TW202136326A - Modified hydrogenated block copolymer - Google Patents

Abstract

Provided are polyolefins that are soluble in organic solvents, have transparency, rigidity, and heat resistance, have excellent adhesiveness with base materials such as metals, and have suppressed generation of toxic gas during combustion. A modified hydrogenated block copolymer which is a product of modification of a hydrogenated block copolymer by an unsaturated carboxylic acid and/or unsaturated carboxylic anhydride, wherein a modified hydrogenated block copolymer is used in which the hydrogenated block copolymer is a product of hydrogenation of a copolymer including a polymer block comprising an aromatic vinyl monomer unit and a polymer block comprising a conjugated diene monomer unit; the hydrogenated product of the polymer block comprising an aromatic vinyl monomer unit is a hydrogenated aromatic vinyl polymer block unit having a hydrogenation level of 90% or higher; and the hydrogenated product of the polymer block comprising a conjugated diene monomer unit is a hydrogenated conjugated diene polymer block unit having a hydrogenation level of 95% or higher.

Description

Modified hydrogenated block copolymer

The object of the present invention is to provide a modified hydrogenated block copolymer which is soluble in organic solvents, has transparency, rigidity and heat resistance, and has excellent adhesion to metal and other substrates.

In general, polyolefins such as polyethylene or polypropylene are lightweight, have water resistance or chemical resistance, and are insulating, and are easy to handle. Therefore, they can be shaped by various molding processes and used in various industrial materials. In addition, since polyolefins are mainly composed of carbon-hydrogen, it is generally difficult to combine with other materials, such as metals, glass, etc., and various inventions have been initiated in order to improve the adhesiveness. Among them, reorganization is achieved by acid modification of organic carboxylic acid or its anhydride, thereby drastically improving the thermal adhesion between polyolefins and metals (Patent Documents 1 and 2).

On the other hand, polyolefins are more difficult to dissolve in various organic solvents due to their higher chemical resistance. Generally speaking, it is more difficult to use in solution in the form of industrial applications. Therefore, in order to improve the solvent solubility of acid-modified polyolefins, various inventions are being made (Patent Documents 3 to 5). [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 3-166283 [Patent Document 2] International Publication No. 2018/180862 [Patent Document 3] Japanese Patent Laid-Open No. 2004-217807 [Patent Document 4] Japanese Patent Laid-Open No. 2017-197651 [Patent Document 5] Japanese Patent Laid-Open No. 2003-012720

[The problem to be solved by the invention]

Polyolefin-based or acid-modified polyolefin-based crystalline resins, whose crystals cause the decrease in solubility in organic solvents. Furthermore, the above-mentioned crystallinity generally hinders the transparency of polyolefins, resulting in poor transparency or color rendering of the coating film. Therefore, in each of the above-mentioned inventions, studies have been carried out as follows: to reduce the crystallinity of polyolefins and to improve the solubility. However, even with these methods, the solubility is not sufficient. In addition, the obtained polyolefins tend to become soft, and the heat resistance may decrease, or the surface of the coating film may feel sticky.

When polyolefins are used as adhesives in a state sandwiched between the attached body and the attached body, the tendency of the polyolefins to become soft plays a role, but from the point of view of general laminates or coating films, it is often not possible Play a role. In addition, in order to improve the solubility, the invention of chlorinating polyolefins is also being carried out. However, the chlorination method is not only not simple, but also has problems in terms of transparency or generation of harmful gases during combustion.

As mentioned above, a material is required that has transparency and heat resistance, does not have a sticky feeling on the surface, can be easily coated or laminated on the attached material, and the generation of toxic gases during combustion is suppressed. The present invention was made in view of such problems. That is, the present invention provides polyolefins that are soluble in organic solvents, have transparency, rigidity, and heat resistance, have excellent adhesion to metal and other substrates, and suppress the generation of toxic gases during combustion. [Technical method to solve the problem]

In order to solve the above-mentioned problems, the inventors have made intensive research and found that by using specific hydrogenated block copolymers belonging to polyolefins and modifying them with unsaturated carboxylic acid and/or unsaturated carboxylic anhydride, The above-mentioned problems can be solved. That is, the present invention has the following characteristics.

[1] A modified hydrogenated block copolymer, which is a modified body produced by modifying a hydrogenated block copolymer by an unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride, and the hydrogenated block copolymer The hydrogenated body of a copolymer comprising a polymer block containing an aromatic vinyl monomer unit and a polymer block containing a conjugated diene monomer unit, the above-mentioned polymer block containing an aromatic vinyl monomer unit The hydrogenation system has a hydrogenated aromatic vinyl polymer block unit with a hydrogenation level of more than 90%, and the above-mentioned polymer block containing a conjugated diene monomer unit has a hydrogenation system with a hydrogenation level of 95% or more of the hydrogenated conjugated diene polymerization物Block unit.

[2] The modified hydrogenated block copolymer as described in [1], wherein the hydrogenated block copolymer has at least two of the hydrogenated aromatic vinyl polymer block units, and has at least one of the hydrogenated copolymer Conjugated diene polymer block unit. [3] The modified hydrogenated block copolymer as described in [1] or [2], wherein the modification rate by the above-mentioned unsaturated carboxylic acid and/or unsaturated carboxylic anhydride is 0.1-2 mass %. [4] The modified hydrogenated block copolymer according to any one of [1] to [3], wherein the above-mentioned unsaturated carboxylic acid and/or unsaturated carboxylic anhydride is maleic anhydride.

[5] The modified hydrogenated block copolymer as described in any one of [1] to [4], wherein the weight average molecular weight (Mw) is 5,000 to 100,000. [6] A modified hydrogenated block copolymer solution or modified hydrogenated block copolymer slurry, which is obtained by making the modified hydrogenated block copolymer described in any one of [1] to [5] to 1 It is dissolved or suspended in an organic solvent with a concentration of ～30% by mass. [7] A laminate containing a modified hydrogenated block copolymer, which is obtained by laminating the modified hydrogenated block copolymer as described in any one of [1] to [5] on a substrate.

[8] The laminate containing the modified hydrogenated block copolymer as described in [7], wherein the modified hydrogenated block copolymer and one or more other thermoplastic resins are subjected to melt co-extrusion molding . [9] The laminate containing the modified hydrogenated block copolymer as described in [7], wherein the modified hydrogenated block copolymer is thermally laminated to a metal, paper, ceramic, thermoplastic resin or thermosetting resin superior. [10] The laminate containing the modified hydrogenated block copolymer as described in [9], wherein the thickness of the layer containing the modified hydrogenated block copolymer is 5 to 500 μm.

[11] A method for producing a modified hydrogenated block copolymer, which is a method for producing the modified hydrogenated block copolymer as described in any one of [1] to [5], using melt kneading and in-solution Any method of reaction or solid phase grafting can graft and modify the above-mentioned hydrogenated block copolymer. [12] A method for producing a modified hydrogenated block copolymer, which is a method for producing the modified hydrogenated block copolymer as described in any one of [1] to [5], and using an unsaturated carboxylic acid And/or unsaturated carboxylic acid anhydride graft-modified the above-mentioned hydrogenated block copolymer.

[13] A method for producing a laminate containing a modified hydrogenated block copolymer by coating the modified hydrogenated block copolymer solution or modified hydrogenated block copolymer slurry as described in [6] After being on the substrate, the solvent is removed to obtain a laminate. [14] The method for producing a laminate containing a modified hydrogenated block copolymer as described in [13], wherein the thickness of the layer containing the modified hydrogenated block copolymer is 1-100 μm. [Effects of Invention]

The modified hydrogenated block copolymer of the present invention is soluble in organic solvents, and by coating on metal, glass, plastic and other substrates, it becomes a coating with transparency, rigidity, heat resistance, and good adhesion strength. Film, thereby obtaining a laminate. Furthermore, since the modified hydrogenated block copolymer of the present invention does not undergo a chlorination reaction or the like, no toxic gas is generated during combustion. In addition, the solution or slurry of the present invention can be coated on metal, glass, plastic and other substrates, and by removing organic solvents, it becomes a coating film with transparency, rigidity, heat resistance, and good adhesion strength. . Furthermore, the laminate of the present invention is transparent, has rigidity and heat resistance, and has good adhesion strength to the substrate.

Hereinafter, the present invention will be described in detail. The following description is an example of an embodiment of the present invention, and the present invention is not limited by the following description as long as it does not exceed the gist. Hereinafter, when the expression of "～" is used, it is used to indicate the numerical value or the physical property value before and after it is included.

The modified hydrogenated block copolymer of the present invention is a modified body produced by modifying an unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride of a hydrogenated block copolymer.

＜Hydrogenated block copolymer＞ The hydrogenated block copolymer used as the raw material for the modified hydrogenated block copolymer of the present invention contains a polymer block containing at least one type of aromatic vinyl monomer unit and at least one type of conjugated diene monomer unit The polymer block is the hydrogenated body of the block copolymer. That is, the hydrogenated block copolymer has a hydrogenated aromatic vinyl polymer block unit and a hydrogenated conjugated diene polymer block unit.

The hydrogenated aromatic vinyl polymer block unit is a hydrogenated body of a polymer block containing an aromatic vinyl monomer unit, and the hydrogenation level is as described later. In addition, the hydrogenated conjugated diene polymer block unit is a hydrogenated product of a polymer block containing a conjugated diene monomer unit, and the hydrogenation level is as described later. In addition, the hydrogenated block copolymer has at least two hydrogenated aromatic vinyl polymer block units and at least one hydrogenated conjugated diene polymer block unit. The hydrogenated block copolymer has excellent transparency and material strength.

Furthermore, in this specification, the so-called "block" refers to a polymer segment that is microlayer separated from a copolymer having polymer segments that are different in structure or composition. Therefore, for example, the term "having at least two block units" means that the hydrogenated block copolymer has at least two polymer segments that undergo microlayer separation.

A monomer represented by the general formula (1) of an aromatic vinyl mono-system as a raw material of the above-mentioned aromatic vinyl monomer unit.

此處，R係氫或烷基，Ar係苯基、聯苯基、鹵代苯基、烷基苯基、烷基鹵代苯基、萘基、吡啶基或蒽基。[化1]

Here, R is hydrogen or alkyl, and Ar is phenyl, biphenyl, halophenyl, alkylphenyl, alkyl halophenyl, naphthyl, pyridyl, or anthracenyl.

The above-mentioned alkyl groups may be mono-substituted or multiple-substituted by functional groups such as halo, nitro, amine, hydroxyl, cyano, carbonyl and carboxyl groups. The carbon number of the alkyl group is preferably 1-6. The aforementioned Ar is preferably a phenyl group or an alkylphenyl group, and more preferably a phenyl group.

As the aromatic vinyl monomer, for example, styrene, α-methylstyrene, vinyl toluene (including all isomers, especially p-vinyl toluene), ethyl styrene, propyl styrene , Butyl styrene, vinyl biphenyl, vinyl naphthalene, vinyl anthracene (all isomers), and mixtures thereof.

The conjugated diene monomer used as the raw material of the above-mentioned conjugated diene monomer unit is not particularly limited as long as it is a monomer having two conjugated double bonds. As the conjugated diene monomer, for example, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2-methyl-1,3-pentadiene Alkenes and similar compounds, and mixtures thereof.

The polybutadiene, which is the polymer of 1,3-butadiene, may include 1, 2 configurations that impart the equivalent of 1-butene repeating units by hydrogenation, or 1, 3-butadiene that imparts equivalents of ethylene repeating units by hydrogenation. Any of 4 configurations.

The hydrogenated body containing the above-mentioned aromatic vinyl monomer or the polymerizable block of the above-mentioned conjugated diene monomer containing 1,3-butadiene belongs to the hydrogenated block copolymer used in the present invention. Preferably, the hydrogenated block copolymer is a block copolymer without functional groups. Furthermore, the so-called "non-functional group" means that there is no functional group in the block copolymer, that is, a group that no longer contains elements other than carbon and hydrogen.

As a preferred example of the above-mentioned hydrogenated aromatic vinyl polymer block unit, a unit containing hydrogenated polystyrene can be cited. As a preferred example of the above-mentioned hydrogenated conjugated diene polymer block unit, hydrogenated polybutylene can be cited. Diene unit. Moreover, as a preferred aspect of the hydrogenated block copolymer, for example, a hydrogenated triblock or pentablock copolymer of styrene and butadiene, preferably does not contain any other functional groups or structural modifications. Quality agent.

The content of the hydrogenated aromatic vinyl polymer block unit is preferably 50 to 99 mol%, and more preferably 60 to 90 mol% relative to the above-mentioned hydrogenated block copolymer. If the ratio of the hydrogenated aromatic vinyl polymer block unit is more than the above lower limit, the rigidity will not decrease, and if it is less than the above upper limit, the brittleness will not deteriorate.

In addition, the content of the hydrogenated conjugated diene polymer block unit is preferably 1 to 50 mol%, and more preferably 10 to 40 mol% with respect to the above-mentioned hydrogenated block copolymer. If the ratio of the hydrogenated conjugated diene polymer block unit is more than the above lower limit, the brittleness will not deteriorate, and if it is less than the above upper limit, the rigidity will not decrease.

The hydrogenated block copolymer of the present invention is obtained by including SBS, SBSBS, SIS, SISIS, and SISBS (here, S refers to polystyrene, B refers to polybutadiene, and I refers to polyisoprene ) It is prepared by hydrogenation of block copolymers including tri-block, multi-block, graded block and star-shaped block copolymers.

The hydrogenated block copolymer of the present invention contains a segment containing an aromatic vinyl polymer at each end. Therefore, the hydrogenated block copolymer of the present invention has at least two hydrogenated aromatic vinyl polymer block units. In addition, there is at least one hydrogenated conjugated diene polymer block unit between the two hydrogenated aromatic vinyl polymer block units.

The block copolymer before hydrogenation can contain several additional blocks, which can be bonded to any position of the triblock polymer backbone. In this manner, the linear block includes, for example, SBS, SBSB, SBSBS, and SBSBSB. The copolymer can also be branched, and the polymer chain can be bonded at any position along the backbone of the copolymer.

The lower limit of the weight average molecular weight (hereinafter referred to as "Mw") of the hydrogenated block copolymer is preferably 10,000 or more, more preferably 20,000 or more. Furthermore, the upper limit of Mw is preferably 120,000 or less, more preferably 100,000 or less, still more preferably 95,000 or less, particularly preferably 90,000 or less, most preferably 85,000 or less, and extremely preferably 80,000 or less. If Mw is more than the aforementioned lower limit, the mechanical strength will not decrease, and if it is less than the aforementioned upper limit, the solvent solubility of the obtained modified hydrogenated block copolymer will be improved. The Mw of the hydrogenated block copolymer is determined by the gel permeation chromatography (GPC) measurement, and the specific measurement method is as described in the section of the examples.

The hydrogenation level of the hydrogenated aromatic vinyl polymer block unit is preferably 90% or more, more preferably 95% or more, still more preferably 98% or more, and particularly preferably 99.5% or more. The hydrogenation level of the above-mentioned hydrogenated conjugated diene polymer block unit is preferably 95% or more, more preferably 99% or more, and still more preferably 99.5% or more. In this way, it is preferable because it exhibits rigidity and heat resistance through high-level hydrogenation.

Furthermore, the hydrogenation level of the hydrogenated aromatic vinyl polymer block unit refers to the ratio of the aromatic vinyl polymer block unit being saturated by hydrogenation, the so-called hydrogenation of the hydrogenated conjugated diene polymer block unit The level refers to the ratio of the conjugated diene polymer block unit being saturated by hydrogenation. The above-mentioned hydrogenation level is determined using proton NMR (Nuclear Magnetic Resonance).

The melt flow rate (MFR) of the hydrogenated block copolymer of the present invention is generally 0.1 g/10 minutes or more, and from the viewpoint of the molding method or the appearance of the molded body, it is preferably 0.5 g/10 minutes or more. In addition, it is generally 200 g/10 minutes or less, and from the viewpoint of material strength, it is preferably 100 g/10 minutes or less, and more preferably 50 g/10 minutes or less. MFR is measured in accordance with ISO R1133 under the conditions of a measurement temperature of 230°C and a measurement load of 2.16 kg.

A hydrogenated block copolymer may be used individually by 1 type, and may use 2 or more types together. As the hydrogenated block copolymer of the present invention, commercially available ones can be used. Specifically, ZELAS (trademark registration) manufactured by Mitsubishi Chemical Corporation can be mentioned.

＜Modification operation of hydrogenated block copolymer＞ Next, the modification operation of the hydrogenated block copolymer will be described. This modification operation is performed as follows: The hydrogenated block copolymer is reacted by adding an unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride as a modifying agent.

As the unsaturated carboxylic acid and/or unsaturated carboxylic anhydride of the above-mentioned modifier, for example, acrylic acid, methacrylic acid, α-ethacrylic acid, maleic acid, fumaric acid, tetrahydro-o- Unsaturated carboxylic acids such as phthalic acid, methyl tetrahydrophthalic acid, methylene succinic acid, methyl maleic acid, crotonic acid, methacrylic acid, and acid-resistant acids, and their anhydrides. Moreover, as an unsaturated carboxylic anhydride, specifically, maleic anhydride, methyl maleic anhydride, and ground-resistant acid anhydride are mentioned. Furthermore, as the terrestrial acid resistance or its anhydride, there may be mentioned: internal cis-bicyclo[2.2.1]heptane-2,3-dicarboxylic acid (resistance to terrestrial acid (trademark)), methyl-internal cis-bicyclo [2.2.1] Heptane-5-ene-2,3-dicarboxylic acid (methyl-resistant acid (trademark)), etc. and their anhydrides.

Among these unsaturated carboxylic acids and/or unsaturated carboxylic acid anhydrides, acrylic acid, maleic acid, tertiary acid, maleic anhydride, tertiary acid anhydride are preferred, and maleic anhydride is more preferred. Unsaturated carboxylic acid and/or unsaturated carboxylic anhydride may be used individually by 1 type, and may use 2 or more types together.

The above-mentioned hydrogenated block copolymer is modified by the above-mentioned unsaturated carboxylic acid and/or unsaturated carboxylic anhydride, whereby a modified hydrogenated block copolymer can be obtained. As a modification method, it is more suitable to use: solution modification, melting modification, solid phase modification by electron beam or ionizing radiation irradiation, modification in supercritical fluid, etc. Among them, melt modification with excellent equipment or cost competitiveness is preferable, and melt-kneading modification with an extruder with excellent continuous productivity is more preferable. As the device used at this time, for example, a single-screw extruder, a twin-screw extruder, a Bamburi mixer, and a roll mixer can be mentioned. Among them, a single-screw extruder and a twin-screw extruder excellent in continuous productivity are preferred.

Generally speaking, the modification of the hydrogenated block copolymer by unsaturated carboxylic acid and/or unsaturated carboxylic anhydride is carried out by grafting reaction as follows: The carbon-hydrogen bond of one of the hydrogenated conjugated diene polymer block units is broken to generate carbon radicals, and the unsaturated functional groups are added to the carbon radicals. As a source of carbon radical generation, in addition to the above-mentioned electron beam or ionizing radiation, a high temperature method can also be used, and radical generators such as azo compounds, inorganic peroxides, and organic peroxides can also be used. As the radical generator, it is preferable to use an organic peroxide from the viewpoint of cost or operability.

Examples of the azo compound include azobisisobutyronitrile, azobisdimethylvaleronitrile, azobis(2-methylbutyronitrile), and diazonitrophenol. Examples of the above-mentioned inorganic peroxide include hydrogen peroxide, potassium peroxide, sodium peroxide, calcium peroxide, magnesium peroxide, and barium peroxide.

Examples of the above-mentioned organic peroxides include organic peroxides belonging to the group of hydroperoxides, dialkyl peroxides, diacetyl peroxides, peroxy esters, and ketone peroxides. Specifically, examples include: hydroperoxides such as cumene hydroperoxide and tertiary butyl hydroperoxide; dicumyl peroxide, di-tertiary butyl peroxide, 2, 5-Dimethyl-2,5-bis(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne-3, etc. Dialkyl peroxides; diethyl peroxides such as lauryl peroxide and benzyl peroxide; t-butyl peroxyacetate, t-butyl peroxybenzoate, t-butyl peroxycarbonic acid Peroxy esters such as isopropyl ester; ketone peroxides such as cyclohexanone peroxide. These radical generators may be used individually by 1 type, and may use 2 or more types together.

As the above-mentioned modification by grafting reaction, for example, the above-mentioned hydrogenated block copolymer is graft-modified by any method of melt kneading, reaction in solution, and solid phase grafting; or by the above-mentioned non- Saturated carboxylic acid and/or unsaturated carboxylic anhydride undergo graft modification.

[Using melt kneading to modify] The commonly used modification by melt kneading is carried out as follows: hydrogenated block copolymer, unsaturated carboxylic acid and/or unsaturated carboxylic anhydride, organic peroxide are formulated and put into a kneader or extruder, While heating, melting, kneading and extruding, the molten resin extruded from the front end die is cooled in a water tank or the like to obtain a modified hydrogenated block copolymer.

Regarding the blending ratio of the hydrogenated block copolymer and the unsaturated carboxylic acid and/or unsaturated carboxylic anhydride, with respect to 100 parts by mass of the hydrogenated block copolymer, the unsaturated carboxylic acid and/or unsaturated carboxylic anhydride It is 0.2-5 parts by mass. If the blending ratio of the unsaturated carboxylic acid and/or unsaturated carboxylic anhydride to the hydrogenated block copolymer is greater than or equal to the above lower limit, a predetermined modification rate required to exert the effects of the present invention can be obtained. Moreover, if it is less than the said upper limit, unreacted unsaturated carboxylic acid and/or unsaturated carboxylic anhydride will not remain, and it will not have a bad influence on adhesive strength.

Regarding the blending ratio of the above-mentioned unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride and the above-mentioned organic peroxide, relative to 100 parts by mass of the above-mentioned unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride, the above-mentioned organic peroxide is 0.2 ~100 parts by mass. If the blending ratio of the organic peroxide with respect to the unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride is greater than or equal to the lower limit, a predetermined modification rate required to exert the effects of the present invention can be obtained. Moreover, if it is less than the above upper limit, deterioration of the hydrogenated block copolymer does not occur, and the hue does not deteriorate.

In addition, as melt-kneading modification conditions, for example, in a single-screw extruder or a twin-screw extruder, extrusion is preferably performed at a temperature of 150 to 300°C.

[Using the modification of the reaction in the solution] The commonly used modification by the reaction in the solution is carried out as follows: the hydrogenated block copolymer, unsaturated carboxylic acid and/or unsaturated carboxylic anhydride, and free radical generator are put into an organic solvent and heated to A modified hydrogenated block copolymer was obtained.

The above-mentioned organic solvent is not particularly restricted as long as it does not have a functional group such as active hydrogen capable of reacting with the radical generator and can dissolve the hydrogenated block copolymer. For example, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, and tertiary butylbenzene can be mentioned. From the viewpoint of solubility and stability, dichlorobenzene is preferred.

The reaction concentration varies according to the solubility of the hydrogenated block copolymer in the organic solvent and the viscosity of the solution, and is preferably 5-20% by mass. If the reaction concentration is more than the above lower limit, the productivity is good, and if the reaction concentration is less than the above upper limit, the viscosity of the solution does not increase, and stirring or heat dissipation is easy. The blending ratio of the unsaturated carboxylic acid and/or unsaturated carboxylic anhydride, and the radical generator to the hydrogenated block copolymer is the same as the modification by melt kneading.

The reaction temperature varies according to the boiling point of the organic solvent or the half-life temperature of the radical generator used, and is preferably 80 to 150°C. If the reaction temperature is more than the above lower limit, the reaction rate will not decrease, and if it is less than the above upper limit, the hydrogenated block copolymer will not decompose and the reaction will be stable. The reaction time varies according to the target value of the grafting rate, and is preferably 1 to 10 hours. After the reaction is completed, the reaction product can be recovered by performing crystallization, filtration, washing, and drying according to a known method.

The above-mentioned crystallization can be carried out by lowering the temperature of the reaction solution, performing vacuum distillation to increase the concentration of the solution, or adding a poor solvent to precipitate a solid. The above-mentioned filtration can be performed using a filter device combined with filter paper, filter cloth, etc. In addition, centrifugal filters, pressure filters, filters that integrate washing and drying can be used.

The above-mentioned washing preferably uses one that does not dissolve the modified hydrogenated block copolymer but dissolves unreacted unsaturated carboxylic acid and/or unsaturated carboxylic anhydride. Specifically, methanol and acetone are preferred. The above-mentioned drying is performed by removing the residual solvent with a hot air dryer or a reduced-pressure dryer. Through these operations, the modified hydrogenated block copolymer obtained by the reaction in the solution can be used for the purpose of the present invention in the same way as the modification by melt kneading.

[Modification by solid phase grafting] The commonly used modification by solid phase grafting is carried out as follows: In a mixer with a heating mantle, the hydrogenated block copolymer is impregnated with unsaturated carboxylic acid and/or unsaturated carboxylic anhydride, and free radicals. The generator then undergoes a graft reaction in a temperature range that does not melt the hydrogenated block copolymer, thereby obtaining a modified hydrogenated block copolymer. In order to facilitate impregnation, it is preferable to feed the hydrogenated block copolymer in a powder state. In addition, the unsaturated carboxylic acid and/or unsaturated carboxylic anhydride are preferably in a liquid state, and in the case of a powder, it is preferable to heat it to about the melting point and put it in as a liquid.

The setting temperature of the stirrer is preferably above the melting point of the unsaturated carboxylic acid and/or the unsaturated carboxylic anhydride, and does not reach the glass transition point of the hydrogenated block copolymer. Therefore, the selected radical generator is preferably one that exhibits activity within the above-mentioned temperature range. The reaction is performed by heating and stirring the mixture. After the reaction is completed, a modified hydrogenated block copolymer is obtained in a solid state.

[Reduce the molecular weight of the modified hydrogenated block copolymer] When the molecular weight of the modified hydrogenated block copolymer is reduced, the blending ratio of the modified hydrogenated block copolymer and the organic peroxide is relative to 100 parts by mass of the modified hydrogenated block copolymer. The organic peroxide is 0.01 to 2 parts by mass. In addition, as melt-kneading modification conditions, for example, in a single-screw extruder or a twin-screw extruder, it is preferable to perform extrusion at a temperature of 150 to 300°C.

[Modification rate] The modification rate of the modified hydrogenated block copolymer modified by the above-mentioned unsaturated carboxylic acid and/or unsaturated carboxylic anhydride is preferably 0.1-2% by mass. If the modification rate is more than the above lower limit, sufficient adhesive strength can be obtained. Moreover, if it is less than the said upper limit, there will be no generation of odor or deterioration of color, and the solubility to an organic solvent will also become favorable. The modification rate of the modified hydrogenated block copolymer is determined using proton NMR after the modified hydrogenated block copolymer is subjected to methyl esterification treatment.

＜Modified hydrogenated block copolymer＞ The modified hydrogenated block copolymer of the present invention is a modified body produced by modifying an unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride of a hydrogenated block copolymer. The hydrogenated block copolymer is a hydrogenated body of a copolymer comprising a polymer block containing an aromatic vinyl monomer unit and a polymer block containing a conjugated diene monomer unit. The hydrogenation system of the above-mentioned polymer block containing aromatic vinyl monomer units is hydrogenated aromatic vinyl polymer block units with a hydrogenation level of 90% or more, and the above-mentioned polymer block containing conjugated diene monomer units is The hydrogenation system has a hydrogenation level of 95% or more of hydrogenated conjugated diene polymer block units.

The hydrogenation level of the hydrogenated aromatic vinyl polymer block unit is preferably 95% or more, more preferably 98% or more, and still more preferably 99.5% or more. In addition, the hydrogenation level of the hydrogenated conjugated diene polymer block unit is preferably 99% or more, more preferably 99.5% or more. In this way, it is preferable because it exhibits rigidity and heat resistance through high-level hydrogenation. Here, the meaning of the hydrogenation level and the method for determining the hydrogenation level are the same as those described in the section of the hydrogenated block copolymer.

The hydrogenated block copolymer has at least two hydrogenated aromatic vinyl polymer block units and at least one hydrogenated conjugated diene polymer block unit. The content of the hydrogenated aromatic vinyl polymer block unit is preferably 50 to 99 mol%, and more preferably 60 to 90 mol% relative to the modified hydrogenated block copolymer. If the ratio of the hydrogenated aromatic vinyl polymer block unit is more than the above lower limit, the rigidity will not decrease, and if it is less than the above upper limit, the brittleness will not deteriorate.

In addition, the content of the hydrogenated conjugated diene polymer block unit is preferably 1 to 50 mol%, and more preferably 10 to 40 mol% relative to the modified hydrogenated block copolymer. If the ratio of the hydrogenated conjugated diene polymer block unit is more than the above lower limit, the brittleness will not deteriorate, and if it is less than the above upper limit, the rigidity will not decrease.

The lower limit of Mw of the modified hydrogenated block copolymer is preferably 5,000 or more, more preferably 10,000 or more. In addition, the upper limit of Mw is preferably 100,000 or less, more preferably 80,000 or less. Specifically, it is preferably 5,000 or more and 100,000 or less, more preferably 5,000 or more and 80,000 or less, or 10,000 or more and 100,000 or less, and still more preferably 10,000 or more and 80,000 or less.

If the Mw of the modified hydrogenated block copolymer is more than the above lower limit, the strength of the material will not decrease, and the adhesiveness and heat resistance will not decrease, so it is preferable. In addition, if Mw is less than or equal to the above upper limit, the solubility in organic solvents will not decrease, which is preferable. The Mw of the modified hydrogenated block copolymer is determined by GPC measurement.

The Mw of the modified hydrogenated block copolymer can be controlled by the amount of organic peroxide used when the hydrogenated block copolymer is modified. The modification operation of the hydrogenated block copolymer is as described above. Also, similar to the modification operation of the hydrogenated block copolymer, the modified hydrogenated block copolymer is further blended with organic peroxide, blended and then put into a kneader or extruder, and heated and melted. It is extruded while kneading to obtain a modified hydrogenated block copolymer with varying Mw.

The hydrogenated block copolymer or the modified hydrogenated block copolymer is treated with an organic peroxide to make the hydrogenated conjugate as one of the block units constituting the hydrogenated block copolymer or the modified hydrogenated block copolymer The carbon-hydrogen bond of the diene polymer block unit is temporarily broken to generate carbon radicals. From the carbon radical structure, the carbon-carbon bond breaks with the separation of β hydrogen, resulting in low molecular weight, which can be reduced by high molecular weight. The hydrogenated block copolymer or modified hydrogenated block copolymer to obtain a low molecular weight modified hydrogenated block copolymer. This operation can be performed after the modification or simultaneously with the modification. That is, since molecular weight reduction and modification are carried out at the same time, by blending more organic peroxides, the molecular weight can be reduced while being modified.

The dielectric constant of the modified hydrogenated block copolymer is preferably lower. Specifically, it is preferably 3.0 or less, and more preferably 2.5 or less. If the dielectric constant is 3.0 or less, the signal transmission speed will not decrease. The dielectric loss factor of the modified hydrogenated block copolymer is preferably lower. Specifically, it is preferably 0.003 or less, and more preferably 0.002 or less. If the dielectric loss factor is less than 0.003, the reliability of the electrical signal will not decrease.

These low dielectric properties are important properties required by materials and resin materials for electrical and electronic parts such as laminates for electrical and electronic circuits. In recent years, in order to increase the amount and speed of information transmission, the frequency of communication is being increased. For example, since the transmission speed of electrical signals is inversely proportional to the square root of the (relative) dielectric constant of the substance, in order to increase the transmission speed of electrical signals, the dielectric constant is preferably lower. In addition, the electrical signal will be lost due to transmission. Since the transmission loss is proportional to the dielectric loss factor of the substance, in order to reduce the transmission loss of the electrical signal, the dielectric loss factor is preferably lower. That is, by using materials with low dielectric constant and low dielectric loss factor, the transmission speed is high and the attenuation of the message signal is less, and the high reliability of communication can be ensured.

＜Solution or slurry of modified hydrogenated block copolymer＞ The modified hydrogenated block copolymer of the present invention can be dissolved or suspended in an organic solvent to prepare a solution or slurry. Here, the term “solution” refers to the state in which the above-mentioned modified hydrogenated block copolymer is dissolved in an organic solvent. That is, it represents a state where the molecules of the modified hydrogenated block copolymer are dispersed in an organic solvent. In addition, the term “slurry” refers to a suspension in which particles of the modified hydrogenated block copolymer are mixed in an organic solvent. Generally speaking, polyolefins have poor solubility in organic solvents. It is assumed that gelation will occur in dissolution and is not suitable for coating. However, the modified hydrogenated block copolymer of the present invention shows specific properties in this respect.

Examples of the organic solvent capable of dissolving the modified hydrogenated block copolymer of the present invention include aromatic solvents, aliphatic solvents, and alicyclic solvents. Examples of aromatic solvents include benzene, toluene, xylene, ethylbenzene, chlorobenzene, and bromonaphthalene. Examples of the aliphatic solvent include hexane, heptane, octane, nonane, and decane. As an alicyclic solvent, cyclopentane, cyclohexane, cycloheptane, and cyclodecane are mentioned, for example. These may be used individually by 1 type, and may use 2 or more types together. Among them, in order to improve operability or ease of distillation, toluene and cyclohexane are preferred.

Moreover, as long as it does not hinder the effect of the present invention, an organic solvent other than the above may be added. Other organic solvents that can be used include, for example, ketones such as acetone, methyl ethyl ketone, cyclohexanone, acetophenone, and benzophenone; alcohols such as methanol, ethanol, isopropanol, butanol, etc. ; Phenols such as phenol, cresol and naphthol; ethers such as ethylene glycol monomethyl ether; amines such as N,N-dimethylformamide and N,N-dimethylacetamide.

The concentration of the modified hydrogenated block copolymer in the above-mentioned solution or slurry is preferably 1 to 30% by mass. If the concentration of the modified hydrogenated block copolymer is more than the above lower limit, the viscosity of the solution is appropriate, and it is more suitable for coating operations. In addition, if it is less than the above upper limit, the viscosity of the solution will be more suitable, and gelation will not occur. The concentration of the modified hydrogenated block copolymer in the above-mentioned solution or slurry is more preferably 5-10% by mass.

＜Other ingredients＞ The solution or slurry of the present invention may contain components other than those listed above for the purpose of further improving its functionality. Examples of such other components include thermosetting resins or photocurable resins, hardening accelerators, ultraviolet light inhibitors, antioxidants, coupling agents, plasticizers, fluxes, flame retardants, colorants, dispersants, Emulsifiers, low elasticizers, diluents, defoamers, ion scavengers, inorganic fillers, organic fillers, etc.

＜Laminate of modified hydrogenated block copolymer＞ The modified hydrogenated block copolymer of the present invention has good bonding strength to metal, glass, plastic and other substrates, can obtain a non-sticky bonding surface, and can obtain a laminate with metal, glass, or plastic substrates. The method of lamination is not particularly limited, and well-known lamination methods such as melt co-extrusion molding, thermal lamination processing, insert injection molding, etc. can be used.

The above-mentioned melt co-extrusion molding is a method of melt co-extrusion molding of the modified hydrogenated block copolymer of the present invention and one or more other thermoplastic resins, whereby a copolymer containing modified hydrogenated block copolymers can be prepared. The layered body of things.

As the above-mentioned other thermoplastic resins, for example, ethylene-α-olefin copolymers such as ethylene-vinyl acetate copolymers, ethylene-(meth)acrylic acid copolymers, and ethylene-(meth)acrylate copolymers; polyethylene; , Polypropylene, polybutene-1 resin and other polyolefin resins; polyphenylene ether resins, nylon 6, nylon 66 and other polyamide resins; aromatic polyamide resins, polyethylene terephthalate, Aromatic polyester resins such as polybutylene terephthalate; aliphatic polyester resins such as polylactic acid, polybutylene succinate, and polycaprolactone; polycarbonate resins; polyarylate resins ; Modified polyphenylene ether resin; polysulfide resin; polyphenylene sulfide resin; polyether sulfide resin; polyether ketone resin; polyether ether ketone resin; polyimide resin; polyoxymethylene homopolymer and polyoxymethylene copolymer Polyoxymethylene series resins; polymethyl methacrylate series resins; silicon-containing soft polymers such as dimethyl polysiloxane, diphenyl polysiloxane, and dihydroxy polysiloxane; polystyrene and other ethylene -Based aromatic polymer; ethylene-propylene copolymer rubber (EPM), ethylene-propylene-non-conjugated diene copolymer rubber (EPDM), ethylene-butene copolymer rubber (EBM), ethylene-propylene-butene copolymer Vinyl elastomers such as polymer rubber; styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene/butylene-styrene block copolymer Styrene-based elastomers such as styrene-ethylene/propylene-styrene block copolymers; polybutadiene; hydrogenated vinyl aromatic polymers, including hydrogenated styrene/butadiene or styrene/isoprene Other hydrogenated vinyl aromatic block copolymers of olefin block copolymers; cyclic olefin (co)polymers. These may be used individually by 1 type, and may use 2 or more types together.

The above-mentioned thermal lamination process is the thermal lamination process of the modified hydrogenated block copolymer of the present invention on a laminated substrate such as metal, paper, ceramics, thermoplastic resin or thermosetting resin, whereby the modified hydrogenated block copolymer can be prepared. A laminate of hydrogenated block copolymers. The above-mentioned thermal lamination process is as follows: a pre-prepared film containing a modified hydrogenated block copolymer is brought into contact with the surface of a film or sheet as a laminate base material, and the surface of the film or sheet is heated to make It's so fused. Specifically, it is a method of heat-melting a plurality of films or sheets by passing them through a heating roller in an overlapped state.

To make the modified hydrogenated block copolymer into a film, a known method can be used. Specifically, a T-shaped melt extrusion die-casting film forming method, an inflation film forming method, a calendering film forming method, and an extrusion lamination forming method can be used. At this time, it can be formed into a single-layer film, or it can be formed into a multiple-layer film by a co-extrusion method. Among them, a T-shaped melt-extrusion die-cast film forming method that has excellent moldability and is relatively easy to adjust is preferred.

In the T-shaped melt extrusion die-casting film forming method, a T-shaped slit die head installed at the front end of a uniaxial or biaxial extruder with a slit width of about 0.1 to 2 mm is used at a temperature of 200 to 300 ℃ The modified hydrogenated block copolymer is melt-extruded, and then the extruded film is brought into contact with the surface of a cooling roll set at 20 to 80° C. to cool it and wind it up to obtain a film. It is also possible to perform corona treatment on the film surface as needed.

The obtained film is arranged to overlap a laminated substrate such as metal, paper, ceramics, thermoplastic resin or thermosetting resin, and the heated metal roller and rubber roller are used to apply pressure while clamping them to perform thermocompression bonding. Use thermal lamination to achieve lamination. In the case of using multiple layers of the film containing the modified hydrogenated block copolymer, it needs to be arranged in such a way that the layer containing the modified hydrogenated block copolymer is in contact with the laminated substrate.

During thermal lamination, the temperature of the heating roller can be set as needed, and it must be above the glass transition point of the modified hydrogenated block copolymer. The temperature of the heating roller varies according to the processing speed of the thermal lamination, the thickness of the film and the laminated substrate, or the pressing pressure, and it is preferably set to be 10～ higher than the glass transition point of the modified hydrogenated block copolymer. 50°C. If the set temperature is 10°C or more of the glass transition point, sufficient bonding strength can be obtained by thermal lamination. In addition, if it is 50°C or less of the glass transition point, the film containing the modified hydrogenated block copolymer will not melt or stick to a roll.

The crimping pressure during the thermal lamination process is based on the linear pressure between the rolls, preferably 1-40 kg/m. If the crimping pressure is more than the above lower limit, sufficient adhesive strength can be obtained by thermal lamination. In addition, if the crimping pressure is below the above upper limit, no wrinkles are generated, and a neat appearance can be obtained. Regarding the processing speed during thermal lamination, in order to balance the bonding strength and productivity, it is preferably 0.5-50 m/min. If the processing speed is equal to or higher than the above lower limit, the productivity is sufficient and it is preferable in terms of economic efficiency. In addition, if the processing speed is equal to or lower than the above upper limit, sufficient adhesive strength can be obtained.

In addition, by coating the solution or slurry of the modified hydrogenated block copolymer of the present invention on a substrate such as metal, glass, or plastic, and then removing the solvent, a laminate can also be obtained. As a coating method, in addition to a bar coater, a knife coater, a die nozzle coater, a gravure roll coater, spray coating, etc., it can also be coated with a brush.

The solvent can also be distilled off from the coated surface after coating. Generally speaking, it is preferable to blow hot air, and it is also possible to combine pressure reduction treatment and heating, or simultaneously pressurize and press.

As a substrate for obtaining the coated material of the above-mentioned laminate, for example, metals or alloys such as copper, aluminum, iron, stainless steel, nickel, zinc, titanium, tungsten, etc.; glass plate, glass fiber mat, glass fiber Glass such as cloth and glass wool; polyethylene, polypropylene, polybutene, ethylene-α olefin copolymer, propylene-α olefin copolymer, ethylene-acrylate copolymer, ethylene-vinyl monomer copolymer, polyamide Amine, ethylene-vinyl acetate copolymer (EVOH) and other plastics. They may be plate-shaped, film-shaped, or given other shapes, may be a single material or a composite material, and may be a single layer or a plurality of layers that are laminated.

Among these substrates, if they are facing electronic components such as circuit boards, copper or stainless steel is preferred if they want to improve conductivity or economy; if they are used for handrails or plywood, if they want to improve economy and rigidity, iron or stainless steel is preferred. ; For battery packaging and other purposes, aluminum is preferred for improving lightness and processability; for food packaging purposes, for gas barrier properties, polyamide or EVOH is preferred.

In the laminate obtained by the thermal lamination process, the thickness of the layer containing the modified hydrogenated block copolymer is preferably 5 to 500 μm. If the thickness of the above-mentioned layer is 5 μm or more, the strength as the layer is sufficient, and as a result, the adhesive strength of the laminate is also sufficient. In addition, if the thickness of the above-mentioned layer is 500 μm or less, the heat transfer during the thermal lamination process will be sufficient, and the rigidity of the layer containing the modified hydrogenated block copolymer will not increase. As a result, the adhesive strength of the laminate will be sufficient. It will not lose its flexibility as a laminate.

In the laminate obtained by coating, the thickness of the layer containing the modified hydrogenated block copolymer is preferably 1-100 μm. If the thickness of the above layer is 1 μm or more, the adhesion strength of the coating film will not decrease. In addition, if the thickness of the above-mentioned layer is 100 μm or less, thickness control during coating can be easily performed, and productivity will not be affected.

＜Use＞ The modified hydrogenated block copolymer of the present invention exhibits the following effects: transparency, heat resistance, excellent solubility in organic solvents, and excellent adhesion to substrates such as metals, glass, and plastics. In addition, the solution containing the modified hydrogenated block copolymer of the present invention also exhibits the following effect: it can provide a laminate with excellent adhesion to substrates such as metals, glass, and plastics. Therefore, it can be used in various fields, such as adhesives, paints, civil construction materials, insulating materials for electrical and electronic parts, etc. It is especially useful as insulating casting, laminated materials, and sealing materials in the electrical and electronic fields.

As an example of the use of the modified hydrogenated block copolymer of the present invention or the solution or paste using it, examples include: copper foil laminates, flexible printed circuit boards, multilayer printed wiring boards, capacitors and other electrical and electronic circuit laminates Boards; film adhesives, liquid adhesives and other adhesives; semiconductor sealing materials, underfill materials, 3D-LSI (3D-Large Scale Integration, three-dimensional large scale integrated circuit) inter-chip filling glue, insulating sheet, Prepreg, heat dissipation substrate.

＜Laminated body containing conductive metal layer＞ The modified hydrogenated block copolymer of the present invention, and the solution or slurry using the same can also be suitably used as laminates containing conductive metal layers, such as the above-mentioned laminates for electrical and electronic circuits. The laminate system containing a conductive metal layer is formed by laminating a layer containing the modified hydrogenated block copolymer of the present invention and a conductive metal layer, as long as the laminate system containing the modified hydrogenated block copolymer of the present invention is laminated Layers and conductive metal layers include not only the above-mentioned electrical and electronic circuits, but also laminates such as circuits with capacitors. Furthermore, in a laminate containing a conductive metal layer, a layer containing two or more types of modified hydrogenated block copolymers may be formed, and as long as the modified hydrogenated block copolymer of the present invention is used in at least one layer That's it. In addition, two or more types of conductive metal layers may be formed. [Example]

Hereinafter, the present invention will be described in more detail with examples, but the present invention is not limited in any way by this embodiment. In addition, in the following Examples and Comparative Examples, various physical properties were measured by the following methods.

<Molecular weight> ・Device: GPC HLC-832GPC/HT manufactured by Tosoh Corporation ・Detector: 1A infrared spectrophotometer manufactured by MIRAN (measurement wavelength: 3.42 μm) ・Tube column: 3 AD806M/S manufactured by Showa Denko Co., Ltd. (The calibration of the column is measured by monodisperse polystyrene manufactured by Tosoh (A500, A2500, F1, F2, F4, F10, F20, F40, F288) Each 0.5 mg/ml solution), the logarithmic value of the dissolution volume and molecular weight is approximated by using the third-order formula) ・Measurement temperature: 135℃ ・Concentration: 20 mg/10mL ・Injection volume: 0.2 ml ・Solvent: o-dichlorobenzene ・Flow rate: 1.0 ml/min

<Polymer block ratio> [Measurement by carbon NMR] ・Device: "AVANCE400 Spectrometer" manufactured by Bruker Corporation ・Solvent: o-dichlorobenzene-h ₄ /p-dichlorobenzene-d ₄ mixed solvent ・Concentration: 0.3 g/2.5 ml ・Measurement: ¹³ C-NMR ・Resonance frequency: 400 MHz ・Tipping angle: 45 degrees ・Data acquisition time: 1.5 seconds ・Pulse repetition time: 15 seconds ・Cumulative count: 3600 ・Measurement temperature: 100 ℃ ・¹ H irradiation: complete decoupling

<Hydrogenation level of hydrogenated aromatic vinyl polymer block unit and hydrogenation level of hydrogenated conjugated diene polymer block unit> [Measurement by proton NMR] ・Device: "AVANCE400 Spectrometer" manufactured by Bruker Corporation ・Solvent : Tetrachloroethane · Concentration: 0.045 g/1.0 ml · Measurement: ¹ H-NMR · Resonance frequency: 400 MHz · Pour angle: 45 degrees · Data acquisition time: 4 seconds · Pulse repetition time: 10 seconds · Cumulative Frequency: 64 ・Measuring temperature: 80℃ ・Hydrogenation level of hydrogenated aromatic vinyl polymer block unit: 6.8～7.5 ppm integral value reduction rate ・Hydrogenation level of hydrogenated conjugated diene polymer block unit: 5.7～ 6.4 ppm of integral value reduction rate

<Modification rate of modified hydrogenated block copolymer> [Measurement by proton NMR] ・Device: "AVANCE400 Spectrometer" manufactured by BRUKER Corporation ・Solvent: Deuterated o-dichlorobenzene ・Concentration: 20 mg/0.62 ml ・Measurement: ¹ H-NMR • Resonance frequency: 400 MHz • Pour angle: 45 degrees • Data acquisition time: 4 seconds • Pulse repetition time: 10 seconds • Cumulative number of times: 64 • Measurement temperature: 120°C • Modified hydrogenation Modification rate of segment copolymer: After the modified hydrogenated block copolymer is methylated, the signal of 3.42～3.94 ppm is counted as dimethyl maleate, and the integral value is 1/ 2 Calculate the modification rate of the modified hydrogenated block copolymer.

＜Transparency＞ Using SE-18D injection molding machine manufactured by Sumitomo Heavy Industries Co., Ltd., injection molding into a flat plate of 2 mm×40 mm×80 mm at a molding temperature of 220°C and a mold temperature of 40°C. Using this plate, the haze measurement was performed in accordance with the measurement method described in JIS K7105 (1981). Based on the measured haze value, the transparency is evaluated. The evaluation results are shown in the table. Furthermore, the lower the haze value, the better the transparency.

＜Heat resistance＞ The three plates obtained above were stacked, and the Vickers softening temperature was measured by the method described in JIS K7206 (1999). Based on the measured value of the Vickers softening temperature, the heat resistance was evaluated. The evaluation results are shown in the table. Furthermore, the higher the Vickers softening temperature, the higher the heat resistance.

＜Dielectric characteristics (dielectric constant, dielectric loss factor)＞ A pressed sheet of 2 mm×100 mm×100 mm was produced at a forming temperature of 240°C. Use this sheet as a test piece and use a vector network analyzer (KEYSIGHT PNA N5227A) to measure the dielectric constant (ε') and dielectric loss factor under the conditions of a measuring frequency of 50 GHz, a temperature of 25 ℃, and a humidity of 40% (tanδ).

＜Adhesion＞ Use JISH4000 A5052P 1 mm×70 mm×150 mm aluminum plate as the aluminum plate. Use JISG4305 SUS304 BA 0.5 mm×70 mm×150 mm stainless steel plate as the stainless steel plate. Use JISH3100 C1100P 0.8 mm×25 mm×150 mm copper plate as the copper plate. Use the following flat plate as the polyamide plate. The flat plate is made of Novamid 1020C manufactured by DSM Co., Ltd., using SE-18D injection molding machine manufactured by Sumitomo Heavy Industries Co., Ltd., at a molding temperature of 240°C and a mold temperature of 40°C. The bottom injection molding is 2 mm×40 mm×80 mm flat plate. Use the following flat plate as the EVOH plate. The flat plate is Eval F101B manufactured by Kuraray, using SE-18D injection molding machine manufactured by Sumitomo Heavy Industries Co., Ltd., and injected at a molding temperature of 220°C and a mold temperature of 40°C. It is formed into a flat plate of 2 mm×40 mm×80 mm.

After wiping the surface of the metal plate and resin plate with acetone, apply the solution to a thickness of 50 μm using a wire bar coater, blow 80°C warm air to remove the solvent, and reduce the pressure In a desiccator, a reduced pressure treatment was carried out at 50°C for 2 hours. After that, use an NT cutter to cut out 100 grids with a width of 1 mm on the coated surface, and stick cloth tape LS NO.123 made by Miqibang on them, and then peel them off and observe the 100 grids The remaining amount in the grid, so as to evaluate the adhesion. The evaluation results are shown in Table 1. The greater the number of remaining grids, the better the adhesion.

＜Raw materials＞ [Hydrogenated block copolymer (a-1)] ZELAS (trademark registration) MC930 manufactured by Mitsubishi Chemical Co., Ltd. ・MFR (230°C, 2.16 kg): 1 g/10 minutes ・Hydrogenated aromatic vinyl polymer block unit: hydrogenated polystyrene with a content of 65 mol% and a hydrogenation level of 99.5% or more ・Hydrogenated conjugated diene polymer block unit: hydrogenated polybutadiene with a content of 35 mol% and a hydrogenation level of 99.5% or more ・Block structure: pentablock structure, total hydrogenation level: 99.5% or more The hydrogenated block copolymer (a-1) is a hydrogenated block copolymer that has not been modified by unsaturated carboxylic acid and/or unsaturated carboxylic anhydride.

[Organic Peroxide] Perhexa 25B manufactured by Nippon Oil & Fat Co., Ltd. ・2,5-Dimethyl-2,5-bis(tert-butylperoxy)hexane

<Example 1> [Modified hydrogenated block copolymer (A-1)] With respect to 100 parts by mass of the hydrogenated block copolymer (a-1), 1.3 parts by mass of maleic anhydride and 0.0065 parts by mass of organic peroxide were blended and sufficiently stirred. After that, use a twin-screw extruder (TEX25αⅢ manufactured by Nippon Steel Co., Ltd.) to melt and knead under the conditions of a cylinder temperature of 280°C, a screw speed of 400 rpm, and a discharge rate of 10 kg/h. The strand is water-cooled and cut to obtain a modified hydrogenated block copolymer (A-1). The physical properties of the obtained A-1 are as follows and are also shown in Table 1. ・MFR (230°C, 2.16 kg): 3 g/10 minutes ・Hydrogenated aromatic vinyl polymer block unit: hydrogenated polystyrene with a content of 65 mol% and a hydrogenation level of 99.5% or more ・Hydrogenated conjugated diene polymer block unit: hydrogenated polybutadiene with a content of 35 mol% and a hydrogenation level of 99.5% or more ・Block structure: pentablock structure, total hydrogenation level: 99.5% or more ・Modification rate of maleic anhydride: 1.2% by mass

Put 5 g of A-1 and 100 ml (86.2 g) of toluene into a 200 ml separable flask, heat at 60°C, and stir for 1 hour. All A-1 is dissolved and becomes a colorless and transparent solution. Using the solutions of A-1 and A-1, each of the above-mentioned evaluations was performed. The evaluation results are shown in Table 1.

<Example 2> [Modified hydrogenated block copolymer (A-2)] With respect to 100 parts by mass of the obtained A-1, 1 part by mass of organic peroxide was blended and stirred sufficiently. After that, melt-kneading was performed in the same manner as in Example 1 to obtain a modified hydrogenated block copolymer (A-2). The physical properties of the obtained A-2 are shown in Table 1.

Except having used A-2 instead of A-1, it carried out similarly to Example 1, and obtained the toluene solution. A-2 is completely dissolved into a colorless and transparent solution. Using the solutions of A-2 and A-2, each of the above-mentioned evaluations was performed. The evaluation results are shown in Table 1.

<Comparative example 1> [Hydrogenated block copolymer (a-1)] Except having used a-1 instead of A-1, it carried out similarly to Example 1, and obtained the toluene solution. a-1 is completely dissolved and becomes a colorless and transparent solution. Using the solutions of a-1 and a-1, each of the above-mentioned evaluations was performed. The evaluation results are shown in Table 1.

＜Comparative example 2＞ [Modified block copolymer (a-2)] As the maleic anhydride modifier of the hydrogenated styrene-butadiene block copolymer, Tuftec M1943 manufactured by Asahi Kasei Co., Ltd. was used. a-2 is a maleic anhydride modified product of block copolymer, and it is a block copolymer of aromatic vinyl polymer as a raw material that has not been hydrogenated. Except having used a-2 instead of A-1, it carried out similarly to Example 1, and obtained the toluene solution. a-2 is completely dissolved and becomes a colorless and transparent solution. Using the solutions of a-2 and a-2, each of the above-mentioned evaluations was performed. The evaluation results are shown in Table 1.

＜Comparative example 3＞ [Modified polyolefin (a-3)] As the propylene-butene copolymer, Mitsui Chemicals Co., Ltd. Tafmer XM7070 was used, and it was modified with maleic anhydride in the same manner as in Example 1, to obtain an acid-modified propylene-butene copolymer (a-3 ). Except having used a-3 instead of A-1, it carried out similarly to Example 1, and obtained the toluene solution. All a-3 is dissolved and becomes a colorless and transparent solution. Using the solutions of a-3 and a-3, each of the above evaluations was performed. Furthermore, since a-3 has poor transparency and heat resistance, the dielectric properties were not evaluated. The evaluation results are shown in Table 1.

<Comparative Example 4> [Modified polyethylene (a-4)] As the acid-modified polyethylene, Modic M704 manufactured by Mitsubishi Chemical Co., Ltd. was used. A-4 was used instead of A-1, except that the operation was the same as in Example 1. Although a-4 was to be dissolved in toluene, a-4 was not completely dissolved, but became a cloudy gel. , Cannot be provided for coating. Therefore, the adhesiveness cannot be evaluated. In addition, since a-4 has poor transparency and heat resistance, the dielectric properties were not evaluated. The evaluation results are shown in Table 1.

<Comparative Example 5> [Modified polypropylene (a-5)] As the acid-modified polypropylene, Modic P908 manufactured by Mitsubishi Chemical Co., Ltd. was used. Except for using a-5 instead of A-1, the operation was performed in the same manner as in Example 1. Although a-5 was to be dissolved in toluene, a-5 was not completely dissolved and could not be used for coating. Therefore, the adhesiveness cannot be evaluated. In addition, since a-5 has poor transparency, the dielectric properties were not evaluated. The evaluation results are shown in Table 1.

<Comparative Example 6> [Block copolymer (a-6)] As the hydrogenated styrene-butadiene block copolymer, Kraton G1652 manufactured by Kraton Polymers was used. a-6 is a block copolymer of aromatic vinyl polymer without hydrogenation or acid modification. a-6 is used to show the level of heat resistance and dielectric properties of previous products, and only the heat resistance and dielectric properties are evaluated. The evaluation results are shown in Table 1.

[Table 1] Comparative example Example Comparative example 1 1 2 2 3 4 5 6 Modified hydrogenated block copolymer, hydrogenated block copolymer or other resins a-1 A-1 A-2 a-2 a-3 a-4 a-5 a-6 Physical properties Modification rate [quality%] 0 1.2 1.2 0.9 0.9 1 0.7 0 Hydrogenation level of hydrogenated aromatic vinyl polymer block unit [%] ≧99.5 ≧99.5 ≧99.5 0 - - - 0 Hydrogenation level of hydrogenated conjugated diene polymer block unit [%] ≧99.5 ≧99.5 ≧99.5 ≧99 - - - ≧99 Mw 76000 68000 55,000 100000 144000 123000 78000 68500 Evaluation Transparency Haze [%] 0.4 0.5 0.8 97 58 82 83 -(*1) Heat resistance Vickers softening temperature [℃] 129 125 118 35 60 98 148 Less than 35 Dielectric properties Dielectric constant (ε') 2.27 2.16 2.28 2.18 -(*1) -(*1) -(*1) 2.26 Dielectric loss factor (tan5) 0.0003 0.0011 0.0008 0.0010 -(*1) -(*1) -(*1) 0.0014 Continuity Aluminum plate 84/100 100/100 100/100 0/100 97/100 -(*2) -(*3) -(*1) Stainless steel plate 0/100 77/100 100/100 0/100 2/100 -(*2) -(*3) -(*1) Copper plate 40/100 99/100 100/100 0/100 83/100 -(*2) -(*3) -(*1) Polyamide board 67/100 100/100 83/100 0/100 96/100 -(*2) -(*3) -(*1) EVOH board 55/100 95/100 99/100 0/100 100/100 -(*2) -(*3) -(*1) Note: *1...Not determined. *2...Because of gelation, it could not be applied to coating and was not evaluated. *3... Since it was not dissolved, it could not be used for coating and was not evaluated.

<Example 3> Using a multilayer film forming machine manufactured by Labtech Engineering, at 260°C and a speed of 5 m/min, use 50 μm a-1 as the surface layer, 10 μm a-1 as the intermediate layer, and 20 μm A-1 is used as a sealing layer to form a three-layer film. Using a laminating machine made by TESTER SANGYO, use a film composed of nylon/aluminum foil and the three-layer film obtained above, and set so that the sealing layer of the three-layer film is in contact with the aluminum surface. The roll temperature is 200°C. , The speed is 0.75 m/min, and the rolling pressure is 0.3 MPa (line pressure 1.5 kg/m) for thermal lamination. After that, it was cut into short strips with a width of 15 mm, and a 90-degree peel test was performed using the following method to measure the aluminum bonding strength. The results are shown in Table 2.

[90 degree peel test] The 90-degree peel test is measured using a normal tensile testing machine and the jig for the 90-degree peel test. Fix the above-mentioned short test piece in the horizontal direction by a clamp, and peel off the end slightly in advance. The upper gripping part of the tensile testing machine grasps the peeled part and stretches it upward, thereby enabling peeling at an angle of 90 degrees with respect to the orientation of the short strip of test piece. Since the peeling point moves horizontally while peeling, the jig holding the short test piece is slid horizontally, so that the peeling point is always located directly under the upper gripping part. The stretching speed is 300 mm/min, and the measuring environment is 23°C and 40%RH.

<Comparative Example 7> Except that a-1 was used for the sealing layer, the same procedure as in Example 3 was carried out, and the aluminum adhesive strength was measured. The results are shown in Table 2.

[Table 2] Evaluation of 3-layer film Example 3 Comparative example 7 Surface layer Thickness 50 μm a-1 a-1 middle layer Thickness 10 μm a-1 a-1 Sealing layer Thickness 20 μm A-1 a-1 Aluminum bonding strength [N] 0.5 0

According to Table 1, it can be seen that the modified hydrogenated block copolymer of the present invention (Examples 1 and 2) has good transparency and heat resistance, and has excellent dielectric properties, and shows good adhesion to various substrates. In contrast, it can be seen that the hydrogenated block copolymer before modification (Comparative Example 1) has good transparency, heat resistance, and excellent dielectric properties, but the adhesion to the substrate is insufficient. Regarding the modified block copolymer in which the aromatic vinyl polymer block unit is not hydrogenated (Comparative Example 2), it can be seen that transparency and heat resistance are poor, and although the dielectric properties are excellent, adhesion to the substrate is hardly obtained.

Regarding the modified polyolefin (Comparative Example 3), it was found that the transparency and heat resistance were poor, and the adhesion to the substrate was insufficient. Regarding the modified polyethylene (Comparative Example 4) and the modified polypropylene (Comparative Example 5), since they were not dissolved in a solvent, it was not possible to evaluate the adhesiveness by coating. The block copolymer (Comparative Example 6) shows the prior art. According to the comparison with Comparative Example 6, it can be seen that the modified hydrogenated block copolymer of the present invention has good heat resistance, and the dielectric properties are equal to or more than that of the prior art.

According to Table 2, it can be seen that the laminate (Example 3) using the modified hydrogenated block copolymer of the present invention was processed on the aluminum foil by thermal lamination, thereby showing good adhesion to the aluminum foil. On the other hand, it can be seen that the laminate using the hydrogenated block copolymer before modification (Comparative Example 7) is hardly able to obtain adhesiveness to the aluminum foil despite the heat lamination process on the aluminum foil.

Claims (14)

A modified hydrogenated block copolymer, which is a modified body produced by modifying the hydrogenated block copolymer by unsaturated carboxylic acid and/or unsaturated carboxylic anhydride, and The hydrogenated block copolymer is a hydrogenated body of a copolymer comprising a polymer block containing an aromatic vinyl monomer unit and a polymer block containing a conjugated diene monomer unit, The hydrogenation system of the above-mentioned polymer block containing aromatic vinyl monomer units is hydrogenated aromatic vinyl polymer block units with a hydrogenation level of 90% or more, and the above-mentioned polymer block containing conjugated diene monomer units is The hydrogenation system has a hydrogenation level of 95% or more of hydrogenated conjugated diene polymer block units. The modified hydrogenated block copolymer of claim 1, wherein the hydrogenated block copolymer has at least two hydrogenated aromatic vinyl polymer block units and at least one hydrogenated conjugated diene polymer block unit. Segment unit. The modified hydrogenated block copolymer according to claim 1 or 2, wherein the modification rate by the above-mentioned unsaturated carboxylic acid and/or unsaturated carboxylic anhydride is 0.1-2% by mass. The modified hydrogenated block copolymer according to any one of claims 1 to 3, wherein the above-mentioned unsaturated carboxylic acid and/or unsaturated carboxylic anhydride is maleic anhydride. The modified hydrogenated block copolymer according to any one of claims 1 to 4 has a weight average molecular weight (Mw) of 5,000 to 100,000. A modified hydrogenated block copolymer solution or modified hydrogenated block copolymer slurry, which dissolves the modified hydrogenated block copolymer according to any one of claims 1 to 5 at a concentration of 1-30% by mass Or suspended in an organic solvent. A laminate containing a modified hydrogenated block copolymer, which is obtained by laminating the modified hydrogenated block copolymer according to any one of claims 1 to 5 on a substrate. For example, the laminate containing the modified hydrogenated block copolymer of claim 7 is formed by melt co-extrusion molding of the modified hydrogenated block copolymer and one or more other thermoplastic resins. For example, the laminate containing the modified hydrogenated block copolymer of claim 7 is formed by thermally laminating the modified hydrogenated block copolymer on metal, paper, ceramics, thermoplastic resin or thermosetting resin. The laminate containing the modified hydrogenated block copolymer according to claim 9, wherein the thickness of the layer containing the modified hydrogenated block copolymer is 5 to 500 μm. A method for producing a modified hydrogenated block copolymer, which is a method for producing the modified hydrogenated block copolymer according to any one of claims 1 to 5, and The above-mentioned hydrogenated block copolymer is grafted and modified by any method of melt kneading, reaction in solution, and solid phase grafting. A method for producing a modified hydrogenated block copolymer, which is a method for producing the modified hydrogenated block copolymer according to any one of claims 1 to 5, and The above-mentioned hydrogenated block copolymer is graft-modified by unsaturated carboxylic acid and/or unsaturated carboxylic anhydride. A method for manufacturing a laminate containing a modified hydrogenated block copolymer, which is after coating the modified hydrogenated block copolymer solution or modified hydrogenated block copolymer slurry as in claim 6 on a substrate, The solvent is removed to obtain a laminate. The method for producing a laminate containing a modified hydrogenated block copolymer according to claim 13, wherein the thickness of the layer containing the modified hydrogenated block copolymer is 1-100 μm.