JP6907854B2 - Block copolymer composition - Google Patents

Description

The present invention relates to a block copolymer composition containing a block copolymer having an aromatic vinyl polymer block and a conjugated diene polymer block, and more particularly, a block having a low viscosity and excellent blocking resistance and adhesive properties. The present invention relates to a copolymer composition.

There are various block copolymers having an aromatic vinyl polymer block such as a styrene-isoprene-styrene block copolymer (SIS) or a styrene-butadiene-styrene block copolymer (SBS) and a conjugated diene polymer block. Since it is a thermoplastic polymer having characteristic properties in terms of surface, it is used for various purposes.

However, a block copolymer having an aromatic vinyl polymer block and a conjugated diene polymer block has a problem that blocking is likely to occur because it has adhesiveness itself. When the block copolymer is formed into, for example, pellets or films and processed, it becomes difficult to handle.
In order to solve this problem, it has been proposed to add a blocking agent. However, it cannot be said that the improvement of blocking resistance is sufficient, and further improvement is required.

By the way, block copolymers having an aromatic vinyl polymer block and a conjugated diene polymer block have various adhesive properties such as adhesive strength, holding power, tack, and flexibility, processability, and thermal stability. Characteristics are required. Extensive research has been conducted on the structure and composition of block copolymers to satisfy these requirements. One of them is a method of making a block copolymer having a low viscosity. However, when the block copolymer has a low viscosity, the problem of blocking becomes particularly remarkable.

Japanese Unexamined Patent Publication No. 2004-155851 Japanese Unexamined Patent Publication No. 9-235316

The present inventors have repeated studies to solve the above problems and focused on water-soluble surfactants. It is known that the water-soluble surfactant is used as a dispersant when producing a block copolymer, for example, as described in Patent Documents 1 and 2. Then, the present inventors further studied and found that although the water-soluble surfactant is effective in suppressing blocking, when it is added in a large amount, the adhesive property is deteriorated.
An object of the present invention is to provide a block copolymer composition having a low viscosity and excellent blocking resistance and adhesive properties.

As a result of diligent research to achieve the above object, the present inventors have made a water-soluble surfactant when the block copolymer having an aromatic vinyl polymer block and a conjugated diene polymer block has a low viscosity. It was found that by blending a predetermined amount of the above, blocking is suppressed and the adhesive properties are well maintained. For example, Patent Document 1 and Patent Document 2 disclose that a surfactant is added as a dispersant when producing a block copolymer, but the composition of the block copolymer containing the block copolymer is contained. It does not specify the amount of surfactant in the product. The present invention has been completed based on the above findings.

Thus, according to the present invention, a block copolymer having at least one aromatic vinyl polymer block and at least one conjugated diene polymer block is contained, and the melt index of the block copolymer is 20 g / 10. Provided is a block copolymer composition which is more than a minute and contains 0.02 to 3.00% by weight of a water-soluble surfactant.

According to the present invention, the melt index of the block copolymer is preferably 30 g / 10 minutes or more.

Further, according to the present invention, the content of the water-soluble surfactant is preferably 0.10 to 2.50% by weight, more preferably 0.12 to 2.00% by weight, and 0. It is more preferably .15 to 1.50% by weight.

According to the present invention, there is provided an adhesive composition containing the above-mentioned block copolymer composition.

According to the present invention, there is provided a stretchable film containing the above-mentioned block copolymer composition.

According to the present invention, elastic fibers containing the above-mentioned block copolymer composition are provided.

According to the present invention, a flexographic plate composition containing the above-mentioned block copolymer composition is provided.

According to the present invention, it is possible to obtain a block copolymer composition having a low viscosity and excellent blocking resistance and adhesive properties.

Hereinafter, the block copolymer composition of the present invention, and the adhesive composition, elastic film, elastic fiber, and flexographic plate composition using the block copolymer composition will be described.

A. Block Copolymer Composition The block copolymer composition of the present invention contains a block copolymer having at least one aromatic vinyl polymer block and at least one conjugated diene polymer block, and the above blocks are used together. It is a composition having a melt index of 20 g / 10 minutes or more of the polymer and containing 0.02 to 3.00% by weight of a water-soluble surfactant.

In the present invention, the melt index of the block copolymer having at least one aromatic vinyl polymer block and at least one conjugated diene polymer block is 20 g / 10 minutes or more, and the viscosity is low, so that blocking is performed. However, if the water-soluble surfactant is contained in a predetermined amount or more, blocking can be suppressed, and the content of the water-soluble surfactant is not more than the predetermined amount. Therefore, the adhesive properties can be maintained well.

1. 1. Block Copolymer The block copolymer used in the present invention (hereinafter, may be referred to as "block copolymer (I)") is an aromatic vinyl simple substance obtained by polymerizing an aromatic vinyl monomer. An aromatic vinyl polymer block composed of a metric unit as a main repeating unit, and a conjugated diene polymer block composed of a conjugated diene monomer unit obtained by polymerizing a conjugated diene monomer as a main repeating unit. , At least one of each. The block copolymer (I) is used as a polymer component of the block copolymer composition of the present invention.

Unless otherwise specified, the term "block copolymer" in the present specification means any aspect of a pure block copolymer, a random block copolymer, and a copolymer having a tapered block structure. Is.

(1) Aromatic Vinyl Polymer Block Block The aromatic vinyl polymer block contained in the copolymer (I) uses an aromatic vinyl monomer unit obtained by polymerizing an aromatic vinyl monomer as a main repeating unit. It is a polymer block composed.

The aromatic vinyl monomer used for forming the aromatic vinyl polymer block is not particularly limited as long as it is an aromatic vinyl compound. For example, styrene; α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2,4-diisopropylstyrene, 2,4- Styrenes having an alkyl group such as dimethylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene as a substituent; 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, 4-bromo Styrenes having halogen atoms such as styrene and 2,4-dibromostyrene as substituents; styrenes having alkyl groups such as 2-methyl-4,6-dichlorostyrene and halogen atoms as substituents; vinylnaphthalene; etc. Can be mentioned. These aromatic vinyl monomers may be used alone or in combination of two or more. Among these, from the viewpoint of availability, styrene and styrenes having an alkyl group as a substituent are preferable, and styrene is particularly preferable.

The aromatic vinyl polymer block may contain other monomer units as long as the aromatic vinyl monomer unit is the main repeating unit. Examples of the monomer constituting the monomer unit other than the aromatic vinyl monomer unit that can be contained in the aromatic vinyl polymer block include 1,3-butadiene and isoprene (2-methyl-1,3-butadiene). Conjugate diene monomers such as; α, β-unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile; unsaturated carboxylic acid monomers such as acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid; Unsaturated carboxylic acid anhydrides such as maleic anhydride, butenyl succinic anhydride, tetrahydrophthalic anhydride, citraconic anhydride; methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylate An unsaturated carboxylic acid ester monomer such as 2-ethylhexyl; a non-conjugated diene monomer having 5 to 12 carbon atoms such as 1,4-pentadiene and 1,4-hexadiene; and the like can be mentioned.

Further, when the block copolymer (I) has a plurality of aromatic vinyl polymer blocks, the plurality of aromatic vinyl polymer blocks may be the same or different from each other.

The content of the aromatic vinyl monomer unit with respect to all the monomer units of the block copolymer (I) is not particularly limited, but is usually selected in the range of 10 to 70% by weight, preferably 12 to 60% by weight. Selected in the range of%. When the content of the aromatic vinyl monomer unit in the block copolymer (I) is in such a range, the adhesive properties and moldability can be excellent. The content of the aromatic vinyl monomer unit in the block copolymer can be measured using ^{1 H NMR.}

(2) Conjugated Diene Polymer Block The conjugated diene polymer block contained in the block copolymer (I) is composed of a conjugated diene monomer unit obtained by polymerizing a conjugated diene monomer as a main repeating unit. It is a coalesced block.

The content of the conjugated diene monomer unit in the conjugated diene polymer block is preferably 80% by weight or more, more preferably 90% by weight or more, and particularly preferably substantially 100% by weight. .. When the content of the conjugated diene monomer unit in the conjugated diene polymer block is in such a range, the adhesive properties can be excellent.

The conjugated diene monomer used for forming the conjugated diene polymer block is not particularly limited as long as it is a conjugated diene compound. For example, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene and the like can be exemplified. .. These conjugated diene monomers may be used alone or in combination of two or more. Among these, 1,3-butadiene and / or isoprene is preferably used, and isoprene is particularly preferable. By constructing the conjugated diene polymer block in isoprene units, it is possible to obtain excellent adhesive properties and flexibility.

The conjugated diene polymer block may contain other monomer units as long as the conjugated diene monomer unit is the main repeating unit. Examples of the monomer constituting the monomer unit other than the conjugated diene monomer unit that can be contained in the conjugated diene polymer block include aromatic vinyl monomers such as styrene and α-methylstyrene, and α, β-non. Examples thereof include a saturated nitrile monomer, an unsaturated carboxylic acid monomer, an unsaturated carboxylic acid anhydride, an unsaturated carboxylic acid ester monomer, and an unconjugated diene monomer. Regarding α, β-unsaturated nitrile monomer, unsaturated carboxylic acid monomer, unsaturated carboxylic acid anhydride, unsaturated carboxylic acid ester monomer, and unconjugated diene monomer, the above aromatics are used. It can be the same as the monomer constituting the monomer unit other than the aromatic vinyl monomer unit that can be contained in the vinyl polymer block.

Further, when the block copolymer (I) has a plurality of conjugated diene polymer blocks, the plurality of conjugated diene polymer blocks may be the same or different from each other. Further, a part of the unsaturated bond of the conjugated diene polymer block may be hydrogenated.

The vinyl bond content of the conjugated diene polymer block (the ratio of 1,2-vinyl bond and 3,4-vinyl bond in the total conjugated diene monomer unit in the conjugated diene polymer block) is not particularly limited. , 1 to 20 mol%, more preferably 2 to 15 mol%, and particularly preferably 3 to 10 mol%. If the vinyl bond content is too high, the obtained block copolymer composition may have poor adhesive properties. The vinyl bond content of the conjugated diene polymer block can be measured using ^{1 H NMR.}

(3) Block Copolymer If the block copolymer (I) has at least one aromatic vinyl polymer block and at least one conjugated diene polymer block, the number of each polymer block and the number thereof. The binding form is not particularly limited.

As a specific example of the form of the block copolymer (I), Ar represents an aromatic vinyl polymer block, D represents a conjugated diene polymer block, and X represents a single bond or a residue of a coupling agent. When n represents an integer of 2 or more, it is represented as an aromatic vinyl-conjugated diene block copolymer represented as Ar-D, Ar-D-Ar or (Ar-D) _n- X. Aromatic vinyl-conjugated diene-aromatic vinyl block copolymer, D-Ar-D or conjugated diene-aromatic vinyl-conjugated diene block copolymer represented as _{(D-Ar) n-X, Ar-D} Examples include aromatic vinyl-conjugated diene-aromatic vinyl-conjugated diene block copolymers represented as −Ar−D, and block copolymers obtained by mixing two or more of these in any combination. However, it is not limited to these.

Among these, the block copolymer (I) preferably used in the present invention is an aromatic vinyl-conjugated diene block copolymer represented as Ar-D, Ar-D-Ar or (Ar-D) _n. Aromatic vinyl-conjugated diene-aromatic vinyl block copolymers represented as −X, and mixtures thereof can be mentioned. In particular, the aromatic vinyl-conjugated diene-aromatic vinyl block copolymer or a mixture of the aromatic vinyl-conjugated diene-aromatic vinyl block copolymer and the aromatic vinyl-conjugated diene block copolymer. Is preferably used.

The aromatic vinyl-conjugated diene-aromatic vinyl block copolymer represented by Ar-D-Ar is a block copolymer having two aromatic vinyl polymer blocks. In this block copolymer, the weight average molecular weights of the two aromatic vinyl polymer blocks may be the same or different. That is, the block copolymer represented by Ar-D-Ar includes an aromatic vinyl polymer block having a predetermined weight average molecular weight, a conjugated diene polymer block, and an aromatic vinyl weight having a predetermined weight average molecular weight. The coalesced block may be a symmetric aromatic vinyl-conjugated diene-aromatic vinyl block copolymer composed of a series in this order, and the combined block may be an aromatic vinyl polymer block having a relatively small weight average molecular weight. , Asymmetric aromatic vinyl-conjugated diene-aromatic vinyl block copolymer composed of a conjugated diene polymer block and an aromatic vinyl polymer block having a relatively large weight average molecular weight in this order. There may be.

Further, the aromatic vinyl-conjugated diene-aromatic vinyl block copolymer represented by (Ar-D) _n- X is a diblock formed by bonding an aromatic vinyl polymer block and a conjugated diene polymer block. A block copolymer composed of two or more bodies bonded directly by a single bond or via a residue of a coupling agent. The coupling agent constituting the residue of the coupling agent will be described later. The number (that is, n) to which the diblock bodies (Ar-D) are bonded is not particularly limited as long as it is 2 or more, and block copolymers to which the diblock bodies are bonded may be mixed in different numbers. .. n is not particularly limited as long as it is an integer of 2 or more, but is usually an integer of 2 to 8, preferably an integer of 2 to 4.

The weight average molecular weight of the block copolymer (I) is not particularly limited, but is usually 30,000 to 500,000, preferably 35,000 to 400,000, and more preferably 40,000 to 250,000. ..
Further, the weight average molecular weight of each polymer block of the block copolymer (I) is not particularly limited, and the weight average molecular weight of the aromatic vinyl polymer block is usually 6,000 to 400,000, preferably 6,. It is 000 to 370,000. If the weight average molecular weight of the aromatic vinyl polymer block is too small, the adhesive properties may be inferior, and if the weight average molecular weight of the aromatic vinyl polymer block is too large, the viscosity becomes high or the block copolymer (I). ) May be difficult to manufacture.
The weight average molecular weight of the conjugated diene polymer block is usually 18,000 to 400,000, preferably 19,000 to 350,000. If the weight average molecular weight of the conjugated diene polymer block is too small, the adhesive properties may be inferior, and if the weight average molecular weight of the conjugated diene polymer block is too large, the viscosity may increase.

The molecular weight represented by the ratio (Mw / Mn) of the block copolymer (I) and the weight average molecular weight (Mw) of each polymer block constituting the block copolymer (I) to the number average molecular weight (Mn). The distribution is also not particularly limited, but is usually 1.1 or less, preferably 1.05 or less, respectively. When the molecular weight distribution of the block copolymer (I) and each polymer block constituting the block copolymer (I) is in such a range, the adhesive properties can be excellent.

The weight average molecular weight and the number average molecular weight of block copolymers and polymer blocks shall be determined based on polystyrene-equivalent values measured by high performance liquid chromatography. The weight average molecular weight and the number average molecular weight can be more specifically determined as polystyrene-equivalent molecular weight by high performance liquid chromatography using tetrahydrofuran having a flow velocity of 0.35 ml / min as a carrier. The device is HLC8320 manufactured by Tosoh Corporation, the column is a combination of three polystyrene KF-404HQ manufactured by Showa Denko Co., Ltd. (column temperature 40 ° C.), the detector is a differential refractometer and an ultraviolet detector, and the molecular weight is calibrated by the polymer laboratory. It can be carried out at 12 points of standard polystyrene (5 to 3 million) manufactured by the company.

The block copolymer (I) can be produced according to a conventional method. As the most common production method, an aromatic vinyl monomer and a conjugated diene monomer are sequentially polymerized by an anion living polymerization method to form a polymer block, and if necessary, coupling is performed. A method of reacting the agents to perform coupling can be mentioned.

For example, the block copolymer (I) is a block copolymer from the step (a) of forming the block copolymer (I) using a polymerization initiator in a solvent and the solution obtained in the above step (a). It can be produced by the step (b) of recovering the polymer (I). For details of the reaction, refer to Japanese Patent Application Laid-Open No. 10-17611 and the like.

In step (a), first, a block copolymer (I) is formed using a polymerization initiator in a solvent.
As the polymerization initiator to be used, those generally known to have anionic polymerization activity with respect to the aromatic vinyl monomer and the conjugated diene monomer can be used, for example, an organic alkali metal compound. , Organic alkaline earth metal compounds, organic lanthanoid series rare earth metal compounds and the like. The polymerization initiators can be used alone or in combination of two or more.

The polymerization reaction is carried out in a hydrocarbon solvent that does not destroy the polymerization initiator. The suitable hydrocarbon solvent is not particularly limited as long as it is used for ordinary solution polymerization, and is, for example, an aliphatic hydrocarbon solvent, an alicyclic hydrocarbon solvent, or an aromatic hydrocarbon. Examples include system solvents. Further, if necessary, an unsaturated hydrocarbon solvent having low polymerizability may be used. These hydrocarbon solvents are used alone or in combination of two or more.

In the present invention, a Lewis basic compound or the like can be added in order to adjust the microstructure of the conjugated diene polymer block and to adjust the start reaction rate and the polymerization reaction rate. Examples of Lewis basic compounds include ethers, amines, amides, alkali metal alkoxides, thioethers and the like. These Lewis basic compounds are used alone or in combination of two or more.

The polymerization reaction is appropriately selected depending on the use of the block copolymer composition. For example, the polymerization temperature is usually in the range of −20 ° C. to + 150 ° C., preferably 30 ° C. to 120 ° C. The polymerization time varies depending on conditions such as the polymerization temperature, but is usually within 24 hours, preferably within the range of 1 to 10 hours. The pressure is selected from the range in which the solvent and the monomer are maintained in the liquid phase within the above polymerization temperature range, and is not particularly limited.

After the above polymerization reaction, a treatment such as a terminal modifier, a coupling agent or hydrogenation may be performed.

Examples of the terminal modifier include ketones, aldehydes, epoxys, carbodiimides, Schiff bases, N-unsubstituted aziridine compounds, N-substituted amides, N-substituted ureas, and N-substituted aminoketones. Examples thereof include N-substituted aminoaldehydes.
The treatment with a terminal denaturant is disclosed in, for example, JP-A-58-162604, JP-A-60-137913, JP-A-62-86074, JP-A-62-119257, and the like. It can be done according to the method.

The coupling agent may be a polyfunctional coupling agent, for example, a tin-based coupling agent, a silicon-based coupling agent, a metal halide-based coupling agent, an unsaturated nitrile-based coupling agent, or a halogenated hydrocarbon. Examples thereof include hydrogen-based coupling agents, ester-based coupling agents, and halide-based coupling agents. Further, as the polyfunctional coupling agent, a compound having two or more radically polymerizable groups in the molecule may be used. Examples of the compound having two or more radically polymerizable groups in the molecule include aromatic divinyl compounds such as divinylbenzene, divinyltoluene, divinylxylene, divinylanthracene, divinylnaphthalene and divinylzulene, and aromatic trivinyl compounds such as trivinylbenzene. , Two or more radically polymerizable groups such as aromatic tetravinyl compounds such as tetravinylbenzene, and radically polymerizable aromatic compounds having an aromatic ring, two or more radically polymerizable groups such as pentaerythritol tetraacrylate, and fats. Examples thereof include radically polymerizable aliphatic compounds having a group group. One type of these coupling agents may be used alone, or two or more types may be used in combination.
The treatment with the coupling agent is, for example, JP-A-56-143209, JP-A-56-17362, JP-A-57-55912, JP-A-58-162605, JP-A-64-. This can be performed according to the method disclosed in Japanese Patent Application Laid-Open No. 81844, Pamphlet No. 81-057049, and the like.

As the catalyst used in the hydrogenation reaction, for example, a supported heterogeneous catalyst in which a metal is supported on a carrier, a uniform catalyst such as a cheegler type catalyst or an organic complex, or the like is used.
The hydrogenation treatment shall be carried out according to the methods disclosed in, for example, Japanese Patent Application Laid-Open No. 42-8704, Japanese Patent Application Laid-Open No. 43-6636, Japanese Patent Application Laid-Open No. 59-133203, Japanese Patent Application Laid-Open No. 60-220147. Can be done.

In addition, a polymerization inhibitor can be added to the solution after the polymerization reaction. Examples of the polymerization terminator include water; alcohols such as methanol, ethanol, propanol, ethylene glycol, and glycerin; inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; acetic acid, propionic acid, octyl acid, capric acid, and lauric acid. Organic acids such as myristic acid, palmitic acid, stearic acid, oleic acid, lactic acid, and citric acid; and the like can be mentioned. These polymerization inhibitors can be used alone or in combination of two or more.

Next, in the step (b), the target block copolymer (I) is recovered from the solution obtained through the above step (a).

The method of collection may be in accordance with a conventional method and is not particularly limited. For example, the block copolymer (I) can be recovered by directly applying a known method such as a drying method or a steam stripping method to the obtained solution. Further, if necessary, a water-soluble surfactant or the like is added to the obtained solution, and then the block copolymer (I) is recovered by applying a direct drying method, a steam stripping method or the like. You can also do it.
For example, when a water-soluble surfactant is added to the obtained solution when recovering the block copolymer (I), both the block copolymer (I) and the block containing the water-soluble surfactant are used. The polymer composition can be efficiently obtained. The water-soluble surfactant will be described later.

Examples of the method of steam stripping in the presence of a water-soluble surfactant include (1) a method of adding a water-soluble surfactant to the solution after the polymerization reaction and then steam stripping, and (2) steam stripping. Examples thereof include a method in which a water-soluble surfactant is previously dissolved in the stripper aqueous solution used in the above and brought into contact with the solution after the polymerization reaction. Generally, the method of dissolving the water-soluble surfactant in the stripper aqueous solution of (2) is performed.

In the steam stripping method, for example, a solution of a hydrocarbon solvent in which the concentration of block copolymer (I) is adjusted to, for example, 10 to 50% by weight by any means is added to the boiling point of the hydrocarbon solvent or water. It is carried out at a temperature higher than the azeotropic temperature. The block copolymer (I) is separated as an aqueous slurry crumb by steam stripping, and the water content crumb is first set to a moisture content of, for example, about 30 to 60% by weight by a vibrating screen, a centrifugal dehydrator or the like, and further, a screw type. The water content is dehydrated to, for example, about 5 to 30% by weight by a dehydrator such as an extrusion dehydrator. The dehydrated crumb has a water content of, for example, less than 5% by weight, preferably 3% by weight or less, by a dryer such as a hot air dryer, an extrusion dryer, or an expansion dryer.

In the direct drying method, similarly to the above, a solution of a hydrocarbon solvent having a predetermined block copolymer (I) concentration is dropped onto a roll heated to a temperature equal to or higher than the boiling point of the hydrocarbon solvent, and the solvent is used. The desolvated block copolymer (I) can be obtained by evaporating the block copolymer (I) or by removing the solvent using a twin-screw extruder with a vent or the like.

Further, when the block copolymer (I) is a mixture of two or more types of block copolymers (hereinafter, referred to as a block copolymer mixture) as described above, a method for obtaining a block copolymer mixture is a method. The production is not particularly limited, and the block copolymer can be produced according to a conventional method for producing a block copolymer.

Further, the block copolymer mixture is represented by, for example, Ar—D—Ar, and the weight average molecular weights of the two aromatic vinyl polymer blocks are different from each other, and the asymmetric aromatic vinyl-conjugated diene-aromatic vinyl block copolymer weight is different. Symmetrical aromatic vinyl-conjugated diene-fragrances represented by coalescence (hereinafter referred to as block copolymer a) and Ar-D-Ar and having the same weight average molecular weight of two aromatic vinyl polymer blocks. When it is a mixture composed of a group vinyl block copolymer (hereinafter referred to as block copolymer b1), or when it is a block copolymer a and an aromatic vinyl represented by _{(Ar−D) n−X.} In the case of a mixture composed of a conjugated diene-aromatic vinyl block copolymer (hereinafter referred to as block copolymer b2), the block copolymer mixture can also be produced by the method described below. For details of the reaction, refer to International Publication No. 2009/123089 Pamphlet, Japanese Patent Application Laid-Open No. 2012-77158, International Publication No. 2015/099163 Pamphlet and the like.

When the block copolymer mixture is a mixture composed of the block copolymer a and the block copolymer b1, it can be specifically produced by the following steps (1a) to (6a).
(1a): Step of polymerizing an aromatic vinyl monomer using a polymerization initiator in a solvent (2a): A solution containing an aromatic vinyl polymer having an active terminal obtained in the above step (1a). Step (3a) of adding the conjugated diene monomer to the above: The aromatic vinyl monomer is added to the solution containing the aromatic vinyl-conjugated diene block copolymer having an active terminal obtained in the step (2a) above. Step (4a): 1 mol equivalent of the active end to the solution containing the aromatic vinyl-conjugated diene-aromatic vinyl block copolymer having the active end obtained in the step (3a) above. Step of adding a polymerization terminator in an amount less than the amount to form the block copolymer b1 (5a): Aromatic vinyl-conjugated diene having an active terminal with the block copolymer b1 obtained in the above step (4a). -Step of adding aromatic vinyl monomer to a solution containing an aromatic vinyl block copolymer to form a block copolymer a (6a): From the solution obtained in the above step (5a). Step of recovering block copolymer mixture

In step (1a), first, the aromatic vinyl monomer is polymerized using a polymerization initiator in a solvent. The polymerization initiator is the same as that described above.

Next, in the step (2a), the conjugated diene monomer is added to the solution containing the aromatic vinyl polymer having the active terminal obtained in the above step (1a). By adding this conjugated diene monomer, a conjugated diene polymer chain is formed from the active terminal, and a solution containing an aromatic vinyl-conjugated diene block copolymer having an active terminal is obtained. The amount of the conjugated diene monomer used at this time is determined according to the weight average molecular weight of the conjugated diene polymer block of the target block copolymer a and the block copolymer b1.

Next, in the step (3a), the aromatic vinyl monomer is added to the solution containing the aromatic vinyl-conjugated diene block copolymer having an active terminal obtained in the above step (2a). By adding this aromatic vinyl monomer, an aromatic vinyl polymer chain is formed from the active end, and a solution containing an aromatic vinyl-conjugated diene-aromatic vinyl block copolymer having an active end is obtained. The obtained aromatic vinyl polymer chain includes a part of an aromatic vinyl polymer block having a relatively large weight average molecular weight of the target block copolymer a and an aromatic vinyl polymer block of the block copolymer b1. And will be configured. Therefore, the amount of the aromatic vinyl monomer used at this time is determined according to the weight average molecular weight of these aromatic vinyl polymer blocks.

Next, in the step (4a), a functional group is added to the solution containing the aromatic vinyl-conjugated diene-aromatic vinyl block copolymer having the active end obtained in the above step (3a) with respect to the active end. The polymerization inhibitor is added in an amount less than 1 molar equivalent. The polymerization terminator is the same as that described above.

When a polymerization inhibitor was added to the solution, some of the active ends of the aromatic vinyl-conjugated diene-aromatic vinyl block copolymer with active ends were inactivated, resulting in the inactivation of the active ends. The polymer will be block copolymer b1. Then, the remaining part of the aromatic vinyl-conjugated diene-aromatic vinyl block copolymer having an active end having an active end that did not react with the polymerization inhibitor will remain in the solution as it is.

Next, in the step (5a), the fragrance is added to the solution containing the block copolymer b1 obtained in the above step (4a) and the aromatic vinyl-conjugated diene-aromatic vinyl block copolymer having an active terminal. Add a group vinyl monomer.
When an aromatic vinyl monomer is added to the solution, the aromatic vinyl-conjugated diene-aromatic vinyl block copolymer having an active end remaining without reacting with the polymerization terminator is the aromatic on the side having the active end. An aromatic vinyl monomer is further polymerized from the vinyl polymer chain to extend the aromatic vinyl polymer chain, and the resulting aromatic vinyl-conjugated diene-aromatic vinyl triblock copolymer is blocked. It becomes the copolymer a. At this time, the extended aromatic vinyl polymer chain constitutes an aromatic vinyl polymer block having a relatively large weight average molecular weight of the block copolymer a. Therefore, the amount of the aromatic vinyl monomer used at this time is set to the target weight average molecular weight of the aromatic vinyl polymer block in consideration of the weight average molecular weight of the aromatic vinyl polymer block before extension. It will be decided accordingly.
By this step, an asymmetric aromatic vinyl-conjugated diene-aromatic vinyl triblock copolymer that constitutes the block copolymer a is formed, and as a result, the block copolymer a and the block copolymer A solution containing b1 is obtained.

Next, in the step (6a), the target block copolymer mixture is recovered from the solution containing the block copolymer a and the block copolymer b1 obtained through the above steps. The method of recovery is the same as the method described above.

When the block copolymer mixture is a mixture composed of the block copolymer a and the block copolymer b2, it can be specifically produced by the following steps (1b) to (5b).
(1b): Step of polymerizing the aromatic vinyl monomer using a polymerization initiator in a solvent (2b): In a solution containing the aromatic vinyl polymer having an active terminal obtained in the above step (1b). , Step of adding conjugated diene monomer (3b): A functional group with respect to the active end in a solution containing an aromatic vinyl-conjugated diene block copolymer having an active end obtained in the above step (2b). Step of adding a coupling agent in an amount less than 1 molar equivalent to form the block copolymer b2 (4b): The block copolymer b2 obtained in the above step (3b) and the aromatic vinyl having an active terminal. -Step of adding aromatic vinyl monomer to a solution containing a conjugated diene block copolymer to form a block copolymer a (5b): From the solution obtained in the above step (4b), block common weight. Steps to recover the coalesced mixture

The steps (1b) and (2b) can be the same as those of the above steps (1a) and (2a), respectively.

Next, in the step (3b), 1 molar equivalent of a functional group is added to the solution containing the aromatic vinyl-conjugated diene block copolymer having an active terminal obtained in the above step (2b) with respect to the active terminal. Add the coupling agent in an amount less than or equal to. The coupling agent is the same as that described above.

The amount of the coupling agent added is determined according to the ratio of the block copolymer a and the block copolymer b2 constituting the block copolymer mixture, and the number of functional groups is 1 with respect to the active terminal of the polymer. The amount is not particularly limited as long as it is less than the molar equivalent, but it is usually in the range of 0.15 to 0.90 molar equivalent of the functional group of the coupling agent with respect to the active terminal of the polymer, and 0.25 to 0.20. It is preferably in the range of 0.70 molar equivalent.

When a coupling agent is added to a solution containing an aromatic vinyl-conjugated diene block copolymer having an active end in an amount such that the functional group is less than 1 molar equivalent with respect to the active terminal, the fragrance having the active end is added. In some of the group vinyl-conjugated diene block copolymers, the conjugated diene polymer blocks are bonded to each other via the residue of the coupling agent, and as a result, the blocks of the block copolymer mixture are co-linked. Polymer b2 is formed. Then, the remaining part of the aromatic vinyl-conjugated diene block copolymer having an active terminal that did not react with the coupling agent remains unreacted in the solution.

Next, in the step (4b), the aromatic vinyl monomer is added to a solution containing the block copolymer b2 obtained in the above step (3b) and the aromatic vinyl-conjugated diene block copolymer having an active terminal. Added.
When an aromatic vinyl monomer is added to the solution, an aromatic vinyl polymer chain is formed from the end of the aromatic vinyl-conjugated diene block copolymer having an active end that remains unreacted with the coupling agent. NS. This aromatic vinyl polymer chain constitutes an aromatic vinyl polymer block having a relatively large weight average molecular weight of the block copolymer a. Therefore, the amount of the aromatic vinyl monomer used at this time is determined according to the target weight average molecular weight of the polymer block.

Next, in the step (5b), the target block copolymer mixture is recovered from the solution containing the block copolymer a and the block copolymer b2 obtained through the above steps. The method of recovery is the same as the method described above.

The block copolymer and the block copolymer mixture obtained as described above may be processed into a pellet shape or the like according to a conventional method before use.

Further, in the present invention, it is also possible to use a commercially available block copolymer. For example, "Quintac (registered trademark)" (manufactured by Zeon Japan), "JSR-SIS (registered trademark)" (manufactured by JSR), "Vector (registered trademark)" (manufactured by DEXCO carriers), "Asaplen (registered)" "Trademark", "Toughpren (registered trademark)", "Toughtech (registered trademark)" (manufactured by Asahi Kasei Chemicals), "Septon (registered trademark)" (manufactured by Kuraray), etc. can be used.

(4) Characteristics The melt index of the block copolymer (I) in the present invention is 20 g / 10 minutes or more, preferably 30 g / 10 minutes. When the melt index of the block copolymer (I) is within the above range, the viscosity becomes low and blocking is likely to occur. However, the block copolymer composition of the present invention contains a predetermined amount or more of a surfactant. Therefore, blocking can be suppressed. The upper limit of the melt index of the block copolymer (I) is not particularly limited, but is usually 2000 g / 10 minutes or less, preferably 1500 g / 10 minutes or less, and more preferably 1000 g / 10 minutes or less. ..
The melt index is a value measured in accordance with ASTM D-1238 (G condition, 200 ° C., 5 kg).

The glass transition temperature of the block copolymer (I) in the present invention is not particularly limited, but is preferably less than −40 ° C. When the glass transition temperature of the block copolymer (I) is in the above range, the material becomes more flexible, and the adhesive property becomes good, for example, when it is used as an adhesive composition. In particular, it has excellent adhesive properties at low temperatures. The lower limit of the glass transition temperature of the block copolymer (I) is not particularly limited, but is usually −62 ° C. or higher.
The glass transition temperature can be measured by using a differential scanning calorimeter (DSC) at a temperature rise of 10 ° C./min.

2. Water-soluble surfactant The block copolymer composition of the present invention contains a water-soluble surfactant in addition to the block copolymer (I) described above.

The water-soluble surfactant used in the present invention may be any of an anionic surfactant, a cationic surfactant, an amphoteric surfactant and a nonionic surfactant.

Examples of anionic surfactants include fatty acid salts (RCOONA), higher alcohol sulfates (ROSO ₃ Na), liquid fatty oil sulfates [R (OSO ₃ Na) COOR], aliphatic amines and aliphatic amides. Sulfate (RCONHR'CH ₂ CH ₃ OSO ₃ Na), aliphatic alcohol phosphate esters [ROP (ONa) ₂ ], dibasic fatty acid ester sulfonates [ROCOCH _2- CH (SO ₃ Na) COCOR' ], Fatty acid amide sulfonates (RCON R'CH ₂ CH ₂ SO ₃ Na), alkylallyl sulfonates (R-Ph-SO ₃ Na) and the like. They may also be used in the form of free acids.

Further, as the anionic surfactant, a polymer-type anionic surfactant can be used, for example, polycarboxylic acid and salts thereof; sulfonic acid group-containing polymer and salts thereof; carboxymethyl cellulose, sodium alginate, etc. Other anionic macromolecules such as rosin soap; can be mentioned. Examples of polycarboxylic acids and salts thereof include polymers of (meth) acrylic acid and salts thereof; polymers of unsaturated dibasic acids such as maleic anhydride, maleic acid, fumaric acid, and itaconic acid, or other monomers. Examples thereof include copolymers with and salts thereof. Examples of the sulfonic acid group-containing polymer include lignin sulfonic acid, formalin condensate of naphthalin (or alkylnaphthalin) sulfonic acid, formalin condensate of benzene (or alkylbenzene) sulfonic acid, and formalin condensate of sulfonated creosort oil. Formalin condensate of aromatic sulfonic acid, polymer of vinyl sulfonic acid and the like can be mentioned.

Among these anionic surfactants, higher alcohol sulfate esters, polycarboxylic acids and salts thereof and the like are preferable, and higher alcohol sulfate esters and polycarboxylic acid salts and the like are particularly preferable.

These anionic surfactants can be used alone or in combination of two or more.

Examples of cationic surfactants include aliphatic amine salts [N (R ¹ R ² R ³ ) · X]; lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, distearyldimethylammonium chloride and the like. Quaternary ammonium salts [N (R ¹ R ² R ³ R ⁴ ) · X]; alkylpyridinium salts; polyoxyethylene alkylamine salts; imidazoline derivatives and the like are used. Among these, quaternary ammonium salts are preferable. Further, cationic polymers such as polyvinylpyridine-based polysoap, acrylic acid ester-based cationic activator, and polyacrylamide-based cationic activator can also be used. These cationic surfactants can be used alone or in combination of two or more.

Examples of the nonionic surfactant include block-condensate polymers of two or more alkylene oxides such as oxyethylene oxypropylene block polymer; higher alcohols such as lauryl alcohol, cetyl alcohol, stearyl alcohol and oleyl alcohol, octylphenol and isooctylphenol. Polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxy, in which alkylene oxide is polymerized and added to alkylphenol such as nonylphenol and alkylnaphthol such as butylnaphthol and octylnaphthol. Polyoxyalkylene ether-based compounds such as ethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, and polyoxyethylene higher alcohol (C _{12 to} C ₁₄ ) ether; higher fatty acids such as lauric acid, palmitic acid, stearic acid, and oleic acid. Polyoxyethylene glycol monolaurate, polyoxyethylene glycol monopalmitate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, etc. Glyceryl monostearate, glyceryl mono, which is an ester compound of a polyhydric alcohol having three or more hydroxyl groups in the molecule, such as glycerin, pentaerythritol, sorbitan, mannitane, hexitane, and a polycondensate thereof, and a higher fatty acid. Oleate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan diolate, mannitan monolaurate, mannitan monostearate, Mannitan distearate, mannitan monooleate, hexitane monolaurate, hexitan monopalmitate, hexitan monostearate, hexitand distearate, hextan tristearate, hexitan monooleate, hexitanji Polyhydric alcohol-based fatty acid ester compounds such as oleate; polyoxyethylene sorbitan monolaurate and polyoxyethyle obtained by polymerizing and adding alkylene oxide to the polyhydric alcohol-based fatty acid ester compound. Polyoxyethylene monostearate, polyoxyethylene sorbitan distearate, polyoxyethylene sorbitan monooleate, polyoxyethylene mannitan monopalmitate, polyoxyethylene mannitan monostearate, polyoxyethylene mannitan monooleate, poly Polyoxyalkylene polyhydric alcohol fatty acid ester compounds such as oxyethylene hextan monolaurate and polyoxyethylene hextan monostearate; polyoxyalkylene alkylamine compounds such as polyoxyethylene alkylamine; alkylalkanolamide compounds; etc. Can be mentioned.

Among these nonionic surfactants, block-condensed polymers containing two or more alkylene oxides, polyoxyalkylene ether compounds, polyoxyalkylene glycol fatty acid ester compounds, polyoxyalkylene polyhydric alcohol fatty acid ester compounds, and poly Polyoxyalkylene-based compounds which are alkylene oxide polymerization adducts such as oxyalkylene alkylamine compounds are preferable, and polyoxyalkylene ether-based compounds, polyoxyalkylene glycol fatty acid ester-based compounds, and polyoxyalkylene polyvalent alcohol-based fatty acid ester compounds are particularly preferable. preferable.

These nonionic surfactants can be used alone or in combination of two or more.

Further, the anionic surfactant, the cationic surfactant, the amphoteric surfactant and the nonionic surfactant can be used alone or in combination of two or more.

The content of the water-soluble surfactant in the block copolymer composition is in the range of 0.02 to 3.00% by weight, preferably in the range of 0.10 to 2.50% by weight. , 0.12 to 2.00% by weight is more preferable, and 0.15 to 1.50% by weight is particularly preferable. When the content of the water-soluble surfactant is within the above range, a block copolymer composition having excellent blocking resistance and adhesive properties can be obtained when the polymer has a low viscosity.

In the present invention, the method for preparing a block copolymer composition containing a block copolymer and a water-soluble surfactant is not particularly limited. For example, as described above, a water-soluble surfactant may be added to the solution containing the block copolymer in the block copolymer production process, or the block copolymer may be added in the block copolymer production process. After recovering, a water-soluble surfactant may be added.
When a water-soluble surfactant is added to a solution containing the block copolymer in the process of producing the block copolymer, the content of the water-soluble surfactant in the block copolymer composition is, for example, gel permeation. It can be measured by ion chromatograph (GPC) analysis.

3. 3. Applications The block copolymer composition of the present invention has a low viscosity and is excellent in blocking resistance and adhesive properties, so that it can be widely used in various applications. Specifically, the block copolymer composition of the present invention includes films, gloves, elastic bands, contraceptives, OA equipment, various rolls for office use, anti-vibration sheets for electrical and electronic equipment, anti-vibration rubber, and impact. Molding materials used for absorbent sheets, shock-absorbing film sheets, residential vibration damping sheets, vibration damping damper materials, etc., adhesive tapes, adhesive sheets, adhesive labels, adhesives used for dust removal rollers, sanitary goods, etc. It can be used for adhesives used for bookbinding, for elastic fibers used for clothing, sports goods, clothing, sanitary goods, and the like.
Further, the block copolymer composition of the present invention may be used, for example, by molding it into a film or fibrous form.

B. Adhesive composition The adhesive composition of the present invention is a composition containing the above-mentioned block copolymer composition. Since the adhesive composition of the present invention contains the above-mentioned block copolymer composition, it has excellent adhesive properties.

The adhesive composition of the present invention contains the above-mentioned block copolymer composition as a base polymer, and for example, contains the above-mentioned block copolymer composition and a tackifier resin. ..

As the tackifier resin, those generally used for a pressure-sensitive adhesive composition can be used.

The blending ratio of the block copolymer composition and the tackifier resin is appropriately adjusted according to the use of the adhesive composition. For example, the blending amount of the tackifier resin can be 5 to 6000 parts by weight, preferably 40 to 4500 parts by weight, based on 100 parts by weight of the block copolymer composition.

The adhesive composition of the present invention may contain a polymer component other than the block copolymer composition described above. Examples of the polymer component other than the above-mentioned block copolymer composition include a block copolymer having an aromatic vinyl polymer block other than the above-mentioned block copolymer (I) and a conjugated diene polymer block, and an aromatic. Vinyl homopolymers, conjugated diene homopolymers, aromatic vinyl-conjugated diene random copolymers, and branched polymers thereof; heat of polyurethane-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, polyester-based thermoplastic elastomers, etc. Plastic elastomers; thermoplastic resins such as polyethylene, polypropylene, polyvinyl chloride, acrylonitrile-styrene copolymers, acrylonitrile-butadiene-styrene copolymers, polyphenylene ethers; and the like.
The content of the polymer component other than the block copolymer composition described above is appropriately adjusted according to the use of the adhesive composition and the like.

The adhesive composition of the present invention can contain various additives such as softeners, plasticizers, antioxidants, fillers and lubricants, if necessary.

The adhesive composition of the present invention can be prepared according to the same method as a general adhesive composition. For example, in the case of a pressure-sensitive adhesive composition, each component can be stirred and mixed in the presence of a solvent to obtain a pressure-sensitive adhesive solution, and a tack-imparting resin pre-emulsified with a latex of a base polymer is stirred and mixed to obtain a pressure-sensitive adhesive. It can also be an agent emulsion. These pressure-sensitive adhesive solutions or pressure-sensitive adhesive emulsions are usually uniformly applied to a desired substrate using a coating machine, dried, and then wound up to produce various adhesive tapes or adhesive label products. In the case of a hot-melt adhesive composition, each component is put into a melting pot at the same time or sequentially from the one having the lowest melt viscosity, heated and melt-mixed at 100 to 200 ° C., and then block-shaped, rod-shaped, or powder. It can be processed into an appropriate shape such as a shape, a film shape, a sheet shape, or can be continuously manufactured using a uniaxial or biaxial extruder.

C. Stretchable film The stretchable film of the present invention is a film containing the above-mentioned block copolymer composition. Since the stretchable film of the present invention contains the above-mentioned block copolymer composition, it is highly stretchable.

The stretchable film of the present invention may contain the above-mentioned block copolymer composition as a base polymer, and may be, for example, one composed of the above-mentioned block copolymer composition, or may be composed of the above-mentioned block copolymer composition. The block copolymer composition of No. 1 and the above-mentioned block copolymer composition may contain a polymer component or an additive other than the above-mentioned block copolymer composition.

The stretchable film of the present invention may contain a polymer component other than the block copolymer composition described above. Examples of the polymer component other than the block copolymer composition described above include olefin resins such as polyethylene and polypropylene, and styrene resins such as polystyrene and impact resistant polystyrene. Further, as the polymer component other than the above-mentioned block copolymer composition, for example, a block copolymer having an aromatic vinyl polymer block other than the above-mentioned block copolymer (I) and a conjugated diene polymer block, Conjugated diene homopolymers, aromatic vinyl-conjugated diene random copolymers, and branched polymers thereof; thermoplastic elastomers such as polyurethane-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, polyester-based thermoplastic elastomers; polychloride Examples thereof include vinyl, acrylonitrile-styrene copolymers, acrylonitrile-butadiene-styrene copolymers, thermoplastic resins such as polyphenylene ethers; and the like.
The content of the polymer component other than the block copolymer composition described above is appropriately adjusted according to the use of the stretchable film and the like.

The stretchable film of the present invention contains various additives such as an antioxidant, a tackifier resin, a softening agent, an antibacterial agent, a light stabilizer, an ultraviolet absorber, a dye, a pigment, and a lubricant, if necessary. Can be done.

The method of mixing the above-mentioned block copolymer composition with other components is not particularly limited. For example, the above-mentioned block copolymer composition is mixed with other polymer components and various additives as necessary. Then, they can be mixed according to a conventional method such as kneading or solution mixing. Specific examples thereof include a method in which each component is dissolved in a solvent and uniformly mixed, and then the solvent is removed by heating or the like, and a method in which each component is melt-mixed by a screw extruder, a kneader or the like. Among these, melt mixing is preferable from the viewpoint of more efficient mixing. The temperature at the time of performing melt mixing is not particularly limited, but is usually in the range of 100 to 200 ° C.

The thickness of the stretchable film is not particularly limited and is adjusted according to the application. For example, in the case of a film for sanitary products such as disposable diapers and sanitary products, the thickness of the elastic film is usually 0.01 to 5 mm, preferably 0.01 to 1 mm, and more preferably 0.02 to 0. It is .2 mm.

The stretchable film of the present invention is obtained by molding a film composition containing the above-mentioned block copolymer composition. The method for molding the composition for a film into a film is not particularly limited, and a conventionally known film molding method can be applied. However, from the viewpoint of obtaining a smooth film with good productivity, extrusion molding is preferable, among others. Extrusion molding using a T-die is particularly suitable. As a specific example of extrusion molding using a T-die, a film composition melted at 150 to 250 ° C. is extruded from a T-die mounted on a single-screw extruder or a twin-screw extruder, and cooled by a take-up roll. However, there is a method of winding up. The film may be stretched as it is cooled by the take-up roll. Further, when the film is wound, it may be formed into a film while coating a melt of the film composition on a substrate made of polyethylene terephthalate, polyethylene, polypropylene, a non-woven fabric or a release paper, or the film composition. The melt may be formed into a film by sandwiching it between these substrates. The film thus obtained may be used as it is in a form integrated with the base material, or may be peeled off from the base material and used.

The stretchable film of the present invention can be used as a single layer as it is, or can be laminated with other members and used as a multilayer body, depending on its use. Specific examples of single-layer use include elastic films used in sanitary products such as disposable diapers and sanitary products, protective films for protecting optical films, and heat used as shrink wrapping and heat shrink labels for containers. Use as a shrinkable film can be mentioned. As a specific example of forming a multilayer body, after slitting the film of the present invention, a hot melt adhesive or the like is applied to the film to form a tape, and the tape is shrunk into a non-woven fabric, woven fabric, plastic film, or the like. Alternatively, a case where an elastic gather member is formed by adhering to these laminated bodies and relaxing the shrinkage of the tape can be mentioned. Further, it is appropriately processed according to a known method according to other uses, and for example, elastic ship base material, gloves, surgical gloves, finger cots, hemostatic bands, contraceptives, headbands, goggles bands, rubber bands and the like. It can also be used as a member.

D. Elastic fiber The elastic fiber of the present invention is a fiber containing the above-mentioned block copolymer composition. Since the elastic fiber of the present invention contains the above-mentioned block copolymer composition, it is highly elastic.

The elastic fiber of the present invention may be any as long as it contains the above-mentioned block copolymer composition as a polymer component, for example, it may be composed of the above-mentioned block copolymer composition, or the above-mentioned block copolymer composition. It may contain a block copolymer composition and a polymer component or additive other than the above-mentioned block copolymer composition.
The polymer components and additives other than the block copolymer composition described above can be the same as those described in the section “C. Stretchable film” above.

The elastic fiber of the present invention can be obtained by spinning a fiber composition containing the above-mentioned block copolymer composition. The spinning method is not particularly limited as long as it can spin the composition for fibers, and a known spinning method can be applied.

Further, the elastic fiber of the present invention may be used as a bare yarn as it is, or may be used as a coating yarn by coating the elastic fiber with another fiber, depending on its use. As the other fiber, a conventionally known fiber can be used.

The elastic fiber of the present invention can be used, for example, as an elastic material such as rubber thread used for sanitary products such as disposable diapers and sanitary products, in addition to being used for clothing, sports equipment, and clothing.

E. Flexographic Plate Composition The flexographic plate composition of the present invention is a composition containing the above-mentioned block copolymer composition. Since the composition for flexographic plates of the present invention contains the above-mentioned block copolymer composition, it is rich in rubber elasticity.

The method for obtaining a flexographic plate using a block copolymer composition is not particularly limited, but a method for obtaining a flexographic plate by forming a photosensitive composition into a sheet and exposing the sheet to light is common. ..

That is, the composition for flexographic plates of the present invention contains the above-mentioned block copolymer composition as a base polymer, for example, the above-mentioned block copolymer composition, an ethylenically unsaturated compound, and photopolymerization. It is preferable to include an initiator.

The ethylenically unsaturated compound is preferably an ethylenically unsaturated compound having a molecular weight of 5000 or less. As the ethylenically unsaturated compound, those generally used in flexographic plate compositions can be used. The content of the ethylenically unsaturated compound is preferably 5 to 60% by weight, more preferably 5 to 50% by weight, based on the total amount of the block copolymer composition and the ethylenically unsaturated compound.

The total amount of the block copolymer composition and the ethylenically unsaturated compound is preferably 50% by weight or more, more preferably 60% by weight or more, and particularly preferably 70% by weight, based on the total amount of the flexographic plate composition. That is all.

As the photopolymerization initiator, those generally used in flexographic plate compositions can be used. The amount of the photopolymerization initiator used is preferably 0.1 to 5% by weight based on the total amount of the block copolymer composition and the ethylenically unsaturated compound.

The flexographic plate composition of the present invention may contain a polymer component other than the block copolymer composition described above. The polymer components other than the block copolymer composition described above can be the same as those described in the section “B. Adhesive composition” above.

The composition for flexo plates of the present invention has, if necessary, a plasticizer, a thermal polymerization inhibitor, an antioxidant, an ozone crack inhibitor, a dye, a pigment, a filler, an additive exhibiting photochromism, a reducing agent, and a relief structure. Additives such as a chemical, a cross-linking agent, a flow improving agent, and a mold release agent can be contained.

The method for producing the flexo plate composition of the present invention is not particularly limited, but for example, a kneader, a roll mill, a Banbury, a single-screw or multi-screw extruder, or the like is used to knead the components constituting the flexo plate composition. Can be manufactured by The obtained flexographic plate composition is usually molded into a sheet-shaped molded product having a desired thickness by using a molding machine such as a single-screw or multi-screw extruder, a compression molding machine, or a calendar molding machine. .. When a single-screw or multi-screw extruder is used, the flexographic plate composition can be prepared and molded into a sheet-like molded product at the same time. Further, a sheet-shaped flexo plate composition can also be produced by dissolving the components constituting the flexo plate composition in an appropriate solvent, injecting this solution into a frame mold, and evaporating the solvent. ..

The thickness of the sheet is usually 0.1 to 20 mm, preferably 1 to 10 mm.

The sheet-shaped flexographic plate composition has a transparent sheet or film made of resin on the surface thereof, and a base sheet layer or a protective film, in order to prevent contamination or damage of the flexographic plate composition during storage or operation. It can be provided as a layer.

On the surface of the sheet-shaped flexographic plate composition, a thin and flexible coating material is used to suppress the adhesiveness of the flexo plate composition surface and allow the negative film to be reused after light irradiation. A layer may be provided. In this case, after the exposure of the flexographic plate composition is completed, when the unexposed portion is removed with a solvent, the dressing layer must be removed at the same time. As the coating material layer, soluble polyamide, cellulose derivative and the like are usually often used.

The flexographic plate can be obtained by exposing the above-mentioned flexographic plate composition to light. The flexographic plate can be produced according to the same method as a general flexographic plate.

As the object to be printed by flexographic printing, for example, various materials such as paper, corrugated cardboard, wood, metal, polyethylene film, polyethylene sheet, polypropylene film, polypropylene sheet and the like can be applied.

The present invention is not limited to the above embodiment. The above embodiment is an example, and any one having substantially the same configuration as the technical idea described in the claims of the present invention and exhibiting the same effect and effect is the present invention. It is included in the technical scope of the invention.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. Unless otherwise specified, parts and% in each example are based on weight.

Various measurements were performed according to the following methods.

[Weight average molecular weight of each block copolymer and block copolymer mixture]
It was determined as a polystyrene-equivalent molecular weight by high performance liquid chromatography using tetrahydrofuran having a flow velocity of 0.35 ml / min as a carrier. The device is HLC8320 manufactured by Tosoh Corporation, the column is a combination of three polystyrene KF-404HQ manufactured by Showa Denko Co., Ltd. (column temperature 40 ° C.), the detector is a differential refractometer and an ultraviolet detector, and the molecular weight is calibrated by the polymer laboratory. It was carried out at 12 points of standard polystyrene (5 to 3 million) manufactured by the company.

[Weight ratio of each block copolymer]
It was determined from the area ratio of the peaks corresponding to each block copolymer in the chart obtained by the above high performance liquid chromatography.

[Weight average molecular weight of styrene polymer block]
Rubber Chem. Technol. , 45, 1295 (1972), the block copolymer was reacted with ozone and reduced with lithium aluminum hydride to decompose the isoprene polymer block of the block copolymer. Specifically, the procedure was as follows. That is, 300 mg of the sample was dissolved in a reaction vessel containing 100 ml of dichloromethane treated with a molecular sieve. This reaction vessel was placed in a cooling tank to a temperature of -25 ° C., and then ozone generated by an ozone generator was introduced while flowing oxygen into the reaction vessel at a flow rate of 170 ml / min. After 30 minutes from the start of the reaction, it was confirmed that the reaction was completed by introducing the gas flowing out of the reaction vessel into the potassium iodide aqueous solution. Next, 50 ml of diethyl ether and 470 mg of lithium aluminum hydride were charged in another reaction vessel substituted with nitrogen, and the solution reacted with ozone was slowly added dropwise to this reaction vessel while cooling the reaction vessel with ice water. Then, the reaction vessel was placed in a water bath, the temperature was gradually raised, and the mixture was refluxed at 40 ° C. for 30 minutes. Then, while stirring the solution, dilute hydrochloric acid was added dropwise to the reaction vessel little by little, and the addition was continued until almost no hydrogen was generated. After this reaction, the solid product produced in the solution was filtered off and the solid product was extracted with 100 ml diethyl ether for 10 minutes. This extract and the filtrate at the time of filtration were combined, and the solvent was distilled off to obtain a solid sample. The weight average molecular weight of the sample thus obtained was measured according to the above-mentioned method for measuring the weight average molecular weight, and the value was taken as the weight average molecular weight of the styrene polymer block.

[Weight average molecular weight of isoprene polymer block]
The weight average molecular weight of the corresponding styrene polymer block is subtracted from the weight average molecular weight of the block copolymer obtained as described above, and the weight average molecular weight of the isoprene polymer block is obtained based on the calculated value. rice field.

[Styrene unit content of block copolymer]
It was determined based on the detection intensity ratio between the differential refractometer and the ultraviolet detector in the above high performance liquid chromatography measurement. In addition, copolymers having different styrene unit contents were prepared in advance, and a calibration curve was prepared using them.

[Styrene unit content of block copolymer mixture]
¹ Obtained based on 1 H NMR measurement.

[Vinyl bond content of conjugated diene polymer block]
¹ Obtained based on 1 H NMR measurement.

[Melt index of block copolymer or block copolymer mixture]
Measurements were made according to ASTM D-1238 (G condition, 200 ° C., 5 kg).

[Content of water-soluble surfactant in block copolymer composition]
Gel permeation chromatography (GPC) measurement was performed on the block copolymer composition, and the block copolymer composition was determined from the area ratio of the peak corresponding to the block copolymer or the block copolymer mixture and the water-soluble surfactant. Specifically, several samples having a known content of the water-soluble surfactant in the block copolymer or the block copolymer mixture were prepared for each water-soluble surfactant species. These GPC measurements were performed, and a calibration curve showing the relationship between the water-soluble surfactant content and the peak area ratio was prepared. GPC measurements were similarly performed on samples having unknown water-soluble surfactant contents in Examples and Comparative Examples, and the content of each water-soluble surfactant was determined from the peak area ratio. When a plurality of types of water-soluble surfactants were contained, the total content of each of the obtained water-soluble surfactants was taken as the total surfactant content in the block copolymer composition.

[Blocking resistance of block copolymer composition]
For blocking resistance, 50 g of block copolymer composition pellets are placed in a 100 mm x 100 mm plastic bag, the opening of the bag is tightly sealed with cellophane tape, and the bag is placed in an oven set at 60 ° C. from above. A SUS plate and a weight of 5 kg were placed on it and left for 10 hours. After that, the presence or absence of blocking between pellets was visually confirmed, and the determination was made according to the following criteria.
◎: Blocking is not observed ○: Blocking is observed but loosened with a weak force ×: Blocking is observed and not loosened with a weak force

[Adhesive tape holding power]
The holding power is in accordance with JIS Z-0237, and an adhesive tape is attached to a stainless steel plate polished with No. 280 water-resistant abrasive paper so that an area of 25 mm x 10 mm is in contact, and a load of 1 kg is applied at 40 ° C. to adhere. The time required for the tape to fall off the stainless steel plate was measured (unit: minutes).

[Adhesive strength of adhesive tape]
Adhesive strength is measured by using a hard polyethylene (HDPE) plate as an adherend, attaching an adhesive tape with a width of 10 mm and a length of 100 mm, and peeling off in the direction of 180 degrees at a speed of 200 mm / min at 23 ° C. did.

[Adhesive tape tack]
A loop tack (N / 25 mm) was evaluated with a tensile tester at an adhesive portion of 25 × 25 mm and a temperature of 23 ° C. using an adhesive tape having a width of 25 mm and a hard polyethylene (HDPE) plate as an adherend. The larger the value, the better the initial adhesive strength.

[Manufacturing Example 1]
To the pressure-resistant reactor, 23.0 kg of cyclohexane, 3 mmol of N, N, N', N'-tetramethylethylenediamine (hereinafter referred to as TMEDA), and 1.6 kg of styrene are added and stirred at 40 ° C. However, 92 mmol of n-butyllithium was added, and the mixture was polymerized for 1 hour while raising the temperature to 50 ° C. The polymerization conversion rate of styrene was 100%. Subsequently, 4.9 kg of isoprene was continuously added to the reactor for 1 hour while controlling the temperature so as to maintain 50 to 60 ° C. After the addition of isoprene was completed, the mixture was polymerized for another 1 hour. The polymerization conversion rate of isoprene was 100%. Next, 15 mmol of dimethyldichlorosilane is added as a coupling agent, and the coupling reaction is carried out for 2 hours to obtain block copolymer b (Ar-D). Symmetrical styrene-isoprene-styrene represented by _n-X. A block copolymer was formed. After that, 110 mmol of methanol is added as a polymerization terminator and mixed well to stop the reaction and deactivate the active end of the styrene-isoprene block copolymer having an active end that did not react with the coupling agent. , A styrene-isoprene block copolymer represented by Ar-D, which is a block copolymer c, was formed. The amounts of each reagent used in the reaction are summarized in Table 1.

A part of the obtained reaction solution was taken out, and the weight average molecular weight of each block copolymer and the block copolymer mixture, the weight average molecular weight of each styrene polymer block, the weight average molecular weight of each isoprene polymer block, and each block The styrene unit content of the polymer, the styrene unit content of the block copolymer mixture, the vinyl bond content of the isoprene polymer block, and the weight ratio of each block copolymer were determined. In addition, the melt index of the block copolymer mixture was measured. These values are shown in Table 2.

[Manufacturing Example 2]
To a pressure resistant reactor, 23.0 kg of cyclohexane, 2 mmol of TMEDA, and 1.4 kg of styrene were added, and while stirring at 40 ° C., 100 mmol of n-butyllithium was added, and the temperature was raised to 50 ° C. 1 Time-polymerized. The polymerization conversion rate of styrene was 100%. Subsequently, 3.6 kg of isoprene was continuously added to the reactor for 1 hour while controlling the temperature so as to maintain 50 to 60 ° C. After the addition of isoprene was completed, the mixture was polymerized for another 1 hour. The polymerization conversion rate of isoprene was 100%. After that, 1.4 kg of styrene was continuously added for 1 hour while controlling the temperature so as to maintain 50 to 60 ° C. After the addition of styrene was completed, the polymer was polymerized for another 1 hour to form a symmetric styrene-isoprene-styrene block copolymer represented by Ar-D-Ar, which became the block copolymer b. The polymerization conversion rate of styrene was 100%. After that, 120 mmol of methanol was added as a polymerization inhibitor and mixed well to terminate the reaction.
A part of the obtained reaction solution was taken out, and the same measurement as in Production Example 1 was carried out.

[Manufacturing Example 3]
To a pressure resistant reactor, 23.0 kg of cyclohexane, 2 mmol of TMEDA, and 1.4 kg of styrene were added, and 139 mmol of n-butyllithium was added while stirring at 40 ° C., and the temperature was raised to 50 ° C. 1 Time-polymerized. The polymerization conversion rate of styrene was 100%. Subsequently, 3.6 kg of isoprene was continuously added to the reactor for 1 hour while controlling the temperature so as to maintain 50 to 60 ° C. After the addition of isoprene was completed, the mixture was polymerized for another 1 hour. The polymerization conversion rate of isoprene was 100%. After that, 1.4 kg of styrene was continuously added for 1 hour while controlling the temperature so as to maintain 50 to 60 ° C. After the addition of styrene was completed, the polymer was polymerized for another 1 hour to form a symmetric styrene-isoprene-styrene block copolymer represented by Ar-D-Ar, which became the block copolymer b. The polymerization conversion rate of styrene was 100%. After that, 167 mmol of methanol was added as a polymerization inhibitor and mixed well to terminate the reaction.
A part of the obtained reaction solution was taken out, and the same measurement as in Production Example 1 was carried out.

[Manufacturing Example 4]
To a pressure resistant reactor, 23.0 kg of cyclohexane, 2 mmol of TMEDA, and 0.8 kg of styrene were added, and while stirring at 40 ° C., 89 mmol of n-butyllithium was added, and the temperature was raised to 50 ° C. 1 Time-polymerized. The polymerization conversion rate of styrene was 100%. Subsequently, 4.2 kg of isoprene was continuously added to the reactor for 1 hour while controlling the temperature so as to maintain 50 to 60 ° C. After the addition of isoprene was completed, the mixture was polymerized for another 1 hour. The polymerization conversion rate of isoprene was 100%. Then, 0.8 kg of styrene was continuously added for 1 hour while controlling the temperature so as to maintain 50 to 60 ° C. After the addition of styrene was completed, the polymerization was carried out for another hour. The polymerization conversion rate of styrene was 100%. Then, by adding 62 mmol of methanol to the reactor, the active terminal of a part of the styrene-isoprene-styrene block copolymer is deactivated, and it is represented by Ar-D-Ar which becomes the block copolymer b. Symmetrical styrene-isoprene-styrene block copolymers were formed. Then, 0.7 kg of styrene was continuously added for 1 hour while controlling the temperature so as to maintain 50 to 60 ° C. After the addition of styrene was completed, the polymer was polymerized for another 1 hour to form an asymmetric styrene-isoprene-styrene block copolymer represented by Ar-D-Ar, which is a block copolymer a. The polymerization conversion rate of styrene was 100%. After that, 107 mmol of methanol was added as a polymerization inhibitor and mixed well to terminate the reaction.
A part of the obtained reaction solution was taken out, and the same measurement as in Production Example 1 was carried out.

[Example 1-1]
To 100 parts by weight of the block copolymer mixture, 0.40 parts by weight of polyoxyalkylene ether as a nonionic surfactant was added to the water supplied during steam stripping to the reaction solution obtained in Production Example 1. Then, steam stripping was performed so that the crumb concentration in the water was 2% by weight. Next, the aqueous slurry of the obtained block copolymer mixture was sent to a screen to separate most of the water, the crumbs of the block copolymer mixture were dehydrated, then dried by a twin-screw extruder and discharged. After cooling the strands in water at 10 ° C., the strands were cut to a length of about 25 mm with a pelletizer, and the block copolymer mixture was recovered as pellets. As a result, the block copolymer composition of Example 1-1 was obtained. The amounts of the water-soluble surfactant are summarized in Table 3. In the table, PHR represents the amount of the water-soluble surfactant with respect to 100 parts by weight of the block copolymer mixture.
The blocking resistance of the obtained block copolymer composition was evaluated. The results are shown in Table 5.

[Examples 1-2 to 1-4]
As shown in Table 3, Example 1 was carried out in the same manner as in Example 1 except that the reaction solutions obtained in Production Examples 2 to 4 were used instead of the reaction solutions obtained in Production Example 1. A block copolymer composition of −2 to 1-4 was obtained.
The blocking resistance of the obtained block copolymer composition was evaluated.

[Example 1-5]
The reaction solution obtained in Production Example 3 contains 0.10 parts by weight of a polycarboxylic acid-type surfactant as an anionic surfactant and polyoxy as a nonionic surfactant with respect to 100 parts by weight of the block copolymer. A block copolymer composition of Example 1-5 was obtained in the same manner as in Example 1-1 except that 0.15 parts by weight of alkylene ether was added.
The blocking resistance of the obtained block copolymer composition was evaluated.

[Example 1-6]
The reaction solution obtained in Production Example 3 contains 0.10 parts by weight of a polycarboxylic acid-type surfactant as an anionic surfactant and polyoxy as a nonionic surfactant with respect to 100 parts by weight of the block copolymer. A block copolymer composition of Example 1-6 was obtained in the same manner as in Example 1-1 except that 1.50 parts by weight of alkylene ether was added.
The blocking resistance of the obtained block copolymer composition was evaluated.

[Example 1-7]
In the reaction solution obtained in Production Example 3, 0.10 parts by weight of alkyltrimethylammonium chloride as a cationic surfactant and 0.10 parts by weight of polyoxyalkylene ether as a nonionic surfactant were added to 100 parts by weight of the block copolymer. The block copolymer composition of Example 1-7 was obtained in the same manner as in Example 1-1 except that 15 parts by weight was added.
The blocking resistance of the obtained block copolymer composition was evaluated.

[Examples 1-8 to 1-11]
As shown in Table 3, in each of the reaction solutions obtained in Production Examples 1 to 4, a polycarboxylic acid-type surfactant was used as an anionic surfactant with respect to 100 parts by weight of a block copolymer or a block copolymer mixture. Block copolymer compositions of Examples 1-8 to 1-11 were obtained in the same manner as in Example 1-1 except that 0.20 parts by weight of the activator was added.
The blocking resistance of the obtained block copolymer composition was evaluated.

[Example 1-12]
The reaction solution obtained in Production Example 3 contains 0.05 parts by weight of a polycarboxylic acid-type surfactant as an anionic surfactant and polyoxy as a nonionic surfactant with respect to 100 parts by weight of the block copolymer. A block copolymer composition of Example 1-12 was obtained in the same manner as in Example 1-1 except that 0.05 parts by weight of alkylene ether was added.
The blocking resistance of the obtained block copolymer composition was evaluated.

[Comparative Example 1-13]
The reaction solution obtained in Production Example 3 contains 0.10 parts by weight of a polycarboxylic acid-type surfactant as an anionic surfactant and polyoxy as a nonionic surfactant with respect to 100 parts by weight of the block copolymer. A block copolymer composition of Comparative Example 1-13 was obtained in the same manner as in Example 1-1 except that 4.00 parts by weight of alkylene ether was added.
The blocking resistance of the obtained block copolymer composition was evaluated.

[Comparative Examples 1-14 to 1-15]
As shown in Table 4, each of the reaction solutions obtained in Production Examples 1 and 2 has a polycarboxylic acid-type surfactant as an anionic surfactant with respect to 100 parts by weight of a block copolymer or a block copolymer mixture. Comparative Examples 1-14-1 to 1-14 in the same manner as in Example 1-1, except that 0.05 parts by weight of the activator and 0.01 parts by weight of the polyoxyalkylene ether as the nonionic surfactant were added. Fifteen block copolymer compositions were obtained.
The blocking resistance of the obtained block copolymer composition was evaluated.

[Comparative Examples 1-16 to 1-17]
As shown in Table 4, each of the reaction solutions obtained in Production Examples 3 to 4 has a polycarboxylic acid-type surfactant as an anionic surfactant with respect to 100 parts by weight of a block copolymer or a block copolymer mixture. Block copolymer compositions of Comparative Examples 1-16 to 1-17 were obtained in the same manner as in Example 1-1 except that 0.10 parts by weight of the activator was added.
The blocking resistance of the obtained block copolymer composition was evaluated.

[Example 2-1]
50 parts of the block copolymer composition of Example 1-1, 50 parts of the styrene isoprene block copolymer (“Quintac (registered trademark) 3450”, manufactured by Nippon Zeon Co., Ltd.), hydrogenated petroleum resin (“Arcon M-100”) , 300 parts of Arakawa Chemical Co., Ltd., 100 parts of paraffin oil ("PW-90", manufactured by Idemitsu Kosan Co., Ltd.), and 1 part of antioxidant ("Irganox (registered trademark) 1010", manufactured by BASF). , 180 ° C. for 1 hour to prepare the adhesive composition of Example 2-1. Next, the adhesive composition was applied to a polyester film having a thickness of 25 μm so as to have a thickness of 40 μm to obtain an adhesive tape. The holding power, adhesive strength and tack of this adhesive tape were measured. The results are summarized in Table 5.

[Examples 2-2-2-7]
The adhesive composition of Examples 2-2-2-7 is the same as that of Example 2-1 except that the block copolymer compositions of Examples 1-2-1-7 are used respectively. And got an adhesive tape. The holding power, adhesive strength and tack of the obtained adhesive tape were measured.

[Examples 2-8 to 2-12]
Adhesive composition of Examples 2-8 to 2-12 in the same manner as in Example 2-1 except that the block copolymer compositions of Examples 1-8 to 1-12 were used respectively. And got an adhesive tape. The holding power, adhesive strength and tack of the obtained adhesive tape were measured.

[Comparative Examples 2-13 to 2-17]
Adhesive composition of Comparative Examples 2-13 to 2-17 in the same manner as in Example 2-1 except that the block copolymer compositions of Examples 1-13 to 1-17 were used respectively. And got an adhesive tape. The holding power, adhesive strength and tack of the obtained adhesive tape were measured.

From Tables 5 and 6, it was found that the compositions of Examples 2-1 to 2-12 were excellent in blocking resistance and adhesive properties. On the other hand, the compositions of Comparative Examples 2-14 to 2-17 were inferior in blocking resistance, and the compositions of Comparative Example 2-13 were inferior in holding power.

Claims (9)

Contains a block copolymer having at least one aromatic vinyl polymer block and at least one conjugated diene polymer block.
The melt index of the block copolymer is 20 g / 10 minutes or more, and the block copolymer has a melt index of 20 g / 10 minutes or more.
Containing 0.02 to 3.00% by weight of a water-soluble surfactant,
A block copolymer composition, wherein the water-soluble surfactant contains at least an anionic surfactant or a cationic surfactant. The block copolymer composition according to claim 1 , wherein the melt index of the block copolymer is 30 g / 10 minutes or more. The block copolymer composition according to claim 1 or 2 , wherein the content of the water-soluble surfactant is 0.10 to 2.50% by weight. The block copolymer composition according to claim 3 , wherein the content of the water-soluble surfactant is 0.12 to 2.00% by weight. The block copolymer composition according to claim 4 , wherein the content of the water-soluble surfactant is 0.15 to 1.50% by weight. A viscous adhesive composition containing the block copolymer composition according to any one of claims 1 to 5. A stretchable film containing the block copolymer composition according to any one of claims 1 to 5. An elastic fiber containing the block copolymer composition according to any one of claims 1 to 5. A flexographic plate composition containing the block copolymer composition according to any one of claims 1 to 5.