KR20130054344A - Block copolymer for adhesive, production method therefor, and adhesive composition - Google Patents

Abstract

[PROBLEMS] To provide a block copolymer for an adhesive with good finish and an adhesive composition having excellent adhesive properties and good performance balance and further excellent solubility and coating property. [Solution] A vinyl in the vinyl aromatic monomer unit polymer block (A), comprising at least two vinyl aromatic monomer unit polymer blocks (A) and a polymer block (B) mainly composed of at least one conjugated diene monomer unit. The aromatic monomer polymer block amount (mass%) is 95.0 to 99.0% with respect to the total vinyl aromatic monomer unit amount (mass%) used for polymerizing the vinyl aromatic monomer unit polymer block (A), and the polymer block A, Block copolymer for adhesives which selectively contains the block copolymer components (a)-(d) which have a specific structure provided with B.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a block copolymer for a pressure-sensitive adhesive,

The present invention relates to a block copolymer for an adhesive, a production method thereof and an adhesive composition.

Recently, a vinyl aromatic monomer-conjugated diene monomer-based block copolymer (SBS: styrene-butadiene-styrene block copolymer, SIS: styrene-isoprene-styrene block copolymer) as a base polymer of a solution type or hot melt adhesive or pressure-sensitive adhesive Is widely used. For example, Patent Literature 1 and Patent Literature 2 disclose compositions for adhesives or compositions for adhesives using SBS. However, since the adhesive composition or adhesive composition using SBS and SIS is insufficient in the adhesive agent property balance of adhesive force, tack, and holding force, improvement in these performance aspects is desired, and patent document 3 and non- In patent document 1, the composition for adhesives containing a triblock copolymer and a diblock copolymer is disclosed.

However, also in any of the above-mentioned pressure-sensitive adhesive compositions and compositions for adhesives, the improvement effect of the various performance aspects is insufficient.

With respect to such improvement requests, Patent Documents 4 and 5 disclose compositions for pressure-sensitive adhesives comprising block copolymers obtained by coupling with specific difunctional coupling agents (aliphatic monoesters, specific dihalogen compounds). .

Japanese Patent Publication No. 44-17037 Japanese Patent Publication No. 56-49958 Japanese Patent Laid-Open No. 61-278578 Japanese Patent Laid-Open No. 61-261310 Japanese Patent Laid-Open No. 3-285978

 Itsui Ishii, "Quality design of SIS base adhesive", adhesion, polymer publication, January 25, 1988 (Showa 63), Vol. 32, No. 1, pages 27-28

However, in addition to the balance of holding force and adhesiveness, the composition for adhesives disclosed in patent documents 4 and 5 needs further improvement from a viewpoint of solubility and coatability.

Therefore, in the present invention, in view of the above-mentioned problems of the prior art, a block copolymer having excellent finish, that is, easy handling and excellent workability, good balance of properties such as adhesive force and holding force, good solubility, It aims at providing the adhesive agent composition excellent also in coatability.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject of the said prior art, the block copolymer for adhesives which combined the block copolymer which has a specific structure, and the adhesive agent composition using the said block copolymer are the said subjects. It has been found to effectively solve the problem and to complete the present invention.

That is, the present invention is as follows.

[1] A block copolymer for an adhesive, comprising a block copolymer having at least two vinyl aromatic monomer unit polymer blocks (A) and a polymer block (B) mainly composed of at least one conjugated diene monomer unit.

The vinyl aromatic monomer polymer block amount (mass%) in the vinyl aromatic monomer unit polymer block (A) is based on the total vinyl aromatic monomer unit amount (mass%) used to polymerize the vinyl aromatic monomer unit polymer block (A). 95.0 to 99.0%, and

The block copolymer for adhesives which consists of 50-80 mass% of following components (a) and 20-50 mass% of at least one component chosen from the group which consists of following components (b), (c), and (d).

(a): Diblock copolymer having a number average molecular weight of 20,000 to 80,000 represented by formula (A-B).

(b): A block copolymer in which _n is an integer of 2 or more and has a number average molecular weight of 40,000 to 160,000 represented by (AB) _n .

(c): a block copolymer in which p is an integer of 1 or more and has a number average molecular weight of 40,000 to 160,000 represented by (AB) _p A.

(d): Branched block copolymer wherein _m is any one of 2, 3, 4 and has a number average molecular weight of 40,000 to 160,000 represented by formula (AB) _m X. In addition, X represents the residue of a coupling agent or the residue of a polymerization initiator.

[2] (iii) The block copolymer for adhesive agent according to the above [1]: 100 parts by mass,

(Ii) tackifier: 100-400 parts by mass,

(Iii) Softener: 50 to 150 parts by mass

Adhesive composition containing a.

[3] The adhesive agent composition according to the above [2], which satisfies the requirements of the following (1) to (3).

(1): roof tack T (N / 15mm) / 50 is 0.8 or more

(2): 180 degree peel adhesive force P (N / 10mm) / 30 with respect to the test plate measured according to the measuring method of peel adhesive force of JISZ0237 is 0.8 or more

(3): holding force C (minutes) / 10 is 0.8 or more

[4] A method for producing the block copolymer for adhesive agent according to the above [1],

Polymerizing the vinyl aromatic monomer unit to prepare the vinyl aromatic monomer unit polymer block (A)

4 minutes or more and 20 minutes or less have passed since the conjugated diene monomeric unit reached the maximum temperature in the process of superposing | polymerizing the said vinyl aromatic monomeric unit and producing the said vinyl aromatic monomeric unit polymer block (A), and the said maximum temperature Process to add at time lower than 1.5 degreeC more

The manufacturing method of the block copolymer for adhesive agents which has a thing.

[5] A method for producing the block copolymer for an adhesive according to the above [1], containing the component (c),

The deactivator for terminating the polymerization of the block copolymer is 4 minutes from the time of reaching the highest temperature in the step after the step of polymerizing the vinyl aromatic monomer unit to produce the vinyl aromatic monomer unit polymer block (A). The manufacturing method of the adhesive agent block copolymer as described in said [4] added more than 20 minutes or less and when it is 1.5 degreeC or more lower than a maximum temperature.

According to the present invention, a block copolymer for an adhesive agent having excellent finish, and an adhesive agent composition having excellent adhesive properties such as adhesive force and holding force, and also having good balance of properties thereof, and further having excellent solubility and coating property Can be provided.

EMBODIMENT OF THE INVENTION Hereinafter, the form (henceforth "this embodiment") for implementing this invention is demonstrated in detail.

In addition, this invention is not limited to the following embodiment, It can variously deform and implement within the range of the summary.

[Block Copolymer for Adhesive Adhesive]

(rescue)

The block copolymer for an adhesive agent of this embodiment mainly comprises at least two vinyl aromatic monomer unit polymer blocks (A): (hereinafter sometimes referred to as polymer block A or A) and at least one conjugated diene monomer unit. Polymer block (B) as follows: A block copolymer having (hereinafter sometimes referred to as polymer block B or B) is included.

The term "mainly" means that the conjugated diene monomer unit is contained by 50 mass% or more, preferably 70 mass% or more, more preferably 85 mass% or more, and the polymer block (B) in the block copolymer for an adhesive agent Are copolymer blocks of conjugated diene compounds and vinyl aromatic hydrocarbons and / or conjugated diene homopolymer blocks.

As for the block copolymer for adhesive agents of this embodiment, the vinyl aromatic monomer polymer block amount (mass%) in a vinyl aromatic monomeric unit polymer block (A), ie, a vinyl aromatic monomer block rate, has a vinyl aromatic monomer unit polymer block (A) It is 95.0 to 99.0% with respect to the total amount of vinyl aromatic monomer units (mass%) used in order to superpose | polymerize.

Moreover, the block copolymer for adhesive agents of this embodiment is at least any one component 20 chosen from the group which consists of 50-80 mass% of following components (a), and the following components (b), (c), and (d). It consists of 50 mass%.

(a): Diblock copolymer having a number average molecular weight of 20,000 to 80,000 represented by formula (A-B).

(b): A block copolymer in which _n is an integer of 2 or more and has a number average molecular weight of 40,000 to 160,000 represented by (AB) _n .

(c): a block copolymer in which p is an integer of 1 or more and has a number average molecular weight of 40,000 to 160,000 represented by (AB) _p A.

(d): Branched block copolymer wherein _m is any one of 2, 3, 4 and has a number average molecular weight of 40,000 to 160,000 represented by formula (AB) _m X. In addition, X represents the residue of a coupling agent or the residue of a polymerization initiator.

The number average molecular weight of the said component (a)-(d) can be measured by the method of describing in the Example mentioned later.

If the number average molecular weight of the said component (a)-(d) is the said range, the outstanding adhesiveness, adhesive force, holding force, solubility, and coatability will be obtained in the adhesive agent composition of this embodiment mentioned later.

About the range of preferable number average molecular weights, the block copolymer of the said component (a) is 40,000-70,000, More preferably, it is 45,000-65,000, The block copolymer of the said components (b), (c) and (d) 80,000-140,000, More preferably, it is 90,000-130,000.

The combination of the above components (a) to (d) comprises component (a) + component (b), component (a) + component (c), component (a) + component (d), and component (a) + component (b). ) + Component (c), component (a) + component (b) + component (d), component (a) + component (c) + component (d), component (a) + component (b) + component (c ) + Component (d).

As mentioned above, the ratio of the mass of the vinyl aromatic monomer polymer block with respect to the total mass of all the vinyl aromatic monomer units used for superposing | polymerizing a vinyl aromatic monomeric unit polymer block (A), ie, a block rate, is 95.0 to 99.0%. In the block copolymer for an adhesive agent of the present embodiment, the block rate is preferably 97.0 to 99.0%, more preferably 97.5 to 98.5%.

When the said block rate is the said numerical range, isolation processing of the adhesive agent block copolymer of this embodiment, ie, a fusion process can be performed smoothly without causing fusion in a finishing process, and high yield is obtained as a result. Moreover, when the coloring of the block copolymer for adhesive agents is considered, it is preferable that it is 99.0% or less.

In addition, when the vinyl aromatic monomer is styrene, the block rate of a vinyl aromatic monomeric unit polymer block (A) is block rate = styrene block content (mass%) of the vinyl aromatic monomer polymer block in a vinyl aromatic monomeric unit polymer block (A). It can calculate by / styrene content (mass%) * 100.

Although content of styrene is not specifically limited in the vinyl aromatic monomeric unit in the block copolymer for adhesive agents of this embodiment, for example, said adhesiveness, (tack-tack) in the adhesive agent composition of this embodiment mentioned later It is preferable that it is 10-60 mass% from a viewpoint of the balance of each adhesive agent characteristic of adhesive force and a holding force, More preferably, it is 20-50 mass%.

If content of a vinyl aromatic monomeric unit is 10 mass% or more, the adhesiveness and retention force which are excellent in the adhesive agent composition of this embodiment mentioned later are obtained, and if it is 60 mass% or less, the outstanding adhesive force will be obtained.

Next, the block copolymer (component (a)-(d)) which is a structural component of the block copolymer for adhesive agents of this embodiment is demonstrated.

The components (a) to (d) are block copolymers having a vinyl aromatic monomer unit polymer block (A) and a polymer block (B) mainly composed of a conjugated diene monomer unit, and the constitution and number average molecular weight as described above. Have

As a vinyl aromatic hydrocarbon which comprises the said components (a)-(d), For example, Alkyl styrene, Paramethoxy styrene, Vinyl naphthalene, such as styrene, (alpha) -methylstyrene, p-methylstyrene, and p-tert- butyl styrene Etc. can be mentioned. Styrene is preferable as a vinyl aromatic hydrocarbon.

The conjugated diene compound constituting the components (a) to (d) is a diolefin having a conjugated double bond, for example, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3 -Dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and the like. As the conjugated diene compound, 1,3-butadiene and isoprene are preferable. The conjugated diene compound may be one kind or two or more kinds.

Moreover, as for the vinyl bond amount of the conjugated diene part in the block copolymer for adhesive agents of this embodiment, less than 20% is preferable.

If the vinyl bond amount of a conjugated diene part is less than 20%, the characteristic excellent in heat stability and weather resistance will be obtained. On the other hand, it is preferable that the said vinyl bond amount shall be 8% or more from a viewpoint of heat resistance (heat distortion temperature).

The amount of vinyl bonds can be calculated by the Hampton method using, for example, measurement using a nuclear magnetic resonance device (manufactured by BRUKER, DPX-400) or an infrared spectrophotometer (device name: FT / IR-230; manufactured by Nippon Spectroscopy). Can be.

In order to adjust the vinyl bond amount of the conjugated diene part in a block copolymer, For example, ethylene glycol dimethyl ether, tetrahydrofuran, (alpha)-methoxy tetrahydrofuran, N, N, such as ethers and tertiary amines, It is preferable to use the regulator which consists of 1 type, or 2 or more types of mixtures chosen from, N ', N'- tetramethylethylenediamine, etc.

Specifically, the vinyl bond amount of the conjugated diene portion in the block copolymer is, for example, ethylene glycol dimethyl ether, tetrahydrofuran, α-methoxytetrahydrofuran, N, N, for example, ethers or tertiary amines. The adjusting agent which consists of 1 type, or 2 or more types of mixtures chosen from, N ', N'- tetramethylethylenediamine, etc. can be adjusted by putting in a polymerization solvent in the step before adding a conjugated diene monomer.

[Method of producing block copolymer for adhesive agent]

The block copolymer for an adhesive agent of this embodiment superposes | polymerizes a vinyl aromatic hydrocarbon, for example styrene, using an organolithium compound as a polymerization initiator, for example in an inert hydrocarbon solvent, and then makes a conjugated diene compound, for example butadiene It is obtained by the method of superposing | polymerizing and if necessary repeating these operations, or the method of superposing | polymerizing separately, for example, a styrene-butadiene block copolymer: components (a)-(d). In addition, when producing the mixture of arbitrary ratios of a component (a) and a component (d), it can manufacture by controlling the addition amount of a coupling agent.

The molecular weight of components (a)-(d) can be adjusted to the said predetermined range by controlling the quantity of the organolithium compound which is a polymerization initiator.

After completion | finish of a polymerization reaction, water, alcohol, an acid, etc. are added to inactivate active species, a solution is steam-striped etc., for example, a polymerization solvent is isolate | separated, and the block copolymer for an adhesive agent is obtained by drying.

Although it does not specifically limit as a polymerization method of the block copolymer of the said components (a)-(d), Polymerization methods, such as coordination polymerization, anionic polymerization, or cationic polymerization, are mentioned. Anionic polymerization is preferred in view of ease of structure control.

As a manufacturing method of the block copolymer component by anionic polymerization, a well-known method can be used, For example, Unexamined-Japanese-Patent No. 36-19286, Unexamined-Japanese-Patent No. 43-17979, and Unexamined-Japanese-Patent No. 46-32415 Japanese Patent Publication No. 49-36975, Japanese Patent Publication No. 48-2423, Japanese Patent Publication No. 48-4106, Japanese Patent Publication No. 56-28925, Japanese Patent Publication No. 59-166518 The method of Unexamined-Japanese-Patent No. 60-186577, etc. are mentioned.

As an inert hydrocarbon solvent used at the superposition | polymerization process of components (a)-(d), For example, Aliphatic hydrocarbons, such as butane, a pentane, hexane, isopentane, heptane, an octane, an isooctane; Alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane; Hydrocarbon solvent, such as aromatic hydrocarbons, such as benzene, toluene, ethylbenzene, and xylene, is mentioned. These may use only 1 type, and may mix and use 2 or more types.

Moreover, as an organolithium compound used at the superposition | polymerization process of components (a)-(d), a well-known compound, for example, ethyl lithium, propyl lithium, n-butyl lithium, sec-butyl lithium, tert- butyl lithium, phenyl Lithium, propenyl lithium, hexyl lithium, and the like. In particular, n-butyllithium and sec-butyllithium are preferable. Only 1 type may be used for an organolithium compound, and 2 or more types of mixtures may be used.

In the block copolymer components (a) to (d), some or all of the unsaturated double bonds derived from the conjugated diene may be hydrogenated. This hydrogenation method is not specifically limited, It is performed using a well-known technique.

The block copolymer (a): general formula: (A-B) can be polymerized by the above-mentioned method.

As mentioned above, A is a vinyl aromatic monomeric unit polymer block, B is a polymer block mainly having a conjugated diene monomeric unit.

Furthermore, the block copolymer (b): general formula: (AB) _n can be polymerized by the above-mentioned method.

As mentioned above, A is a vinyl aromatic monomeric unit polymer block, B is a polymer block mainly having a conjugated diene monomeric unit. n is an integer of 2 or more.

Furthermore, the block copolymer (c): general formula: (AB) _p A can be polymerized by the above-described method.

As mentioned above, A is a vinyl aromatic monomeric unit polymer block, B is a polymer block mainly having a conjugated diene monomeric unit. p is an integer of 1 or more.

Furthermore, the block copolymer (d): general formula: (AB) _m X can be polymerized by the above-described method.

As mentioned above, A is a vinyl aromatic monomeric unit polymer block, B is a polymer block mainly having a conjugated diene monomeric unit.

X represents the residue of each coupling agent, or the residue of initiators, such as each functional organolithium compound.

m is either 2, 3, or 4, and each numerical value shows a functional number.

The coupling agent is selected by the value of m in the formula of the desired block copolymer (d).

That is, all the well-known thing can be used as a bifunctional coupling agent among the said coupling agents, It does not specifically limit. For example epoxy compounds; Halogenated silicon compounds such as dichlordimethylsilane and phenylmethyldichlorosilane; Alkoxysilicon compounds such as dimethyldimethoxysilane and dimethyldiethoxysilane; Tin compounds such as dichlordimethyltin; Ester compounds such as methyl benzoate, ethyl benzoate, phenyl benzoate, and phthalate esters; And vinylarene such as divinylbenzene and the like.

As a trifunctional coupling agent, all well-known thing can be used and it is not specifically limited. Tin compounds such as, for example, methyl trichloride and tributylchlorotin; Silane compounds such as trimethoxysilane and triethoxysilane; And silicon halide compounds such as methyl trichloride and trimethylchlorosilicon.

As a tetrafunctional coupling agent, all well-known thing can be used and it is not specifically limited. Halogenated tin compounds such as, for example, tin tetrachloride; Allyl tin compounds such as tetraallyl tin and tetra (2-octenyl) tin; Tin compounds such as tetraphenyltin and tetrabenzyltin; Silicon halide compounds such as silicon tetrachloride and silicon tetrabromide; Alkoxy silicon compounds, such as tetraphenoxy silicon and tetraethoxy silicon, etc. are mentioned.

As a method of mixing each block copolymer (a)-(d), the method of mixing the solution after completion | finish of polymerization, or the method of blending each block copolymer component obtained by drying with a roll etc. are mentioned.

In addition, when obtaining a mixture of a block copolymer (a) and (d), the mixture ratio of arbitrary ratios with a block copolymer (a) is controlled by controlling the coupling rate at the time of manufacturing a block copolymer (d) as mentioned above. Is obtained.

As for the mixing ratio of each component in the said block copolymer, 20-50 are at least one component chosen from the group which consists of 50-80 mass% of components (a), a component (b), (c), and (d). It is the ratio of mass%.

As for the mixing ratio of each preferable component, 25-45 mass% of at least one component chosen from the group which consists of 55-75 mass% of components (a), components (b), (c), and (d) is more preferable. The mixing ratio of each component is 30-40 mass% of at least one component chosen from the group which consists of 60-70 mass% of components (a), and a component (b), (c), and (d).

Thereby, in the adhesive agent composition of this embodiment mentioned later, the outstanding adhesiveness, adhesive force, holding force, solubility, and coatability are obtained. In particular, since the solubility is good, heat mixing time can be shortened and discoloration by heat deterioration can be prevented.

As mentioned above, the block copolymer for adhesive agents of this embodiment contains at least 2 vinyl aromatic monomeric unit polymer block (A), and the said vinyl aromatic monomeric unit polymer block (A) is the said vinyl aromatic monomeric unit The vinyl aromatic monomer polymer block amount (mass%) with respect to the total vinyl aromatic monomer unit amount (mass%) used in order to superpose | polymerize a polymer block (A), ie, a block rate, is 95 to 99%.

In order to obtain the vinyl aromatic monomeric unit polymer block (A) having the block rate of 95 to 99%, the timing at which the vinyl aromatic monomeric unit is polymerized, the addition of the conjugated diene monomeric unit and the end of the polymerization of the block copolymer are selected. Just do it. In general, as the timing at which the monomers are almost completely polymerized, the elapsed time from when the peak temperature at the end of the polymerization is reached is considered to be about 10 minutes, and the next monomer is added. Or the deactivator for terminating superposition | polymerization is added.

In the block copolymer of the present embodiment, the timing of adding the conjugated diene monomer unit or the timing of terminating the polymerization of the block copolymer is determined by the vinyl aromatic monomer unit in the polymerization step of the vinyl aromatic monomer unit polymer block (A). After 4 to 20 minutes have elapsed since reaching the peak temperature appearing at the end of polymerization, preferably 5 to 15 minutes have elapsed, and the temperature is lowered to 1.5 ° C. or higher, preferably 3 ° C. or higher than the peak temperature. .

The problem that the vinyl aromatic monomeric unit polymer block (A) whose block rate is 95.0 to 99.0% is not obtained when the elapsed time from when the peak temperature is reached is less than 4 minutes and the fall temperature from the peak temperature is less than 1.5 ° C. Causes

In addition, when adding a deactivator in order to complete superposition | polymerization of a block copolymer, the timing of adding a deactivator is the time of completion | finish of superposition | polymerization of a vinyl aromatic monomeric unit, ie, the completion | finish time of the polymerization process of a vinyl aromatic monomeric unit polymer block (A). 4 to 20 minutes, preferably 5 to 15 minutes, more preferably 5 to 12 minutes have elapsed since the peak temperature attained is reached, and further 1.5 ° C. or higher, preferably 3 ° C. or higher, more preferably higher than the peak temperature. Preferably, the temperature is lowered by 3.5 ° C or higher.

If the deactivator is added when the elapsed time from when the peak temperature is reached is less than 4 minutes, a sufficient block rate is not obtained, which is not preferable. In addition, when the elapsed time from the time of reaching the peak temperature is 20 minutes or more, the block rate is increased, but the living end is inactivated, and the tape performance of the tape adhesive of the adhesive agent composition containing the obtained block copolymer is used. Each characteristic balance falls. Moreover, it is not preferable, such that the obtained block copolymer may color.

In addition, the addition timing of the deactivator for terminating superposition | polymerization is suitably selected according to the structure of a block copolymer. That is, in the case of component (c), it becomes after addition of a vinyl aromatic monomeric unit, and in the case of components (a), (b) and (d), it becomes after addition of a conjugated diene monomeric unit.

In the manufacturing method of the block copolymer for adhesive agents of this embodiment, the process of deliming metals derived from a polymerization initiator etc. can be employ | adopted as needed. Moreover, the process of adding a reaction terminator, antioxidant, neutralizing agent, surfactant, etc. can also be employ | adopted as needed.

The block copolymer for an adhesive agent of this embodiment which can be produced as mentioned above has a so-called modified polymer or block copolymer component in which the polar group-containing functional group selected from nitrogen, oxygen, silicon, phosphorus, sulfur and tin is bonded to the polymer. The modified block copolymer modified | denatured with modifiers, such as maleic anhydride, may be obtained, and it is obtained by performing a well-known modification reaction.

As mentioned above, after manufacturing the block copolymer of components (a)-(d) which comprise the block copolymer for adhesive agents of this embodiment, isolation | blocking, ie finishing, of a block polymer is performed by the method mentioned later. .

The polymerization step of the block copolymers (a) to (d) is carried out in an inert hydrocarbon solvent as described above. Therefore, in order to isolate a block copolymer, it is necessary to remove a solvent.

As a method of removing a specific solvent, the method of obtaining a block copolymer by obtaining a water-containing cram by steam stripping and drying the obtained water-containing cram is mentioned.

As a preferred embodiment for removing the solvent by steam stripping, it is common to use a surfactant as the cramating agent in steam stripping, and examples of such surfactants include anionic surfactants, cationic surfactants and nonionic surfactants. These surfactants are generally added in an amount of 0.1 to 3000 ppm relative to the water of the stripping band.

In addition to the above surfactants, water-soluble salts of metals such as Li, Na, Mg, Ca, Al, and Zn can also be used as dispersing aids for cram.

The concentration of the block copolymer of the cram phase dispersed in the water obtained through the polymerization process of the block copolymer and the steam stripping is generally 0.1 to 20% by mass (ratio of stripping band to water). It is possible to obtain a cram having a good particle size without causing. The water content is adjusted to 1-30 mass% by dehydration, the cram of the block copolymer containing the moisture obtained above is dried until water content becomes 1 mass% or less after that.

In the dehydration step of the cram, dehydration in a compression press dehydrator such as a roll, a Banbury dehydrator, a screw extruder compression dehydrator, or a dehydration and drying may be performed simultaneously with a conveyor or a box-type hot air dryer.

If the block rate of the block A which comprises the block copolymer for adhesive agents of this embodiment is 95.0 to 99.0% of range, a block copolymer will not fuse and can dry smoothly. When the block rate is less than 95.0%, the block copolymers tend to be fused to adhere to the conveyor surface or adhere to the wall surface of the box dryer.

[Adhesive Composition]

(Configuration)

The adhesive agent composition of this embodiment contains the block copolymer for adhesives (i) mentioned above, the tackifier (ii) mentioned later, and the softener mentioned later (i), and are mentioned later as needed It contains an ingredient.

Moreover, it is preferable to select the number average molecular weight of components (a)-(d) in a block copolymer according to a use, and to prepare the compounding quantity of each of a tackifier and a softener.

The adhesive agent composition of this embodiment is the block copolymer for (i) adhesive agents of this embodiment mentioned above: 100 mass parts, (ii) tackifier: 100-400 mass parts, and (iii) softener: 50- It is preferable to contain 150 mass parts.

Thereby, the adhesiveness, adhesive force, holding force, solubility, and coatability which are excellent in the adhesive agent composition of this embodiment are obtained.

In the above-mentioned adhesive agent composition, the more preferable amount of the (ii) tackifier is 150-400 mass parts, More preferably, it is 200-400 mass parts. Moreover, the quantity of the more preferable (viii) softener is 70-130 mass parts.

(Tacking agent)

The tackifier which comprises the adhesive agent composition of this embodiment can be variously selected according to the use of the adhesive agent composition obtained, and performance required.

For example, coumarone resin, aromatic hydrocarbon resin, rosin resin, terpene resin, petroleum resin, phenolic resin, terpene-phenolic resin, alicyclic hydrocarbon resin, hydrogenated terpene resin, hydrogenated rosin resin Known tackifier resins, such as these, are mentioned.

These tackifier resins may be used alone or in combination of two or more thereof.

(Softener)

The softener which comprises the adhesive agent composition of this embodiment is not restrict | limited, A well-known paraffin type or a naphthenic process oil and these mixed oil can be used.

(Other components)

Stabilizers, such as antioxidant and a light stabilizer, and other additive can be added to the adhesive agent composition of this embodiment as needed.

As antioxidant, 2, 6- di-t- butyl- 4-methyl phenol, n-octadecyl-3- (4'-hydroxy-3 ', 5'- di-t- butylphenyl) propio Nate, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 2,4-bis [(octyl Thio) methyl] -O-cresol, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate, 2,4-di-t-amyl -6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenylacrylate, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl Hindered phenol-type antioxidants, such as an acrylate; Sulfur-based antioxidants such as dilaurylthiodipropionate and laurylstearylthiodipropionate pentaerythritol tetrakis (β-laurylthiopropionate); Phosphorus antioxidants such as tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, and the like.

Although the addition amount of antioxidant is arbitrary, Preferably it is 5 mass parts or less with respect to 100 mass parts of adhesive agent compositions.

Examples of the light stabilizer include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-t-butylphenyl) benzotriazole, 2- Benzotriazole-based ultraviolet absorbers such as (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole and benzo such as 2-hydroxy-4-methoxybenzophenone A phenone ultraviolet absorber, a hindered amine light stabilizer, etc. are mentioned.

In addition to the stabilizer, the adhesive composition of the present embodiment may include pigments such as bengalla and titanium dioxide, if necessary; Waxes such as paraffin wax, microcrystalline wax and low molecular weight polyethylene wax; Polyolefin-based or low molecular weight vinyl aromatic thermoplastic resins such as amorphous polyolefins and ethylene-ethyl acrylate copolymers; caoutchouc; Polyisoprene rubber, polybutadiene rubber, styrene-butadiene rubber, ethylene-propylene rubber, chloroprene rubber, acrylic rubber, isoprene-isobutylene rubber, polypentenamer rubber, and block air constituting the adhesive agent composition of the present embodiment Synthetic rubbers, such as predetermined styrene-isoprene-type block copolymers other than coalescence, can also be added.

(characteristic)

As for the performance of the adhesive tape obtained from the adhesive agent composition of this embodiment, looptack T: (N / 15mm) / 50 is 0.8 or more, adhesive force P: (N / 10mm) / 10 is 0.8 or more, holding force C: (minutes) / It is preferable that 10 is 0.8 or more. It is more preferable that the numerical value of each item is 0.9 or more, and it is still more preferable that it is 0.95 or more.

The performance of the adhesive tape obtained from the adhesive agent composition of this embodiment can be measured according to the measurement conditions shown in the Example using the adhesive tape produced by the conditions shown in the Example mentioned later.

[Method for Producing Adhesive Composition]

The adhesive agent composition of this embodiment can be manufactured by mixing the above-mentioned block copolymer, a tackifier, and a softener by a well-known method.

As a mixing method, the method of homogeneously mixing a block copolymer, a tackifier, and a softener with a mixer, kneader, etc. under heating conditions is mentioned, for example.

As for the temperature in the said mixing process, 130 degreeC-210 degreeC is preferable. If it is less than 130 degreeC, a block copolymer does not melt enough and there exists a possibility of causing a dispersion defect. Moreover, when it exceeds 210 degreeC, there exists a possibility that the adhesive agent characteristic may deteriorate by crosslinking of a block copolymer, evaporation of the low molecular weight component of a tackifier, etc. Preferable mixing temperature is 140 to 200 degreeC, More preferably, it is 150 to 190 degreeC.

The mixing time is preferably 5 to 90 minutes. If it is less than 5 minutes, there exists a possibility that each component may not be disperse | distributed uniformly. Moreover, when it exceeds 90 minutes, there exists a possibility of causing deterioration of an adhesive agent characteristic by crosslinking of a block copolymer, evaporation of the low molecular weight component of a tackifier, etc. Preferable mixing time is 10 minutes-80 minutes, More preferably, it is 20 minutes-70 minutes.

As said tackifier, aliphatic cyclic hydrocarbon resin (for example, Arakawa Chemical Co., Ltd. make: Alcon M100), a polyterpene resin (for example, Yashara Chemical Co., Ltd. make: Cearon M115), etc. are used preferably. Can be.

As a softener, a paraffinic process oil (for example, Idemitsu Chemical Co., Ltd. make: PW-90) can be used preferably from a viewpoint of color tone.

Looptack T: (N / 15mm) / 50 is 0.8 or more, adhesive force P: (N / 10mm) / 10 is 0.8 or more, and retention force C: (minutes) / 10 is 0.8 or more of the adhesive agent composition of this embodiment. to be. Looptack, adhesive force, and holding force can be measured by the method as described in the Example mentioned later.

The roof tack can be improved by increasing the amount of the softener component. In addition, when the amount of the softener component used is increased, the holding force is lowered, so the blending ratio is adjusted according to the desired characteristics.

Adhesive force can be improved by increasing the usage-amount of the said tackifier. Increasing the amount of the tackifier causes a decrease in the roof tack and the holding force, so that the blending ratio is adjusted according to the desired characteristics.

The holding force can be improved by increasing the amount of the block copolymer used. In addition, when the amount of the block copolymer is increased, the blending ratio may be reduced depending on the desired characteristics, because it may cause a decrease in the loop tack or the melt viscosity of the adhesive composition of the present embodiment may be increased, and workability (solubility and coatability) may decrease. Adjust it.

[Usage]

The adhesive agent composition of this embodiment has favorable solubility and coating property, is excellent in adhesiveness, adhesive force, and holding force, and these adhesive agent balance is also favorable. Taking advantage of these features, it can be used for various adhesive tapes, labels, pressure-sensitive thin plates, pressure-sensitive sheets, surface protection sheets and films, back pastes for fixing various lightweight plastic molded products, back pastes for carpet fixing, back pastes for tile fixing, adhesives, etc. It is especially useful as an adhesive for adhesive tapes, adhesive sheets and films, adhesive labels, surface protective sheets and films, and sanitary materials.

<Examples>

EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated in detail, giving a specific Example and a comparative example, this invention is not limited to a following example.

In addition, in the following Example and the comparative example, the measurement of the characteristic and physical property of a polymer was performed as follows.

[Characteristics of (I) Block Copolymer]

<Finishability of (I-1) Block Copolymer>

After steam stripping the polymerization solution to remove the solvent, the hydrocracker was then sent to a single screw extruder type compression dehydrator, and the dehydrated cram (block copolymer) was dried in a box-type hot air dryer at 85 ° C for 1 hour. The adhesion state of the block copolymer and the inner wall of the box of a hot air dryer was observed.

As a criterion of the finish, the block copolymer is not adhered to the inner wall of the box at all from the better evaluation one by one. (Triangle | delta) was evaluated as x by the block copolymer firmly adhering to the inner wall of a box, and peeling only by applying a very strong force.

<(I-2) Styrene Content>

A certain amount of block copolymer was dissolved in chloroform, measured with an ultraviolet spectrophotometer (UV-2450, manufactured by Shimadzu Corporation), and the styrene content was calculated from the peak intensity of the absorption wavelength (262 nm) attributable to the styrene component. .

<(I-3) Styrene Block Content>

Approximately 0.07 g of block copolymer is precisely dissolved in 10 mL of chloroform, and 20 mL of osmic acid / tertiarybutyl hydroperoxide (concentration: 0.1 g / 33 mL) is added to the chloroform solution in a 90-95 ° C. hot water bath. The mixture was refluxed for 15 minutes, and the double bond of the butadiene component was cleaved.

Methanol was added to precipitate the undecomposed component, and then filtered using a glass filter, and the filtrate was dissolved in chloroform.

The obtained solution was measured with the ultraviolet spectrophotometer (The Shimadzu Corporation make, UV-2450), and the styrene block content was computed from the peak intensity of the absorption wavelength (262 nm) which originates in a styrene component.

<(I-4) Molecular Weight>

It measured by gel permeation chromatography (GPC: the apparatus made by Waters), tetrahydrofuran was used for the solvent, and the measurement conditions were performed at 35 degreeC.

Molecular weight is the quantity average molecular weight calculated | required using the analytical curve (made using the peak molecular weight of standard polystyrene) calculated | required the molecular weight of the peak of a chromatogram from the measurement of commercial standard polystyrene.

In addition, the molecular weight in case there exist multiple peaks in a chromatogram means the average molecular weight calculated | required from the molecular weight of each peak and the composition ratio (obtained from the area ratio of each peak of a chromatogram) of each peak.

<Vinyl bond content of (I-5) butadiene part>

It measured using the infrared spectrophotometer (Perkin Elmer make model 1710), and measured by the Hampton method (described in "Analytical Chem., 21, 943 ('43)").

[(II) Measurement of Physical Properties of Adhesive Adhesive Composition]

<Solubility of (II-1) Adhesive Adhesive Composition>

The torque change of the pressurized kneader (D0.3-3 type kneader manufactured by Moriyama Co., Ltd.) used as a mixing apparatus was read out, and it was set as the time which melt | dissolved the time when the change rate became less than 1%.

As for the criterion of solubility, from the one with good evaluation, the dissolution time evaluated (circle), 40-60 minutes as (triangle | delta) and 60 minutes or more as x for 40 minutes or less.

<(II-2) Melt Viscosity of Adhesive Adhesive Composition>

The melt viscosity of the adhesive agent composition was measured by the Brookfield type viscometer (DV-III by Brookfield) at the temperature of 180 degreeC.

<Softening point of (II-3) adhesive agent composition>

When the softening point of the adhesive agent composition is filled with a sample in a prescribed ring in accordance with JIS-K2207, supported horizontally in water, a 3.5g sphere is placed in the center of the sample, and the liquid temperature is raised at a rate of 5 ° C / min. The temperature of the sample in contact with the bottom plate of the annulus was measured by the weight of the sphere.

<(II-4) Coatability>

The melted adhesive composition was poured onto a hot plate heated at 160 ° C, and the adhesive coated surface after coating with an applicator heated at 160 ° C was visually observed.

The criterion of applicability is △ to ○, non-uniformity of △ to ○, nonuniformity of △ to ○, nonuniformity of △, nonuniformity of 50% or more as × Evaluated.

The melted adhesive composition was cooled to room temperature, dissolved in toluene, coated on a polyester film with an applicator, and then toluene was completely evaporated at room temperature for 30 minutes, in an oven at 70 ° C for 7 minutes, and the adhesive tape having a thickness of 50 μm. Was produced.

The adhesiveness (looptack), adhesive force, and the holding force of the adhesive agent composition were measured by the following method.

<(II-5) Adhesiveness (Loop Tack)>

Using a loop-shaped sample of 250 mm long x 15 mm wide, the contact area with respect to the PE (polyethylene) plate was measured at 15 mm x 50 mm, adhesion time 3 sec, and adhesion and peeling rate: 500 mm / min.

The measured value T (N / 15mm) / 50 was used as a score, and it was judged that it was practically sufficient performance that it was 1.0 or more, and practically sufficient performance if it was 0.8 or more.

<(II-6) Adhesion>

Method for Measuring Peel Adhesion of JIS Z0237 1: According to the method for measuring 180 ° peel adhesion to a test plate, a 25 mm wide sample was attached to a polyethylene plate, and 180 ° adhesion was measured at a peel rate of 300 mm / min.

Measured value P (N / 10mm) / 30 was made into the score, and when it was 1.0 or more, it was judged that it was practically excellent performance, and if it was 0.8 or more, it was practically sufficient performance.

<(II-7) Holding force>

The holding force was affixed to the stainless steel plate and the PE plate so that the area of 25 mm x 25 mm contact | connected the said adhesive tape sample, and it applied the load of 1 kg at 60 degreeC, and measured the time until the adhesive tape shift | deviates and fell.

The measured value C (minutes) / 10 was used as a score, and when it was 1.0 or more, it was judged that it was practically excellent performance, and if it was 0.8 or more, it was practically sufficient performance.

Moreover, it was judged that the one where the total point of the said adhesiveness, adhesive force, and the holding force was higher was excellent in the performance balance as an adhesive agent composition.

[Preparation of (III) Block Copolymer Component]

Polymer 1: Bifunctional Coupling Styrene-Butadiene Block Copolymer

A 10L stainless steel autoclave equipped with a stirrer and a jacket was washed, dried, and nitrogen-substituted, 5720 g of cyclohexane and 280 g of styrene purified beforehand were charged, and the contents were set to about 40 ° C by passing hot water through the jacket.

Next, n-butyllithium cyclohexane solution (1.5 g in pure fraction) was added to initiate polymerization of styrene.

After 6 minutes after reaching the highest temperature (53 ° C) by polymerization of styrene, after 2 ° C is lowered from the highest temperature, 520 g of butadiene (1,3-butadiene) is added to continue the polymerization, and the butadiene is almost completely 30 seconds after superposition | polymerization and reaching maximum temperature (89 degreeC), ethyl benzoate was added as a coupling agent and it couple | coupled.

Ten minutes after the coupling agent was added, 1.6 g of water was added to inactivate it.

0.3 mass part of octadecyl-3- (3,5-dibutyl- t-butyl-4-hydroxyphenyl) propionate is added to the obtained block copolymer solution with respect to 100 mass parts of said block copolymers, and it fully mixes It was. When steam stripping the polymerization solution described above, a mixture of dihydrodiene phosphate ester and monohydrodiene phosphate ester of α- (p-nonylphenyl) -ω-hydroxypoly (oxyethylene) as a cramming agent was added to the stripping water. 30 ppm was used and the solvent was removed at the temperature of 90-98 degreeC.

The concentration of the polymer cram in the slurry in the solvent removal tank was about 5 mass%.

Subsequently, the water dispersion slurry of the cram-like block copolymer obtained above was sent to the rotary screen, and the water content cram of 45 mass% of water content was obtained. This hydrous cram was sent to a single screw extruder type compression dehydrator to obtain a dehydrated polymer. The cram was dried for 1 hour in a box-shaped hot air dryer at 85 ° C (the obtained block copolymer was called polymer 1). Obtained polymer 1 was colorless and transparent.

The styrene content used for polymerizing a vinyl aromatic monomeric unit polymer block (A) is 35 mass% with respect to the whole polymer 1, and the polymer 1 has a styrene block content (mass%) in a vinyl aromatic monomeric unit polymer block (A). It is 97.5% (it is called styrene block rate. The same is hereafter) with respect to the total amount of styrene monomer units (mass%) used for superposing | polymerizing a vinyl aromatic monomeric unit polymer block (A), and the number average molecular weight of component (a) is 6.3 However, the number average molecular weight of component (d) was 12.8 million.

Moreover, the block copolymer of the diblock structure of styrene-butadiene which is a component (a) equivalence product contained 70 mass%. In addition, the vinyl bond amount of the butadiene part was 12.5%.

Polymer 1 was a mixture of m = 2 of component (d): ((AB) _m X) and component (a): (AB).

Polymer 2: Trifunctional Coupling Styrene-Butadiene Block Copolymer

A 10L stainless steel autoclave equipped with a stirrer and a jacket was washed, dried, and nitrogen-substituted, 5720 g of cyclohexane and 240 g of styrene purified beforehand were added thereto, and water was passed through the jacket to set the contents to about 40 ° C.

Next, n-butyllithium cyclohexane solution (1.4 g in pure fraction) was added to initiate polymerization of styrene.

 After 5 minutes after reaching the highest temperature (51 ° C) by polymerization of styrene, after 2 ° C is lowered from the highest temperature, 560 g of butadiene (1,3-butadiene) is added to continue the polymerization, and the butadiene is almost completely 35 seconds after superposition | polymerization and reaching maximum temperature (91 degreeC), triethoxysilane was added and couple | coupled as a coupling agent.

Ten minutes after the coupling agent was added, 1.6 g of water was added to inactivate it.

To the obtained block copolymer solution, 0.3 parts by mass of octadecyl-3- (3,5-dibutyl-t-butyl-4-hydroxyphenyl) propionate is added to 100 parts by mass of the block copolymer. Thereafter, the solution was subjected to steam stripping in the same manner as in the above-described polymer 1 production process to separate the polymerization solvent, and then dried (the obtained block copolymer was referred to as polymer 2). Obtained polymer 2 was colorless transparent.

The content of styrene used for polymerizing a vinyl aromatic monomeric unit polymer block (A) of polymer 2 is 30 mass% with respect to the whole polymer 2, the said styrene block rate is 95.8%, and the number average molecular weight of component (a) is 3.8 However, the number average molecular weight of component (d) was 11.20,000.

Moreover, 75 mass% of block copolymers of the diblock structure of styrene-butadiene were contained. In addition, the vinyl bond amount of the butadiene part was 13.5%.

Polymer 2 was a mixture of m = 3 of component (d): ((AB) _m X) and component (a): (AB).

<Polymer 3: mixture of styrene-butadiene block copolymer and styrene-butadiene-styrene block copolymer>

A 10L stainless steel autoclave equipped with a stirrer and a jacket was washed, dried, and nitrogen-substituted, 5720 g of cyclohexane and 120 g of styrene purified beforehand were charged, and the contents were set to 40 ° C by passing hot water through the jacket.

Next, n-butyllithium cyclohexane solution (1.4 g in pure fraction) was added to initiate polymerization of styrene.

After 7 minutes after reaching the highest temperature (50 ° C) by polymerization of styrene, after falling 2.5 ° C from the highest temperature, 560 g of butadiene (1,3 butadiene) is added to continue the polymerization and the butadiene is almost completely polymerized. After 40 seconds after reaching the maximum temperature (88 ° C), 120 g of styrene was added again to continue the polymerization, and 8 minutes after reaching the maximum temperature (95 ° C) by polymerization of styrene, After the temperature was lowered, 0.5 g of water was added to inactivate it.

A polymer solution obtained by adding 0.3 part by mass of octadecyl-3- (3,5-dibutyl-t-butyl-4-hydroxyphenyl) propionate to 100 parts by mass of the block copolymer to the obtained block copolymer solution; After mixing the polymer (styrene-butadiene block copolymer) solution before coupling of the polymer 1, the solution was subjected to steam stripping in the same manner as in the above-described production process of the polymer 1, the polymerization solvent was separated, and then dried (the obtained copolymer). As polymer 3). Obtained polymer 3 was colorless and transparent.

The content of styrene used for polymerizing a vinyl aromatic monomeric unit polymer block (A) is 33.5 mass% with respect to the whole polymer 3, the said styrene block rate is 97.3%, and the number average molecular weight of component (a) is 6.3. However, the number average molecular weight of component (c) was 120,000. In addition, the vinyl bond amount of the butadiene part was 12.8%.

Polymer 3 was a mixture of p = 1 of component (a): (AB) and component (c): ((AB) _p A).

<Polymer 4: mixture of styrene-butadiene block copolymer and styrene-butadiene-styrene-butadiene block copolymer>

A 10L stainless steel autoclave equipped with a stirrer and a jacket was washed, dried, and nitrogen-substituted, 5720 g of cyclohexane and 120 g of styrene purified beforehand were charged, and the contents were set to 40 ° C by passing hot water through the jacket.

Next, n-butyllithium cyclohexane solution (1.35 g in pure fraction) was added to initiate polymerization of styrene.

After 6 minutes after reaching the highest temperature (51 ° C) by polymerization of styrene, after the temperature was lowered by 2 ° C from the highest temperature, 520 g of butadiene (1,3 butadiene) was added to continue the polymerization, and the butadiene was almost completely polymerized. After 40 seconds after reaching the maximum temperature (86 ° C.), 120 g of styrene was added again to continue polymerization, and 7 minutes after reaching the maximum temperature (93 ° C.) by polymerization of styrene, butadiene (1, 40 g of 3 butadiene) was further added to continue the polymerization, butadiene was almost completely polymerized, and after 50 seconds after reaching the highest temperature (97 ° C), the temperature was lowered by 3 ° C from the highest temperature, and then 0.5 g of water was added to deactivate it. I was.

Polymer solution in which 0.3 part by mass of octadecyl-3- (3,5-dibutyl-t-butyl-4-hydroxyphenyl) propionate was added to 100 parts by mass of the block copolymer ( Polymer mass: 35% by mass) and the polymer (styrene-butadiene block copolymer) solution (polymer mass: 65% by mass) before coupling of the polymer 1 described above, and then in the same manner as in the manufacturing process of polymer 1 described above. Steam stripping was carried out to separate the polymerization solvent and then dried (the obtained copolymer was designated as Polymer 4). Obtained polymer 4 was colorless and transparent.

The content of styrene used for polymerizing a vinyl aromatic monomeric unit polymer block (A) in polymer 4 is 33.25 mass% with respect to the whole polymer 4, the said styrene block rate is 97.1%, and the number average molecular weight of component (a) is 6.3. However, the number average molecular weight of component (c) was 140,000. In addition, the vinyl bond amount of the butadiene part was 12.5%.

Polymer 4 was a mixture of n = 2 of component (a): (AB) and component (b): ((AB) _n ).

&Lt; Polymer 5: 2-functional-coupled styrene-butadiene block copolymer >

3.5 minutes after reaching maximum temperature (53 degreeC) by superposition | polymerization of styrene, after falling 1 degreeC from the maximum temperature, 520g of butadiene (1, 3- butadiene) was added. Other conditions obtained the polymer 5 using the method similar to the manufacturing process of polymer 1 mentioned above. Obtained polymer 5 was colorless and transparent.

As for the polymer 5, content of the styrene used for superposing | polymerizing a vinyl aromatic monomeric unit polymer block (A) is 35 mass% with respect to the whole polymer 5, the said styrene block rate is 92.1%, and the number average molecular weight of component (a) is 6.1 However, the number average molecular weight of component (d) was 125,000.

Moreover, the block copolymer of the diblock structure of styrene-butadiene which is a component (a) equivalence product contained 70 mass%. In addition, the vinyl bond amount of the butadiene part was 12.5%.

Polymer 5 was a mixture of m = 2 of component (d): ((AB) _m X) and component (a): (AB).

Polymer 6: Bifunctional Coupling Styrene-Butadiene Block Copolymer

After adding 240 g of styrene and 21 minutes after reaching the highest temperature (53 degreeC) by the superposition | polymerization of styrene, and further decreasing 6 degreeC from the highest temperature, 560g of butadiene (1, 3- butadiene) was added. Other conditions obtained the polymer 6 using the method similar to the manufacturing process of the polymer 1 mentioned above. The obtained polymer 6 was yellowish.

The content of styrene used for polymerizing a vinyl aromatic monomeric unit polymer block (A) of polymer 6 is 30 mass% with respect to the whole polymer 6, the said styrene block rate is 99.5%, and the number average molecular weight of component (a) is 6.2 However, the number average molecular weight of component (d) was 12.6 million.

Moreover, the block copolymer of the diblock structure of styrene-butadiene which is a component (a) equivalence product contained 70 mass%. In addition, the vinyl bond amount of the butadiene part was 12.2%.

Polymer 6 was a mixture of m = 2 of component (d): ((AB) _m X) and component (a): (AB).

Polymer 7: Bifunctional Coupling Styrene-Butadiene Block Copolymer

The coupling rate was changed by varying the amount of ethyl benzoate of the coupling agent. Other conditions obtained the polymer 7 using the method similar to the manufacturing process of polymer 1 mentioned above. Obtained polymer 7 was colorless and transparent.

As for the polymer 7, content of styrene used for superposing | polymerizing a vinyl aromatic monomeric unit polymer block (A) is 35 mass% with respect to the whole polymer 7, the said styrene block rate is 97.4%, and the number average molecular weight of component (a) is 63,000 , The number average molecular weight of component (d) was 12.8 million.

Moreover, 40 mass% of block copolymers of the diblock structure of styrene-butadiene which are a component (a) equivalent product were contained. In addition, the vinyl bond amount of the butadiene part was 12.5%.

Polymer 7 was a mixture of m = 2 of component (d): ((AB) _m X) and component (a): (AB).

Polymer 8: Bifunctional Coupling Styrene-Butadiene Block Copolymer

The coupling rate was changed by varying the amount of ethyl benzoate of the coupling agent. Other conditions obtained the polymer 8 using the method similar to the manufacturing process of polymer 1 mentioned above. The obtained polymer 8 was colorless transparent.

The content of styrene used for polymerizing a vinyl aromatic monomeric unit polymer block (A) in polymer 8 is 35 mass% with respect to the whole polymer 8, the said styrene block rate is 97.3%, and the number average molecular weight of component (a) is 6.3 However, the number average molecular weight of component (d) was 12.8 million.

Moreover, 85 mass% of block copolymers of the diblock structure of styrene-butadiene which are a component (a) equivalent product were contained. In addition, the vinyl bond amount of the butadiene part was 12.5%.

Polymer 8 was a mixture of m = 2 of component (d): ((AB) _m X) and component (a): (AB).

Polymer 9: Bifunctional Coupling Styrene-Butadiene Block Copolymer

A 10L stainless steel autoclave equipped with a stirrer and a jacket was washed, dried, and nitrogen-substituted, 5720 g of cyclohexane and 280 g of styrene purified beforehand were charged, and the contents were set to about 40 ° C by passing hot water through the jacket.

Next, n-butyllithium cyclohexane solution (1.79 g in pure water) was added to initiate polymerization of styrene.

5 minutes after reaching the highest temperature (55 ° C) by polymerization of styrene, and after falling 2.5 ° C from the highest temperature, 520 g of butadiene (1,3-butadiene) is added to continue the polymerization, and the butadiene is almost completely 25 seconds after superposition | polymerization and reaching maximum temperature (91 degreeC), ethyl benzoate was added as a coupling agent and it couple | coupled.

Ten minutes after the coupling agent was added, 1.6 g of water was added to inactivate it.

To the obtained block copolymer solution, 0.3 parts by mass of octadecyl-3- (3,5-dibutyl-t-butyl-4-hydroxyphenyl) propionate was added to 100 parts by mass of the block copolymer, In the same manner as in the production process of Polymer 1, the solution was subjected to steam stripping to separate the polymerization solvent and then dried (the obtained block copolymer was referred to as Polymer 9). Obtained polymer 9 was colorless and transparent.

As for the polymer 9, content of the styrene used for superposing | polymerizing a vinyl aromatic monomeric unit polymer block (A) is 35 mass% with respect to the whole polymer 9, the said styrene block rate is 96.0%, and the number average molecular weight of component (a) is 1.5 However, the number average molecular weight of component (d) was 3.0 million.

Moreover, the block copolymer of the diblock structure of styrene-butadiene which is a component (a) equivalence product contained 70 mass%. In addition, the vinyl bond amount of the butadiene part was 12.4%.

Polymer 9 was a mixture of m = 2 of component (d): ((AB) _m X) and component (a): (AB).

Polymer 10: Bifunctional Coupling Styrene-Butadiene Block Copolymer

A 10L stainless steel autoclave equipped with a stirrer and a jacket was washed, dried, and nitrogen-substituted, 5720 g of cyclohexane and 280 g of styrene purified beforehand were charged, and the contents were set to about 40 ° C by passing hot water through the jacket.

Next, n-butyllithium cyclohexane solution (1.39 g in pure fraction) was added to start polymerization of styrene.

After 7 minutes after reaching the highest temperature (52 ° C) by polymerization of styrene, after 2 ° C is lowered from the highest temperature, 520 g of butadiene (1,3-butadiene) is added to continue the polymerization, and the butadiene is almost completely 25 seconds after superposition | polymerization and reaching maximum temperature (88 degreeC), ethyl benzoate was added as a coupling agent and it couple | coupled.

Ten minutes after the coupling agent was added, 1.6 g of water was added to inactivate it.

To the obtained block copolymer solution, 0.3 parts by mass of octadecyl-3- (3,5-dibutyl-t-butyl-4-hydroxyphenyl) propionate was added to 100 parts by mass of the block copolymer, In the same manner as in the production process of Polymer 1, the solution was subjected to steam stripping to separate the polymerization solvent, and then dried (the obtained block copolymer was referred to as Polymer 10). The obtained polymer 10 was colorless and transparent.

As for the polymer 10, content of the styrene used for superposing | polymerizing a vinyl aromatic monomeric unit polymer block (A) is 35 mass% with respect to the whole polymer 10, the said styrene block rate is 96.7%, and the number average molecular weight of component (a) is 9.8 However, the number average molecular weight of component (d) was 19.6 million.

Moreover, the block copolymer of the diblock structure of styrene-butadiene which is a component (a) equivalence product contained 70 mass%. In addition, the vinyl bond amount of the butadiene part was 12.7%.

Polymer 10 was a mixture of m = 2 of component (d): ((AB) _m X) and component (a): (AB).

Next, the adhesive agent composition was produced using the above-mentioned various block copolymers for adhesive agents.

Example 1

300 parts by mass of Alcon M100 (manufactured by Arakawa Chemical Co., Ltd.) as a tackifier and 100 parts by mass of a block copolymer (polymer 1) as a tackifier and 100% by mass of Diana process oil PW-90 (manufactured by Idemitsu Hungsan Co., Ltd.). It mix | blended in the compounding ratio of mass part, melt-kneading with the pressurized twin arm type | mold kneader (model: D0.3-3, the Moriyama Corporation make), and obtained the pale yellow uniform hot melt type adhesive composition.

In addition, the adhesive agent composition contains 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl as a stabilizer based on 100 parts by mass of the block copolymer (polymer 1). 1 mass part of acrylates were mix | blended.

As a result of measuring according to the measuring method of the physical property of the adhesive agent composition mentioned above, melt viscosity (at. 180 degreeC) was 920 (mPa * s) and the softening point was 89.8 degreeC.

Moreover, coating property was favorable, the roof tack was 53.4N / 15mm, the adhesive force was 30.7N / 10mm, the holding force was 10.3 minutes, and it was enough practical enough.

[Examples 2 to 4], [Comparative Examples 1 to 10]

According to the mixing | blending shown in following Table 1, Table 2, the adhesive agent composition was produced using Alcon M100 for tackifier and Diana process oil PW-90 for the softener, respectively, and the characteristic was evaluated by the method similar to Example 1.

If the torque was not stabilized even after kneading for 40 minutes, the mixture was kneaded until the torque was stabilized.

It was found that all of the block copolymers for polymer adhesives of Examples 1 to 4 (polymers 1 to 4) had a good finish in practical use.

In addition, it was found that the compositions for the adhesives of Examples 1 to 4 were all excellent in the adhesive properties of the roof tack (adhesiveness), the adhesive force, and the holding force, and were excellent in their performance balance, and also excellent in solubility and coating property. .

This application is based on the JP Patent application (Japanese Patent Application No. 2010-232925) of the Japan Patent Office on October 15, 2010, The content is taken in here as a reference.

Industrial Applicability

The adhesive agent composition of this invention is a various adhesive tape label, a pressure-sensitive thin plate, a pressure-sensitive sheet, a surface protection sheet film, a back pool for fixing various lightweight plastic molded articles, a back pool for fixing a carpet, a back pool for fixing a tile, an adhesive It can be used for the adhesive and the like, and in particular, there is industrial applicability as an adhesive for adhesive tapes, adhesive sheets and films, adhesive labels, surface protective sheets and films, and sanitary materials.

Claims (5)

It is a block copolymer for adhesives containing a block copolymer which has at least 2 vinyl aromatic monomeric unit polymer block (A) and a polymer block (B) mainly having at least 1 conjugated diene monomeric unit,
The vinyl aromatic monomer polymer block amount (mass%) in the vinyl aromatic monomer unit polymer block (A) is based on the total amount of vinyl aromatic monomer units (mass%) used to polymerize the vinyl aromatic monomer unit polymer block (A). 95.0 to 99.0%, and
The block copolymer for adhesives which consists of 50-80 mass% of following components (a) and 20-50 mass% of at least one component chosen from the group which consists of following components (b), (c), and (d).
(a): diblock copolymer having a number average molecular weight of 20,000 to 80,000 represented by formula (AB)
(b): a block copolymer in which _n is an integer of 2 or more and has a number average molecular weight of 40,000 to 160,000 represented by (AB) _n
(c): block copolymer in which p is an integer of 1 or more and has a number average molecular weight of 40,000 to 160,000 represented by (AB) _p A
(d): branch having a number average molecular weight of 40,000 to 160,000 represented by formula (AB) mX, wherein _m is any of 2, 3, 4 and X represents a residue of a coupling agent or a residue of a polymerization initiator. Block copolymers. (Iii) Block copolymer for adhesive agent of Claim 1: 100 mass parts,
(Ii) tackifier: 100-400 parts by mass,
(Iii) Softener: 50 to 150 parts by mass
Adhesive composition containing a. The adhesive agent composition of Claim 2 which satisfy | fills the requirements of following (1)-(3).
(1): roof tack T (N / 15mm) / 50 is 0.8 or more
(2): 180 degree peel adhesive force P (N / 10mm) / 30 with respect to the test plate measured according to the measuring method of peel adhesive force of JISZ0237 is 0.8 or more
(3): holding force C (minutes) / 10 is 0.8 or more It is a manufacturing method of the block copolymer for adhesive agents of Claim 1,
Polymerizing a vinyl aromatic monomer unit to produce the vinyl aromatic monomer unit polymer block (A);
Process of adding a conjugated diene monomeric unit at the time when 4 minutes or more and 20 minutes or less pass after it reached | attained the highest temperature in the process of superposing | polymerizing the said vinyl aromatic monomeric unit, and were 1.5 degreeC or more lower than the said highest temperature.
The manufacturing method of the block copolymer for adhesive agents which has a thing. The method according to claim 4, which is a method for producing the block copolymer for adhesive agent according to claim 1, containing the component (c),
The deactivator for terminating the polymerization of the block copolymer is 4 from the time when the maximum temperature in the step is reached after the step of polymerizing the vinyl aromatic monomer unit to produce the vinyl aromatic monomer unit polymer block (A). The manufacturing method of the adhesive agent block copolymer which adds at the time after more than 20 minutes or less and 1.5 degreeC or more fall from the highest temperature.