar alcohol acid anhydride distearate, hexitan tristearate, hexitan monoleate, hexitan dioleate It is fatty acid ester compound；Epoxyalkane is set to polymerize polyoxyethylene mountain made of addition with the polyalcohol system fatty acid ester compound Pears sugar alcohol acid anhydride monolaurate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitol acid anhydride distearate, Polyoxyethylene sorbitan monooleate, polyoxyethylene mannitol acid anhydride monopalmitate, polyoxyethylene mannitol acid anhydride list are stearic Acid esters, polyoxyethylene mannitol acid anhydride monoleate, polyoxyethylene hexitan monolaurate, polyoxyethylene hexitan list are hard The polyoxyalkylene polyols such as resin acid ester system fatty acid ester compound；The polyoxyalkylene alkyl amines compound such as polyoxyethylene alkyl amine； Alkylalkanol amide compound etc..
In these nonionic surfactants, preferably epoxyalkane is block polycondensate of more than two kinds, polyoxyalkylene Ether based compound, polyoxyalkylene diols fatty acid ester based compound, polyoxyalkylene polyol system fatty acid ester compound, polyoxygenated The polyoxyalkylene based compound of the epoxyalkane polymer adduct such as allylic alkylation amine compounds, particularly preferred polyoxyalkylene ether system chemical combination Object, polyoxyalkylene diols fatty acid ester based compound, polyoxyalkylene polyol system fatty acid ester compound.
These nonionic surfactants can separately be applied in combination using or by two or more.
In addition, anionic surfactant, cationic system surfactant, amphoteric surfactant and nonionic system Surfactant can use individually or two or more is applied in combination.
In the range of the content of water soluble surfactant active in block copolymer composition is 0.02~3.00 weight %, In the range of preferably 0.10~2.50 weight %, in the range of more preferably 0.12~2.00 weight %, particularly preferably In the range of 0.15~1.50 weight %.In content above range by making water soluble surfactant active, thus even if In the case that polymer is low viscosity, resistance to blocking and the excellent block copolymer composition of bonding characteristic can be also obtained.
In the present invention, the side of the block copolymer composition containing block copolymer and water soluble surfactant active is prepared Method is not particularly limited.For example, block copolymer can be being contained as described above in the manufacturing process of block copolymer Water soluble surfactant active is added in solution, furthermore can also recycle block copolymer in the manufacturing process of block copolymer Afterwards, cooperate water soluble surfactant active.
In the manufacturing process of block copolymer, water soluble surfactant active is added in the solution containing block copolymer In the case where, the content of the water soluble surfactant active in block copolymer composition is able to use such as cohesion permeation chromatography (GPC) it analyzes and measures.
3. purposes
Block copolymer composition of the invention due to for low viscosity and resistance to blocking and bonding characteristic it is excellent, can It is widely used for various uses.Specifically, block copolymer composition of the invention can be used in: being used for film, gloves, elasticity The various rollers such as band, contraceptive, OA instrument, office use, electric electronic Instrument shockproof sheet, Shockproof rubber, vibration damping sheet, impact resistance The moulding material purposes of Buddhist nun's diaphragm, house vibration-damping sheet, damping material etc.；For adhesive tape, bonding sheet, adhesive label, The binder purposes of cleaning roller etc.；For amenities, the cement purposes of bookbinding；For dress material product, sports goods, dress ornament The purposes such as the elastomer purposes of product, amenities etc..
In addition, block copolymer composition of the invention can be molded into for example membranaceous, fibrous and use.
B. adhesive composite
Adhesive composite of the invention is the composition containing above-mentioned block copolymer composition.Bonding of the invention For agent composition due to containing above-mentioned block copolymer composition, bonding characteristic is excellent.
Adhesive composite of the invention contains above-mentioned block copolymer composition as basic polymer, such as containing Above-mentioned block copolymer composition and tackifying resin.
As tackifying resin, it is able to use the usually tackifying resin used in adhesive composite.
The mixing ratio of block copolymer composition and tackifying resin can suitably be adjusted according to the purposes of adhesive composite Section.For example, the use level of tackifying resin can be set as 5~6000 weight relative to the block copolymer composition of 100 parts by weight Part, it is preferably set to 40~4500 parts by weight.
Adhesive composite of the invention may include the component of polymer in addition to above-mentioned block copolymer composition. It as the component of polymer in addition to above-mentioned block copolymer composition, can enumerate for example: except above-mentioned block copolymer (I) Block copolymer, the aromatic ethenyl with aromatic vinyl polymer block and conjugated diolefin polymer block in addition Homopolymer, conjugated diene homopolymers, aromatic ethenyl-conjugated diene random copolymer and their branched polymers； The thermoplastic elastomer (TPE)s such as polyurethane series thermoplastic elastomer (TPE), Thermoplastic polyamide elastomer, Polyester thermoplastic elastomer (TPE)；It is poly- Ethylene, polypropylene, polyvinyl chloride, acrylonitritrile-styrene resin, acrylonitrile-butadiene-styrene copolymer, polyphenylene oxide etc. Thermoplastic resin etc..
The content of component of polymer in addition to above-mentioned block copolymer composition can be according to the use of adhesive composite Way etc. is appropriate to be adjusted.
Adhesive composite of the invention can contain softening agent, plasticizer, antioxidant, filler, cunning as needed The various additives such as agent.
Adhesive composite of the invention can be prepared according to method same as common adhesive composite.Example Such as, for adhesive composition, each ingredient can be stirred in the presence of the solvent and binder solution is made, Also, it can also be stirred the tackifying resin emulsified in advance in the latex of base polymer and bonding agent emulsion is made. These binder solutions or bonding agent emulsion are uniformly applied to desired substrate usually using coating machine, are wound after dry And manufacture various adhesive tapes or adhesive label product.It, can be in molten-bath for hot-melt adhesive composition It simultaneously puts into each ingredient or successively puts into each ingredient since the low ingredient of melt viscosity, in 100~200 DEG C of heating meltings After mixing, be processed into the proper shapes such as blocky, rodlike, powdered, membranaceous, sheet or this, be also able to use uniaxially or biaxially Extruder and continuously manufactured.
C. retractility film
Retractility film of the invention is the film containing above-mentioned block copolymer composition.Retractility film of the invention due to Containing above-mentioned block copolymer composition, therefore rich in retractility.
If retractility film of the invention contains above-mentioned block copolymer composition as basic polymer, such as It can be formed by above-mentioned block copolymer composition, in addition it is also possible to containing above-mentioned block copolymer composition and remove Component of polymer, additive other than above-mentioned block copolymer composition.
Retractility film of the invention may include the component of polymer in addition to above-mentioned block copolymer composition.As Component of polymer in addition to above-mentioned block copolymer composition can be enumerated for example: the olefin-baseds tree such as polyethylene, polypropylene Rouge；Phenylethylene resin series such as polystyrene, impact resistant polystyrene etc..In addition, as above-mentioned block copolymer combinations are removed Component of polymer other than object can be enumerated for example: have aromatic ethenyl polymerization in addition to above-mentioned block copolymer (I) Object block and the block copolymer of conjugated diolefin polymer block, conjugated diene homopolymers, aromatic ethenyl-conjugated diene without Advise copolymer and their branched polymers；Polyurethane series thermoplastic elastomer (TPE), gathers Thermoplastic polyamide elastomer The thermoplastic elastomer (TPE)s such as ester based thermoplastic elastomer；Polyvinyl chloride, acrylonitritrile-styrene resin, acrylonitrile-butadiene-benzene Thermoplastic resins such as ethylene copolymer, polyphenylene oxide etc..
The content of component of polymer in addition to above-mentioned block copolymer composition can be according to the purposes etc. of retractility film It is appropriate to adjust.
It is steady that retractility film of the invention can contain as needed antioxidant, tackifying resin, softening agent, antibacterial agent, light Determine the various additives such as agent, ultraviolet absorbing agent, dyestuff, pigment, lubrication prescription.
The method that above-mentioned block copolymer composition and other ingredients mix is not particularly limited, it can be for example upper Cooperate other component of polymer, various additives in the block copolymer composition stated as needed, on this basis, according to mixed The conventional methods such as refining, solution mixing mix them.Specifically, can enumerate: dissolving respective ingredient and uniform in a solvent After ground mixing, pass through the method for the removing solvent such as heating；Melting mixing is carried out to each ingredient using screw extruder, kneader etc. Method.In these, from the viewpoint of more efficiently being mixed, preferred molten mixing.In addition, when carrying out melting mixing Temperature be not particularly limited, usually 100~200 DEG C of range.
The thickness of retractility film is not particularly limited, and can adjust depending on the application.As such as paper diaper, physiological articles etc. In the case where the film of amenities, the thickness of retractility film is usually 0.01~5mm, preferably 0.01~1mm, more preferably 0.02~0.2mm.
Retractility film of the invention is to obtain the film composition molding containing above-mentioned block copolymer composition 's.The method that film composition is shaped to film is not particularly limited, the conventionally known film method of forming can be applied, from good Productivity obtain smooth film from the perspective of, preferably extrusion molding, wherein particularly preferably use T mould extrusion molding.Make For use T mould extrusion molding specific example, the T mould installed from single axle extruding machine, biaxial extruder can be enumerated and squeezed out exist 150~250 DEG C of film compositions melted, the method being wound while carrying out cooling using pulling roller.Using leading When withdrawing roll is cooled down, film can be stretched.In addition, in wound film, it can be on one side by the fusant of film composition Coated in being carried out on one side on the substrate formed by polyethylene terephthalate, polyethylene, polypropylene, non-woven fabrics or processing release paper Membranization can also clamp the fusant of film composition with these substrates and carry out membranization.Obtained from carrying out as described above Film can by with substrate it is integrated in the form of directly use, can also from substrate remove and use.
Retractility film of the invention can be used according to its purposes with the state of single layer, also can carry out layer with other components It folds and is used in the form of layered body.Specific example in the case where using as the state with single layer can be enumerated for paper The retractility film of the amenities such as urine pants, physiological articles, the protective film for protecting optical film etc., the shrink pack as container The heat-shrinkable film of dress, thermal contractive label.As specific example the case where layered body is made, following situations can be enumerated: After carrying out cutting processing to film of the invention, hot melt cement etc. is applied to it and adhesive tape is made, the shape which is shunk State is engaged in non-woven fabrics, woven fabric, plastic foil or their laminated body, discharges the contraction of adhesive tape, and the close pleat of retractility is consequently formed Component.In turn, suitably processed according to known methods according to other purposes, for example, can also act as retractility chip substrate, The retractilities component such as gloves, surgical glove, fingerstall, tourniquet, contraceptive, headband, goggles, rubber band.
D. elastomer
Elastomer of the invention is the fiber containing above-mentioned block copolymer composition.Elastomer of the invention by In containing above-mentioned block copolymer composition, therefore rich in retractility.
If elastomer of the invention contains above-mentioned block copolymer composition as component of polymer, such as It can be formed by above-mentioned block copolymer composition, in addition it is also possible to containing above-mentioned block copolymer composition and remove Component of polymer, additive other than above-mentioned block copolymer composition.
In addition, about component of polymer and additive in addition to above-mentioned block copolymer composition, can with it is above-mentioned It is set in the same manner documented by " C. retractility film " item.
Elastomer of the invention can by will include above-mentioned block copolymer composition fiber composition into Row spinning and obtain.As spinning process, as long as can especially do not limited then with the method that composition carries out spinning fiber It is fixed, well known spinning process can be applied.
It, can also be with other in addition, elastomer of the invention can use directly in the form of naked silk according to its purposes Fiber is coated elastomer and uses as coating silk.As other fibers, it is able to use conventionally known fiber.
Elastomer of the invention is other than it can be used in such as dress material product, sports goods, furnishings, additionally it is possible to as The telescopic material of silk rubber for amenities such as paper diaper, physiological articles etc. and utilize.
E. flexographic plate composition
Flexographic plate composition of the invention is the composition containing above-mentioned block copolymer composition.Of the invention is soft Property version composition due to contain above-mentioned block copolymer composition composition, rich in caoutchouc elasticity.
The means that flexographic plate is obtained using block copolymer composition are not particularly limited, and common means are formed into sense After photosensitiveness composition, slabbing is formed, makes the piece is photosensitive thus to obtain flexographic plate.
That is, flexographic plate of the invention uses composition to contain above-mentioned block copolymer composition as basic polymer, example Such as preferably comprise above-mentioned block copolymer composition, olefinic unsaturated compound and Photoepolymerizationinitiater initiater.
As olefinic unsaturated compound, preferred molecular weight is 5000 olefinic unsaturated compounds below.As olefinic Unsaturated compound is able to use the workable olefinic unsaturated compound usually in flexographic plate composition.Olefinic insatiable hunger Total amount with the content of compound relative to block copolymer composition and olefinic unsaturated compound, preferably 5~60 weights Measure %, more preferably 5~50 weight %.
In addition, the total amount of block copolymer composition and olefinic unsaturated compound is total relative to flexographic plate composition Amount is preferably 50 weight % or more, more preferably 60 weight % or more, particularly preferably 70 weight % or more.
As Photoepolymerizationinitiater initiater, it is able to use the workable Photoepolymerizationinitiater initiater usually in flexographic plate composition. Total amount of the usage amount of Photoepolymerizationinitiater initiater relative to block copolymer composition and olefinic unsaturated compound, preferably 0.1~5 weight %.
Flexographic plate of the invention with composition may include the polymer in addition to above-mentioned block copolymer composition at Point.It, can be with above-mentioned " B. adhesive composite " item about the component of polymer in addition to above-mentioned block copolymer composition It is documented to set in the same manner.
Flexographic plate composition of the invention can contain plasticizer, thermal polymerization inhibitor, antioxidant, smelly as needed Oxygen be cracked preventing agent, dyestuff, pigment, filler, the photochromic additive of display, reducing agent, the medicament for improving embossment structure, The additives such as crosslinking agent, flow improver, release agent.
The manufacturing method of flexographic plate of the invention composition is not particularly limited, can by using kneader, The ingredient for constituting flexographic plate composition is kneaded and is made by roller mill, banbury mixers, single shaft or multiple screw extruder etc. It makes.Obtained flexographic plate is with composition usually using the molding such as uniaxial or multiple screw extruder, compacting shape machine, stack molding machine Machine is molded into the sheet molding compound with expectation thickness.In addition, also can using uniaxial or multiple screw extruder The preparation of flexographic plate composition and the molding of sheet molding compound are carried out simultaneously.It is further possible to be dissolved in solvent appropriate The solution is injected in frame mould, evaporates solvent by the ingredient for constituting flexographic plate composition, thus manufactures the flexographic plate of sheet Use composition.
The thickness of piece is usually 0.1~20mm, preferably 1~10mm.
Pollution, the damage of flexographic plate composition when storing or operate in order to prevent, the flexographic plate composition of sheet The slide being formed by resin or film can be set as substrate lamella or protective film layer on its surface.
In order to which the egative film after inhibiting the caking property on flexographic plate composition surface, light being enable to irradiate recycles, Ke Yi The surface setting of the flexographic plate composition of sheet is imbued with the flexible thin coated material bed of material.In this case, soft in end Property version composition exposure after when removing unexposed portion using solvent, it is necessary to also remove the coated material bed of material simultaneously.As quilt Material layer is covered, usually mostly using soluble polyamide, cellulose derivative etc..
Flexographic plate can be obtained and above-mentioned flexographic plate is carried out photosensitive with composition.Flexographic plate can according to it is logical The same method of normal flexographic plate is manufactured.
As the printed object of flexible version printing, it can be applied to such as paper, carton, timber, metal, polyethylene film, gather The various printed objects such as piece of vinyl, polypropylene screen, polypropylene foil.
The present invention is not limited to above embodiment.Above embodiment is example, has and protects with request of the invention Substantially the same composition of technical idea documented by the range of shield realizes that the embodiment of identical function and effect is both contained in Technical scope of the invention.
Embodiment
Hereinafter, enumerating embodiment and comparative example, the present invention is more particularly described.In addition, part and % in each example, It is weight basis as long as no other explanation.
Various measurements carry out as follows.
[weight average molecular weight of each block copolymer and block copolymer mixture]
Use the tetrahydrofuran for being 0.35ml/ minutes using flow velocity as the high performance liquid chromatography of carrier, as polystyrene Conversion molecular weight and acquire.Device is TOSOH CORPORATION manufacture HLC8320, column is 3 Showa electrician company manufactures Column (column temperature is 40 DEG C) that Shodex KF-404HQ links, detector are differential refractometer and UV detector, molecular weight 12 points of standard polystyren (500 to 3,000,000) for manufacturing in Polymer Laboratory company of correction implement.
[weight ratio of each block copolymer]
According to the face at the peak corresponding to each block copolymer of the chart as obtained from above-mentioned high performance liquid chromatography Product compares and acquires.
[weight average molecular weight of styrene polymer block]
According to Rubber Chem.Technol., method documented by 45,1295 (1972) makes block copolymer and ozone Reaction, is restored using lithium aluminium hydride reduction, thus decomposes the isoprene polymer block of block copolymer.Specifically, pressing It is carried out according to following steps.That is, the sample of 300mg to be dissolved in the use processed methylene chloride of molecular sieve that joined 100ml Reaction vessel in.The reaction vessel is put into after becoming -25 DEG C in cooling bath, on one side in the reaction vessel with 170ml/ The flow of minute flows into oxygen, imports the ozone generated by ozone generation device on one side.Autoreaction started after 30 minutes, will be from The gas flowed out in reaction vessel imports in potassium iodide aqueous solution, thereby confirms that reaction terminates.Then, it is replaced in addition through nitrogen Reaction vessel in, the diethyl ether of 50ml and the lithium aluminium hydride reduction of 470mg is added, on one side with the cooling reaction vessel of ice water, on one side will It is added dropwise in the reaction vessel at leisure with the solution of ozone reaction.Then, which is put into water-bath, is risen gradually Temperature makes it flow back 30 minutes at 40 DEG C.Then, dilute hydrochloric acid is marginally bit by bit added dropwise in anti-on one side for one side agitating solution It answers in container, lasting be added dropwise generates until hydrogen is substantially not confirmed.After the reaction, the solid shape generated in filtering solution Product, use the Anaesthetie Ether of 100ml to extract product 10 minutes of solid shape.Merge the filter when extracting solution and filtering Liquid, is distilled off solvent, thus obtains the sample of solid shape.To sample obtained from carrying out like this, according to above-mentioned weight The measuring method of average molecular weight measures weight average molecular weight, using the value as the weight average molecular weight of styrene polymer block.
[weight average molecular weight of isoprene polymer block]
Corresponding styrene is subtracted from the weight average molecular weight for the block copolymer that as described above carry out is acquired respectively The weight average molecular weight of polymer blocks is based on the calculated value, acquires the weight average molecular weight of isoprene polymer block.
[the styrene units content of block copolymer]
The detection intensity ratio of differential refractometer and UV detector in measurement based on above-mentioned high performance liquid chromatography And it acquires.In addition, preparing the copolymer with different styrene units contents in advance, standard curve is made using them.
[the styrene units content of block copolymer mixture]
It is based on1The measurement of H NMR and acquire.
[vinyl bond content of conjugated diolefin polymer block]
It is based on1The measurement of H NMR and acquire.
[melt index of block copolymer or block copolymer mixture]
It is measured according to ASTM D-1238 (G condition, 200 DEG C, 5kg).
[content of the water soluble surfactant active in block copolymer composition]
Gel permeation chromatography (GPC) measurement is carried out to block copolymer composition, according to corresponding to block copolymer or embedding Section copolymer mixture and water soluble surfactant active peak area ratio and acquire.Specifically, respectively to every kind of water solubility Surfactant kind has made the content of the water soluble surfactant active in multiple block copolymers or block copolymer composition The sample known.The GPC measurement for carrying out them, is made the standard for indicating the relationship of water soluble surfactant active's content and peak area ratio Curve.The sample unknown to water soluble surfactant active's content of embodiment and comparative example is carried out similarly GPC measurement, according to peak Area ratio acquires the content of respective water soluble surfactant active.It, will in the case where the water soluble surfactant active containing there are many Total total surfactant as in block copolymer composition of obtained respective water soluble surfactant active's content contains Amount.
[resistance to blocking of block copolymer composition]
The block copolymer composition of 50g is packed into the polybag of 100mm × 100mm, it is secured using cellophane tape The opening portion of ground hermetic bag is placed in the baking oven for being set as 60 DEG C, and the SUS plate placement 10 for carrying the weight of 5kg on it is small When, then, whether there is or not adhesions each other for visual confirmation particle, determine resistance to blocking according to benchmark below.
◎: adhesion is found no
〇: though discovery has adhesion, with faint power with regard to peelable
X: discovery has adhesion, and can not be removed with faint power
[retentivity of adhesive tape]
Retentivity is measured as follows: according to JIS Z-0237, with the side of the contact area of 25mm × 10mm Adhesive tape is pasted on the stainless steel plate polished using No. 280 water-fast polishing papers by formula, applies the negative of 1kg at 40 DEG C Lotus measures adhesive tape from stainless steel plate and falls off the required time (unit: minute).
[cohesive force of adhesive tape]
Cohesive force is measured in accordance with the following methods: being used hard polyethylene (HDPE) plate as adherend, is pasted wide 10mm × long 100mm adhesive tape, is removed with 200mm/ minutes speed along the direction of 180 degree at 23 DEG C.
[initial bonding strength of adhesive tape]
The adhesive tape of wide 25mm is made, uses hard polyethylene (HDPE) plate as adherend, joint portion 25 × 25mm, 23 DEG C of temperature use extensiometers evaluate annular initial bonding strength (N/25mm).Value is bigger, and initial stage engaging force is more excellent.
[Production Example 1]
In voltage-resistant reactor, the hexamethylene of 23.0kg, the N, N, N of 3 mmoles are added ', N '-tetramethylethylenediamine (hereinafter, Referred to as TMEDA.) and 1.6kg styrene, be stirred at 40 DEG C, at this point, addition 92 mmoles n-BuLi, rise on one side Temperature polymerize 1 hour on one side to 50 DEG C.The polymerisation conversion of styrene is 100%.Then, on one side with 50~60 DEG C of holding of side Formula controls temperature, on one side continuously makes an addition to the isoprene of 4.9kg in reactor after 1 hour.Terminate isoprene After addition, further it polymerize 1 hour.The polymerisation conversion of isoprene is 100%.Then, the dimethyl two of 15 mmoles is added Chlorosilane carries out 2 hours coupling reactions as coupling agent, forms the use (Ar-D) as block copolymer bn- X indicates symmetrical Styrene-isoprene-styrene block copolymer.Then, the methanol for adding 110 mmoles is sufficiently mixed as polymerization terminator It closes, terminates reaction, and make the work of the styrene-isoprene block copolymer for the active end that do not react with coupling agent Property end lose activity, form the styrene-isoprene block copolymer indicated with Ar-D as block copolymer c.Separately Outside, the amount for each reagent of reaction is summarized in table 1.
Obtained a part of reaction solution is taken out, dividing equally again for each block copolymer and block copolymer mixture is acquired Sub- amount, the weight average molecular weight of each styrene polymer block, the weight average molecular weight of each isoprene polymer block, each block are total Styrene units content, the styrene units content of block copolymer mixture, the second of isoprene polymer block of polymers The weight ratio of alkenyl linkage content and each block copolymer.In addition, the melt index of measurement block copolymer mixture.They Value be shown in table 2.
[table 1]
[table 2]
[Production Example 2]
In voltage-resistant reactor, the styrene of the hexamethylene of 23.0kg, the TMEDA and 1.4kg of 2 mmoles is added, 40 It DEG C is stirred, at this point, the n-BuLi of 100 mmoles of addition, is warming up to 50 DEG C on one side, polymerize 1 hour on one side.Styrene gathers Closing conversion ratio is 100%.Then, temperature is controlled in a manner of being kept for 50~60 DEG C on one side, on one side goes through the isoprene of 3.6kg It was continuously made an addition in reactor through 1 hour.After the addition for terminating isoprene, further it polymerize 1 hour.Isoprene gathers Closing conversion ratio is 100%.Then, temperature is controlled in a manner of being kept for 50~60 DEG C on one side, was continuously added after 1 hour on one side The styrene of 1.4kg.After the addition for terminating styrene, further polymerization 1 hour, forms as block copolymer b and uses Ar-D- The symmetrical styrene-isoprene-styrene block copolymer that Ar is indicated.The polymerisation conversion of styrene is 100%.So Afterwards, the methanol for adding 120 mmoles is sufficiently mixed as polymerization terminator, terminates reaction.
A part of obtained reaction solution is taken out, similarly measured with Production Example 1.
[Production Example 3]
In voltage-resistant reactor, the styrene of the hexamethylene of 23.0kg, the TMEDA and 1.4kg of 2 mmoles is added, 40 It DEG C is stirred, at this point, the n-BuLi of 139 mmoles of addition, is warming up to 50 DEG C on one side, polymerize 1 hour on one side.Styrene gathers Closing conversion ratio is 100%.Then, temperature is controlled in a manner of being kept for 50~60 DEG C on one side, on one side goes through the isoprene of 3.6kg It was continuously made an addition in reactor through 1 hour.After the addition for terminating isoprene, further it polymerize 1 hour.Isoprene gathers Closing conversion ratio is 100%.Then, temperature is controlled in a manner of being kept for 50~60 DEG C on one side, was continuously added after 1 hour on one side The styrene of 1.4kg.After the addition for terminating styrene, further polymerization 1 hour, forms as block copolymer b and uses Ar-D- The symmetrical styrene-isoprene-styrene block copolymer that Ar is indicated.The polymerisation conversion of styrene is 100%.So Afterwards, the methanol for adding 167 mmoles is sufficiently mixed as polymerization terminator, terminates reaction.
A part of obtained reaction solution is taken out, similarly measured with Production Example 1.
[Production Example 4]
In voltage-resistant reactor, the styrene of the hexamethylene of 23.0kg, the TMEDA and 0.8kg of 2 mmoles is added, 40 It DEG C is stirred, at this point, the n-BuLi of 89 mmoles of addition, is warming up to 50 DEG C on one side, polymerize 1 hour on one side.Styrene gathers Closing conversion ratio is 100%.Then, temperature is controlled in a manner of being kept for 50~60 DEG C on one side, on one side goes through the isoprene of 4.2kg It was continuously made an addition in reactor through 1 hour.After the addition for terminating isoprene, further it polymerize 1 hour.Isoprene gathers Closing conversion ratio is 100%.Then, temperature is controlled in a manner of being kept for 50~60 DEG C on one side, was continuously added after 1 hour on one side The styrene of 0.8kg.After the addition for terminating styrene, further it polymerize 1 hour.The polymerisation conversion of styrene is 100%.It connects , by adding the methanol of 62 mmoles in the reactor, to keep the styrene-isoprene-phenylethene block of a part total The reactive terminal of polymers loses activity, and forms the symmetrical styrene-isoamyl indicated with Ar-D-Ar as block copolymer b Styrene block copolymer.Then, temperature is controlled in a manner of being kept for 50~60 DEG C on one side, it is continuous after 1 hour on one side The styrene of ground addition 0.7kg.After the addition for terminating styrene, further polymerization 1 hour, is formed as block copolymer a's The asymmetrical styrene-isoprene-styrene block copolymer indicated with Ar-D-Ar.The polymerisation conversion of styrene is 100%.Then, the methanol for adding 107 mmoles is sufficiently mixed as polymerization terminator, terminates reaction.
A part of obtained reaction solution is taken out, similarly measured with Production Example 1.
[embodiment 1-1]
It is the conduct nonionic system surface-active of 0.40 parts by weight by the block copolymer mixture relative to 100 parts by weight The polyoxyalkylene ether of agent makes an addition in the water supplied when stripping, is stripped to reaction solution obtained in Production Example 1 so that in water Granule concentration become 2 weight %.Then, the aqueous slurry of obtained block copolymer mixture is sent to sieve, separation The granule of block copolymer mixture is placed in dewaterer by most water, is then squeezed out drying machine using twin shaft and is done It is dry, in 10 DEG C of water after the stock of cooling discharge, the length of about 25mm is cut into using granulator, block is recycled as particle Copolymer mixture.The block copolymer composition of embodiment 1-1 is obtained as a result,.In addition, the amount of water soluble surfactant active is converged Always in table 3.In table, PHR indicates amount of the water soluble surfactant active relative to the block copolymer mixture of 100 parts by weight.
The resistance to blocking of obtained block copolymer composition is evaluated.The results are shown in Table 5.
[table 3]
[table 4]
[embodiment 1-2~1-4]
As shown in table 3 like that, instead of reaction solution obtained in Production Example 1, respectively using anti-obtained in Production Example 2~4 Liquid is answered, in addition to this, is carried out similarly with embodiment 1-1, obtains the block copolymer composition of embodiment 1-2~1-4.
The resistance to blocking of obtained block copolymer composition is evaluated.
[embodiment 1-5]
In the obtained reaction solution of Production Example 3, adding relative to the block copolymer of 100 parts by weight is 0.10 parts by weight The polyocarboxy acid type surfactant as anionic surfactant and the block copolymer relative to 100 parts by weight For the polyoxyalkylene ether as nonionic surfactants of 0.15 parts by weight, in addition to this, in the same manner as embodiment 1-1 into Row, obtains the block copolymer composition of embodiment 1-5.
The resistance to blocking of obtained block copolymer composition is evaluated.
[embodiment 1-6]
In the obtained reaction solution of Production Example 3, adding relative to the block copolymer of 100 parts by weight is 0.10 parts by weight The polyocarboxy acid type surfactant as anionic surfactant and the block copolymer relative to 100 parts by weight For the polyoxyalkylene ether as nonionic surfactants of 1.50 parts by weight, in addition to this, in the same manner as embodiment 1-1 into Row, obtains the block copolymer composition of embodiment 1-6.
The resistance to blocking of obtained block copolymer composition is evaluated.
[embodiment 1-7]
In the obtained reaction solution of Production Example 3, adding relative to the block copolymer of 100 parts by weight is 0.10 parts by weight Be as the alkyl trimethyl ammonium chloride of cationic system surfactant and the block copolymer relative to 100 parts by weight The polyoxyalkylene ether as nonionic surfactants of 0.15 parts by weight, in addition to this, in the same manner as embodiment 1-1 into Row, obtains the block copolymer composition of embodiment 1-7.
The resistance to blocking of obtained block copolymer composition is evaluated.
[embodiment 1-8~1-11]
As shown in table 3 like that, in the obtained respective reaction solution of Production Example 1~4, relative to the embedding of 100 parts by weight Section copolymer or block copolymer mixture add the polyocarboxy acid type table as anionic surfactant of 0.20 parts by weight Face activating agent is carried out similarly with embodiment 1-1 in addition to this, obtains the block copolymer combinations of embodiment 1-8~1-11 Object.
The resistance to blocking of obtained block copolymer composition is evaluated.
[embodiment 1-12]
In the obtained reaction solution of Production Example 3, adding relative to the block copolymer of 100 parts by weight is 0.05 parts by weight The polyocarboxy acid type surfactant as anionic surfactant and the block copolymer relative to 100 parts by weight For the polyoxyalkylene ether as nonionic surfactants of 0.05 parts by weight, in addition to this, in the same manner as embodiment 1-1 into Row, obtains the block copolymer composition of embodiment 1-12.
The resistance to blocking of obtained block copolymer composition is evaluated.
[comparative example 1-13]
In the obtained reaction solution of Production Example 3, adding relative to the block copolymer of 100 parts by weight is 0.10 parts by weight The polyocarboxy acid type surfactant as anionic surfactant and the block copolymer relative to 100 parts by weight For the polyoxyalkylene ether as nonionic surfactants of 4.00 parts by weight, in addition to this, in the same manner as embodiment 1-1 into Row, obtains the block copolymer composition of comparative example 1-13.
The resistance to blocking of obtained block copolymer composition is evaluated.
[comparative example 1-14~1-15]
As shown in table 4 like that, it in the obtained respective reaction solution of Production Example 1~2, adds relative to 100 parts by weight Block copolymer or block copolymer mixture be 0.05 parts by weight the polyocarboxy acid type as anionic surfactant Surfactant and block copolymer relative to 100 parts by weight or block copolymer mixture are the work of 0.01 parts by weight It is carried out similarly in addition to this with embodiment 1-1 for the polyoxyalkylene ether of nonionic surfactants, obtains comparative example 1- The block copolymer composition of 14~1-15.
The resistance to blocking of obtained block copolymer composition is evaluated.
[comparative example 1-16~1-17]
As shown in table 4 like that, it in the obtained respective reaction solution of Production Example 3~4, adds relative to 100 parts by weight Block copolymer or block copolymer mixture be 0.10 parts by weight the polyocarboxy acid type as anionic surfactant Surfactant is carried out similarly with embodiment 1-1 in addition to this, obtains the block copolymer group of comparative example 1-16~1-17 Close object.
The resistance to blocking of obtained block copolymer composition is evaluated.
[embodiment 2-1]
By the block copolymer composition of 50 parts of embodiment 1-1,50 parts of styrene isoprene block copolymer (manufacture of " Quintac (registered trademark) 3450 ", Zeon Corp), 300 parts of hydrogenated petroleum resin (" ARKON M- 100 ", Arakawa Chemical Industries, Ltd. manufacture), 100 parts of paraffin oil (" PW-90 ", Chu Guangxingchan company Manufacture) and 1 part of antioxidant (" Irganox (registered trademark) 1010 ", BASF AG manufacture) at 180 DEG C to be kneaded 1 small When, prepare the adhesive composite of embodiment 2-1.Then, above-mentioned adhesive composite is applied on 25 μm of thickness of polyester film So that thickness becomes 40 μm, adhesive tape is obtained.To adhesive tape measurement retentivity, cohesive force and initial bonding strength.As a result it converges Always it is shown in table 5.
[table 5]
[table 6]
[embodiment 2-2~2-7]
Respectively use embodiment 1-2~1-7 block copolymer composition, in addition to this, in the same manner as embodiment 2-1 into Row, obtains the adhesive composite and adhesive tape of embodiment 2-2~2-7.To obtained adhesive tape measurement retentivity, bond Power and initial bonding strength.
[embodiment 2-8~2-12]
The block copolymer composition for using embodiment 1-8~1-12 respectively, in addition to this, in the same manner as embodiment 2-1 It carries out, obtains the adhesive composite and adhesive tape of embodiment 2-8~2-12.To obtain adhesive tape measurement retentivity, Cohesive force and initial bonding strength.
[comparative example 2-13~2-17]
The block copolymer composition for using embodiment 1-13~1-17 respectively, in addition to this, in the same manner as embodiment 2-1 It carries out, obtains the adhesive composite and adhesive tape of comparative example 2-13~2-17.To obtain adhesive tape measurement retentivity, Cohesive force and initial bonding strength.
According to table 5 and table 6 it is found that the resistance to blocking and bonding characteristic of the composition of embodiment 2-1~2-12 are excellent.It is another The resistance to blocking of aspect, the composition of comparative example 2-14~2-17 is poor, and the retentivity of the composition of comparative example 2-13 is poor.

Claims (9)

1. a kind of block copolymer composition, which is characterized in that containing block copolymer, the block copolymer has at least 1 A aromatic vinyl polymer block and at least one conjugated diolefin polymer block,
The melt index of the block copolymer is 20g/10 minutes or more,
The block copolymer composition contains the water soluble surfactant active of 0.02~3.00 weight %.
2. block copolymer composition according to claim 1, which is characterized in that the melt index of the block copolymer It is 30g/10 minutes or more.
3. block copolymer composition according to claim 1 or 2, which is characterized in that the water soluble surfactant active Content be 0.10~2.50 weight %.
4. block copolymer composition according to claim 3, which is characterized in that the water soluble surfactant active's contains Amount is 0.12~2.00 weight %.
5. block copolymer composition according to claim 4, which is characterized in that the water soluble surfactant active's contains Amount is 0.15~1.50 weight %.
6. a kind of adhesive composite contains block copolymer combinations described in any one of claims 1 to 5 Object.
7. a kind of retractility film contains block copolymer composition described in any one of claims 1 to 5.
8. a kind of elastomer contains block copolymer composition described in any one of claims 1 to 5.
9. a kind of flexographic plate composition, contains block copolymer combinations described in any one of claims 1 to 5 Object.
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CN112898785A (en) * 2021-01-22 2021-06-04 盛嘉伦橡塑(河源)有限公司 Thermoplastic elastomer material and preparation method and application thereof

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JP7415511B2 (en) * 2019-12-10 2024-01-17 日本ゼオン株式会社 Adhesives for surface protection materials and surface protection materials

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JPH0967502A (en) * 1995-09-01 1997-03-11 Daicel Chem Ind Ltd Epoxidized block copolymer composition
JPH09235316A (en) * 1996-02-29 1997-09-09 Nippon Zeon Co Ltd Production of polymer

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Publication number Priority date Publication date Assignee Title
JPH0967502A (en) * 1995-09-01 1997-03-11 Daicel Chem Ind Ltd Epoxidized block copolymer composition
JPH09235316A (en) * 1996-02-29 1997-09-09 Nippon Zeon Co Ltd Production of polymer

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Publication number Priority date Publication date Assignee Title
CN112898785A (en) * 2021-01-22 2021-06-04 盛嘉伦橡塑(河源)有限公司 Thermoplastic elastomer material and preparation method and application thereof

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