JP5235094B2 - Modified block copolymer and composition thereof - Google Patents

Description

  The present invention relates to a modified block copolymer having excellent adhesion strength with aqueous ink and excellent in mechanical strength, impact resistance, and transparency.

  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.

Styrene-based resins are used as packaging materials for sheets, films, etc., 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. There has been disclosed a modified polymer modified with a functional oligomer having

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-based resin sheet or film. However, even with corona discharge treatment and primer treatment, when water-based ink is used, it is still possible to print characters and images that are sufficiently good in practice from the viewpoint of glossiness, sharpness, and gradation. Is not yet reached.

  Therefore, in the present invention, in view of the above-described problems of the prior art, highly versatile styrene having good adhesion to water-based ink, good mechanical strength such as tensile elastic modulus, and excellent transparency. It aims at providing a system resin.

In the invention of claim 1, a block copolymer comprising at least one polymer block A mainly composed of vinyl aromatic hydrocarbon and at least one polymer block B mainly composed of conjugated diene, Functionality of the primary modified block copolymer or its hydrogenated product (2) is reacted with the primary modified block copolymer or its hydrogenated product (2) obtained by addition reaction of a functional group-containing modifier. A modified block copolymer (Z) in which a monomer (3) having a monomer having an acid anhydride and / or a carboxyl group and a vinyl aromatic hydrocarbon is bonded ,
The primary modified block copolymer (2) comprises at least one polymer block A mainly composed of the vinyl aromatic hydrocarbon and at least one polymer block B mainly composed of a conjugated diene. The vinyl aromatic hydrocarbon content in the block copolymer is 70 to 95% by mass,
From the hydroxyl group, epoxy group, amino group, silanol group, alkoxysilane group, 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. Provided is a modified block copolymer (Z) having a function of generating an atomic group having at least one selected functional group .

In the invention of claim 2, wherein the copolymer (3) is a styrene - modified block according to claim 1 maleic anhydride copolymer, or a portion thereof is a copolymer which is the carboxyl group A copolymer (Z) is provided.

In the invention of claim 3, modified block copolymer according to 請 Motomeko 1 or 2 (Z) 1 to 99 wt%, the modified block copolymer composition comprising 99 to 1 wt.% Thermoplastic resin provide.

According to the present invention, the adhesiveness with the water-based ink is good, and sufficient rigidity is provided from a practical aspect,
We were able to provide a highly versatile styrene resin with excellent transparency.

  Hereinafter, the best mode for carrying out the present invention (hereinafter 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 in the present embodiment comprises a block copolymer comprising 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 polymer or its hydrogenated product (1) has a structure in which a monomer having an acid anhydride and / or a carboxyl group and a vinyl aromatic hydrocarbon copolymer (3) are bonded to each other. Is.

  First, a block copolymer comprising 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 ).

The polymer block A mainly composed of a vinyl aromatic hydrocarbon is a copolymer block of a vinyl aromatic hydrocarbon and a conjugated diene containing a vinyl aromatic hydrocarbon content of 50% by mass or more, or a vinyl aromatic hydrocarbon. A homopolymer block shall be indicated.
The polymer block B mainly composed of a conjugated diene means a conjugated diene and a vinyl aromatic hydrocarbon copolymer block or a conjugated diene homopolymer block containing the conjugated diene in an amount of more than 50% by mass. .

  When a random copolymer portion 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 hydrocarbon may be distributed uniformly in the polymer block or may be distributed in a tapered shape. Further, the copolymer portion may coexist with a plurality of portions where vinyl aromatic hydrocarbons are uniformly distributed and / or portions where they are distributed in a tapered shape.

  When the modified block copolymer of the present embodiment has a plurality of polymer blocks A (or B), they may be different from each other 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. 43-17799, 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. Although it 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 disclosed in the present embodiment, The production conditions for each constituent polymer are 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- (B-A) n (a)
A- (BA) n-B (b)
B- (AB) n + 1 (c)
However, 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 of 1 or more, generally 1 to 5.

The polymer structure of the block copolymer (1) includes the following structures (d) to (g) in addition to the linear block copolymer.
[(AB) k] m-X (d)
[(A−B) k−A] m−X (e)
[(BA) k] m-X (f)
[(B-A) k-B] m-X (g)

  However, A and B are the same as the above formulas (a) to (c), and k and m are integers of 1 or more, generally 1 to 5. 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), or a block copolymer of these Mixtures of any polymer structure of coalescence can be used.

  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 etc. are mentioned. Styrene is particularly preferable. 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, and 1,3-hexadiene. In particular, 1,3-butadiene and isoprene are preferable. 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, isoprene is preferably 10% by mass or more, more preferably 25% by mass or more, and more preferably 40% by mass with respect to the total mass of 1,3-butadiene and isoprene. % Or more is particularly preferable. If the isoprene content is 10% by mass or more, a modified block copolymer and a composition thereof having good balance of appearance characteristics and mechanical strength are obtained because thermal decomposition does not occur during molding at high temperature and the molecular weight does not decrease. can get.

  In the step of synthesizing the block copolymer (1), a hydrocarbon solvent is used. For example, aliphatic hydrocarbons such as butane, pentane, hexane, isopentane, heptane, octane; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane; benzene, toluene, ethylbenzene, xylene, etc. Aromatic hydrocarbons and the like 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. For example, as the organic lithium compound, an organic monolithium compound, an organic dilithium compound, an organic polylithium compound, or the like in which one or more lithium atoms are bonded in the molecule can be applied.
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 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, it is necessary to take care not to mix impurities that inactivate the catalyst and living polymer, such as water, oxygen, and carbon dioxide, into the polymerization system.

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

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%.
A block ratio of 50% or more is preferable because excellent rigidity is obtained in the modified block polymer and the resin composition thereof in the present embodiment.
The block ratio of the vinyl aromatic hydrocarbon block is the weight of the vinyl aromatic hydrocarbon and the conjugated diene in the step 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 weight ratio, the polymerization reactivity ratio, and the like.
Specifically, (a) a mixture of vinyl aromatic hydrocarbon and 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)], and the vinyl aromatic hydrocarbon polymer block component (excluding vinyl aromatic hydrocarbon polymer components having an average degree of polymerization of about 30 or less) was determined. Furthermore, it is calculated | required by the following formula.

Vinyl aromatic of block copolymer (1)
Mass% of hydrocarbon polymer block
Block rate (%) = ――――――――――――――――― × 100
Total vinyl of block copolymer (1)
% By mass of aromatic hydrocarbon

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, excellent rigidity and impact resistance can be obtained, and molding processability and transparency can be improved.
(Mn) is a method of oxidizing and 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)] can be obtained by gel permeation chromatography (GPC).
That is, GPC measurement of monodisperse polystyrene for GPC is performed, a calibration curve between the peak count number and the molecular weight of the monodisperse polystyrene is prepared, and can be calculated according to a conventional method (for example, “Gel Chromatography <Basics> Issued by Kodansha”). .

Next, a hydrogenated block copolymer (1) comprising at least one polymer block A mainly composed of vinyl aromatic hydrocarbons and at least one polymer block B mainly composed of conjugated diene. ) (Hereinafter simply referred to as hydrogenated product of block copolymer (1)).
The hydrogenated product (1) of the block copolymer is obtained by hydrogenating the block copolymer obtained above.

The hydrogenation catalyst used in the hydrogenation is not particularly limited, and a conventionally known catalyst, for example, (1) a metal such as Ni, Pt, Pd, or Ru is supported on carbon, silica, alumina, diatomaceous earth, or the like. Supported heterogeneous hydrogenation catalyst, (2) so-called Ziegler-type hydrogenation catalyst 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 (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, compounds described in JP-A-8-109219 can be used. Specific examples thereof include (substitution) such as biscyclopentadienyl titanium dichloride and monopentamethylcyclopentadienyl titanium trichloride. Examples thereof include 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 further 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 product (1) of the block copolymer, the total hydrogenation rate of unsaturated double bonds based on the conjugated diene compound is not particularly limited.
In the hydrogenated block copolymer (1), 70% or more, preferably 80% or more, more preferably 90% or more of the unsaturated double bond based on the conjugated diene compound may be hydrogenated, Only a part 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. Thereby, the thermal stability is 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.
Further, the hydrogenation rate of the aromatic double bond based on the vinyl aromatic hydrocarbon in the block copolymer is not particularly limited, but is preferably 50% or less, more preferably 30% or less. More preferably, it is 20% or less.
The hydrogenation rate and the amount of vinyl bonds based on the conjugated diene compound can be measured with a nuclear magnetic resonance apparatus (NMR).

A modified block is obtained by bonding a monomer having an acid anhydride and / or a carboxyl group and a vinyl aromatic hydrocarbon copolymer (3) to the block copolymer or hydrogenated product (1). A polymer (X) is obtained.
This will be described later (second embodiment) and can be performed in the same process.

(Second Embodiment)
The modified block copolymer in the present embodiment is a block copolymer comprising at least one polymer block A mainly composed of vinyl aromatic hydrocarbon and at least one polymer block B mainly composed of conjugated diene. A primary modified block copolymer obtained by adding a functional group-containing modifier to a polymer or a hydrogenated product (2) thereof is an acid anhydride having reactivity with the functional group of the primary modified block copolymer. And / or a modified block copolymer modified with a copolymer (3) of a monomer having a carboxyl group and a vinyl aromatic hydrocarbon.

The primary modified block copolymer or the hydrogenated product (2) thereof includes at least one polymer block A mainly composed of vinyl aromatic hydrocarbons and at least one polymer block mainly composed of conjugated diene. The block copolymer comprising B or its hydrogenated product (1) is subjected to an addition reaction with a functional group-containing modifier.
The block copolymer or its hydrogenated product (1) is added to a 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 A functional group selected from a group, an isocyanate group, an isothiocyanate group, a silanol group, an alkoxysilane, a halogenated silicon group, a halogenated tin group, an alkoxytin group, a phenyltin group, and the like are bonded.
A method of obtaining such a block copolymer having a functional group bonded thereto is an atom having at least one functional group selected from the above functional groups in the block copolymer by an addition reaction with the living end of the block copolymer. Addition reaction of a functional group-containing modifier that produces a primary modified block copolymer to which a group is bonded, or a functional group-containing modifier to which an atomic group in which the functional group is protected by a known method is bonded Can be obtained by a method (first method) of 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 or amino group may be an organometallic salt at the stage of reaction. In such a case, treatment with a compound having active hydrogen such as water or alcohol By doing so, a hydroxyl group, an amino group, or the like can be obtained.

  When the functional group-containing modifier is reacted with the living terminal of the block copolymer (1), the partially modified block copolymer (1) is mixed in the primary modified block copolymer. It may be like that. The proportion of the unmodified block copolymer is preferably 70 wt% or less, more preferably 60 wt% or less, and even more preferably 50 wt% or less.

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

R ^{1 to} R ⁴ are carbon atoms having 1 to 24 carbon atoms having a functional group selected from 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. Indicates a hydrogen group.
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 a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group.
Further, in the hydrocarbon group of R ^{1 to} R ⁴ and the hydrocarbon chain of R ⁵ , oxygen, nitrogen, silicon, etc., 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, and more than 0.7 equivalents and 5 equivalents or less with respect to 1 equivalent of the living terminal of the block copolymer. It is more preferable that 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 primary modified block copolymer can be obtained by subjecting the primary modified block copolymer 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 the mechanical strength of the primary modified block copolymer or the hydrogenated product thereof or a composition comprising the same. From the viewpoint of what is intended, 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 the thermoplastic resin. The weight average molecular weight is more preferably in the range of 40,000 to 800,000, and further 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. Can be determined 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.
As a method for separating the solvent, for example, a polar solvent that becomes a poor solvent for the primary modified block copolymer such as acetone or alcohol or the hydrogenated product thereof in the solution after polymerization or after hydrogenation. In which the primary modified block copolymer or its hydrogenated product is precipitated and recovered, and the solution of the primary modified block copolymer or its hydrogenated product is poured into hot water under stirring, Examples thereof include a method of removing the solvent by ripping and collecting, or a method of directly heating the solution and distilling 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 process of monomer having acid anhydride and / or carboxyl group and copolymer (3) of vinyl aromatic hydrocarbon)
The modified block copolymer (Z) according to the second embodiment is an acid anhydride having reactivity with a functional group bonded to the primary modified block copolymer or its hydrogenated product (2). And / or a monomer having a carboxyl group and a copolymer (3) of a vinyl aromatic hydrocarbon.

Examples of the monomer having an acid anhydride include acid anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid, and maleic anhydride is particularly preferable.
Examples of the monomer having a carboxyl group include acrylic acid and methacrylic acid.
Examples of the aromatic vinyl hydrocarbon include styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene, vinylanthracene, 1,1. -Diphenylethylene etc. are mentioned, Styrene is especially preferable.

The weight average molecular weight of the copolymer (3) of the monomer having an acid anhydride and / or carboxyl group and the vinyl aromatic hydrocarbon is preferably 1000 to 50000, and more preferably 1000 to 30000.
The copolymer (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.
Further, the acid anhydride of the obtained copolymer (3) may be esterified or partially esterified with alcohol or the like.

As a copolymer (3), a styrene-maleic anhydride copolymer is mentioned as a suitable example, for example.
A suitable example is a copolymer obtained by esterifying maleic anhydride of a styrene-maleic anhydride copolymer with an alcohol or the like, or a copolymer obtained by partially esterifying.

  When the primary modified block copolymer or its hydrogenated product (2) is reacted with the copolymer (3), it is copolymerized with the primary modified block copolymer or its hydrogenated product (2). The coalescence (3) is preferably 99.9 / 0.1 to 50/50 by weight, more preferably 99/1 to 70/30, and 99/1 to 80/20. More preferably.

The reaction method of the primary modified block copolymer or its hydrogenated product (2) and the copolymer (3) is not particularly limited, and a known method 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, and 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). Can be determined using).

(Third embodiment)
By blending at least one component (Y) selected from thermoplastic resins into the modified block copolymers (X) and (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 such as ethylene, propylene, butylene, vinyl chloride, vinylidene chloride, vinyl acetate, acrylic acid esters such as acrylic acid and acrylic methyl, methacrylic acid And copolymer resins with methacrylic acid esters such as 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 a polyvinyl chloride resin that is a copolymer of vinyl chloride and / or vinylidene chloride containing 50 wt% or more of vinylidene chloride and another monomer copolymerizable therewith.
Further, a polyvinyl acetate resin which is a copolymer of vinyl acetate having a vinyl acetate content of 50 wt% or more and other monomers copolymerizable therewith, a hydrolyzate thereof, acrylic acid and its ester or amide A polymer of methacrylic acid and its ester or amide, a polyacrylate resin which is a copolymer with another copolymerizable monomer containing 50 wt% or more of these acrylic acid monomers, acrylonitrile and / or Examples thereof include methacrylonitrile polymers and nitrile resins which are copolymers with other copolymerizable monomers containing 50 wt% 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 Polycondensation polymers, polycondensation polymers of hexamethylenediamine and dibasic acids such as adipic acid and sebacic acid, specifically nylon-46, nylon-6, nylon-66, nylon-610, nylon-11, nylon- 12, polyamide-based resins such as nylon-6-nylon-12 copolymer.
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 A dibasic acid or a derivative thereof such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanediol, P-xylene glycol, bisphenol A and the like ( Or a condensation polymer with 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.
In addition, a linear polymer in which the structural units of the polymer are bonded by repeating carbonate bonds, such as 4,4′-dihydroxydiphenylalkane, 4,4′-dihydroxydiphenyl sulfide, and the like obtained by reaction of phosgene with a dihydroxy compound. Or a polymer obtained by transesterification of the dihydroxy compound and diphenyl carbonate, specifically, a polycarbonate-based polymer such as poly-4,4'-dioxydiphenyl-2,2'-propane carbonate Is mentioned.
Also, thermoplastic polysulfones such as polyethersulfone and polyallylsulfone, specifically polysulfone resins such as poly (ether sulfone), poly (4,4′-bisphenol ether sulfone), poly (thioether sulfone), formaldehyde or Examples include trioxane polymers, polyoxymethylene resins such as copolymers of formaldehyde or trioxane with 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, which are polycondensation polymers, specifically, polyketone resins such as polyetheretherketone.
In addition, polymers 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, tetrafluoro Fluorine resins such as ethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, tetrafluoroethylene-ethylene copolymer, chlorotrifluoroethylene-ethylene copolymer, polyvinylidene fluoride, polyvinyl fluoride, etc. .
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 imide bonds in the main chain, such as polyimide, polyaminobismaleimide (polybismaleimide), bismaleimide / triazine resin, polyamideimide, polyetherimide and other polyimide resins, 1,2-polybutadiene, transpolybutadiene And the like.

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 further more preferable.
In addition, the said thermoplastic resin may be used independently and may use 2 or more types together.

A predetermined additive may be blended in the modified block copolymer (X), (Z) or the composition using the same, if necessary.
As the additive, any one commonly used in the thermoplastic resin composition can be applied.
For example, calcium carbonate, magnesium carbonate, magnesium hydroxide, calcium sulfate, barium sulfate, silica, clay, talc, mica, wollastonite, montmorillonite, zeolite, alumina, titanium oxide, magnesium oxide, zinc oxide, slug wool, glass fiber Inorganic fillers such as carbon black, pigments such as iron oxide, lubricants such as stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, ethylene bisstearamide, mold release agents, paraffinic process oil, Examples include naphthenic process oils, aromatic process oils, and paraffins.
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.
In addition, those disclosed in “rubber / plastic compounding chemicals” (edited by Rubber Digest Co., Ltd.) and the like 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 further 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 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 with respect to n-butyllithium, 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) Block Styrene Ratio 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)] was quantified and determined from the following formula.

(P-1) to (P-9) each vinyl aromatic
Mass% of hydrocarbon polymer block
Block styrene ratio (%) = ――――――――――――――――― × 100
(P-1) to (P-9) All vinyls
% By mass of aromatic hydrocarbon

(3) Ratio of modified block copolymer About a sample solution in which 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 are dissolved in 20 ml of tetrahydrofurofuran, GPC (apparatus: LC10 manufactured by Shimadzu Corporation) Column: Measured by Shinpac GPC805 + GPC804 + GPC804 + GPC803 manufactured by Tsu Seisakusho. 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. Moreover, about the said sample solution, the modification | denaturation with respect to a standard polystyrene is carried out from the chromatogram obtained by performing the GPC measurement by the same method except using the column of Zorbax (silica-type gel filler) which is a column made from US DuPont. The percentage of polymer 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.
(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 1-4, Reference Example 5, Examples 6-8 ]
Next, the primary modified block copolymers (P-1) to (P-8) prepared as described above, an acid anhydride and / or a monomer having a carboxyl group, and a vinyl aromatic hydrocarbon Modified block copolymers (MP-1) to (MP-8) were prepared using styrene-maleic anhydride copolymers shown in Table 2 below, which are copolymers.

Primary modified block copolymer / styrene-maleic anhydride copolymer = 90/10 parts blended, melt kneaded at 220 ° C. and screw rotation speed 100 rpm using a 30 mmφ twin screw extruder, and reacted. A secondary modified block copolymer was prepared.
For the production of the secondary modified block copolymer, one of the following three types of styrene-maleic anhydride copolymers was selected.
SMA1000 (registered trademark Gart made by SARTOMER, GPC has a weight average molecular weight of about 5500, styrene / maleic anhydride ratio is 1/1)
SMA2000 (registered trademark of SARTOMER, weight average molecular weight by GPC is about 7500, styrene / maleic anhydride ratio is 2/1)
SMA 1440 (registered trademark of SARTOMER, resin whose weight average molecular weight by GPC is about 7500, and styrene-maleic anhydride copolymer is esterified with alcohol)

In FIG. 1, the gel permeation chromatography (GPC) of the modified block copolymer (MP-1) which is Example 1 was shown.
The GPC curves of the primary modified block copolymer (P-1) alone and the styrene-maleic anhydride copolymer (SMA-3) alone are also shown.
The modified block copolymer (MP-1) is a copolymer obtained by reacting a primary modified block copolymer (P-1) with a styrene-maleic anhydride copolymer (SMA-3). SMA-
3 disappears and the molecular weight is high, so (P-1) has (S
It was confirmed that MA-3) was bound.
The modified block copolymers (MP-2) to (MP-8) of Examples 2 to 4, Reference Example 5 and Examples 6 to 8 were also measured by gel permeation chromatography (GPC). Similarly, it was confirmed that the primary modified block copolymer and the styrene-maleic anhydride copolymer were bonded.

[ Examples 9 to 17, Reference Example 18 ], [Comparative Examples 1 to 3]
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 (PS Japan Co., Ltd.)
Company made polystyrene SC004)
Primary modified block copolymer (P-1)
Block copolymer (P-9)
P-9 / SMA-3: Blended at a ratio of 90/10 parts, and melt-kneaded using a 30 mmφ twin screw extruder at 220 ° C. and a screw rotation speed of 100 rpm. Measurement by GPC was performed, and it was confirmed that SMA-3 was not bonded to the block copolymer.

Each raw material pellet was charged into a hopper of a union plastics T-die mounting extruder (USV type / barrel diameter 40 mmφ, L / D = 28, width 400 mmT die mounting) according to the formulation shown in Table 3 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 9 to 17, Reference Example 18 ] and [Comparative Examples 1 to 3] 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) Total light transmittance and haze (cloudiness value)
In accordance with JIS K7105, a Nippon Denshoku Co., Ltd. haze meter (1001DP) was used. The measurement was performed by applying liquid paraffin.
(3) Wetting index Measured with a wetting index reagent in accordance with JIS K6768.
(4) Adhesiveness with water-based ink Surface of the resin sheet produced using water-based gravure ink (Ramipure: manufactured by Sakata Inx Co., Ltd.) using a gravure mini proofing machine (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.
Scratches are made up to 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) is closely contacted, obliquely The printing surface is peeled off instantaneously in an angle direction of 45 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.

  Table 3 below shows the measurement results of tensile modulus, total light transmittance, haze (fogging), wetting index, and adhesiveness with aqueous ink.

Examples 9 to 15, which are modified block copolymers of modified block copolymers (MP-1) to (MP-8) and styrene-maleic anhydride copolymers, are excellent in mechanical strength and have a wetting index. It was found to be high and to have good adhesion to water-based ink.
Although the modified block copolymers (MP-1) to (MP-8), the styrene-maleic anhydride copolymer, and 16 to 19 using a general-purpose thermoplastic resin had higher haze values depending on the blending ratio. In addition, practically good wetting index and adhesiveness with water-based ink were obtained.
Since Comparative Examples 1-3 did not use the modified block copolymers (MP-1) to (MP-8), 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 has excellent adhesion strength with water-based ink, and also has good transparency, so that it can be industrially used as a packaging film and various sheet materials. Have.

The GPC curves of GPC of the modified block copolymer (MP-1), the primary modified block copolymer (P-1) alone, and the styrene-maleic anhydride copolymer (SMA-3) alone are shown.

Claims (3)

Addition reaction of functional group-containing modifier to block copolymer comprising at least one polymer block A mainly composed of vinyl aromatic hydrocarbon and at least one polymer block B mainly composed of conjugated diene To the primary modified block copolymer or the hydrogenated product (2) thereof,
Copolymer of monomer having vinyl anhydride and / or acid anhydride and / or carboxyl group having reactivity with the functional group of the primary modified block copolymer or hydrogenated product (2) thereof (3) Is a modified block copolymer (Z) bonded ,
The primary modified block copolymer (2) comprises at least one polymer block A mainly composed of the vinyl aromatic hydrocarbon and at least one polymer block B mainly composed of a conjugated diene. The vinyl aromatic hydrocarbon content in the block copolymer is 70 to 95% by mass,
The functional group-containing modifier is converted into a primary modified block by an addition reaction with a block copolymer.
To the copolymer or hydrogenated product (2), hydroxyl group, epoxy group, amino group, silanol group,
A modified block copolymer (Z) having a function of generating an atomic group having at least one functional group selected from coxisilane groups. The modified block copolymer (Z) according to claim 1 , wherein the copolymer (3) is a styrene-maleic anhydride copolymer or a copolymer in which a part thereof is a carboxyl group. A modified block copolymer composition comprising 1 to 99% by weight of the modified block copolymer (Z) according to claim 1 or 2 and 99 to 1% by weight of a thermoplastic resin.

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