CN103080166B - Block copolymer for adhesive, production method therefor, and adhesive composition - Google Patents

Abstract

To provide a block copolymer for adhesive that has a good finish, and an adhesive composition that has an excellent adhesive property and a good performance balance, and further an excellent solubility and coatability. [Solution] A block copolymer for adhesive, containing at least two polymer blocks of vinyl aromatic monomer unit (A) and at least one polymer block (B) containing conjugated diene monomer unit as a main component, wherein the amount (% by mass) of polymer blocks of vinyl aromatic monomer unit in the polymer block of vinyl aromatic monomer unit (A) is 95.0 to 99.0% relative to the total amount of vinyl aromatic monomer unit (% by mass) that has been used for polymerizing the polymer block of vinyl aromatic monomer unit (A), and the block copolymer for adhesive selectively contains block copolymer components (a) to (d); that have a specific structure provided with the polymer blocks (A) and (B).

Description

Adhesion binding agent segmented copolymer, its manufacture method and adhesion adhesive composition

Technical field

The present invention relates to adhesion binding agent segmented copolymer, its manufacture method and adhesion adhesive composition.

Background technology

In recent years, as the binding agent of solution-type, hot-melting type and the base polymer of tackiness agent, widely use vinyl aromatic monomers-conjugate diene monomer based block copolymer (SBS: styrene-butadiene-styrene block copolymer, SIS: styrene isoprene styrene block copolymer (SIS)).Such as, in patent documentation 1 and patent documentation 2, disclose the binding agent composition or tackiness agent composition that use SBS.But, for the binding agent composition or the tackiness agent composition that employ SBS or SIS, the adhesion binding agent balance of properties of its bounding force, initial bonding strength and confining force is insufficient, therefore be desirably in these aspect of performances to improve to some extent, as these modification methods, in patent documentation 3 and non-patent literature 1, disclose the binding agent composition containing triblock copolymer and Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock.

But in any one above-mentioned tackiness agent composition and binding agent composition, the improved effect of above-mentioned various aspect of performance is also insufficient.

Improve requirement for this, in patent documentation 4,5, disclose a kind of tackiness agent composition, it contains and utilizes specific 2 functional-type coupling agents (fatty family monoesters, specific dihalide compound) to carry out coupling and the segmented copolymer that obtains.

Prior art document

Patent documentation

Patent documentation 1: Japanese Patent Publication 44-17037 publication

Patent documentation 2: Japanese Patent Publication 56-49958 publication

Patent documentation 3: Japanese Laid-Open Patent Publication 61-278578 publication

Patent documentation 4: Japanese Laid-Open Patent Publication 61-261310 publication

Patent documentation 5: Japanese Unexamined Patent Publication 3-285978 publication

Non-patent literature

Non-patent literature 1: Shi Jing escapes bright, " Quality Design of SIS basis tackiness agent " (SIS ベ ー ス adhesion drug product Quality Let Meter), bonding, the meeting of polymer publication, (Showa 63 years) January 25 in 1988, the 32nd volume, No. 1,27 pages ~ 28 pages.

Summary of the invention

Invent problem to be solved

But, for the tackiness agent composition disclosed in patent documentation 4,5, from the view point of confining force and fusible balance and solvability, coating, need further to improve.

Therefore in the present invention, in view of the problem points of above-mentioned prior art, object is to provide that a kind of finishability is excellent, namely operability is easily and the segmented copolymer of workability excellence; The adhesion adhesive composition that good and then solvability, coating are also excellent with the balance of properties such as bounding force and confining force.

For solving the method for problem

The present inventor conducts in-depth research in order to the problem solving above-mentioned prior art, found that, the adhesion binding agent segmented copolymer being combined with the segmented copolymer with ad hoc structure and the adhesion adhesive composition employing this segmented copolymer can solve above-mentioned problem effectively, thus complete the present invention.

That is, the present invention as described below.

[1]

A kind of adhesion binding agent segmented copolymer, it contains segmented copolymer as described below, namely this segmented copolymer possesses at least 2 vinyl aromatic monomers unit polymer blocks (A) and at least 1 polymer blocks (B) based on conjugated diene monomeric unit, wherein

Vinyl aromatic monomers polymer blocks amount (quality %) in described vinyl aromatic monomers unit polymer blocks (A) is 95.0% ~ 99.0% relative to the whole vinyl aromatic monomers quantity of units (quality %) used to be polymerized this vinyl aromatic monomers unit polymer blocks (A)

Further,

Described adhesion binding agent segmented copolymer is made up of the following compositions (a) of 50 quality % ~ 80 quality % and at least any one composition be selected from the group be made up of following compositions (b), (c) and (d) of 20 quality % ~ 50 quality %

(a): what represent with general formula (A-B) has 20,000 ~ 80, the Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock of the number-average molecular weight of 000;

(b): with (A-B) _nwhat represent has 40,000 ~ 160, the segmented copolymer of the number-average molecular weight of 000, and n is the integer of more than 2;

(c): with (A-B) _pwhat A represented has 40, the segmented copolymer of the number-average molecular weight of 000 ~ 160,000, and p is the integer of more than 1;

(d): with general formula (A-B) _mwhat X represented has 40, and the branched block copolymer of the number-average molecular weight of 000 ~ 160,000, wherein, m is any one numerical value in 2,3,4, and X represents the residue of coupling agent or the residue of polymerization starter.

[2]

A kind of adhesion adhesive composition, it contains:

Adhesion binding agent segmented copolymer described in (i) above-mentioned [1]: 100 mass parts;

(ii) tackifier: 100 mass parts ~ 400 mass parts;

(iii) tenderizer: 50 mass parts ~ 150 mass parts.

[3]

Adhesion adhesive composition as described in above-mentioned [2], it meets the condition of following (1) ~ (3):

(1): annular initial bonding strength T (N/15mm)/50 is more than 0.8;

(2): what measure according to the measuring method of the peel adhesion of JIS Z0237 is more than 0.8 for test board 180 ° of peel adhesion P (N/10mm)/30;

(3): confining force C (minute)/10 are more than 0.8.

[4]

Adhere the manufacture method of binding agent segmented copolymer, it is the manufacture method of the adhesion binding agent segmented copolymer described in above-mentioned [1], and wherein, this manufacture method has following operation:

The operation of being polymerized the described vinyl aromatic monomers unit polymer blocks (A) of preparation is carried out to vinyl aromatic monomers unit; With

When from arrive described to carry out vinyl aromatic monomers unit being polymerized the top temperature in the operation of the described vinyl aromatic monomers unit polymer blocks (A) of preparation through more than 4 minutes less than 20 minutes and have dropped more than 1.5 DEG C than described top temperature when, the operation of interpolation conjugated diene monomeric unit.

[5]

The manufacture method of the adhesion binding agent segmented copolymer as described in above-mentioned [4], it is the manufacture method containing the adhesion binding agent segmented copolymer described in above-mentioned [1] of described composition (c), wherein,

Described to carry out being polymerized the operation of the described vinyl aromatic monomers unit polymer blocks (A) of preparation to vinyl aromatic monomers unit after, when when have dropped more than 1.5 DEG C than top temperature, adding the deactivator for making the polymerization of described segmented copolymer stop through more than 4 minutes less than 20 minutes from arriving the top temperature of this operation.

The effect of invention

Can provide the adhesion binding agent segmented copolymer of finishability excellence according to the present invention, and the adhesion such as bounding force and confining force bonding characteristic is excellent and these balance of properties also have excellent solvability, the adhesion adhesive composition of coating well, further.

Embodiment

Below, be described in detail to for implementing mode of the present invention (hereinafter referred to as " present embodiment ").

It should be noted that, the present invention is not limited to following embodiment, can carry out various distortion to implement in the scope of its main idea.

[adhesion binding agent segmented copolymer]

(structure)

The adhesion binding agent segmented copolymer of present embodiment contains segmented copolymer as described below, namely this segmented copolymer possesses at least 2 vinyl aromatic monomers unit polymer blocks (A) (being also sometimes expressed as polymer blocks A or A below) and at least 1 polymer blocks (B) (following, to be sometimes also expressed as polymer blocks B or B) based on conjugated diene monomeric unit.

" for main body " refers to the conjugated diene monomeric unit containing more than 50 quality %, preferably containing more than 70 quality %, more preferably containing more than 85 quality %, the polymer blocks (B) in adhesion binding agent segmented copolymer is copolymer block and/or the conjugated diene homopolymers block of conjugated diene compound and vinyl aromatic hydrocarbon.

For the adhesion binding agent segmented copolymer of present embodiment, relative to the whole vinyl aromatic monomers quantity of units (quality %) used in order to polymerizable vinyl aromatic monomeric unit polymer blocks (A), vinyl aromatic monomers polymer blocks amount (quality %) the i.e. vinyl aromatic monomers block rate in vinyl aromatic monomers unit polymer blocks (A) is 95.0% ~ 99.0%.

In addition, the adhesion binding agent segmented copolymer of present embodiment is made up of the following compositions (a) of 50 quality % ~ 80 quality % and any one composition be selected from the group be made up of following compositions (b), (c) and (d) of 20 quality % ~ 50 quality %

(a): what represent with general formula (A-B) has 20,000 ~ 80, the Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock of the number-average molecular weight of 000.

(b): with (A-B) _nwhat represent has 40,000 ~ 160, and the segmented copolymer of the number-average molecular weight of 000, n is the integer of more than 2.

(c): with (A-B) _pwhat A represented has 40, and the segmented copolymer of the number-average molecular weight of 000 ~ 160,000, p is the integer of more than 1.

(d): with general formula (A-B) _mwhat X represented has 40, and the branched block copolymer of the number-average molecular weight of 000 ~ 160,000, m is any one numerical value in 2,3,4.It should be noted that, X represents the residue of coupling agent or the residue of polymerization starter.

The number-average molecular weight of described composition (a) ~ (d) can be measured by the method recorded in embodiment described later.

If the number-average molecular weight of described composition (a) ~ (d) is in above-mentioned scope, then can obtain excellent cohesiveness, bounding force, confining force, solvability, coating in the adhesion adhesive composition of present embodiment described later.

For the scope of preferred number-average molecular weight, the segmented copolymer of described composition (a) is 40,000 ~ 70,000, be more preferably 45,000 ~ 65,000, the segmented copolymer of described composition (b), (c) and (d) is 80,000 ~ 140,000, be more preferably 90,000 ~ 130,000.

Described composition (a) ~ (d) be combined as in composition (a)+composition (b), composition (a)+composition (c), composition (a)+composition (d), composition (a)+composition (b)+composition (c), composition (a)+composition (b)+composition (d), composition (a)+composition (c)+composition (d), composition (a)+composition (b)+composition (c)+composition (d) any one.

As mentioned above, relative to the all-mass of the whole vinyl aromatic monomers unit used in order to polymerizable vinyl aromatic monomeric unit polymer blocks (A), the ratio of the quality of vinyl aromatic monomers polymer blocks and block rate are 95.0% ~ 99.0%.In the adhesion binding agent segmented copolymer of present embodiment, described block rate is preferably 97.0% ~ 99.0%, is more preferably 97.5% ~ 98.5%.

If described block rate is above-mentioned numerical range, then can not cause fusion in the independent separation and finishing step of the adhesion binding agent segmented copolymer of present embodiment, successfully can carry out drying treatment, result can obtain high yield.In addition, if consider the painted of adhesion binding agent segmented copolymer, more than 99.0% is preferably.

It should be noted that, under vinyl aromatic monomers is cinnamic situation, the block rate of vinyl aromatic monomers unit polymer blocks (A) can be calculated by block rate=styrene block content (quality the %)/styrene content (quality %) × 100 of the vinyl aromatic monomers polymer blocks in vinyl aromatic monomers unit polymer blocks (A).

Content for the vinyl aromatic monomers unit (vinylbenzene in such as above-mentioned example) in the adhesion binding agent segmented copolymer of present embodiment is not particularly limited, but the viewpoint of the balance of each adhesion binding agent characteristic of the binding property of the adhesion adhesive composition from present embodiment described later (annular initial bonding strength), bounding force and confining force is preferably 10 quality % ~ 60 quality %, is more preferably 20 quality % ~ 50 quality %.

Below 60 quality % if the content of vinyl aromatic monomers unit is more than 10 quality %, then can obtain excellent binding property, confining force in the adhesion adhesive composition of present embodiment described later, if then can obtain excellent bounding force.

Then, the constituent of the adhesion binding agent segmented copolymer of present embodiment and segmented copolymer (composition (a) ~ (d)) are described.

Composition (a) ~ (d) is the segmented copolymer possessing vinyl aromatic monomers unit polymer blocks (A) and the polymer blocks based on conjugated diene monomeric unit (B), and has formation described above and number molecular-weight average.

As the vinyl aromatic hydrocarbon forming described composition (a) ~ (d), the ring-alkylated styrenes such as such as vinylbenzene, alpha-methyl styrene, p-methylstyrene, p-tert-butylstyrene can be enumerated; To methoxy styrene; Vinyl naphthalene etc.Vinylbenzene is preferably as vinyl aromatic hydrocarbon.

The conjugated diene compound forming described composition (a) ~ (d) is the diolefine with conjugated double bond.Such as 1,3-butadiene, 2-methyl isophthalic acid can be enumerated, 3-divinyl (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene etc.As conjugated diene compound, preferred 1,3-butadiene, isoprene.Conjugated diene compound can be a kind, also can be two or more.

In addition, the vinyl bonds resultant of the conjugated diene portion in the adhesion binding agent segmented copolymer of present embodiment is preferably less than 20%.

If the vinyl bonds resultant of conjugated diene portion is less than 20%, then the characteristic can obtain thermostability, having excellent weather resistance.On the other hand from the view point of thermotolerance (heat-drawn wire), described vinyl bonds resultant is preferably more than 8%.

Vinyl bonds resultant can by such as nuclear magnetic resonance device (BRUKER company manufacture, DPX-400) measure, or use infrared spectrophotometer (device name: FT/IR-230, light splitting commercial firm of Japan manufactures), calculate according to Hampton (Hampton) method.

In order to adjust the vinyl bonds resultant of the conjugated diene portion in segmented copolymer, the adjusting agent that preferred use is made up of following substances: such as, ethers or tertiary amines, be selected from glycol dimethyl ether, tetrahydrofuran (THF), α-methoxyl group tetrahydrofuran (THF), N specifically, N, N ', N ' one kind or two or more mixture in-Tetramethyl Ethylene Diamine etc.

Particularly, the vinyl bonds resultant of the conjugated diene portion in segmented copolymer can be passed through such as will by being selected from ethers or tertiary amines, being selected from glycol dimethyl ether, tetrahydrofuran (THF), α-methoxyl group tetrahydrofuran (THF), N specifically in the previous stage of dropping into conjugate diene monomer, N, N ', N ' adjusting agent that forms of one kind or two or more mixture in-Tetramethyl Ethylene Diamine etc. puts in advance in polymer solvent and adjusts.

(manufacture method of adhesion binding agent segmented copolymer)

The adhesion binding agent segmented copolymer of present embodiment can be obtained by following method: such as, in unreactive hydrocarbons solvent, using organolithium compound as polymerization starter, vinyl aromatic hydrocarbon (such as vinylbenzene) is polymerized, then, conjugated diene compound (such as divinyl) is polymerized, according to circumstances repeats the method for these operations further; Or be polymerized such as styrene butadiene block copolymer in advance respectively: composition (a) ~ (d) and mixing method.In addition, when the mixture of prepared composition (a) and composition (d) arbitrary proportion, can be manufactured by the addition controlling coupling agent.

The molecular weight of composition (a) ~ (d) can by controlling the scope being adjusted to afore mentioned rules as the organolithium compound amount of polymerization starter.

After polyreaction stops, add water, alcohol, acid etc. and make spike inactivation, after solution being carried out to the operations such as such as stripping and isolating polymer solvent, obtain by drying binding agent segmented copolymer of adhering.

Polymerization process as the segmented copolymer of described composition (a) ~ (d) is not particularly limited, and can enumerate the polymerization processs such as polycoordination, anionoid polymerization or cationoid polymerisation.Preferred anionic polymerization in the easness this point of structure control.

Manufacture method as the block copolymer component based on anionoid polymerization can use known method, can enumerate the method that such as Japanese Patent Publication 36-19286 publication, Japanese Patent Publication 43-17979 publication, Japanese Patent Publication 46-32415 publication, Japanese Patent Publication 49-36975 publication, Japanese Patent Publication 48-2423 publication, Japanese Patent Publication 48-4106 publication, Japanese Patent Publication 56-28925 publication, Japanese Laid-Open Patent Publication 59-166518 publication, Japanese Laid-Open Patent Publication 60-186577 publication etc. are described.

As the unreactive hydrocarbons solvent used in the polymerization process of composition (a) ~ (d), the aliphatic hydrocarbons such as such as butane, pentane, hexane, iso-pentane, heptane, octane, octane-iso can be enumerated; The alicyclic hydrocarbon such as pentamethylene, methylcyclopentane, hexanaphthene, methylcyclohexane, ethylcyclohexane; The hydrocarbon solvents such as aromatic hydrocarbons such as benzene, toluene, ethylbenzene, dimethylbenzene.These can only use a kind, also can mix two or more to use.

In addition, as the organolithium compound used in the polymerization process of composition (a) ~ (d), known compound can be enumerated, such as lithium ethide, propyl lithium, n-Butyl Lithium, s-butyl lithium, tert-butyl lithium, phenyl lithium, propenyl lithium, hexyl lithium etc.Be particularly preferably n-Butyl Lithium, s-butyl lithium.Organolithium compound can only use a kind, also can use mixture of more than two kinds.

It should be noted that, in block copolymer component (a) ~ (d), can to derive from conjugated diolefine unsaturated double-bond partly or entirely carry out hydrogenation.This method of hydrotreating is not particularly limited, uses known method to carry out.

Segmented copolymer (a) can be polymerize: general formula (A-B) according to aforesaid method.

As mentioned above, A is vinyl aromatic monomers unit polymer blocks, and B is the polymer blocks based on conjugated diene monomeric unit.

In addition, segmented copolymer (b) can be polymerize by above-mentioned method: general formula (A-B) _n.

As mentioned above, A is vinyl aromatic monomers unit polymer blocks, and B is the polymer blocks based on conjugated diene monomeric unit.N is the integer of more than 2.

And then, can segmented copolymer (c) be polymerize by above-mentioned method: general formula (A-B) _pa.

As mentioned above, A is vinyl aromatic monomers unit polymer blocks, and B is the polymer blocks based on conjugated diene monomeric unit.P is the integer of more than 1.

In addition, segmented copolymer (d) can also be polymerize by above-mentioned method: general formula (A-B) _mx.

As mentioned above, A is vinyl aromatic monomers unit polymer blocks, and B is the polymer blocks based on conjugated diene monomeric unit.

X represents the residue of the initiator such as residue or each sense organolithium compound of each coupling agent.

M is any one numerical value in 2,3,4, each numeric representation functional number.

Described coupling agent is selected according to the value of the m in the general formula of the segmented copolymer (d) as target.

That is, in described coupling agent, any one known material can be used as 2 functional-type coupling agents, be not particularly limited.Such as epoxy compounds can be enumerated; The halogenated silicon compound that dichlorodimethylsilane, phenylmethyldichloroislane are such; The alkoxy-silicon compound that dimethyldimethoxysil,ne, dimethyldiethoxysilane are such; The tin compound that dimethyl tin dichloride is such; The ester cpds that methyl benzoate, ethyl benzoate, phenol benzoate, phthalate are such; The vinyl propadiene class that Vinylstyrene etc. are such; Etc..

Any one known material can be used as 3 functional-type coupling agents, be not particularly limited.The tin compound that such as tin methyltrichloride, tributyltin chloride are such can be enumerated; The silane compound that Trimethoxy silane, triethoxyl silane are such; The halogenated silicon compound etc. that methyl trichlorosilicane, trimethylsilyl chloride are such.

As 4 functional-type coupling agents, any one known material can be used, be not particularly limited.The tin halides compound that such as tin tetrachloride is such can be enumerated; The allyltin compound that tetra allylic tin, four (2-octenyl) tin are such; The tin compound that tin tetraphenyl, tetrabenzyl tin are such; The such halogenated silicon compound of silicon tetrachloride, Silicon bromide; The alkoxy-silicon compound that tetraphenoxy-silicane, tetraethoxy-silicane are such; Etc..

The method mixed each segmented copolymer (a) ~ (d) can enumerate the method that the method mixed the solution after polymerization stops or each block copolymer component utilizing roller etc. drying to be obtained mix.

In addition, when obtaining the mixture of segmented copolymer (a) and (d), the mixture that can to obtain with segmented copolymer (a) by Conjugate ratio when preparing segmented copolymer (d) be as described above arbitrary proportion.

In described segmented copolymer, the blending ratio of each composition is following ratio: composition (a) is 50 quality % ~ 80 quality %, selects free component (b), at least any one composition is 20 quality % ~ 50 quality % in group that (c) and (d) forms.

The blending ratio of preferred each composition is composition (a) is 55 quality % ~ 75 quality %; Select free component (b), at least any one composition is 25 quality % ~ 45 quality % in group that (c) and (d) forms, the blending ratio of preferred each composition is composition (a) is 60 quality % ~ 70 quality %, selects free component (b), at least any one composition is 30 quality % ~ 40 quality % in group that (c) and (d) forms.

Thus, excellent binding property, bounding force, confining force, solvency power, coating can be obtained in the adhesion adhesive composition of present embodiment described later.Especially, due to favorable solubility, heating mixing time can be shortened, the variable color produced due to thermal degradation when can be prevented.

As mentioned above, the adhesion binding agent of present embodiment at least contains 2 vinyl aromatic monomers unit polymer blocks (A) with segmented copolymer, for this vinyl aromatic monomers unit polymer blocks (A), relative in order to be polymerized whole vinyl aromatic monomers quantity of units (quality %) that this vinyl aromatic monomers unit polymer blocks (A) uses, vinyl aromatic monomers polymer blocks amount (quality %) i.e. block rate is 95% ~ 99%.

In order to obtain the vinyl aromatic monomers unit polymer blocks (A) that described block rate is 95% ~ 99%, vinyl aromatic monomers unit is polymerized, and the opportunity and opportunity that the polymerization of segmented copolymer is stopped of adding conjugated diene monomeric unit is selected.Usually, being considered to the opportunity of being almost polymerized completely as monomer from reaching the elapsed time the peak temperature that represents when polymerization stops is about 10 minutes, adds lower a kind of monomer.Or, add the deactivator for making polymerization stop.

In the segmented copolymer of present embodiment, for adding the opportunity of conjugated diene monomeric unit or stopping opportunity of polymerization of segmented copolymer, its be peak temperature represented when stopping from the polymerization reaching vinyl aromatic monomers unit in the polymerization process of vinyl aromatic monomers unit polymer blocks (A) after 4 minutes ~ 20 minutes (after 5 minutes ~ 15 minutes) and have dropped than peak temperature after more than 1.5 DEG C (preferably more than 3 DEG C) when.

If being less than 4 minutes from reaching the elapsed time peak temperature, the temperature declined from peak temperature is less than 1.5 DEG C, then can produce and cannot obtain the such problem of vinyl aromatic monomers unit polymer blocks (A) that block rate is 95.0% ~ 99.0%.

In addition, when adding the deactivator of polymerization for stopping segmented copolymer, for the interpolation opportunity of deactivator, it have passed through 4 minutes ~ 20 minutes (preferably 5 minutes ~ 15 minutes represented peak temperature when stopping from the polymerization reaching vinyl aromatic monomers unit and when the polymerization process of vinyl aromatic monomers unit polymer blocks (A) stops, more preferably 5 minutes ~ 12 minutes) and moment of more than 1.5 DEG C (preferably more than 3 DEG C, more preferably more than 3.5 DEG C) is have dropped than peak temperature.

If from reach the elapsed time peak temperature be less than 4 minutes time just add deactivator, then cannot obtain sufficient block rate, so not preferred.It should be noted that, if be more than 20 minutes from reaching the elapsed time peak temperature, block rate raises, reactive terminal generation inactivation, contains each balance of properties deterioration of adhesive tape (tape) performance of the adhesion adhesive composition of obtained segmented copolymer and annular initial bonding strength, bounding force, confining force.In addition, the segmented copolymer obtained can produce painted etc., so not preferred.

It should be noted that, the interpolation of the deactivator stopped for making polymerization is suitably selected according to the structure of segmented copolymer opportunity.That is, being when composition (c) after the interpolation of vinyl aromatic monomers unit, is when composition (a), (b), (d) after the interpolation of conjugated diene monomeric unit.

In the manufacture method of the adhesion binding agent segmented copolymer of present embodiment, the operation of the metal species deriving from polymerization starter etc. being carried out to deliming can be adopted as required.In addition, the operation of adding reaction stopping agent, antioxidant, neutralizing agent, tensio-active agent etc. can also be adopted as required.

The adhesion binding agent segmented copolymer of the mode of the present invention as above prepared can be containing be selected from nitrogen, oxygen, silicon, phosphorus, sulphur, tin isopolarity base functional group to combine on polymer so-called polymer-modified; Or utilize the properties-correcting agent such as maleic anhydride to carry out the modified block copolymer of modification to block copolymer component, can by carrying out known modified-reaction to obtain.

After producing the segmented copolymer of composition (a) ~ (d) of the adhesion binding agent segmented copolymer forming present embodiment as described above, carried out the independent separation of segmented copolymer by method described later, i.e. precision work.

As mentioned above, the polymerization process of segmented copolymer (a) ~ (d) carries out in unreactive hydrocarbons solvent.Therefore, need except desolventizing to isolate separately segmented copolymer.

As the concrete method except desolventizing, can enumerate and obtain containing water particle bits (Network ラ system) by steam stripped, by carrying out containing water particle bits the method that drying obtains segmented copolymer to what obtain.

Desolventizing is removed preferred embodiment for utilizing steam stripped, generally tensio-active agent is used as grain bits agent during steam stripped, as the example of this tensio-active agent, aniorfic surfactant, cationic surfactant, nonionic surface active agent can be enumerated.These tensio-active agents generally add 0.1ppm ~ 3000ppm relative to the water of stripping band.

Except above-mentioned tensio-active agent, also can use the dispersing auxiliary that the water-soluble salt of the metals such as Li, Na, Mg, Ca, Al, Zn is considered to be worth doing as grain.

The concentration of the segmented copolymer of the grain the be dispersed in water bits shape obtained through the polymerization process of segmented copolymer and described steam stripped is generally 0.1 quality % ~ 2 quality % (ratio relative to the water of stripping band), if this scope then can not cause the interference in running, the grain bits with good particle diameter can be obtained.After water ratio being adjusted to 1 quality % ~ 30 quality % by dewatering to the grain bits of the segmented copolymer containing moisture obtained above, carry out drying until water ratio is below 1 quality %.

In the dehydration procedure of described grain bits, the pressurized water extrusion machines such as roller, Banbury (Banbury) formula water extracter, screw extrusion press formula extruding-desiccation machine can be utilized to dewater simultaneously, or utilize travelling belt, box hot air dryer carries out dewatering and dry.

If the block rate forming the block A of the adhesion binding agent segmented copolymer of this real mode is the scope of 95.0% ~ 99.0%, then segmented copolymer can not fuse and can carry out drying smoothly.If block rate is less than 95.0%, segmented copolymer fuses to each other, tends to be bonded in and transmits on zone face or be attached on the wall of compartment dryer.

[adhesion adhesive composition]

(formation)

The adhesion adhesive composition of present embodiment contains above-mentioned (i) adheres binding agent segmented copolymer and (ii) tackifier described later and (iii) described later tenderizer, and as required containing other compositions described later.

It should be noted that, preferably select according to the number-average molecular weight of purposes to composition (a) ~ (d) in segmented copolymer, adjustment tackifier, tenderizer use level separately.

The adhesion adhesive composition of present embodiment (i) preferably containing the above-mentioned present embodiment of 100 mass parts is adhered binding agent segmented copolymer, (ii) tackifier of 100 mass parts ~ 400 mass parts and (iii) tenderizer of 50 mass parts ~ 150 mass parts.

Thus, excellent binding property, bounding force, confining force, solvability, coating can be obtained in the adhesion adhesive composition of present embodiment.

In above-mentioned adhesion adhesive composition, more preferably the amount of (ii) tackifier is 150 mass parts ~ 400 mass parts, more preferably 200 mass parts ~ 400 mass parts.In addition, more preferably the amount of (iii) tenderizer is 70 mass parts ~ 130 mass parts.

(tackifier)

Form present embodiment adhesion adhesive composition tackifier can according to the purposes of the adhesion adhesive composition that will obtain, require that performance carries out diversified selection.

The known tackifier resins such as such as coumarone system resin, fragrant family hydrocarbon resin, rosin series resin, terpine resin, petroleum resin, phenolic aldehyde system resin, terpene-phenolic system resin, alicyclic ring family hydrocarbon resin, hydriding terpene system resin, staybelite system resin can be enumerated.

These tackifier resins can be used alone, and also can mix two or more and use.

(tenderizer)

Tenderizer for the adhesion adhesive composition forming present embodiment is not particularly limited, and can use treated oil and their mixing oil of known alkane hydrocarbon system or cycloalkanes hydrocarbon system.

(other compositions)

The stablizer such as antioxidant, photostabilizer can be added as required in the adhesion adhesive composition of present embodiment, and other additives.

As antioxidant, such as 2 can be enumerated, 6-di-tert-butyl-4-methy phenol, Octadecane base-3-(4 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) propionic ester, 2, 2 '-methylene-bis (4-methyl-6-tert-butylphenol), 2, 2 '-methylene-bis(4-ethyl-6-t-butyl phenol), 2, two [(pungent sulfenyl) methyl] ortho-cresol of 4-, the 2-tertiary butyl-6-(the 3-tertiary butyl-2-hydroxy-5-methyl base benzyl)-4-aminomethyl phenyl acrylate, 2, 4-bis--tert-pentyl-6-[1-(3, 5-bis-tert-pentyl-2-hydroxyphenyl) ethyl] phenyl acrylate, 2-[1-(2-hydroxyl-3, 5-di-tert-pentyl-phenyl)] the hindered phenol system antioxidant such as acrylate, the sulphur system antioxidants such as Tyox B, thio-2 acid bay octadecyl ester, tetramethylolmethane four (β-lauryl thiopropionate), the phosphorous antioxidants etc. such as three (nonyl phenyl) phosphorous acid ester, three (2,4-di-tert-butyl-phenyl) phosphorous acid ester

The addition of antioxidant is arbitrary, is preferably below 5 mass parts relative to the adhesion adhesive composition of 100 mass parts.

As photostabilizer, can enumerate such as 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-tert-butyl-phenyl) the benzotriazole system UV light absorber such as benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chlorobenzotriazole; The benzophenone series UV light absorber such as ESCALOL 567; Or hindered amine system photostabilizer etc.

Except aforementioned stable agent, also can add the pigment such as red iron oxide, titanium dioxide in the adhesion adhesive composition of present embodiment as required; The wax classes such as paraffin, Microcrystalline Wax, low molecular weight polyethylene wax; The polyolefin such as amorphous polyolefin, ethylene-ethyl acrylate copolymer or low-molecular-weight vinyl aromatic based thermoplastic resin; Natural rubber; The synthetic rubber such as the styrene-isoprene based block copolymer of the regulation beyond the segmented copolymer of the adhesion adhesive composition of polyisoprene rubber, polybutadiene rubber, styrene butadiene rubbers, ethylene-propylene rubber, neoprene, acrylic rubber, isoprene-isobutene rubbers, polycyclic amylene rubber and formation present embodiment.

(characteristic)

The performance of the adhesive tape obtained by the adhesion adhesive composition of present embodiment is preferably, annular initial bonding strength: (N/15mm)/50 are more than 0.8; Bounding force P:(N/10mm)/10 be more than 0.8; Confining force C:(minute)/10 be more than 0.8.The numeral of projects is more preferably more than 0.9, and more preferably more than 0.95.

The performance of the adhesive tape obtained by the adhesion adhesive composition of present embodiment can use the adhesive tape prepared according to the condition shown in embodiment described later, measures according to the condition determination shown in embodiment.

[manufacture method of adhesion adhesive composition]

The adhesion adhesive composition of present embodiment can manufacture by mixing above-mentioned segmented copolymer and tackifier and tenderizer according to known method.

As blending means, can enumerate and such as utilize mixing machine, kneader etc. in a heated condition to the mixed uniformly method of segmented copolymer, tackifier and tenderizer.

Temperature in described mixed processes is preferably 130 DEG C ~ 210 DEG C.If be less than 130 DEG C, segmented copolymer likely cannot fully melting, causes dispersion bad.In addition, if more than 210 DEG C, likely because the evaporation etc. of the low molecular weight compositions of the crosslinked of segmented copolymer and tackifier causes the deterioration of adhesion bonding characteristic.Preferred mixing temperature is 140 DEG C ~ 200 DEG C, is more preferably 150 DEG C ~ 190 DEG C.

Mixing time is preferably 5 minutes ~ 90 minutes.If be less than 5 minutes, each composition likely cannot be dispersed.In addition, if more than 90 minutes, likely because the evaporation etc. of the low molecular weight compositions of the crosslinked of segmented copolymer and tackifier causes the deterioration of adhesion bonding characteristic.Preferred mixing time is 10 minutes ~ 80 minutes, is more preferably 20 minutes ~ 70 minutes.

As described tackifier, preferably can use fatty family cyclic hydrocarbon resin (such as, Arakawa Chemical Industries, Ltd. of Japan manufactures: ARKON M100), (such as, Yasuhara Chemical Co., Ltd. manufactures terpine resin: Network リ ア ロ Application M115) etc.

As tenderizer, from the view point of tone, (such as, Idemitsu Kosen Co., Ltd. manufactures: PW-90) preferably can to use paraffin series treated oil.

For the adhesion adhesive composition of present embodiment, annular initial bonding strength T:(N/15mm)/50 be more than 0.8; Bounding force P:(N/10mm)/10 be more than 0.8; Confining force: C (minute)/10 are more than 0.8.Annular initial bonding strength, bounding force and confining force can be measured by the method recorded in embodiment described later.

The raising of annular initial bonding strength can be realized by the usage quantity increasing described emollient ingredients.It should be noted that, if increase the usage quantity of emollient ingredients, the decline of confining force can be caused, therefore will adjust mixing ratio according to the characteristic expected.

The raising of bounding force can be realized by the usage quantity increasing described tackifier.It should be noted that, if increase the usage quantity of tackifier, the decline of annular initial bonding strength, confining force can be caused, therefore will adjust mixing ratio according to the characteristic expected.

The raising of confining force can be realized by the usage quantity increasing described segmented copolymer.It should be noted that, if increase the usage quantity of segmented copolymer, then likely can cause the decline of annular initial bonding strength, the melt viscosity of the adhesion adhesive composition of present embodiment raises, processibility (solvability, coating) deterioration, therefore will adjust mixing ratio according to the characteristic expected.

[purposes]

The adhesion adhesive composition of present embodiment has good solubility, coating, and its binding property, bounding force and confining force are excellent, and these adhesion bonding characteristic balances are also good.Owing to producing above-mentioned feature; so various adhesive tape labels class can be used in, back side paste, binding agent etc. that back side paste that back side paste (Li paste) that pressure-sensitive thin plate, pressure-sensitive sheet, surface protective plate film, various lightweight plastic material products formed are fixed, carpet are fixed, ceramic tile are fixed, particularly as binding property adhesive tape with the adhesion binding agent of, binding property sheet film, binding property label, surface protective plate film, sanitary material with being useful.

Embodiment

Below, enumerate specific embodiment and comparative example is described in detail the present invention, but the present invention is not limited to following embodiment.

It should be noted that, in following embodiment and comparative example, the mensuration of the characteristic transitivity of polymkeric substance is carried out according to following.

[characteristic of (I) segmented copolymer]

The finishability > of < (I-1) segmented copolymer

Steam stripped is carried out except after desolventizing to polymeric solution, to deliver to Single screw extrusion type hydraulic pressure crusher containing water particle bits, the bond state for the inwall of the case of the segmented copolymer of grain bits (segmented copolymer) having utilized the box type hot air drying machine of 85 DEG C to dehydration after dry 1 hour and hot air dryer is observed.

As accurately machined benchmark, evaluate from well as follows successively: the average evaluation do not bondd completely by the inwall of segmented copolymer and case is zero; Will slightly visible bonding but the average evaluation that can naturally peel off is Δ ~ zero; By visible some bondings but the average evaluation that can peel off with autograph letter list is Δ; If the inwall secure bond of segmented copolymer and case is not applied great power, the state evaluation that cannot peel off for ×.

< (I-2) styrene content >

A certain amount of segmented copolymer is dissolved in chloroform, with ultraviolet spectrophotometer, (Shimadzu Seisakusho Ltd. manufactures, UV-2450) measure, utilize typical curve to calculate styrene content according to the peak intensity of the absorbing wavelength caused by styrene content (262nm).

< (I-3) styrene block content >

Accurate weighing is about the segmented copolymer of 0.07g, be dissolved in the chloroform of 10mL, the solution of the osmic acid/tertbutyl peroxide (concentration: 0.1g/33mL) of 20mL is added in chloroformic solution, reflux 15 minutes in the hot water bath of 90 DEG C ~ 95 DEG C, cut off the double bond of butadiene component.

Add methyl alcohol, after making undecomposed components settle, use glass filter to filter, filtrate is dissolved in chloroform.

The soln using ultraviolet spectrophotometer obtained (Shimadzu Seisakusho Ltd. manufactures, UV-2450) is measured, utilizes typical curve to calculate styrene block content according to the peak intensity of the absorbing wavelength caused by styrene content (262nm).

< (I-4) molecular weight >

Utilize gel permeation chromatograph (GPC: device is that Waters manufactures) to measure, tetrahydrofuran (THF) is used as solvent, and condition determination is measure the temperature of 35 DEG C.

Molecular weight is the number-average molecular weight using the typical curve calculated by measuring commercially available polystyrene standard (using the peak molecular weight of polystyrene standard to make) to obtain the molecular weight of the peak value of chromatogram.

It should be noted that, have in chromatogram 2 with upward peak when, molecular weight refers to the molecular-weight average calculated by the molecular weight at each peak and the ratio of components (being obtained by the area ratio of chromatogram peak value separately) at each peak.

The vinyl bond content > in < (I-5) divinyl portion

Use Infrared spectrophotometer (Perkinelmer manufactures, model 1710) to measure, measure according to Hampton method (being recorded in " Analytical Chem., 21,943 (' 43) ").

The mensuration of physical property of adhesive composition [(II) adhere]

< (II-1) adheres the solvability > of adhesive composition

Reading the change in torque of the adding pressure type kneader (manufactured by Co., Ltd.'s gloomy mountain making, D0.3-3 type kneader) being used as mixing device, is the time of dissolving when velocity of variation is within 1%.

For deliquescent judgment standard, evaluating from well as follows successively: be average evaluation within 40 minutes by dissolution time be zero, is Δ by the average evaluation of 40 minutes ~ 60 minutes, by the average evaluation of more than 60 minutes be ×.

< (II-2) adheres the melt viscosity > of adhesive composition

The melt viscosity of adhesion adhesive composition measures by utilizing cloth (Brookfield) viscometer (Brookfield company manufactures DV-III) the temperature of 180 DEG C.

< (II-3) adheres the softening temperature > of adhesive composition

The softening temperature of adhesion adhesive composition measures as follows, according to JIS-K2207, sample is filled in the ring of regulation, horizontal support in water, the ball of 3.5g is placed in the central authorities of sample, when making fluid temperature rise with the speed of 5 DEG C/min, the weight measured due to ball makes the temperature during contacts baseplate of sample and land.

< (II-4) coating >

Be dropped in by the adhesion adhesive composition of melting on the hot plate being heated to 160 DEG C, visual observation is carried out in the adhesion adhesive-coated face after being coated with using the coating machine being heated to 160 DEG C.

For the judgment standard of coating, evaluate from well as follows successively: will uneven state evaluation do not had completely to be zero; Be Δ ~ zero by the uneven state evaluation being less than 20%; Be more than 20% and the state evaluation being less than 50% is Δ by uneven; By uneven be more than 50% state evaluation for ×.

By the adhesion adhesive composition cool to room temperature of melting, be dissolved in toluene, utilize coating machine to be coated on polyester film, afterwards, keep 30 minutes at room temperature, keep 7 minutes in the baking oven of 70 DEG C, toluene is evaporated completely, prepares the adhesive tape that thickness is 50 μm.

Binding property (annular initial bonding strength), bounding force, the confining force of adhesion adhesive composition are measured by following method.

< (II-5) binding property (annular initial bonding strength) >

Use the Both ring sam that 205mm length × 15mm is wide, the condition of the contact area according to PE (polyethylene) plate: 15mm × 50mm, tack time 3sec, bonding and peeling rate: 500mm/min measures.

With measured value T (N/15mm)/50 for mark, if more than 1.0 are then judged as having practical excellent performance, if more than 0.8 is then judged as having practical sufficient performance.

< (II-6) bounding force >

Measuring method 1 according to the peel adhesion of JIS Z0237: to the measuring method of test board 180 ° of peel adhesion, is attached on polyethylene board by sample wide for 25mm, is that the condition of 300mm/min measures 180 ° of bounding forces with peeling rate.

With measured value P (N/10mm)/30 for mark, if more than 1.0 are then judged as having practical excellent performance, if more than 0.8 is then judged as having practical sufficient performance.

< (II-7) confining force >

For confining force, attach described adhesive tape sample according to the mode making the area of 25mm × 25mm contact with stainless steel plate and PE plate, apply the load of 1kg at 60 DEG C, measure the time till adhesive tape comes off.

With measured value C (minute)/10 for mark, if more than 1.0 are then judged as having practical excellent performance, if more than 0.8 is then judged as having practical sufficient performance.

It should be noted that, the summation score of above-mentioned binding property, bounding force, confining force is high, be then judged as that the performance balance as adhesion adhesive composition is excellent.

[preparation of (III) block copolymer component]

< polymkeric substance 1:2 official can coupling styrene-butadiene block copolymer >

By the inner capacities with stirrer and chuck be the stainless steel autoclave of 10L clean, dry, carry out nitrogen replacement, load 5720g hexanaphthene, vinylbenzene that 280g refines in advance, in chuck, pass into warm water content is set in about 40 DEG C.

Then, add n-Butyl Lithium cyclohexane solution (pure be divided into 1.5g), start cinnamic polymerization.

Due to cinnamic polymerization, from reaching top temperature (53 DEG C) after 6 minutes, decline after 2 DEG C from top temperature, add 520g divinyl (1,3-divinyl), continue polymerization, from divinyl almost completely polymerization to reach top temperature (89 DEG C) after 30 seconds, add the ethyl benzoate as coupling agent, make it carry out coupling.

Add coupling agent after 10 minutes, add 1.6g water and make its inactivation.

In the block copolymer solution obtained, add 0.3 mass parts octadecyl-3-(3,5-dibutyl-tert-butyl-hydroxy phenyl) propionic ester relative to the above-mentioned segmented copolymer of 100 mass parts and fully mix.When carrying out steam stripped to above-mentioned polymeric solution, as grain bits agent, α-(to nonyl phenyl)-ω-hydroxyl that use is 30ppm relative to the water of stripping band gathers the dihydro diolefine phosphoric acid ester of (oxygen ethene) and the mixture of a hydrogen diolefine phosphoric acid ester, at 90 DEG C ~ 98 DEG C except desolventizing.

The concentration of the polymer beads bits in the slurry in solvent removing groove is about 5 quality %.

Then, the water-dispersion slurry of being considered to be worth doing shape segmented copolymer by grain obtained above is delivered on rotary aperture plate (screen), obtains considering to be worth doing containing water particle of water ratio 45 quality %.This is delivered to Single screw extrusion type hydraulic pressure crusher containing water particle bits, obtains the polymkeric substance of dehydration.Dry 1 hour (segmented copolymer obtained is set to polymkeric substance 1) of the box type hot air drying machine of 85 DEG C is utilized to these bits.Polymkeric substance 1 water white transparency obtained.

In polymkeric substance 1, the styrene content used in order to polymerizable vinyl aromatic monomeric unit polymer blocks (A) is 35 quality % relative to polymkeric substance 1 entirety, styrene block content (quality %) in vinyl aromatic monomers unit polymer blocks (A) is 97.5% (be called styrene block rate relative to the whole styrenic monomer units amounts (quality %) used to be polymerized this vinyl aromatic monomers unit polymer blocks (A), identical below), the number-average molecular weight of composition (a) is 6.3 ten thousand, the number-average molecular weight of composition (d) is 12.8 ten thousand.

In addition, the segmented copolymer as the diblock structure of the styrene butadiene of the suitable product of composition (a) contains 70 quality %.It should be noted that, the vinyl bonds amount in divinyl portion is 12.5%.

Polymkeric substance 1 is composition (d): ((A-B) _mx) (m=2) and composition (a): the mixture of (A-B).

< polymkeric substance 2:3 official can coupling styrene-butadiene block copolymer >

By the inner capacities with stirrer and chuck be the stainless steel autoclave of 10L clean, dry, carry out nitrogen replacement, load 5720g hexanaphthene, vinylbenzene that 240g refines in advance, in chuck, pass into warm water content is set in about 40 DEG C.

Then, add n-Butyl Lithium cyclohexane solution (pure be divided into 1.4g), start cinnamic polymerization.

Due to cinnamic polymerization, from reaching top temperature (51 DEG C) after 5 minutes, decline after 2 DEG C from top temperature, add 560g divinyl (1,3-divinyl), continue polymerization, from divinyl almost completely polymerization to reach top temperature (91 DEG C) after 35 seconds, add the triethoxyl silane as coupling agent, make it carry out coupling.

Add coupling agent after 10 minutes, add 1.6g water and make its inactivation.

In the block copolymer solution obtained, 0.3 mass parts octadecyl-3-(3 is added relative to the above-mentioned segmented copolymer of 100 mass parts, 5-dibutyl-tert-butyl-hydroxy phenyl) propionic ester, afterwards, in the same manner as the manufacturing process of above-mentioned polymkeric substance 1, steam stripped is carried out to solution, after isolating polymer solvent, carry out drying (segmented copolymer obtained is set to polymkeric substance 2).Polymkeric substance 2 water white transparency obtained.

In polymkeric substance 2, the styrene content used in order to polymerizable vinyl aromatic monomeric unit polymer blocks (A) is 30 quality % relative to polymkeric substance 2 entirety, described styrene block rate is 95.8%, the number-average molecular weight of composition (a) is 3.8 ten thousand, and the number-average molecular weight of composition (d) is 11.2 ten thousand.

In addition, the segmented copolymer of the diblock structure of styrene butadiene contains 75 quality %.It should be noted that, the ethylenic linkage amount in divinyl portion is 13.5%.

Polymkeric substance 2 is compositions (d): ((A-B) _mx) (m=3) and composition (a): the mixture of (A-B).

< polymkeric substance 3: the mixture > of styrene-butadiene block copolymer and styrene-butadiene-styrene block copolymer

By the inner capacities with stirrer and chuck be the stainless steel autoclave of 10L clean, dry, carry out nitrogen replacement, load 5720g hexanaphthene, vinylbenzene that 120g refines in advance, in chuck, pass into warm water content is set in 40 DEG C.

Then, add n-Butyl Lithium cyclohexane solution (pure be divided into 1.4g), start cinnamic polymerization.

Due to cinnamic polymerization, from reaching top temperature (50 DEG C) after 7 minutes, decline after 2.5 DEG C from top temperature, add 560g divinyl (1,3-divinyl), continue polymerization, from divinyl almost completely polymerization to reach top temperature (88 DEG C) after 40 seconds, again add 120g vinylbenzene and proceed polymerization, due to cinnamic polymerization, from reaching top temperature (95 DEG C) after 8 minutes, declining after 3 DEG C from top temperature, adding 0.5g water and make its inactivation.

In the block copolymer solution obtained, 0.3 mass parts octadecyl-3-(3 is added relative to the above-mentioned segmented copolymer of 100 mass parts, 5-dibutyl-tert-butyl-hydroxy phenyl) propionic ester, after the polymers soln obtained is mixed with polymkeric substance (styrene-butadiene block copolymer) solution before the coupling of polymkeric substance 1, in the same manner as the manufacturing process of above-mentioned polymkeric substance 1, steam stripped is carried out to solution, after isolating polymer solvent, carry out drying (segmented copolymer obtained is set to polymkeric substance 3).Polymkeric substance 3 water white transparency obtained.

In polymkeric substance 3, the styrene content used in order to polymerizable vinyl aromatic monomeric unit polymer blocks (A) is 33.5 quality % relative to polymkeric substance 3 entirety, described styrene block rate is 97.3%, the number-average molecular weight of composition (a) is 6.3 ten thousand, and the number-average molecular weight of composition (c) is 120,000.In addition, the ethylenic linkage amount in divinyl portion is 12.8%.

Polymkeric substance 3 is compositions (a): (A-B) and composition (c): ((A-B) _pa) mixture of (p=1).

< polymkeric substance 4: the mixture > of styrene-butadiene block copolymer and styrene-butadiene-styrene-butadiene block copolymer

By the inner capacities with stirrer and chuck be the stainless steel autoclave of 10L clean, dry, carry out nitrogen replacement, load 5720g hexanaphthene, vinylbenzene that 120g refines in advance, in chuck, pass into warm water content is set in 40 DEG C.

Then, add n-Butyl Lithium cyclohexane solution (pure be divided into 1.35g), start cinnamic polymerization.

Due to cinnamic polymerization, from reaching top temperature (51 DEG C) after 6 minutes, decline after 2 DEG C from top temperature, add 520g divinyl (1, 3-divinyl), continue polymerization, from divinyl almost completely polymerization to reach top temperature (86 DEG C) after 40 seconds, again add 120g vinylbenzene and proceed polymerization, due to cinnamic polymerization, from reaching top temperature (93 DEG C) after 7 minutes, further interpolation 40g divinyl (1, 3 divinyl), continue polymerization, from divinyl almost completely polymerization to reach top temperature (97 DEG C) after 50 seconds, decline after 3 DEG C from top temperature, add 0.5g water and make its inactivation.

In the block copolymer solution obtained, 0.3 mass parts octadecyl-3-(3 is added relative to the above-mentioned segmented copolymer of 100 mass parts, 5-dibutyl-tert-butyl-hydroxy phenyl) propionic ester, by the polymers soln obtained, (polymkeric substance converts: after 35 quality %) mixing with polymkeric substance (styrene-butadiene block copolymer) solution (polymkeric substance converts: 65 quality %) before the coupling of above-mentioned polymkeric substance 1, in the same manner as the manufacturing process of above-mentioned polymkeric substance 1, steam stripped is carried out to solution, after isolating polymer solvent, carry out drying (segmented copolymer obtained is set to polymkeric substance 4).Polymkeric substance 4 water white transparency obtained.

In polymkeric substance 4, the styrene content used in order to polymerizable vinyl aromatic monomeric unit polymer blocks (A) is 33.25 quality % relative to polymkeric substance 4 entirety, described styrene block rate is 97.1%, the number-average molecular weight of composition (a) is 6.3 ten thousand, and the number-average molecular weight of composition (c) is 140,000.In addition, the ethylenic linkage amount in divinyl portion is 12.5%.

Polymkeric substance 4 is compositions (a): (A-B) and composition (b): ((A-B) _n) mixture of (n=1).

< polymkeric substance 5:2 official can coupling styrene-butadiene block copolymer >

Due to cinnamic polymerization, from reaching top temperature (53 DEG C) after 3.5 minutes, declining after 1 DEG C from top temperature, adding 520g divinyl (1,3-butadiene).Other conditions use the method same with the manufacturing process of above-mentioned polymkeric substance 1, obtain polymkeric substance 5.Polymkeric substance 5 water white transparency obtained.

In polymkeric substance 5, the styrene content used in order to polymerizable vinyl aromatic monomeric unit polymer blocks (A) is 35 quality % relative to polymkeric substance 5 entirety, described styrene block rate is 92.1%, the number-average molecular weight of composition (a) is 6.1 ten thousand, and the number-average molecular weight of composition (d) is 12.5 ten thousand.

In addition, the segmented copolymer as the diblock structure of the styrene butadiene of the suitable product of composition (a) contains 70 quality %.It should be noted that, the ethylenic linkage amount in divinyl portion is 12.5%.

Polymkeric substance 5 is compositions (d): ((A-B) _mx) (m=2) and composition (a): the mixture of (A-B).

< polymkeric substance 6:2 official can coupling styrene-butadiene block copolymer >

Add 240g vinylbenzene, due to cinnamic polymerization, from reaching top temperature (53 DEG C) after 21 minutes, and declining after 6 DEG C from top temperature, adding 560g divinyl (1,3-butadiene).Other conditions use the method same with the manufacturing process of above-mentioned polymkeric substance 1, obtain polymkeric substance 6.The polymkeric substance 6 obtained is in yellow.

In polymkeric substance 6, the styrene content used in order to polymerizable vinyl aromatic monomeric unit polymer blocks (A) is 30 quality % relative to polymkeric substance 6 entirety, described styrene block rate is 99.5%, the number-average molecular weight of composition (a) is 6.2 ten thousand, and the number-average molecular weight of composition (d) is 12.6 ten thousand.

In addition, the segmented copolymer as the diblock structure of the styrene butadiene of the suitable product of composition (a) contains 70 quality %.It should be noted that, the ethylenic linkage amount in divinyl portion is 12.2%.

Polymkeric substance 6 is compositions (d): ((A-B) _mx) (m=2) and composition (a): the mixture of (A-B).

< polymkeric substance 7:2 official can coupling styrene-butadiene block copolymer >

Conjugate ratio is changed by carrying out change to the amount of coupling agent ethyl benzoate.Other conditions use the method same with the manufacturing process of above-mentioned polymkeric substance 1, obtain polymkeric substance 7.Polymkeric substance 7 water white transparency obtained.

In polymkeric substance 7, the styrene content used in order to polymerizable vinyl aromatic monomeric unit polymer blocks (A) is 35 quality % relative to polymkeric substance 7 entirety, described styrene block rate is 97.4%, the number-average molecular weight of composition (a) is 6.3 ten thousand, and the number-average molecular weight of composition (d) is 12.8 ten thousand.

In addition, the segmented copolymer as the diblock structure of the styrene butadiene of the suitable product of composition (a) contains 40 quality %.It should be noted that, the ethylenic linkage amount in divinyl portion is 12.5%.

Polymkeric substance 7 is compositions (d): ((A-B) _mx) (m=2) and composition (a): the mixture of (A-B).

< polymkeric substance 8:2 official can coupling styrene-butadiene block copolymer >

Conjugate ratio is changed by carrying out change to the amount of coupling agent ethyl benzoate.Other conditions use the method same with the manufacturing process of above-mentioned polymkeric substance 1, obtain polymkeric substance 8.Polymkeric substance 8 water white transparency obtained.

In polymkeric substance 8, the styrene content used in order to polymerizable vinyl aromatic monomeric unit polymer blocks (A) is 35 quality % relative to polymkeric substance 8 entirety, described styrene block rate is 97.3%, the number-average molecular weight of composition (a) is 6.3 ten thousand, and the number-average molecular weight of composition (d) is 12.8 ten thousand.

In addition, the segmented copolymer as the diblock structure of the styrene butadiene of the suitable product of composition (a) contains 85 quality %.It should be noted that, the ethylenic linkage amount in divinyl portion is 12.5%.

Polymkeric substance 7 is compositions (d): ((A-B) _mx) (m=2) and composition (a): the mixture of (A-B).

< polymkeric substance 9:2 official can coupling styrene-butadiene block copolymer >

By the inner capacities with stirrer and chuck be the stainless steel autoclave of 10L clean, dry, carry out nitrogen replacement, load 5720g hexanaphthene, vinylbenzene that 280g refines in advance, in chuck, pass into warm water content is set in about 40 DEG C.

Then, add n-Butyl Lithium cyclohexane solution (pure be divided into 1.79g), start cinnamic polymerization.

Due to cinnamic polymerization, from reaching top temperature (55 DEG C) after 5 minutes, decline after 2.5 DEG C from top temperature, add 520g divinyl (1,3-divinyl), continue polymerization, from divinyl almost completely polymerization to reach top temperature (91 DEG C) after 25 seconds, add the ethyl benzoate as coupling agent, make it carry out coupling.

Add coupling agent after 10 minutes, add 1.6g water and make its inactivation.

In the block copolymer solution obtained, 0.3 mass parts octadecyl-3-(3 is added relative to the above-mentioned segmented copolymer of 100 mass parts, 5-dibutyl-tert-butyl-hydroxy phenyl) propionic ester, in the same manner as the manufacturing process of above-mentioned polymkeric substance 1, steam stripped is carried out to solution, after isolating polymer solvent, carry out drying (segmented copolymer obtained is set to polymkeric substance 9).Polymkeric substance 9 water white transparency obtained.

In polymkeric substance 9, the styrene content used in order to polymerizable vinyl aromatic monomeric unit polymer blocks (A) is 35 quality % relative to polymkeric substance 9 entirety, described styrene block rate is 96.0%, the number-average molecular weight of composition (a) is 1.5 ten thousand, and the number-average molecular weight of composition (d) is 3.0 ten thousand.

In addition, the segmented copolymer as the diblock structure of the styrene butadiene of the suitable product of composition (a) contains 70 quality %.It should be noted that, the ethylenic linkage amount in divinyl portion is 12.4%.

Polymkeric substance 9 is compositions (d): ((A-B) _mx) (m=2) and composition (a): the mixture of (A-B).

< polymkeric substance 10:2 official can coupling styrene-butadiene block copolymer >

By the inner capacities with stirrer and chuck be the stainless steel autoclave of 10L clean, dry, carry out nitrogen replacement, load 5720g hexanaphthene, vinylbenzene that 280g refines in advance, in chuck, pass into warm water content is set in about 40 DEG C.

Then, add n-Butyl Lithium cyclohexane solution (pure be divided into 1.39g), start cinnamic polymerization.

Due to cinnamic polymerization, from reaching top temperature (52 DEG C) after 7 minutes, decline after 2 DEG C from top temperature, add 520g divinyl (1,3-divinyl), continue polymerization, from divinyl almost completely polymerization to reach top temperature (88 DEG C) after 25 seconds, add the ethyl benzoate as coupling agent, make it carry out coupling.

Add coupling agent after 10 minutes, add 1.6g water and make its inactivation.

In the block copolymer solution obtained, 0.3 mass parts octadecyl-3-(3 is added relative to the above-mentioned segmented copolymer of 100 mass parts, 5-dibutyl-tert-butyl-hydroxy phenyl) propionic ester, in the same manner as the manufacturing process of above-mentioned polymkeric substance 1, steam stripped is carried out to solution, after isolating polymer solvent, carry out drying (segmented copolymer obtained is set to polymkeric substance 10).Polymkeric substance 10 water white transparency obtained.

In polymkeric substance 10, the styrene content used in order to polymerizable vinyl aromatic monomeric unit polymer blocks (A) is 35 quality % relative to polymkeric substance 10 entirety, described styrene block rate is 96.7%, the number-average molecular weight of composition (a) is 9.8 ten thousand, and the number-average molecular weight of composition (d) is 19.6 ten thousand.

In addition, the segmented copolymer as the diblock structure of the styrene butadiene of the suitable product of composition (a) contains 70 quality %.It should be noted that, the ethylenic linkage amount in divinyl portion is 12.7%.

Polymkeric substance 10 is compositions (d): ((A-B) _mx) (m=2) and composition (a): the mixture of (A-B).

Then, use above-mentioned various adhesion binding agent segmented copolymers to prepare adhesion adhesive composition.

[embodiment 1]

Relative to 100 mass parts segmented copolymers (polymkeric substance 1), coordinate with the proportioning of 100 mass parts as the Diana Process Oil PW-90 (Idemitsu Kosen Co., Ltd. manufactures) of tenderizer according to the ARKONM100 (Arakawa Chemical Industries, Ltd.'s manufacture) of 300 mass parts as tackifier, utilize the two wrist type kneader (model: D0.3-3 of pressurization, the gloomy mountain of Co., Ltd. makes manufactured) carry out the melting mixing of 180 DEG C × 30 minutes, obtain flaxen uniform hot-melting type adhesion adhesive composition.

It should be noted that, in adhesion adhesive composition, relative to segmented copolymer described in 100 mass parts (polymkeric substance 1), coordinate 1 mass parts as the 2-tertiary butyl-6-(the 3-tertiary butyl-2-hydroxy-5-methyl base the benzyl)-4-aminomethyl phenyl acrylate of stablizer.

According to the measuring method of above-mentioned adhesion adhesive composition, measurement result is as follows: melt viscosity (in 180 DEG C) is 920 (mPas), and softening temperature is 89.8 DEG C.

In addition, coating is good, and annular initial bonding strength is 53.4N/15mm, and bounding force is 30.7N/10mm, and confining force is 10.3 minutes, very good in practicality.

[embodiment 2 ~ 4], [comparative example 1 ~ 10]

According to the cooperation shown in following table 1, table 2, according to method similarly to Example 1, use ARKON M100 as tackifier, use Diana Process Oil PW-90 as tenderizer, preparation adhesion adhesive composition, evaluates its characteristic respectively.

It should be noted that, carry out 40 minutes mixing moments of torsion still in unstabilized situation, always mixing to torque levels.

[table 1]

[table 2]

The adhesion binding agent segmented copolymer (polymkeric substance 1 ~ 4) of known embodiment 1 ~ 4 all has practical good finishability.

In addition, in the adhesion binding agent composition of known embodiment 1 ~ 4, respectively adhesion binding agent characteristic is good for any one annular initial bonding strength (binding property), bounding force, confining force etc., and these performance balances are excellent, and solvability, coating are also excellent.

Its content, based on the Japanese patent application (Patent 2010-232925) submitted to Japanese Patent Office on October 15th, 2010, is incorporated herein by the application as a reference.

Industrial applicibility

Back side paste, binding agent etc. that back side paste, ceramic tile that the back side paste that adhesion adhesive composition of the present invention can be used in various tapes labels class, pressure-sensitive thin plate, pressure-sensitive sheet, surface protective plate film, various lightweight plastic material products formed are fixed, carpet are fixed are fixed, particularly have industrial applicibility as the binding property adhesive tape adhesion binding agent of, binding property sheet film, binding property label, surface protective plate film, sanitary material.

Claims (5)

1. an adhesion binding agent segmented copolymer, it contains segmented copolymer as described below, this segmented copolymer possesses at least 2 vinyl aromatic monomers unit polymer blocks (A) and at least 1 polymer blocks (B) based on conjugated diene monomeric unit, wherein

Vinyl aromatic monomers polymer blocks amount (quality %) in described vinyl aromatic monomers unit polymer blocks (A) is 95.0% ~ 99.0% relative to the whole vinyl aromatic monomers quantity of units (quality %) used to be polymerized this vinyl aromatic monomers unit polymer blocks (A)

Further,

Described adhesion binding agent segmented copolymer is made up of the following compositions (a) of 50 quality % ~ 80 quality % and at least any one composition be selected from the group be made up of following compositions (b), (c) and (d) of 20 quality % ~ 50 quality %

(a): what represent with general formula (A-B) has 20,000 ~ 80, the Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock of the number-average molecular weight of 000;

(b): with (A-B) _nwhat represent has 40,000 ~ 160, the segmented copolymer of the number-average molecular weight of 000, and n is the integer of more than 2;

(c): with (A-B) _pwhat A represented has 40, the segmented copolymer of the number-average molecular weight of 000 ~ 160,000, and p is the integer of more than 1;

(d): with general formula (A-B) _mwhat X represented has 40, the branched block copolymer of the number-average molecular weight of 000 ~ 160,000, wherein, m be 2 or 3, X represent the residue of coupling agent or the residue of polymerization starter.

2. an adhesion adhesive composition, it contains:

(i) adhesion binding agent according to claim 1 segmented copolymer: 100 mass parts;

(ii) tackifier: 100 mass parts ~ 400 mass parts;

(iii) tenderizer: 50 mass parts ~ 150 mass parts.

3. adhere as claimed in claim 2 adhesive composition, wherein, this adhesion adhesive composition meets the condition of following (1) ~ (3):

(1): annular initial bonding strength T (N/15mm)/50 is more than 0.8;

(2): what measure according to the measuring method of the peel adhesion of JIS Z0237 is more than 0.8 for test board 180 ° of peel adhesion P (N/10mm)/30;

(3): confining force C (minute)/10 are more than 0.8.

4. adhere the manufacture method of binding agent segmented copolymer, it is the manufacture method of adhesion binding agent segmented copolymer according to claim 1, and wherein, this manufacture method has following operation:

The operation of being polymerized the described vinyl aromatic monomers unit polymer blocks (A) of preparation is carried out to vinyl aromatic monomers unit; With

When from the top temperature arrived in described operation of being polymerized vinyl aromatic monomers unit through more than 4 minutes less than 20 minutes and when have dropped more than 1.5 DEG C than described top temperature, the operation of interpolation conjugated diene monomeric unit.

5. the manufacture method of adhesion binding agent segmented copolymer as claimed in claim 4, it is the manufacture method of the adhesion binding agent segmented copolymer according to claim 1 containing described composition (c), wherein,

Described to carry out being polymerized the operation of the described vinyl aromatic monomers unit polymer blocks (A) of preparation to vinyl aromatic monomers unit after, when when have dropped more than 1.5 DEG C than top temperature, adding the deactivator for making the polymerization of described segmented copolymer stop through more than 4 minutes less than 20 minutes from arriving the top temperature of this operation.