JP2011094073A - Modified block copolymer and composition of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a styrenic resin having good adhesiveness with water-based ink, good mechanical strength such as a tensile modulus, and high versatility. <P>SOLUTION: The modified block copolymer (Z) is provided, which comprises: a primary modified block copolymer or its hydrogenated product (2), prepared by an addition reaction of a functional group-containing modifier to a block copolymer containing at least one polymer block (A) essentially comprising a vinyl aromatic hydrocarbon and at least one polymer block (B) essentially comprising a conjugated diene; and a polymer (3) bonded to the primary modified block copolymer or its hydrogenated product, the polymer (3) having at least one bonding group or a functional group having reactivity with the functional group of the primary modified block copolymer or its hydrogenated product (2), the functional group selected from a group consisting of an ester bond, urethane bond, epoxy group, amino group, amide group, hydroxy group, silanol group and alkoxysilane group. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a modified block copolymer and a composition thereof.

  Styrenic resins have been widely used as molding materials for household goods, electrical products, packaging, etc. because of their excellent moldability, rigidity, and transparency, low specific gravity, and low cost. Has been made.

Styrenic resins are used as packaging materials for sheets, films, and the like, but images such as letters and designs are printed with organic solvent-based inks or the like in order to improve design properties.
For example, in Patent Document 1 and Patent Document 2, a vinyl aromatic hydrocarbon-conjugated diene block copolymer is modified with a hydroxyl group, an epoxy group, an amino group or the like as a styrene resin, and then an acid anhydride group or the like. A modified polymer modified with a functional oligomer having the following is disclosed.

On the other hand, in the printing industry that performs gravure printing and the like, there is an increasing tendency to refrain from using organic solvent-based inks from the viewpoint of preventing environmental pollution caused by the release of organic solvents and improving the working environment.
In addition, when used in food packaging packs and films, water-based inks are increasingly used in place of organic solvent-based printing inks from the viewpoint of being unfavorable for hygiene when organic solvents and the like migrate to foods. .

JP 2003-327702 A JP 2003-327704 A

However, styrenic resins have poor wettability, and there is a problem that water-based ink by gravure printing does not adhere and good printability cannot be obtained.
In view of this problem, for example, a method has been proposed in which surface modification is performed by performing corona discharge treatment, primer treatment, or the like as a pre-printing process on the surface of a styrene resin sheet or film. However, even if corona discharge treatment or primer treatment is used, when water-based ink is used, from the viewpoint of glossiness, sharpness, and gradation, it is still possible to print characters and images that are sufficiently good for practical use. Is not yet reached.

  Therefore, in the present invention, in view of the above-described problems of the prior art, to provide a highly versatile styrenic resin that has good adhesion to water-based ink and good mechanical strength such as tensile elastic modulus. Objective.

As a result of intensive studies to solve the above problems, the present inventors have found that at least one polymer block mainly composed of vinyl aromatic hydrocarbons and at least one polymer block mainly composed of conjugated dienes. The present invention has found that a block copolymer modified by bonding to a block copolymer containing or a hydrogenated product thereof with a polymer having a specific bonding group or functional group can solve the above problems. Was completed.
Further, as another polymer, a functional block copolymer comprising at least one polymer block mainly composed of vinyl aromatic hydrocarbon and at least one polymer block mainly composed of conjugated diene is functionalized. A block copolymer modified by bonding a polymer having a specific bonding group or functional group to a primary modified block copolymer obtained by addition reaction of a group-containing modifier or a hydrogenated product thereof is the above-mentioned problem. The present invention has been completed.

That is, the present invention is as follows.
[1]
A block copolymer containing at least one polymer block A mainly composed of vinyl aromatic hydrocarbons and at least one polymer block B mainly composed of conjugated diene, or a hydrogenated product thereof (1) ,
A modified block copolymer to which a polymer (3) having at least one bonding group or functional group selected from the group consisting of an ester bond, a urethane bond, an epoxy group, an amino group, an amide group, a hydroxyl group, a silanol group, and an alkoxysilane group is bonded. Polymer (X).
[2]
A functional group-containing modifier is added to a block copolymer containing at least one polymer block A mainly composed of vinyl aromatic hydrocarbons and at least one polymer block B mainly composed of conjugated dienes. To the primary modified block copolymer or hydrogenated product (2) obtained by reaction,
It consists of an ester bond, a urethane bond, an epoxy group, an amino group, an amide group, a hydroxyl group, a silanol group, and an alkoxysilane group that are reactive with the functional group of the primary modified block copolymer or its hydrogenated product (2). A modified block copolymer (Z) to which a polymer (3) having at least one bonding group or functional group selected from the group is bonded.
[3]
The functional group-containing modifier is added to the primary modified block copolymer or its hydrogenated product (2) by an addition reaction with the block copolymer, to a hydroxyl group, an epoxy group, an amino group, a silanol group, or an alkoxysilane group. The modified block copolymer (Z) according to the above [2], which has a function of generating an atomic group having at least one functional group selected from the group consisting of:
[4]
The modified block copolymer (X) according to the above [1], wherein the polymer (3) is at least one polymer selected from the group consisting of the following a) to m).
a) Maleic anhydride-ethylene-ethyl acrylate-acrylonitrile-styrene copolymer b) Maleic anhydride-methyl methacrylate-styrene copolymer c) Maleic anhydride-ethylene-vinyl acetate copolymer d) Vinyl acetate-styrene copolymer Polymer e) Alkoxysilane bond-ethylene-vinyl acetate copolymer f) Polyurethane g) Glycidyl methacrylate-styrene copolymer h) Ethylene-glycidyl methacrylate-styrene copolymer i) Ethylene-glycidyl methacrylate-acrylonitrile-styrene copolymer Compound j) Glycidyl methacrylate-acrylonitrile-styrene-polycarbonate copolymer k) Ethylene-glycidyl methacrylate-butyl acrylate-methyl methacrylate copolymer l) Epoxy group-containing- Styrene - butadiene copolymer m) polyester.
[5]
The modified block copolymer (Z) according to the above [2] or [3], wherein the polymer (3) is at least one polymer selected from the group consisting of the following a) to m).
a) Maleic anhydride-ethylene-ethyl acrylate-acrylonitrile-styrene copolymer b) Maleic anhydride-methyl methacrylate-styrene copolymer c) Maleic anhydride-ethylene-vinyl acetate copolymer d) Vinyl acetate-styrene copolymer Polymer e) Alkoxysilane bond-ethylene-vinyl acetate copolymer f) Polyurethane g) Glycidyl methacrylate-styrene copolymer h) Ethylene-glycidyl methacrylate-styrene copolymer i) Ethylene-glycidyl methacrylate-acrylonitrile-styrene copolymer Compound j) Glycidyl methacrylate-acrylonitrile-styrene-polycarbonate copolymer k) Ethylene-glycidyl methacrylate-butyl acrylate-methyl methacrylate copolymer l) Epoxy group-containing- Styrene - butadiene copolymer m) Polyester [6]
1 to 99 masses of the modified block copolymer (X) described in [1] or [4] above or the modified block copolymer (Z) described in any of [2], [3] and [5] above. %, A modified block copolymer composition containing 99 to 1% by mass of a thermoplastic resin.
[7]
A block copolymer containing at least one polymer block A mainly composed of vinyl aromatic hydrocarbons and at least one polymer block B mainly composed of conjugated diene, or a hydrogenated product thereof (1) ,
Including a step of bonding a polymer (3) having at least one bonding group or functional group selected from the group consisting of an ester bond, a urethane bond, an epoxy group, an amino group, an amide group, a hydroxyl group, a silanol group, and an alkoxysilane group. The manufacturing method of modified block copolymer (X).
[8]
A functional group-containing modifier is added to a block copolymer containing at least one polymer block A mainly composed of vinyl aromatic hydrocarbons and at least one polymer block B mainly composed of conjugated dienes. To the primary modified block copolymer or hydrogenated product (2) obtained by reaction,
It consists of an ester bond, a urethane bond, an epoxy group, an amino group, an amide group, a hydroxyl group, a silanol group, and an alkoxysilane group that are reactive with the functional group of the primary modified block copolymer or its hydrogenated product (2). A method for producing a modified block copolymer (Z), comprising a step of bonding a polymer (3) having at least one bonding group or functional group selected from the group.

  According to the present invention, it is possible to provide a highly versatile styrenic resin that has good adhesion to water-based ink and good mechanical strength such as tensile elastic modulus.

The GPC curve of the modified block copolymer (MP-1), and the GPC curve of the primary modified block copolymer (P-1) alone and polyurethane (TPU) alone are shown.

  Hereinafter, a mode for carrying out the present invention (hereinafter also referred to as “the present embodiment”) will be described in detail. The present invention is not limited to the present embodiment, and can be implemented with various modifications within the scope of the gist.

(First embodiment)
The modified block polymer (X) in the present embodiment comprises at least one polymer block A mainly composed of vinyl aromatic hydrocarbons and at least one polymer block B mainly composed of conjugated diene. The block copolymer or its hydrogenated product (1) contains at least one bonding group or functional group selected from an ester bond, a urethane bond, an epoxy group, an amino group, an amide group, a hydroxyl group, a silanol group, and an alkoxysilane group. It has a structure in which the polymer (3) it has is bonded.

First, a block copolymer containing at least one polymer block A mainly composed of a vinyl aromatic hydrocarbon and at least one polymer block B mainly composed of a conjugated diene, or a hydrogenated product thereof (1 ) (Hereinafter also referred to as block copolymer (1) and hydrogenated product of block copolymer (1), respectively).

  The polymer block A mainly composed of vinyl aromatic hydrocarbon is a copolymer block of vinyl aromatic hydrocarbon and conjugated diene containing 50% by mass or more of vinyl aromatic hydrocarbon, or vinyl aromatic hydrocarbon alone The polymer block of is shown.

  The polymer block B mainly composed of a conjugated diene is a copolymer block of a conjugated diene and a vinyl aromatic hydrocarbon containing the conjugated diene in an amount exceeding 50% by mass, or a polymer block of a conjugated diene alone. .

  When a random copolymer block of vinyl aromatic hydrocarbon and conjugated diene is present in polymer block A mainly composed of vinyl aromatic hydrocarbon or polymer block B mainly composed of conjugated diene, The vinyl aromatic hydrocarbons may be distributed uniformly in the random copolymer block or may be distributed in a tapered shape. The copolymer block may have a plurality of portions where vinyl aromatic hydrocarbons are uniformly distributed and / or portions where tapes are distributed.

  When the modified block copolymer of the present embodiment has a plurality of polymer blocks A (or B), they may be different in molecular weight, composition, type, and the like.

The block copolymer (1) can be basically synthesized by a conventionally known method.
For example, Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43-17879, Japanese Patent Publication No. 48-2423, Japanese Patent Publication No. 49-36957, Japanese Patent Publication No. 57-49567, Japanese Patent Publication No. 58-11446, etc. Can be synthesized by a block copolymerization method of a conjugated diene and a vinyl aromatic hydrocarbon using an anionic initiator such as an organolithium compound in a hydrocarbon solvent. However, in this Embodiment, the manufacturing conditions of each constituent polymer shall be set as described later.

Examples of the polymer structure of the block copolymer (1) include linear block copolymers such as the following (a) to (c).
A- (BA) n (a)
A- (B-A) n-B (b)
B- (A-B) n + 1 (c)
Here, A is a polymer block mainly composed of vinyl aromatic hydrocarbons, and B is a polymer block mainly composed of conjugated dienes. The boundary between the A block and the B block does not necessarily have to be clearly distinguished. n is an integer greater than or equal to 1, and is generally 1-5.

Moreover, as a polymer structure of a block copolymer (1), the radial block copolymer like following (d)-(g) other than the said linear block copolymer is mentioned.
[(A−B) k] m−X (d)
[(A−B) k−A] m−X (e)
[(B−A) k] m−X (f)
[(B−A) k−B] m−X (g)

  Here, A and B are synonymous with the above (a) to (c), k is an integer of 1 or more, m is an integer of 3 or more, and generally 3 to 5. The polymer in which m is 3 to 5 may include a polymer in which m is 1 and / or 2. X represents a residue of a coupling agent such as silicon tetrachloride or tin tetrachloride or a residue of an initiator such as a polyfunctional organolithium compound.

  Examples of the vinyl aromatic hydrocarbon include styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene, vinylanthracene, 1,1. -Diphenylethylene and the like can be mentioned. Among them, styrene is preferable because of its good reactivity and high strength. These may use only 1 type and may mix and use 2 or more types.

The conjugated diene is a diolefin having a pair of conjugated double bonds, such as 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3- Examples include butadiene, 1,3-pentadiene, 1,3-hexadiene,
1,3-butadiene and isoprene are preferred. These may use only 1 type and may mix and use 2 or more types.

  When 1,3-butadiene and isoprene are used in combination as the conjugated diene, the proportion of isoprene is preferably 10% by mass or more and 25% by mass or more with respect to the total mass of 1,3-butadiene and isoprene. More preferably, it is more preferably 40% by mass or more. If the isoprene content is 10% by mass or more, it is difficult to cause thermal decomposition during molding at a high temperature and the molecular weight does not decrease. Therefore, a modified block copolymer having a good balance between appearance characteristics and mechanical strength and composition thereof Tends to be obtained.

  In the step of synthesizing the block copolymer (1), a hydrocarbon solvent is used. Examples of the hydrocarbon solvent include aliphatic hydrocarbons such as butane, pentane, hexane, isopentane, heptane, and octane; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane; benzene, Aromatic hydrocarbons such as toluene, ethylbenzene and xylene can be used. These may use only 1 type and may mix and use 2 or more types.

In the step of synthesizing the block copolymer (1), an anionic initiator is used. Examples of the anionic initiator include organic monolithium compounds, organic dilithium compounds, and organic polylithium compounds in which one or more lithium atoms are bonded in the molecule.
Specific examples include ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, hexamethylene dilithium, butadienyl dilithium, and isoprenyl dilithium. . These may use only 1 type and may mix and use 2 or more types.

In the step of synthesizing the block copolymer (1), the polymerization rate is adjusted, the microstructure of the polymerized conjugated diene part (the ratio of cis, trans, vinyl), the reaction ratio of the conjugated diene and the vinyl aromatic hydrocarbon A polar compound or a randomizing agent can be used for the purpose of adjustment.
Examples of polar compounds and randomizing agents include ethers such as tetrahydrofuran, diethylene glycol dimethyl ether and diethylene glycol dibutyl ether; amines such as triethylamine and tetramethylethylenediamine; thioethers; phosphines; phosphoramides; alkylbenzene sulfonates; Examples thereof include sodium alkoxide.

The polymerization temperature condition of the block copolymer (1) is generally in the range of −10 ° C. to 150 ° C., preferably in the range of 40 ° C. to 120 ° C.
The time required for polymerization varies depending on the conditions, but in general, it can be carried out within 48 hours, and can be carried out in 1 to 10 hours by selecting particularly good conditions.
Moreover, it is preferable that the atmosphere of the system at the time of the polymerization is in a state where it is substituted with an inert gas such as nitrogen gas.
The pressure at the time of carrying out the polymerization is not particularly limited as long as it is in a range sufficient to maintain the monomer and solvent in the liquid layer within the above polymerization temperature range.
Furthermore, care should be taken not to mix impurities, such as water, oxygen, carbon dioxide, etc., that inactivate the catalyst and living polymer into the polymerization system.

  The vinyl aromatic hydrocarbon content in the block copolymer (1) is preferably in the range of 30 to 95% by mass, more preferably in the range of 50 to 95% by mass, and still more preferably in the range of 70 to 95% by mass. It is a range. When the vinyl aromatic hydrocarbon content in the block copolymer (1) is in the range of 30 to 95% by mass, a resin having excellent impact resistance and rigidity balance performance and excellent transparency can be obtained. It is in.

  The block ratio of the vinyl aromatic hydrocarbon polymer block incorporated in the block copolymer (1) is preferably in the range of 50 to 100%. It is preferable for the block ratio of the vinyl aromatic hydrocarbon polymer block to be 50% or more because excellent rigidity tends to be obtained in the modified block copolymer and the resin composition thereof in the present embodiment.

The block ratio of the vinyl aromatic hydrocarbon polymer block is the mass of the vinyl aromatic hydrocarbon and the conjugated diene in the process of copolymerizing at least a part of the vinyl aromatic hydrocarbon and the conjugated diene during the production of the block copolymer. It can be controlled by adjusting the mass ratio, the polymerization reactivity ratio, and the like.
Specifically, (a) a mixture of a vinyl aromatic hydrocarbon and a conjugated diene is continuously supplied to the polymerization system for polymerization, and / or (b) a polar compound or a randomizing agent is used. And a method of copolymerizing vinyl aromatic hydrocarbon and conjugated diene.

  Examples of the polar compound or randomizing agent include ethers such as tetrahydrofuran, diethylene glycol dimethyl ether and diethylene glycol dibutyl ether, amines such as triethylamine and tetramethylethylenediamine; thioethers; phosphines; phosphoramides; alkylbenzene sulfonates; And sodium alkoxide.

The block ratio of the aromatic hydrocarbon polymer block is a method of oxidatively decomposing a block copolymer with di-tertiary butyl hydroperoxide using osmium tetroxide as a catalyst [I. M.M. KOLTHOFF, et al. , J .; Polym. Sci. 1
, 429 (1946)] is quantified with the vinyl aromatic hydrocarbon polymer block component (excluding vinyl aromatic hydrocarbon polymer components having an average degree of polymerization of about 30 or less). , Using the following formula.

  The number average molecular weight (Mn) of the vinyl aromatic hydrocarbon polymer block in the block copolymer (1) is preferably in the range of 10,000 to 150,000, and more preferably in the range of 20,000 to 120,000. When the (Mn) is 10,000 or more and 150,000 or less, there is a tendency that even more excellent rigidity and impact resistance are obtained, and further, molding processability and transparency tend to be good.

The number average molecular weight (Mn) is obtained by oxidatively decomposing a block copolymer with di-tertiary butyl hydroperoxide using osmium tetroxide as a catalyst [I. M.M. KOLTHOFF, et al. , J .; Polym. Sci. 1, 429 (1946)] from the vinyl aromatic hydrocarbon polymer block component obtained by gel permeation chromatography (GPC).
That is, GPC measurement of monodisperse polystyrene for GPC is performed, a calibration curve is created between the peak count number and the molecular weight of the monodisperse polystyrene, and calculation is performed according to a conventional method (for example, “Gel Chromatography <Basics> Issued by Kodansha”). can do.

Next, a hydrogenated block copolymer (1) containing at least one polymer block A mainly composed of vinyl aromatic hydrocarbons and at least one polymer block B mainly composed of conjugated diene. ).
The block copolymer hydrogenated product (1) is obtained by subjecting the block copolymer (1) obtained above to hydrogenation (hereinafter also abbreviated as “hydrogenated”). .

The hydrogenation catalyst used in the hydrogenation is not particularly limited, and conventionally known catalysts, for example, (1) metals such as Ni, Pt, Pd, and Ru are supported on carbon, silica, alumina, diatomaceous earth, and the like. Supported so-called heterogeneous hydrogenation catalyst, (2) so-called Ziegler-type hydrogenation using an organic acid salt such as Ni, Co, Fe, Cr, or a transition metal salt such as acetylacetone salt and a reducing agent such as organic aluminum A catalyst, (3) a homogeneous hydrogenation catalyst such as a so-called organometallic complex, such as an organometallic compound such as Ti, Ru, Rh, or Zr, can be applied.
Specifically, JP-B-42-8704, JP-B-43-6636, JP-B-63-4841, JP-B-1-37970, JP-B-1-53851, JP-B-2-9041 Can be applied.

Preferable examples of the hydrogenation catalyst include a mixture of a titanocene compound and a reducing organometallic compound.
As the titanocene compound, for example, a compound described in JP-A-8-109219 can be used. Specific examples include (substituted) such as biscyclopentadienyl titanium dichloride and monopentamethylcyclopentadienyl titanium trichloride. And compounds having at least one ligand having a cyclopentadienyl skeleton, an indenyl skeleton, or a fluorenyl skeleton.
Examples of the reducing organometallic compound include organic alkali metal compounds such as organolithium, organomagnesium compounds, organoaluminum compounds, organoboron compounds, and organozinc compounds.

The temperature condition for carrying out the hydrogenation reaction on the block copolymer is preferably in the range of 0 to 200 ° C, more preferably in the range of 30 to 150 ° C.
The pressure of hydrogen used for the hydrogenation reaction is preferably 0.1 to 15 MPa, more preferably 0.2 to 10 MPa, and still more preferably 0.3 to 5 MPa.
The hydrogenation reaction time is preferably 3 minutes to 10 hours, more preferably 10 minutes to 5 hours.
The hydrogenation reaction can be performed by a batch process or a continuous process, and these may be performed alone or in combination.

In the hydrogenated block copolymer (1), the hydrogenation rate of the unsaturated double bond based on the conjugated diene compound is not particularly limited, but is preferably 70% or more, more preferably 80% or more. More preferably, 90% or more is hydrogenated, and the unsaturated double chain is incorporated in the block copolymer in a 1,2-bond, 3,4-bond, or 1,4-bond bond mode. Only some of the bonds may be hydrogenated. When only a part is hydrogenated, the hydrogenation rate is preferably 10% or more and less than 70%, more preferably 15% or more and less than 65%, and more preferably 20% or more and less than 60%. Further preferred.
Furthermore, in the hydrogenated product (1) of the block copolymer, the hydrogenation rate of the vinyl bond based on the conjugated diene before hydrogenation is preferably 85% or more, more preferably 90% or more. And more preferably 95% or more. By setting the hydrogenation rate within the above range, the thermal stability tends to be improved.
In addition, the hydrogenation rate of the said vinyl bond means the ratio of the vinyl bond hydrogenated among the vinyl bonds based on the conjugated diene before hydrogenation incorporated in the block copolymer.

In the hydrogenated product (1) in the block copolymer, the hydrogenation rate of the aromatic double bond based on the vinyl aromatic hydrocarbon is not particularly limited, but is preferably 50% or less. % Or less, more preferably 20% or less.
The hydrogenation rate and the vinyl bond amount based on the conjugated diene compound can be measured by a nuclear magnetic resonance apparatus (NMR).

  At least one bonding group selected from the group consisting of an ester bond, a urethane bond, an epoxy group, an amino group, an amide group, a hydroxyl group, a silanol group, and an alkoxysilane group to the block copolymer or the hydrogenated product (1) described above. Alternatively, the modified block copolymer (X) is obtained by bonding the polymer (3) having a functional group. This will be described later (second embodiment) and can be performed in the same process.

(Second Embodiment)
The modified block copolymer (Z) in the present embodiment includes at least one polymer block A mainly composed of vinyl aromatic hydrocarbons, and at least one polymer block B mainly composed of conjugated dienes, A primary modified block copolymer obtained by addition-reacting a functional group-containing modifier to a block copolymer containing a hydrogenated product (2) is reactive with the functional group of the primary modified block copolymer. Modified with a polymer (3) having at least one bonding group or functional group selected from the group consisting of an ester bond, a urethane bond, an epoxy group, an amino group, an amide group, a hydroxyl group, a silanol group, and an alkoxysilane group. Modified block copolymer.

  The primary modified block copolymer or its hydrogenated product (2) (hereinafter also referred to as block copolymer (2) and hydrogenated product of block copolymer (2), respectively) is the vinyl aromatic described above. The block copolymer containing at least one polymer block A mainly composed of hydrocarbons and at least one polymer block B mainly composed of conjugated dienes or a hydrogenated product thereof (1) It is obtained by addition reaction of the containing modifier.

  The primary modified block copolymer or hydrogenated product (2) thereof is added to the block copolymer or hydrogenated product (1) thereof by hydroxyl group, carboxyl group, carbonyl group, thiocarbonyl group, acid halide group, Acid anhydride group, carboxylic acid group, thiocarboxylic acid group, aldehyde group, thioaldehyde group, carboxylic acid ester group, amide group, sulfonic acid group, sulfonic acid ester group, phosphoric acid group, phosphoric acid ester group, amino group, imino Group, nitrile group, pyridyl group, quinoline group, epoxy group, thioepoxy group, sulfide group, isocyanate group, isothiocyanate group, silanol group, alkoxysilane, silicon halide group, tin halide group, alkoxytin group, phenyltin group, etc. It has a structure in which a functional group selected from

  As a method for obtaining a block copolymer to which the functional group is bonded, at least a functional group selected from the above functional groups is added to the block copolymer by an addition reaction with the living end of the block copolymer (1). A method of adding a functional group-containing modifier that produces a primary modified block copolymer to which one atomic group is bonded, or a function to which an atomic group in which the functional group is protected by a known method is bonded It can be obtained by a method (first method) in which a group-containing modifier is subjected to an addition reaction. As a second method, the block copolymer or its hydrogenated product (1) is reacted with an organic alkali metal compound such as an organolithium compound (metalation reaction), and the block copolymer is added with an organic alkali metal added thereto. A method in which the functional group-containing modifier is added to the coalescence is mentioned.

  Depending on the type of functional group-containing modifier, the hydroxyl group, amino group, or the like may be an organometallic salt at the stage of reacting these, but in that case, the compound having active hydrogen such as water or alcohol may be used. By treatment, a hydroxyl group, an amino group, or the like can be obtained.

When the functional group-containing modifier is reacted with the living end of the block copolymer (1), the partially unmodified (unmodified) block copolymer (1) is converted into the primary modified block copolymer. It may be mixed in the polymer. The proportion of the unmodified block copolymer in the primary modified block copolymer is preferably 70% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass or less.

Preferred examples of the primary modified block copolymer or its hydrogenated product (2) are given below.
Examples of the primary modified block copolymer or hydrogenated product (2) thereof include a primary bonded with a functional group selected from the group consisting of a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group. Examples thereof include a modified block copolymer or a hydrogenated product thereof.
Examples of the structure near the functional group selected from the group consisting of a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group include the following formulas (I) to (XIII).

Here, R ^{1 to} R ⁴ are each independently a functional group selected from the group consisting of hydrogen, a hydrocarbon group having 1 to 24 carbon atoms, or a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group. The C1-C24 hydrocarbon group which has these.
R ⁵ represents a hydrocarbon chain having 1 to 48 carbon atoms or a hydrocarbon chain having 1 to 48 carbon atoms having a functional group selected from the group consisting of a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group.
In addition, in the hydrocarbon groups of R ^{1 to} R ⁴ and the hydrocarbon chain of R ⁵ , oxygen, nitrogen, silicon, etc. are bonded in a bonding mode other than a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group. Elements may be bonded.
R ⁶ represents hydrogen or an alkyl group having 1 to 8 carbon atoms.

An atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group, which is suitable as the primary modified block copolymer or a hydrogenated product thereof, is bonded. The functional group-containing modifier used for obtaining the primary modified block copolymer or the hydrogenated product (2) thereof is shown below.
For example, tetraglycidylmetaxylenediamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, tetraglycidyl-p-phenylenediamine, tetraglycidyldiaminodiphenylmethane, diglycidylaniline, diglycidylorthotoluidine, γ-glycidoxyethyltrimethoxy Silane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxy Silane can be used.
Also, 1- [3- (triethoxysilyl) -propyl] -4-methylpiperazine, 1- [3- (diethoxyethylsilyl) -propyl] -4-methylpiperazine, 1- [3- (trimethoxysilyl) ) -Propyl] -3-methylimidazolidine, 1- [3- (diethoxyethylsilyl) -propyl] -3-ethylimidazolidine, 1- [3- (triethoxysilyl) -propyl] -3-methylhexa Hydropyrimidine, 1- [3- (dimethoxymethylsilyl) -propyl] -3-methylhexahydropyrimidine, 3- [3- (tributoxysilyl) -propyl] -1-methyl-1,2,3,4 Tetrahydropyrimidine, 3- [3- (dimethoxymethylsilyl) -propyl] -1-ethyl-1,2,3,4-tetrahydropyrimidine, 1- (2-ethoxyethyl) -3 -[3- (Trimethoxysilyl) -propyl] -imidazolidine, (2- {3- [3- (trimethoxysilyl) -propyl] -tetrahydropyrimidin-1-yl} -ethyl) dimethylamine can be used.
Also, γ-glycidoxypropyltriphenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylmethyl Diethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-glycyl Sidoxypropyldiethylethoxysilane, γ-glycidoxypropyldimethylethoxysilane, and γ-glycidoxypropyldimethylphenoxysilane can be used.
In addition, γ-glycidoxypropyl diethylmethoxysilane, γ-glycidoxypropylmethyl diisopropeneoxysilane, bis (γ-glycidoxypropyl) dimethoxysilane, bis (γ-glycidoxypropyl) diethoxysilane, Bis (γ-glycidoxypropyl) dipropoxysilane, bis (γ-glycidoxypropyl) dibutoxysilane, bis (γ-glycidoxypropyl) diphenoxysilane, bis (γ-glycidoxypropyl) methylmethoxy Silane, bis (γ-glycidoxypropyl) methylethoxysilane, bis (γ-glycidoxypropyl) methylpropoxysilane, bis (γ-glycidoxypropyl) methylbutoxysilane, bis (γ-glycidoxypropyl) Methylphenoxysilane can be used.
Further, tris (γ-glycidoxypropyl) methoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxymethyltrimethoxysilane, γ-methacryloxyethyltriethoxysilane, Bis (γ-methacryloxypropyl) dimethoxysilane, tris (γ-methacryloxypropyl) methoxysilane, β- (3,4-epoxycyclohexyl) ethyl-trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl- Triethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-tripropoxysilane, β- (3,4-epoxycyclohexyl) ethyl-tributoxysilane, β- (3,4-epoxycyclohexyl) ethyl-triphenoxy Silane You can use.
Β- (3,4-epoxycyclohexyl) propyl-trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-ethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-ethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldipropoxysilane , Β- (3,4-epoxycyclohexyl) ethyl-methyldibutoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldiphenoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylmethoxysilane , Β- (3,4-epoxycyclohexyl) ) Ethyl - diethyl ethoxysilane can be used.
Β- (3,4-epoxycyclohexyl) ethyl-dimethylethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylpropoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylbutoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylphenoxysilane, β- (3,4-epoxycyclohexyl) ethyl-diethylmethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldiisopropeneoxysilane 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, N, N′-dimethylpropyleneurea and N-methylpyrrolidone can be used.

  When the functional group-containing modifier is added to the living end of the block copolymer, the living end of the block copolymer may be either polymer block A or polymer block B. From the viewpoint of obtaining a composition having good mechanical strength and the like, the living end of the polymer block A is preferable.

The amount of the functional group-containing modifier used is preferably more than 0.5 equivalent and 10 equivalents or less, more than 0.7 equivalents and 5 equivalents or less, with respect to 1 equivalent of the living terminal of the block copolymer. More preferably, it is more than 1 equivalent and 4 equivalents or less.
The amount of the living terminal of the block copolymer may be calculated from the amount of the organic lithium compound used for the polymerization and the number of lithium atoms bonded to the organic lithium compound, or the obtained block copolymer weight. You may calculate from the number average molecular weight of a coalescence.

  The hydrogenated product (2) of the primary modified block copolymer can be obtained by subjecting the primary modified block copolymer (2) obtained above to a hydrogenation treatment. Further, the functional group is added to a polymer obtained by reacting a hydrogenated product of a block copolymer with an organic alkali metal compound such as an organolithium compound (metalation reaction) and adding the organic alkali metal to the hydrogenated product of the block copolymer. It can also be obtained by addition reaction of the containing modifier.

The weight average molecular weight of the primary modified block copolymer or hydrogenated product (2) described above is excellent in mechanical strength of the primary modified block copolymer or hydrogenated product thereof or a composition containing the same. From the viewpoint of, it is preferably 30,000 or more. On the other hand, it is preferably 1 million or less from the viewpoint of ensuring good processability and compatibility with a thermoplastic resin. The weight average molecular weight is more preferably in the range of 40,000 to 800,000, and still more preferably in the range of 50,000 to 600,000.
The weight average molecular weight was measured by gel permeation chromatography (GPC), and the molecular weight of the chromatogram peak was determined from a calibration curve obtained from measurement of commercially available standard polystyrene (the peak molecular weight of standard polystyrene was used. The value obtained using

The above-mentioned primary modified block copolymer or hydrogenated product (2) thereof is obtained as a solution in the synthesis step, but if necessary, the catalyst residue is removed and separated from the solution.
Examples of the separation method from the solution include, for example, a polarity that becomes a poor solvent for the primary modified block copolymer such as acetone or alcohol or the hydrogenated product thereof after the polymerization or the hydrogenated solution. A method in which a primary modified block copolymer or a hydrogenated product thereof is precipitated and recovered by adding a solvent, and a solution of the primary modified block copolymer or the hydrogenated product thereof is poured into hot water with stirring, and steam is added. Examples include a method of removing the solvent by stripping and recovering, or a method of directly heating the solution to distill off the solvent.

  The primary modified block copolymer or the hydrogenated product (2) thereof may be provided with stabilizers such as various phenol stabilizers, phosphorus stabilizers, sulfur stabilizers, amine stabilizers, etc., as necessary. It may be added.

(Reaction step with polymer (3) having at least one bonding group or functional group selected from the group consisting of ester bond, urethane bond, epoxy group, amino group, amide group, hydroxyl group, silanol group, and alkoxysilane group)
The modified block copolymer (X) according to the first embodiment is obtained by adding an ester bond, a urethane bond, an epoxy group, an amino group, an amide group, a hydroxyl group, and a silanol to the block copolymer or its hydrogenated product (1). It is obtained by reacting a polymer (3) having at least one bonding group or functional group selected from the group consisting of a group and an alkoxysilane group.
The modified block copolymer (Z) according to the second embodiment is an ester having reactivity with the functional group bonded to the primary modified block copolymer or its hydrogenated product (2). It is obtained by reacting a polymer (3) having at least one bonding group or functional group selected from the group consisting of a bond, a urethane bond, an epoxy group, an amino group, an amide group, a hydroxyl group, a silanol group, and an alkoxysilane group. .

The ester bond in the polymer having an ester bond may be in the main chain or may be pendant with respect to the main chain.
Examples of the polymer having an ester bond in the main chain include dibasic acids such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid, P, P′-dicarboxydiphenyl, 2,6-naphthalene dicarboxylic acid, and the like. And the degeneracy of ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanediol, P-xylene glycol, bisphenol A and the like (or diol) Coalescence is mentioned. Specifically, for example, polyethylene terephthalate (PET) which is a copolymer of terephthalic acid and ethylene glycol, and amorphous polyethylene terephthalate (PET-G) which is a copolymer of terephthalic acid, ethylene glycol and cyclohexanedimethanol. Other examples include, but are not limited to, polybutylene terephthalate and glyphtal resin. In particular, PET-G is preferable in terms of transparency.

  In addition, a linear polymer in which structural units of the polymer are bonded by repeating carbonate ester bonds, for example, by reaction of a phosgene with a dihydroxy compound such as 4,4′-dihydroxydiphenylalkane or 4,4′-dihydroxydiphenyl sulfide. Polymer obtained or polymer obtained by transesterification reaction of the dihydroxy compound and diphenyl carbonate, specifically, polycarbonate system such as poly-4,4′-dioxydiphenyl-2,2′-propane carbonate A polymer is mentioned.

  Examples of the ester bond group in the polymer in which the ester bond is bonded in a pendant form to the main chain include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, glycidyl ( Examples thereof include those having a meth) acrylate as a polymer component, and vinyl carboxylates such as vinyl acetate vinyl propionate and vinyl butyrate as a polymer component.

  Examples of the polymer having an epoxy group include those in which glycidyl methacrylate or glycidyl acrylate is used as a monomer substance and bonded to the main chain of the polymer in a pendant manner, and those in which an epoxy group is bonded in the main chain.

  These may be copolymerized not only with a homopolymer but also with other copolymerizable monomers. Examples of the other copolymerizable monomer include styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene, vinylanthracene, 1 , 1-diphenylethylene and other aromatic vinyl hydrocarbons, acrylonitrile, ethylene, propylene, butene and other α-olefins, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3- Conjugated dienes such as dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, acid anhydrides such as maleic acid, itaconic acid, citraconic acid, aconitic acid, acrylic acid, methacrylic acid, etc. Examples include monomers having a carboxyl group.

  Polymers having a urethane bond include ring-opening polymer polyester resins such as pivalolactone, β-propiolactone, and ε-caprolactone, poly (1,4-butylene adipate), and poly (1,6-hexaneadipate). Glycol components selected from polyester diols such as polycaprolactone, polyether diols such as polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and the like Obtained by polyaddition reaction with diisocyanate components such as aromatic, alicyclic or aliphatic diisocyanates such as tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, etc. Thermoplastic polyurethane polymers.

  Silanol group or alkoxysilane group can be introduced into the polymer by, for example, an exchange reaction between an alcoholic hydroxyl group and an alkoxysilane alkoxy group, such as vinyl acetate, polyvinyl alcohol, polyurethane, and bisphenol A. A polymer in which an alkoxysilane is bonded to an epoxy resin, a phenol novolac epoxy resin, a phenol resin, a polyamic acid, a polyamideimide, or the like can be used.

  The polymer having an amino group is, in addition to a polymer having acrylic amine as a monomer, for example, in a condensation reaction of diamine and dicarboxylic acid, a polyamide in which one end or both ends have a diamine structure by excessively adjusting the diamine, or It can also be obtained by reacting a diamine with a polymer having a carboxylic acid structure in the molecule such as a styrene-methacrylic acid copolymer.

Examples of the polymer having an amide group include linear polymers in which structural units of the polymer are bonded by repeating amide group bonding, for example, ring-opening polymers such as ε-aminocaprolactam and ω-aminolaurolactam, and copolymer Polymer, condensation polymer of ε-aminoundecanoic acid, condensation polymer of hexamethylenediamine and dibasic acid such as adipic acid, sebacic acid, specifically, nylon-46, nylon-6, nylon-66, nylon And polyamide resins such as -610, nylon-11, nylon-12, and nylon-6-nylon-12 copolymers.
Examples of the polymer having a hydroxyl group include a polymer using vinyl alcohol as a monomer, for example, a polymer in which the above-mentioned silanol is bonded, polyester, and the like in addition to polyvinyl alcohol.

  The polymer (3) can be produced by a known method. For example, it can be produced by an anionic polymerization method, a cationic polymerization method, a radical polymerization method, a condensation polymerization method, a polyaddition reaction, or the like.

Examples of the polymer (3) include the following a) to m).
a) Maleic anhydride-ethylene-ethyl acrylate-acrylonitrile-styrene copolymer b) Maleic anhydride-methyl methacrylate-styrene copolymer c) Maleic anhydride-ethylene-vinyl acetate copolymer d) Vinyl acetate-styrene copolymer Polymer e) Alkoxysilane bond-ethylene-vinyl acetate copolymer f) Polyurethane g) Glycidyl methacrylate-styrene copolymer h) Ethylene-glycidyl methacrylate-styrene copolymer i) Ethylene-glycidyl methacrylate-acrylonitrile-styrene copolymer Combined j) Glycidyl methacrylate-acrylonitrile-styrene-polycarbonate copolymer.
k) Ethylene-glycidyl methacrylate-butyl acrylate-methyl methacrylate copolymer l) Epoxy group-containing-styrene-butadiene copolymer m) Polyester is a preferred example. A commercial item may be used for the polymer.

  When the block copolymer or its hydrogenated product (1) or primary modified block copolymer or its hydrogenated product (2) is reacted with the polymer (3), the block copolymer or its The ratio of the hydrogenated product (1) or the primary modified block copolymer or the hydrogenated product (2) and the polymer (3) may be 99.9 / 0.1 to 25/70 by mass ratio. Preferably, it is 99/1 to 50/50, more preferably 99/1 to 80/20.

The reaction method of the block copolymer or its hydrogenated product (1) or the primary modified block copolymer or its hydrogenated product (2) and the polymer (3) is not particularly limited, Known methods can be used.
For example, a melt kneading method in which reaction is performed using a general mixer such as a Banbury mixer, a single screw extruder, a twin screw extruder, a kneader, or a multi-screw extruder, and each component is dissolved or dispersed in a solvent or the like Then, after the reaction, a method of removing the solvent by heating can be applied.

  In the case of the melt kneading method, the kneading temperature is preferably 50 to 250 ° C, more preferably 100 to 230 ° C. The kneading time is preferably within 3 hours, more preferably several seconds to 1 hour.

  When performing the said reaction process by melt | dissolving or disperse | distributing each component in a solvent etc., the solvent to apply should just melt | dissolve or disperse | distribute each component and is not restrict | limited in particular. For example, in addition to hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons, halogen-containing solvents, ester solvents, ether solvents, and the like can be used.

  -10-150 degreeC is preferable and, as for the temperature conditions in the said reaction process, 30-120 degreeC is more preferable. The time required for the reaction varies depending on the conditions, but is generally within 3 hours, preferably several seconds to 1 hour.

  The weight average molecular weight of the modified block copolymer produced in the first embodiment and the second embodiment is 30,000 or more from the viewpoint of the mechanical strength of the modified block copolymer and its composition. Is preferably 1,000,000 or less, more preferably 40,000 to 800,000, and still more preferably 5 to 600,000 from the viewpoint of compatibility with thermoplasticity and thermoplastic resin.

  The weight average molecular weight of the modified block copolymer was measured by gel permeation chromatography (GPC), and the molecular weight of the chromatogram peak was determined from a calibration curve obtained from the measurement of commercially available standard polystyrene (peak molecular weight of standard polystyrene). The value obtained by using).

The method for producing the modified block copolymer (X) of the present embodiment includes at least one polymer block A mainly composed of vinyl aromatic hydrocarbon and at least one polymer block mainly composed of conjugated diene. B, and a block copolymer containing hydrogenated product (1)
Including a step of bonding a polymer (3) having at least one bonding group or functional group selected from the group consisting of an ester bond, a urethane bond, an epoxy group, an amino group, an amide group, a hydroxyl group, a silanol group, and an alkoxysilane group. Is the method.

Further, the method for producing the modified block copolymer (Z) of the present embodiment comprises at least one polymer block A mainly composed of vinyl aromatic hydrocarbons and at least one heavy polymer mainly composed of conjugated dienes. A primary modified block copolymer obtained by subjecting a block copolymer containing a combined block B to an addition reaction of a functional group-containing modifier, or a hydrogenated product (2) thereof,
It consists of an ester bond, a urethane bond, an epoxy group, an amino group, an amide group, a hydroxyl group, a silanol group, and an alkoxysilane group that are reactive with the functional group of the primary modified block copolymer or its hydrogenated product (2). The method includes a step of bonding a polymer (3) having at least one bonding group or functional group selected from the group.

  Each material, conditions, etc. in the production method of the modified block copolymer (X) and the modified block copolymer (Z) are as described above.

(Third embodiment)
By blending at least one component (Y) selected from thermoplastic resins into the modified block copolymer (X) or (Z) obtained by the first embodiment and the second embodiment described above. A resin composition is obtained.
The amount of the component (Y) used is a ratio of the modified block copolymer component (X) or (Z) / component (Y), preferably 1/99 to 99/1, more preferably 3/97 to 97/3. 5/95 to 95/5 are more preferable.

The thermoplastic resin used as the component (Y) is not particularly limited, but the following thermoplastic resins can be used.
For example, a block copolymer resin of a conjugated diene compound and a vinyl aromatic compound having a structure different from that of the modified block copolymer or the hydrogenated product thereof described in the first embodiment and the second embodiment, Vinyl aromatic compound polymer resins such as polystyrene, vinyl aromatic compounds and other vinyl monomers (for example, acrylic esters such as ethylene, propylene, butylene, vinyl chloride, vinylidene chloride, vinyl acetate, acrylic acid and acrylmethyl, methacryl And a copolymer resin with methacrylic acid esters such as acid and methyl methacrylate, acrylonitrile, methacrylonitrile, and the like).

  Also, rubber-modified styrene resin (HIPS), acrylonitrile-butadiene-styrene copolymer resin (ABS), methacrylate ester-butadiene-styrene copolymer resin (MBS), polyvinyl chloride, polyvinylidene chloride, vinyl chloride and / or Examples thereof include polyvinyl chloride resin which is a copolymer of vinyl chloride and / or vinylidene chloride containing 50% by mass or more of vinylidene chloride and other monomers copolymerizable therewith.

  Further, a polyvinyl acetate resin which is a copolymer of vinyl acetate having a vinyl acetate content of 50% by mass or more and another monomer copolymerizable therewith, and its hydrolyzate, acrylic acid and its ester, Polymers of amides, polymers of methacrylic acid and esters thereof and amides, polyacrylate resins which are copolymers with other copolymerizable monomers containing 50% by mass or more of these acrylic acid monomers, acrylonitrile and Examples thereof include methacrylonitrile polymers and nitrile resins which are copolymers with other copolymerizable monomers containing 50% by mass or more of these acrylonitrile monomers.

  Further, linear polymers in which the structural units of the polymer are bonded by repeating amide group bonds, for example, ring-opening polymers and copolymers such as ε-aminocaprolactam and ω-aminolaurolactam, ε-aminoundecanoic acid A polycondensation polymer of hexamethylenediamine and a dibasic acid such as adipic acid or sebacic acid, specifically, nylon-46, nylon-6, nylon-66, nylon-610, nylon-11, Examples thereof include polyamide resins such as nylon-12 and nylon-6-nylon-12 copolymers.

  Also, linear polymers in which the structural units of the polymer are bonded by repeating ester bonds, such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid, P, P′-dicarboxydiphenyl, 2,6-naphthalene dicarboxylic acid Dibasic acids such as acids or derivatives thereof, and glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanediol, P-xylene glycol, bisphenol A, etc. (Or a diol).

  In addition, polyester-based resins of ring-opening polymers such as pivalolactone, β-propiolactone, and ε-caprolactone, polyester diols such as poly (1,4-butylene adipate), poly (1,6-hexaneadipate), and polycaprolactone Glycol components such as polyethylene glycol, polypropylene glycol, polyether diol such as polyoxytetramethylene glycol, glycols such as ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and aromatic and alicyclic Alternatively, thermoplastic polyurethane polymerization obtained by polyaddition reaction with diisocyanate components such as aliphatic diisocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate And the like.

  Also, a linear polymer in which the structural units of the polymer are bonded by repeating carbonate ester bonds, for example, by reaction of a phosgene with a dihydroxy compound such as 4,4′-dihydroxydiphenylalkane or 4,4′-dihydroxydiphenyl sulfide. Or a polymer obtained by a transesterification reaction between the dihydroxy compound and diphenyl carbonate, for example, a polycarbonate polymer such as poly-4,4′-dioxydiphenyl-2,2′-propane carbonate. Can be mentioned.

Also, thermoplastic polysulfones such as polyethersulfone and polyallylsulfone, polysulfone resins such as poly (ether sulfone), poly (4,4′-bisphenol ether sulfone), poly (thioether sulfone), and the like of formaldehyde or trioxane. Examples thereof include polyoxymethylene resins such as copolymers, copolymers with formaldehyde or trioxane, other aldehydes, cyclic ethers, epoxides, isocyanates, vinyl compounds and the like.

  Also, polyphenylene ether resins such as poly (2,6-dimethyl-1,4-phenylene) ether, polyphenylene sulfide resins such as polyphenylene sulfide and poly 4,4′-diphenylene sulfide, bisphenol A and phthalic acid components Polyarylate resins, polyetherketone polymers or copolymers that are polycondensation polymers, such as polyketone resins such as polyetheretherketone.

  Further, a polymer having a structure in which part or all of the hydrogen of the chain hydrocarbon polymer compound is substituted with fluorine, specifically, polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetra Fluorine resins such as fluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, tetrafluoroethylene-ethylene copolymer, chlorotrifluoroethylene-ethylene copolymer, polyvinylidene fluoride, and polyvinyl fluoride It is done.

  In addition, polyoxybenzoyl heavy polymers such as polymers or copolymers produced by solution polycondensation or melt polycondensation using paraoxybenzoic acid, terephthalic acid, isophthalic acid, 4,4′-dihydroxydiphenyl or derivatives thereof. Polymers having an imide bond in the main chain, such as polyimide, polyaminobismaleimide (polybismaleimide), bismaleimide / triazine resin, polyamideimide, polyetherimide and other polyimide resins, 1,2-polybutadiene, trans Examples thereof include polybutadiene resins such as polybutadiene.

1000 or more are preferable, as for the number average molecular weight of the thermoplastic resin used as a component (Y), 5000-5 million are more preferable, and 10,000-1 million are still more preferable.
In addition, the said thermoplastic resin may be used independently and may use 2 or more types together.

You may mix | blend various additives with the modified block copolymer (X), (Z) mentioned above, or the composition using this as needed.
As additives, any of those commonly used in thermoplastic resin compositions can be applied. For example, calcium carbonate, magnesium carbonate, magnesium hydroxide, calcium sulfate, barium sulfate, silica, clay, talc, mica, Inorganic fillers such as llastonite, montmorillonite, zeolite, alumina, titanium oxide, magnesium oxide, zinc oxide, slug wool, glass fiber; pigments such as carbon black and iron oxide; stearic acid, behenic acid, zinc stearate, calcium stearate And lubricants such as magnesium stearate and ethylene bisstearamide; mold release agents; paraffinic process oil, naphthenic process oil, aromatic process oil, and paraffin.

Also, softeners / plasticizers such as organic polysiloxane and mineral oil, hindered phenol antioxidants, antioxidants such as phosphorus heat stabilizers, hindered amine light stabilizers, benzotriazole ultraviolet absorbers, flame retardants Further, reinforcing agents such as antistatic agents, organic fibers, glass fibers, carbon fibers, and metal whiskers, coloring agents, and the like are also used.
As other additives, those disclosed in “rubber / plastic compounding chemicals” (edited by Rubber Digest Co., Ltd.) such as a mixture thereof can also be used.

It does not restrict | limit especially about the method of manufacturing the modified block copolymer composition mentioned above, A well-known method can be utilized.
For example, a melt kneading method using a general mixer such as an open roll, a Banbury mixer, a single screw extruder, a twin screw extruder, a kneader, a multi-screw extruder, etc., after dissolving or dispersing and mixing each component, A method of removing the solvent by heating can be applied. In particular, a melt kneading method using an extruder is preferable from the viewpoints of productivity and good kneading properties.

  The melt kneading temperature takes into consideration the melting point, melt viscosity, block copolymer or hydrogenated product (1) thereof, and thermal degradation of the primary modified block copolymer or hydrogenated product (2) thereof. And 100-350 degreeC is preferable, 150-350 degreeC is more preferable, and 180-330 degreeC is still more preferable.

  The melt kneading time (or the average residence time of the melt kneading step) is the degree of kneading (dispersibility), productivity, block copolymer or hydrogenated product (1), and primary modified block copolymer or water thereof. In consideration of deterioration of the additive (2), the thermoplastic resin, etc., 0.2 to 60 minutes is preferable, 0.5 to 30 minutes is more preferable, and 1 to 20 minutes is still more preferable.

  First, primary modified block copolymers (P-1) to (P-8) and a block copolymer (P-9) as raw materials were produced.

[Primary modified block copolymer (P-1)]
Using an autoclave with a stirrer, 0.080 parts by mass of n-butyllithium was added to a cyclohexane solution containing 25 parts by mass of styrene under a nitrogen gas atmosphere, and polymerization was performed at 80 ° C. for 20 minutes.
Next, (ii) a cyclohexane solution containing 15 parts by mass of styrene and 24 parts by mass of 1,3-butadiene was continuously added for 60 minutes and polymerized at 80 ° C.
Next, (iii) A cyclohexane solution containing 36 parts by mass of styrene was continuously added for 25 minutes to polymerize at 80 ° C., and then held at 80 ° C. for 10 minutes.
Thereafter, 1,3-dimethyl-2-imidazolidinone (hereinafter referred to as modifier M1) as a modifier was equimolarly reacted with the n-butyllithium used for the polymerization in the living polymer.
After completion of the reaction, methanol was added in an equimolar amount to n-butyllithium in the polymerization vessel, and 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4, 0.5 part by mass of 6-di-t-pentylphenyl acrylate was added to 100 parts by mass of the block copolymer.
Thereafter, the solvent was removed to obtain a primary modified block copolymer (P-1).
The primary modified block copolymer (P-1) is polymer block A in which styrene / 1,3-butadiene = 100/0 mass ratio, styrene / 1,3-butadiene = 38.5 / 61.5 mass. It is an ABA type block polymer composed of a polymer block B having a ratio of styrene / 1,3-butadiene = 100/0 mass ratio.

[Primary modified block copolymers (P-2) to (P-6)]
Styrene added in (i), (ii), (iii) during the production process of the primary modified block copolymer (P-1) according to the same method as the primary modified block copolymer (P-1) The amount of 1,3-butadiene and the amount of n-butyllithium were appropriately controlled to polymerize the living polymer to produce primary modified block copolymers (P-2) to (P-6). .

[Primary modified block copolymer (P-7)]
Styrene added in (i), (ii), (iii) during the production process of the primary modified block copolymer (P-1) according to the same method as the primary modified block copolymer (P-1) The living polymer is polymerized by appropriately controlling the addition amount of 1,3-butadiene and the addition amount of n-butyllithium, and tetraglycidyl-1,3-bisaminomethylcyclohexane (hereinafter referred to as modifier M2) as a modifier. )It was used. Other conditions were the same as the said primary modified block copolymer (P-1), and produced the primary modified block copolymer (P-7).

[Primary modified block copolymer (P-8)]
Styrene added in (i), (ii), (iii) during the production process of the primary modified block copolymer (P-1) according to the same method as the primary modified block copolymer (P-1) The living polymer is polymerized by appropriately controlling the addition amount of 1,3-butadiene and the addition amount of n-butyllithium, and γ-glycidoxypropyltrimethoxysilane (hereinafter referred to as a modifier M3) is used as a modifier. used. Other conditions were the same as the said primary modified block copolymer (P-1), and produced the primary modified block copolymer (P-8).

[Block copolymer (P-9)]
A block copolymer (P-9) was produced in the same manner as the primary modified block copolymer (P-1) except that no modifier was added.

Composition evaluation of the primary modified block copolymers (P-1) to (P-8) and the block copolymer (P-9) produced as described above was performed by the following method.
(1) Styrene content It computed from the absorption intensity of 262 nm using the ultraviolet spectrophotometer (Hitachi UV200).

(2) Styrene block ratio Method of oxidizing and decomposing block copolymer with di-tertiary butyl hydroperoxide using osmium tetroxide as a catalyst [I. M.M. KOLTHOFF, et al. , J .; Polym. Sci. 1,429 (1946)] was quantified and determined from the following formula.

(3) Ratio of modified block copolymer (modification rate)
A sample solution prepared by dissolving 10 mg of a modified polymer and 10 mg of a low molecular weight internal standard polystyrene having a weight average molecular weight of 8000 in 20 mL of tetrahydrofuran furan is obtained by GPC (equipment: LC10 manufactured by Shimadzu Corporation, column: Shimpac GPC805 + GPC804 + GPC804 + GPC803 manufactured by Tsu Seisakusho). It was measured. Tetrahydrofuran was used as the solvent, and the measurement was performed at a temperature of 35 ° C. From the obtained chromatogram, the ratio of the modified polymer to the standard polystyrene was determined. In addition, for the above sample solution, GPC was used in the same manner except that a column of Zorbax (silica gel filler), a column manufactured by DuPont, USA was used.
From the chromatogram obtained by the measurement, the ratio of the modified polymer to the standard polystyrene was determined. Since the modified polymer is adsorbed on the GPC column using the silica gel as a filler, the ratio of the modified polymer is the ratio of the polymer adsorbed on the silica column. By comparing these two ratios, the ratio of the modified block copolymer was determined and used as the modification ratio.

(4) Melt flow rate Measured according to ASTM D1238 under the conditions of 200 ° C. and a load of 5 kg.

  Styrene content, styrene block rate, melt flow rate of the primary modified block copolymers (P-1) to (P-8) and the block copolymer (P-9) produced as described above, The types of functional group-containing modifiers and the modification rate are shown in Table 1 below.

[Examples 1 to 17]
Next, a modified block copolymer using the primary modified block copolymers (P-1) to (P-8) prepared as described above and the polymer (3) shown in Table 2 below. (MP-1) to (MP-17) were prepared.

Primary modified block copolymer / polymer (3) Blended at a ratio of 90/10 parts by mass, melt-kneaded using a 30 mmφ twin screw extruder at 220 ° C. and screw rotation speed of 100 rpm, reacted, 2 Next modified block copolymer was prepared.
For the production of the secondary modified block copolymer, one of the following 12 types of polymers (3) was selected.
・ Elastolan ET860D (registered trademark of BASF, polyurethane resin)
Modiper A4400 (registered trademark of NOF Corporation, grafted product of ethylene-glycidyl methacrylate copolymer (EGMA) and acrylonitrile-styrene copolymer (AS). EGMA / AS ratio = 70/30, glycidyl methacrylate in EGMA) Content = 15% by mass)
Modiper SV30B (registered trademark manufactured by NOF Corporation, block copolymer of polyvinyl acetate (PVAc) and polystyrene (PS), PVAc / PS ratio = 30/70)
Delpet 980N (registered trademark manufactured by Asahi Kasei Chemicals Corporation, maleic anhydride (MAH) -methyl methacrylate (MMA) -styrene (ST) copolymer)
・ Epofriend AT501 (registered trademark, epoxy-modified styrene-butadiene copolymer manufactured by Daicel Chemical Industries, Ltd.)
Modiper CL430-G (registered trademark of NOF Corporation, polycarbonate (PC), glycidyl methacrylate (GMA) and AS copolymer)
・ Malproof G1005S (registered trademark, GMA-ST copolymer manufactured by NOF Corporation)
Modiper A4300 (registered trademark manufactured by NOF Corporation, graft product of EGMA and butyl acrylate (BA) -MMA copolymer (P (BA / MMA)), EGMA / P (BA / MMA) ratio = 70/30, (GMA content in EGMA = 15 mass%)
・ Primalloy A1706C (registered trademark of Mitsubishi Chemical Corporation, polyethylene terephthalate containing rubber component)
・ Linkron XVF600N (registered trademark of Mitsubishi Chemical Corporation, alkoxysilane bond-ethylene-vinyl acetate copolymer (EVA))

FIG. 1 shows gel permeation chromatography (GPC) of the modified block copolymer (MP-1) in Example 1.
The GPC curves of the primary modified block copolymer (P-1) alone and polyurethane (TPU) alone are also shown.
The modified block copolymer (MP-1) is a copolymer obtained by reacting the primary modified block copolymer (P-1) with polyurethane (TPU). From the graph of FIG. Disappeared and the molecular weight was high, it was confirmed that (TPU) was bound to (P-1).
The modified block copolymers (MP-2) to (MP-17) of Examples 2 to 17 were also measured by gel permeation chromatography (GPC). It was confirmed that the coalescence and the polymer (3) were bonded.

[Examples 18 to 36], [Comparative Examples 1 to 14]
Next, a resin sheet was produced as follows. The materials are shown below.
Modified block copolymers (MP-1) to (MP-8)
Thermoplastic resin (R-1): Polystyrene 685 (manufactured by PS Japan Ltd.)
Thermoplastic resin (R-2): styrene-butyl acrylate copolymer (polystyrene SC004 manufactured by PS Japan Co., Ltd.)
Primary modified block copolymer (P-1)
Block copolymer (P-9)
(P-9) / Polymer (3) described in Table: Blended at a ratio of 90/10 parts, and melt-kneaded at 220 ° C. and a screw rotation speed of 100 rpm using a 30 mmφ twin screw extruder. Measurement by GPC was performed, and it was confirmed that each polymer (3) was not bonded to the block copolymer (P-9).

Each raw material pellet was introduced into a hopper of a union plastics T die mounting extruder (USV type / barrel diameter 40 mmφ, L / D = 28, width 400 mm T die mounting) according to the formulation shown in Tables 3 to 5 below. .
The resin temperature in the cylinder of the extruder and the temperature of the T die were adjusted, and a sheet having a thickness of 0.3 mm was extruded and produced.

The following evaluation was performed on the resin sheets of [Examples 18 to 36] and [Comparative Examples 1 to 14] produced as described above.
(1) Tensile modulus Based on ASTM D638, the tensile modulus was measured at a test speed of 5 mm / min using a TG-5KN type tester manufactured by Minebea Co., Ltd.

(2) Wetting index Measured with a wetting index reagent in accordance with JIS K6768.

(3) Adhesiveness with water-based ink Surface of the resin sheet produced using water-based gravure ink (Ramipure: Sakata Inx Co., Ltd.) using a gravure mini proofreader (manufactured by Nissho Gravure Co., Ltd.) Printed. The coating film adhesion was evaluated by a cross-cut method based on JIS 5400 and 5600, and the adhesion to the aqueous gravure ink was evaluated.
After storing the printed resin sheet for 1 week under conditions of 50 ° C. and 80% humidity, the scratches are put on the resin sheet with a blade so that the surface printed with ink becomes 100 squares at 1 mm intervals, and Nichiban adhesive tape (CT-18 or LP-18, adhesive force 4.01 N / cm) was brought into intimate contact, and the printed surface was peeled off instantaneously in an angle direction of 30 degrees. Judgment was made based on the number of printing inks peeled off, and the complete adhesion was expressed as 0/100, and the total extinction was expressed as 100/100.

  Tables 3 to 5 below show the measurement results of tensile modulus, wetness index, and adhesiveness with water-based ink.

Examples 18 to 33, which are the modified block copolymers (MP-1) to (MP-17) in the present embodiment, have excellent mechanical strength, a high wetting index, and good adhesion to aqueous ink. I found out.
In Examples 34 to 36 using the modified block copolymers (MP-2) and (MP-6) and a general-purpose thermoplastic resin, a practically good wetting index and adhesiveness with water-based ink can be obtained. It was.
Since Comparative Examples 1-14 did not use the modified block copolymers (MP-1) to (MP-17), it was found that the wetting index was low and the adhesiveness with the water-based ink was extremely inferior.

  The modified block copolymer of the present invention is excellent in adhesion strength with water-based ink, and has industrial applicability as a heat-shrinkable film to be covered on a packaging film, a beverage container or the like, and various sheet materials.

Claims (8)

A block copolymer containing at least one polymer block A mainly composed of vinyl aromatic hydrocarbons and at least one polymer block B mainly composed of conjugated diene, or a hydrogenated product thereof (1) ,
A modified block copolymer to which a polymer (3) having at least one bonding group or functional group selected from the group consisting of an ester bond, a urethane bond, an epoxy group, an amino group, an amide group, a hydroxyl group, a silanol group, and an alkoxysilane group is bonded. Polymer (X). A functional group-containing modifier is added to a block copolymer containing at least one polymer block A mainly composed of vinyl aromatic hydrocarbons and at least one polymer block B mainly composed of conjugated dienes. To the primary modified block copolymer or hydrogenated product (2) obtained by reaction,
It consists of an ester bond, a urethane bond, an epoxy group, an amino group, an amide group, a hydroxyl group, a silanol group, and an alkoxysilane group that are reactive with the functional group of the primary modified block copolymer or its hydrogenated product (2). A modified block copolymer (Z) to which a polymer (3) having at least one bonding group or functional group selected from the group is bonded.   The functional group-containing modifier is added to the primary modified block copolymer or its hydrogenated product (2) by an addition reaction with the block copolymer, to a hydroxyl group, an epoxy group, an amino group, a silanol group, or an alkoxysilane group. The modified block copolymer (Z) according to claim 2, which has a function of generating an atomic group having at least one functional group selected from the group consisting of: The modified block copolymer (X) according to claim 1, wherein the polymer (3) is at least one polymer selected from the group consisting of the following a) to m).
a) Maleic anhydride-ethylene-ethyl acrylate-acrylonitrile-styrene copolymer b) Maleic anhydride-methyl methacrylate-styrene copolymer c) Maleic anhydride-ethylene-vinyl acetate copolymer d) Vinyl acetate-styrene copolymer Polymer e) Alkoxysilane bond-ethylene-vinyl acetate copolymer f) Polyurethane g) Glycidyl methacrylate-styrene copolymer h) Ethylene-glycidyl methacrylate-styrene copolymer i) Ethylene-glycidyl methacrylate-acrylonitrile-styrene copolymer Compound j) Glycidyl methacrylate-acrylonitrile-styrene-polycarbonate copolymer k) Ethylene-glycidyl methacrylate-butyl acrylate-methyl methacrylate copolymer l) Epoxy group-containing- Styrene - butadiene copolymer m) polyester. The modified block copolymer (Z) according to claim 2 or 3, wherein the polymer (3) is at least one polymer selected from the group consisting of the following a) to m).
a) Maleic anhydride-ethylene-ethyl acrylate-acrylonitrile-styrene copolymer b) Maleic anhydride-methyl methacrylate-styrene copolymer c) Maleic anhydride-ethylene-vinyl acetate copolymer d) Vinyl acetate-styrene copolymer Polymer e) Alkoxysilane bond-ethylene-vinyl acetate copolymer f) Polyurethane g) Glycidyl methacrylate-styrene copolymer h) Ethylene-glycidyl methacrylate-styrene copolymer i) Ethylene-glycidyl methacrylate-acrylonitrile-styrene copolymer Compound j) Glycidyl methacrylate-acrylonitrile-styrene-polycarbonate copolymer k) Ethylene-glycidyl methacrylate-butyl acrylate-methyl methacrylate copolymer l) Epoxy group-containing- Styrene - butadiene copolymer m) polyester   The modified block copolymer (X) according to claim 1 or 4, or the modified block copolymer (Z) according to any one of claims 2, 3 and 5, 1 to 99% by mass, a thermoplastic resin. A modified block copolymer composition containing 99 to 1% by mass. A block copolymer containing at least one polymer block A mainly composed of vinyl aromatic hydrocarbons and at least one polymer block B mainly composed of conjugated diene, or a hydrogenated product thereof (1) ,
Including a step of bonding a polymer (3) having at least one bonding group or functional group selected from the group consisting of an ester bond, a urethane bond, an epoxy group, an amino group, an amide group, a hydroxyl group, a silanol group, and an alkoxysilane group. The manufacturing method of modified block copolymer (X). A functional group-containing modifier is added to a block copolymer containing at least one polymer block A mainly composed of vinyl aromatic hydrocarbons and at least one polymer block B mainly composed of conjugated dienes. To the primary modified block copolymer or hydrogenated product (2) obtained by reaction,
It consists of an ester bond, a urethane bond, an epoxy group, an amino group, an amide group, a hydroxyl group, a silanol group, and an alkoxysilane group that are reactive with the functional group of the primary modified block copolymer or its hydrogenated product (2). A method for producing a modified block copolymer (Z), comprising a step of bonding a polymer (3) having at least one bonding group or functional group selected from the group.