Modified hydrogenated block copolymer

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

Technical Field

[0001] An object of the present invention is to provide a modified hydrogenated block copolymer that is soluble in an organic solvent, has transparency, has rigidity and heat resistance, and has excellent adhesiveness to a substrate such as metal.

Background Art

[0002] Generally, polyolefins such as polyethylene and polypropylene are lightweight, have water resistance, chemical resistance, and insulation properties, and are easy to handle. Therefore, they are given shapes by various molding processes and are used as various industrial materials. In addition, since polyolefins are mainly composed of carbon and hydrogen, it is generally difficult to compound them with other materials such as metals and glasses, and various inventions have been made to improve their adhesiveness. Among them, the thermal adhesiveness to metals has been remarkably improved by modification by acid modification with an organic carboxylic acid or its anhydride (Patent Documents 1 and 2).

[0003] On the other hand, since polyolefins have high chemical resistance, it is difficult to dissolve them in various organic solvents, and industrial use as a solution is generally difficult. For this reason, various inventions have been made to improve the solvent solubility of acid-modified polyolefins (Patent Documents 3 to 5).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Summary of the Invention

Problems to be Solved by the Invention

[0005] Polyolefins or acid-modified polyolefins are crystalline resins, and their crystals are factors that reduce solubility in organic solvents. Furthermore, such crystallinity usually inhibits the transparency of polyolefins, and the transparency and color development of the coating film are not favorable. For this reason, in each of the above inventions, studies have been made to reduce the crystallinity of polyolefins and improve solubility. However, in addition to the insufficient solubility with these methods, the resulting polyolefins tend to become soft, and there is a risk of reduced heat resistance or a sticky coating film surface.

[0006] This tendency for polyolefins to become soft may be useful in some cases as an adhesive in a state sandwiched between an adherend and an adherend, but it is often not useful from the perspective of general laminates and coating films. In addition, an invention has been made to chlorinate polyolefins in order to improve solubility, but the chlorination method is not simple, and problems occur in terms of transparency and the generation of harmful gases during combustion.

[0007] As described above, there is a demand for a material that has transparency and heat resistance, does not stick to the surface, can be easily applied or laminated to an adherend, and suppresses the generation of toxic gases during combustion. The present invention has been 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, are excellent in adhesiveness to substrates such as metals, and suppress the generation of toxic gases during combustion.

Means for Solving the Problems

[0008] As a result of intensive studies to solve the above problems, the present inventor has found that by using a specific hydrogenated block copolymer as polyolefins and modifying this with an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride, the above problems can be solved. That is, the present invention has the following characteristics.

[0009] [1] A modified hydrogenated block copolymer which is a modified product of a hydrogenated block copolymer with an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride, wherein the hydrogenated block copolymer is a hydrogenated product of a copolymer containing a polymer block composed of aromatic vinyl monomer units and a polymer block composed of conjugated diene monomer units, and the hydrogenated product of the polymer block composed of aromatic vinyl monomer units is a hydrogenated aromatic vinyl polymer block unit having a hydrogenation level of 90% or more, and the hydrogenated product of the polymer block composed of conjugated diene monomer units is a hydrogenated conjugated diene polymer block unit having a hydrogenation level of 95% or more.

[0010] [2] The modified hydrogenated block copolymer according to [1], wherein the hydrogenated block copolymer has at least 2 hydrogenated aromatic vinyl polymer block units and at least 1 hydrogenated conjugated diene polymer block unit. [3] The modified hydrogenated block copolymer according to [1] or [2], wherein the modification rate with the unsaturated carboxylic acid and / or the unsaturated carboxylic anhydride is 0.1 to 2% by mass. [4] The modified hydrogenated block copolymer according to any one of [1] to [3], wherein the unsaturated carboxylic acid and / or the unsaturated carboxylic anhydride is maleic anhydride.

[0011] [5] The modified hydrogenated block copolymer according to any one of [1] to [4], having a weight average molecular weight (Mw) of 5,000 to 100,000. [6] A modified hydrogenated block copolymer solution or a modified hydrogenated block copolymer slurry obtained by dissolving or suspending the modified hydrogenated block copolymer according to any one of [1] to [5] in an organic solvent at a concentration of 1 to 30% by mass. [7] A modified hydrogenated block copolymer-containing laminate in which the modified hydrogenated block copolymer according to any one of [1] to [5] is laminated on a substrate.

[0012] [8] The modified hydrogenated block copolymer-containing laminate according to [7], wherein the modified hydrogenated block copolymer is melt coextruded with one or more other thermoplastic resins. [9] The modified hydrogenated block copolymer-containing laminate according to [7], wherein the modified hydrogenated block copolymer is thermally laminated onto metal, paper, ceramics, a thermoplastic resin, or a thermosetting resin.

[10] The modified hydrogenated block copolymer-containing laminate according to [9], wherein the thickness of the layer containing the modified hydrogenated block copolymer is 5 to 500 μm.

[0013]

[11] A method for producing a modified hydrogenated block copolymer according to any one of [1] to [5], wherein the hydrogenated block copolymer is graft-modified by any method of melt kneading, reaction in solution, or solid-phase grafting.

[12] A method for producing a modified hydrogenated block copolymer according to any one of [1] to [5], wherein the hydrogenated block copolymer is graft-modified with an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride.

[0014]

[13] A method for producing a modified hydrogenated block copolymer-containing laminate, wherein a solution or slurry of the modified hydrogenated block copolymer according to [6] is applied to a substrate, and then the solvent is removed to obtain a laminate.

[14] The method for producing a modified hydrogenated block copolymer-containing laminate according to

[13] , wherein the thickness of the layer containing the modified hydrogenated block copolymer is 1 to 100 μm. [Effect of the Invention]

[0015] The modified hydrogenated block copolymer of the present invention is soluble in an organic solvent and, when applied to a substrate such as metal, glass, or plastic, forms a coating film having transparency, rigidity, heat resistance, and good adhesive strength, enabling the production of a laminate. Furthermore, since the modified hydrogenated block copolymer of the present invention does not undergo chlorination or the like, no toxic gas is generated during combustion. Also, the solution or slurry of the present invention can be applied to a substrate such as metal, glass, or plastic, and by removing the organic solvent, a coating film having transparency, rigidity, heat resistance, and good adhesive strength is formed. Furthermore, the laminate of the present invention is transparent, has rigidity and heat resistance, and has good adhesive strength to the substrate.

Embodiments for Carrying Out the Invention

[0016] The present invention will be described in detail below. However, the following description is only an example of the embodiments of the present invention, and the present invention is not limited to the following description as long as it does not exceed the gist of the invention. In the following, when the expression "~" is used, it shall be used as an expression including the numerical values or physical property values before and after it.

[0017] The modified hydrogenated block copolymer of the present invention is a modified product of a hydrogenated block copolymer with an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride.

[0018] <Hydrogenated block copolymer> The hydrogenated block copolymer that is a raw material of the modified hydrogenated block copolymer of the present invention is a hydrogenated product of a block copolymer containing a polymer block composed of at least one aromatic vinyl monomer unit and a polymer block composed of at least one conjugated diene monomer unit. That is, the hydrogenated block copolymer has a hydrogenated aromatic vinyl polymer block unit and a hydrogenated conjugated diene polymer block unit.

[0019] The hydrogenated aromatic vinyl polymer block unit is a hydrogenated product of a polymer block composed of aromatic vinyl monomer units, and its hydrogenation level is as described below. Also, the hydrogenated conjugated diene polymer block unit is a hydrogenated product of a polymer block composed of conjugated diene monomer units, and its hydrogenation level is as described below. Further, the hydrogenated block copolymer has at least two of the hydrogenated aromatic vinyl polymer block units and at least one of the hydrogenated conjugated diene polymer block units. The hydrogenated block copolymer is excellent in transparency and material strength.

[0020] In this specification, "block" refers to a polymerization segment that is micro-layer separated from a copolymer having structurally or compositionally different polymerization segments. Therefore, for example, "having at least two block units" means that the hydrogenated block copolymer has at least two polymerization segments that are micro-layer separated.

[0021] The aromatic vinyl monomer that is the raw material of the aromatic vinyl monomer unit is a monomer represented by the general formula (1).

[0022]

Chemical formula

[0023] The alkyl group may be mono-substituted or multi-substituted with functional groups such as a halo group, a nitro group, an amino group, a hydroxy group, a cyano group, a carbonyl group, and a carboxyl group. The number of carbon atoms of the alkyl group is preferably 1 to 6. The above Ar is preferably a phenyl group or an alkylphenyl group, and more preferably a phenyl group.

[0024] Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, vinyltoluene (including all isomers, particularly p-vinyltoluene), ethylstyrene, propylstyrene, butylstyrene, vinylbiphenyl, vinylnaphthalene, vinylanthracene (all isomers), and mixtures thereof.

[0025] The conjugated diene monomer serving as a raw material for the conjugated diene monomer unit may be any monomer having two conjugated double bonds and is not particularly limited. Examples of the conjugated diene monomer include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2-methyl-1,3-pentadiene and similar compounds, and mixtures thereof.

[0026] The polybutadiene which is a polymer of 1,3-butadiene may include either a 1,2 configuration that gives an equivalent of a 1-butene repeating unit upon hydrogenation or a 1,4 configuration that gives an equivalent of an ethylene repeating unit upon hydrogenation.

[0027] The hydrogenated product of the polymerizable block composed of the aromatic vinyl monomer and the conjugated diene monomer including 1,3-butadiene is included in the hydrogenated block copolymer used in the present invention. Preferably, the hydrogenated block copolymer is a block copolymer having no functional group. In addition, "having no functional group" means that there is no functional group, that is, a group containing an element other than carbon and hydrogen, in the block copolymer.

[0028] Preferred examples of the hydrogenated aromatic vinyl polymer block unit include units composed of hydrogenated polystyrene, and preferred examples of the hydrogenated conjugated diene polymer block unit include units composed of hydrogenated polybutadiene. And a preferred embodiment of the hydrogenated block copolymer includes a hydrogenated triblock or pentablock copolymer of styrene and butadiene, and preferably does not contain any other functional group or structural modifier.

[0029] The content ratio of the hydrogenated aromatic vinyl polymer block unit is preferably 50 to 99 mol%, more preferably 60 to 90 mol% with respect to the hydrogenated block copolymer. If the ratio of the hydrogenated aromatic vinyl polymer block unit is not less than the above lower limit, the rigidity will not decrease, and if it is not more than the above upper limit, the brittleness will not deteriorate.

[0030] Also, the content ratio of the hydrogenated conjugated diene polymer block unit is preferably 1 to 50 mol%, more preferably 10 to 40 mol% with respect to the hydrogenated block copolymer. If the ratio of the hydrogenated conjugated diene polymer block unit is not less than the above lower limit, the brittleness will not deteriorate, and if it is not more than the above upper limit, the rigidity will not decrease.

[0031] The hydrogenated block copolymer of the present invention is produced by hydrogenating block copolymers including triblock, multiblock, tapered block and star block copolymers such as SBS, SBSBS, SIS, SISIS, and SISBS (wherein S means polystyrene, B means polybutadiene, and I means polyisoprene).

[0032] The hydrogenated block copolymer of the present invention includes segments made of aromatic vinyl polymers at each end. For this reason, the hydrogenated block copolymer of the present invention has at least two hydrogenated aromatic vinyl polymer block units. And between these two hydrogenated aromatic vinyl polymer block units, there will be at least one hydrogenated conjugated diene polymer block unit.

[0033] The block copolymer before hydrogenation may contain several additional blocks, and these blocks may be bonded to any position of the triblock polymer backbone. Thus, linear blocks include, for example, SBS, SBSB, SBSBS, and SBSBSB. The copolymer may be branched, and the polymerization chain may be bonded to any position along the backbone of the copolymer.

[0034] The lower limit of the weight-average molecular weight of the hydrogenated block copolymer (hereinafter abbreviated as "Mw") is preferably 10,000 or more, more preferably 20,000 or more. Also, 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 equal to or higher than the above lower limit, the mechanical strength will not decrease, and if it is equal to or lower than the above 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 measurement using gel permeation chromatography (GPC), and the specific measurement method is as described in the Examples section.

[0035] 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 hydrogenated conjugated diene polymer block unit is preferably 95% or more, more preferably 99% or more, and still more preferably 99.5% or more. Such a high level of hydrogenation is preferable for expressing rigidity and heat resistance.

[0036] The hydrogenation level of the hydrogenated aromatic vinyl polymer block unit indicates the ratio at which the aromatic vinyl polymer block unit is saturated by hydrogenation, and the hydrogenation level of the hydrogenated conjugated diene polymer block unit indicates the ratio at which the conjugated diene polymer block unit is saturated by hydrogenation. The hydrogenation level is determined using proton NMR.

[0037] The melt flow rate (MFR) of the hydrogenated block copolymer of the present invention is usually 0.1 g / 10 min or more, preferably 0.5 g / 10 min or more from the viewpoints of the molding method and the appearance of the molded article. It is usually 200 g / 10 min or less, preferably 100 g / 10 min or less, more preferably 50 g / 10 min or less from the viewpoint of material strength. The MFR was measured according to ISO R1133 under the conditions of a measurement temperature of 230 °C and a measurement load of 2.16 kg.

[0038] The hydrogenated block copolymer may be used alone or in combination of two or more. As the hydrogenated block copolymer of the present invention, commercially available products can be used, specifically, Zelas (registered trademark) manufactured by Mitsubishi Chemical Corporation.

[0039] <Modification operation of hydrogenated block copolymer> Next, the modification operation of the hydrogenated block copolymer will be described. This modification operation is carried out by adding an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride as a modifier to the hydrogenated block copolymer and reacting them.

[0040] Examples of the unsaturated carboxylic acid and / or unsaturated carboxylic anhydride as the above-mentioned modifier include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acids, and anhydrides thereof. Specific examples of the unsaturated carboxylic anhydride include maleic anhydride, citraconic anhydride, and nadic anhydrides. Examples of the nadic acids or their anhydrides include endo-cis-bicyclo[2.2.1]hept-2,3-dicarboxylic acid (nadic acid (trademark)), methyl-endo-cis-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid (methyl nadic acid (trademark)), and their anhydrides.

[0041] Among these unsaturated carboxylic acids and / or unsaturated carboxylic acid anhydrides, acrylic acid, maleic acid, nadic acid, maleic anhydride, and nadic anhydride are preferred, and maleic anhydride is more preferred. The unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride may be used alone or in combination of two or more.

[0042] By modifying the above hydrogenated block copolymer with the above unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride, a modified hydrogenated block copolymer can be obtained. As the modification method, solution modification, melt modification, solid-phase modification by irradiation with electron beams or ionizing radiation, modification in supercritical fluids, etc. are preferably used. Among them, melt modification, which is excellent in equipment and cost competitiveness, is preferred, and melt kneading modification using an extruder with excellent continuous productivity is more preferred. Examples of the apparatus used at this time include a single-screw extruder, a twin-screw extruder, a Banbury mixer, and a roll mixer. Among them, a single-screw extruder and a twin-screw extruder with excellent continuous productivity are preferred.

[0043] Generally, the modification of the hydrogenated block copolymer with an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride is carried out by a graft reaction in which a carbon-hydrogen bond of a hydrogenated conjugated diene polymer block unit, which is one of the block units constituting the hydrogenated block copolymer, is cleaved to generate a carbon radical, and an unsaturated functional group is added thereto. As the source of carbon radicals, in addition to the above-mentioned electron beams and ionizing radiation, methods of raising the temperature, or radical generators such as azo compounds, inorganic peroxides, and organic peroxides can also be used. From the viewpoints of cost and operability, it is preferable to use an organic peroxide as the radical generator.

[0044] Examples of the above azo compounds include azobisisobutyronitrile, azobisdimethylvaleronitrile, azobis(2-methylbutyronitrile), and dinitrophenol diazo. Examples of the inorganic peroxide include hydrogen peroxide, potassium peroxide, sodium peroxide, calcium peroxide, magnesium peroxide, and barium peroxide.

[0045] Examples of the organic peroxide include those contained in the group of hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxyester, and ketone peroxide. Specifically, hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide; dialkyl peroxides such as dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, and 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3; diacyl peroxides such as lauryl peroxide and benzoyl peroxide; peroxyesters such as t-butyl peroxyacetate, t-butyl peroxybenzoate, and t-butyl peroxyisopropyl carbonate; and ketone peroxides such as cyclohexanone peroxide can be mentioned. These radical generators may be used alone or in combination of two or more.

[0046] Examples of the modification by the graft reaction include graft modification of the hydrogenated block copolymer by any method of melt kneading, reaction in solution, and solid phase graft, and graft modification by the above-mentioned unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride.

[0047] [Modification by Melt Kneading] The generally used modification by melt kneading is to blend a hydrogenated block copolymer, an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride, and an organic peroxide, put them into a kneader or an extruder, perform extrusion while heating and melt kneading, and cool the molten resin coming out from the tip die in a water tank or the like to obtain a modified hydrogenated block copolymer.

[0048] The blending ratio of the above hydrogenated block copolymer and the above unsaturated carboxylic acid and / or unsaturated carboxylic anhydride is 0.2 to 5 parts by mass of the above unsaturated carboxylic acid and / or unsaturated carboxylic anhydride with respect to 100 parts by mass of the above hydrogenated block copolymer. If the blending ratio of the above unsaturated carboxylic acid and / or unsaturated carboxylic anhydride with respect to the above hydrogenated block copolymer is at least the above lower limit, a predetermined modification rate necessary for achieving the effects of the present invention can be obtained. Further, if it is at most the above upper limit, unreacted unsaturated carboxylic acid and / or unsaturated carboxylic anhydride will not remain, and the adhesive strength will not be adversely affected.

[0049] The blending ratio of the above unsaturated carboxylic acid and / or unsaturated carboxylic anhydride and the above organic peracid is 0.2 to 100 parts by mass of the above organic peracid with respect to 100 parts by mass of the above unsaturated carboxylic acid and / or unsaturated carboxylic anhydride. If the blending ratio of the above organic peracid with respect to the above unsaturated carboxylic acid and / or unsaturated carboxylic anhydride is at least the above lower limit, a predetermined modification rate necessary for achieving the effects of the present invention can be obtained. Further, if it is at most the above upper limit, deterioration of the hydrogenated block copolymer will not occur and the hue will not deteriorate.

[0050] As the melt-kneading modification conditions, for example, in a single-screw extruder or a twin-screw extruder, it is preferable to extrude at a temperature of 150 to 300°C.

[0051] [Modification by reaction in solution] The generally used modification by reaction in solution is to obtain a modified hydrogenated block copolymer by charging a hydrogenated block copolymer, an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride, and a radical generator into an organic solvent and heating.

[0052] The organic solvent is not particularly limited as long as it has no functional group such as active hydrogen that can react with the radical generator and can dissolve the hydrogenated block copolymer. For example, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, t-butylbenzene can be mentioned, and from the viewpoints of solubility and stability, dichlorobenzene is preferred.

[0053] The reaction concentration depends on the solubility of the hydrogenated block copolymer in the organic solvent and the viscosity of the solution, but is preferably 5 to 20% by mass. If the reaction concentration is at least the above lower limit, the productivity is good, and if it is at most the above upper limit, the solution viscosity does not increase and stirring and heat removal become easy. The blending ratios of the unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride and the radical generator with respect to the hydrogenated block copolymer are the same as those in the modification by melt kneading.

[0054] The reaction temperature depends on the boiling point of the organic solvent and the half-life temperature of the radical generator used, but is preferably 80 to 150°C. If the reaction temperature is at least the above lower limit, there is no decrease in the reaction rate, and if it is at most the above upper limit, there is no decomposition of the hydrogenated block copolymer and the reaction is stabilized. The reaction time depends on the target value of the graft ratio, but is preferably 1 to 10 hours. After completion of the reaction, the reaction product can be recovered by crystallization, filtration, washing, and drying according to a known method.

[0055] For the crystallization, solids can be precipitated by lowering the temperature of the reaction solution, distilling off under reduced pressure to increase the solution concentration, or adding a poor solvent. The filtration can be carried out using a filtration device combined with filter paper, filter cloth, etc. Also, devices such as a centrifugal filter, a pressure filter, and a wash and dry filter can be used.

[0056] For the washing, it is preferable to use a solvent that does not dissolve the modified hydrogenated block copolymer but dissolves the unreacted unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride. Specifically, methanol and acetone are preferred. The drying is performed by removing the residual solvent with a hot air dryer or a vacuum dryer. By these operations, the modified hydrogenated block copolymer obtained by the solution reaction can be used for the purpose of the present invention in the same manner as the modification by melt kneading.

[0057] [Modification by Solid Phase Grafting] Generally used modification by solid phase grafting is to impregnate an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride, and a radical generator into a hydrogenated block copolymer in a stirrer with a heating jacket, and then perform a graft reaction in a temperature range where the hydrogenated block copolymer does not melt to obtain a modified hydrogenated block copolymer. In order to facilitate impregnation, it is preferable to introduce the hydrogenated block copolymer in a powder state. Further, the unsaturated carboxylic acid and / or the unsaturated carboxylic anhydride is preferably in a liquid state, and when it is in a powder state, it is preferably heated to about the melting point and introduced as a liquid.

[0058] The set temperature of the stirrer is preferably not less than the melting point of the unsaturated carboxylic acid and / or the unsaturated carboxylic anhydride and less than the glass transition point of the hydrogenated block copolymer. Therefore, the radical generator selected is preferably one that shows activity in the above temperature range. The reaction proceeds by stirring while heating the mixture, and after the reaction is completed, the modified hydrogenated block copolymer is obtained in a solid state.

[0059] [Decrease in Molecular Weight of Modified Hydrogenated Block Copolymer] When decreasing the molecular weight of the above-mentioned modified hydrogenated block copolymer, the blending ratio of the modified hydrogenated block copolymer and the organic peroxide is 0.01 to 2 parts by mass of the above-mentioned organic peroxide with respect to 100 parts by mass of the above-mentioned modified hydrogenated block copolymer. As the melt kneading modification conditions, for example, in a single-screw extruder or a twin-screw extruder, it is preferable to extrude at a temperature of 150 to 300°C.

[0060] [Modification Rate] The modification rate of the above-mentioned modified hydrogenated block copolymer with the above-mentioned unsaturated carboxylic acid and / or unsaturated carboxylic anhydride is preferably 0.1 to 2% by mass. If the modification rate is at least the above lower limit, sufficient adhesive strength can be obtained. Also, if it is at most the above upper limit, there is no generation of odor or deterioration of color, and the solubility in an organic solvent is also good. The modification rate of the above-mentioned modified hydrogenated block copolymer is determined using proton NMR after subjecting the above-mentioned modified hydrogenated block copolymer to methyl esterification treatment.

[0061] <Modified hydrogenated block copolymer> The modified hydrogenated block copolymer of the present invention is a modified product of a hydrogenated block copolymer with an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride. The hydrogenated block copolymer is a hydrogenated product of a copolymer containing a polymer block composed of an aromatic vinyl monomer unit and a polymer block composed of a conjugated diene monomer unit. The hydrogenated product of the polymer block composed of the above-mentioned aromatic vinyl monomer unit is a hydrogenated aromatic vinyl polymer block unit having a hydrogenation level of 90% or more, and the hydrogenated product of the polymer block composed of the above-mentioned conjugated diene monomer unit is a hydrogenated conjugated diene polymer block unit having a hydrogenation level of 95% or more.

[0062] The hydrogenation level of the above-mentioned hydrogenated aromatic vinyl polymer block unit is preferably 95% or more, more preferably 98% or more, and still more preferably 99.5% or more. Also, the hydrogenation level of the above-mentioned hydrogenated conjugated diene polymer block unit is preferably 99% or more, more preferably 99.5% or more. Such a high level of hydrogenation is preferable for expressing rigidity and heat resistance. Here, the meaning of the hydrogenation level and the method for determining the hydrogenation level are the same as those described in the section on hydrogenated block copolymers.

[0063] The hydrogenated block copolymer has at least two units of the hydrogenated aromatic vinyl polymer block and at least one unit of the hydrogenated conjugated diene polymer block. The content ratio of the hydrogenated aromatic vinyl polymer block unit is preferably 50 to 99 mol%, more preferably 60 to 90 mol%, based on the modified hydrogenated block copolymer. If the ratio of the hydrogenated aromatic vinyl polymer block unit is at least the above lower limit, the rigidity will not decrease, and if it is at most the above upper limit, the brittleness will not deteriorate.

[0064] Also, the content ratio of the hydrogenated conjugated diene polymer block unit is preferably 1 to 50 mol%, more preferably 10 to 40 mol%, based on the modified hydrogenated block copolymer. If the ratio of the hydrogenated conjugated diene polymer block unit is at least the above lower limit, the brittleness will not deteriorate, and if it is at most the above upper limit, the rigidity will not decrease.

[0065] The lower limit of Mw of the modified hydrogenated block copolymer is preferably 5,000 or more, more preferably 10,000 or more. Also, the upper limit of Mw is preferably 100,000 or less, more preferably 80,000 or less. Specifically, 5,000 or more and 100,000 or less is preferable, 5,000 or more and 80,000 or less, or 10,000 or more and 100,000 or less is more preferable, and 10,000 or more and 80,000 or less is even more preferable.

[0066] If the Mw of the modified hydrogenated block copolymer is at least the above lower limit, it is preferable because the material strength does not decrease and the adhesiveness and heat resistance do not decrease. Also, if the Mw is at most the above upper limit, it is preferable because the solubility in an organic solvent does not decrease. The Mw of the modified hydrogenated block copolymer is determined by GPC measurement.

[0067] The Mw of the modified hydrogenated block copolymer can be controlled by the amount of the organic peroxide used when modifying the hydrogenated block copolymer. The modification operation of the hydrogenated block copolymer is as described above. Also, similar to the modification operation of the hydrogenated block copolymer, an organic peroxide is further compounded with the modified hydrogenated block copolymer, blended, and charged into a kneader or an extruder, and extrusion is performed while heating and melt-kneading to obtain a modified hydrogenated block copolymer with a changed Mw.

[0068] By treating the hydrogenated block copolymer or the modified hydrogenated block copolymer with an organic peroxide, the carbon-hydrogen bond of the hydrogenated conjugated diene polymer block unit, which is one of the block units constituting the hydrogenated block copolymer or the modified hydrogenated block copolymer, is once cleaved, and from the generated carbon radical structure, carbon-carbon bond cleavage accompanied by β-hydrogen elimination occurs, causing molecular weight reduction, and a modified hydrogenated block copolymer with a low molecular weight can be obtained from a high molecular weight hydrogenated block copolymer or modified hydrogenated block copolymer. This operation may be performed after modification or simultaneously with modification. That is, in order to perform molecular weight reduction simultaneously with modification, by adding a large amount of organic peroxide, molecular weight reduction can be caused simultaneously with modification.

[0069] The dielectric constant of the modified hydrogenated block copolymer is preferably low. Specifically, 3.0 or less is preferable, and 2.5 or less is more preferable. If the dielectric constant is 3.0 or less, the signal transmission speed does not decrease. The dielectric tangent of the modified hydrogenated block copolymer is preferably low. Specifically, 0.003 or less is preferable, and 0.002 or less is more preferable. If the dielectric tangent is 0.003 or less, the reliability of the electrical signal does not decrease.

[0070] These low dielectric properties are important performances required for materials of electrical and electronic components such as laminates for electrical and electronic circuits and resin materials. In recent years, due to the improvement of information transmission volume and speed, the communication frequency has been increasing. For example, since the transmission speed of an electrical signal is inversely proportional to the square root of the (relative) dielectric constant of a substance, a lower dielectric constant is preferred to improve the transmission speed of the electrical signal. Also, although electrical signals incur losses during transmission, and the transmission loss is proportional to the dielectric tangent of the substance, a lower dielectric tangent is preferred to reduce the transmission loss of the electrical signal. Using a substance with a low dielectric constant and a low dielectric tangent means that information signals can be transmitted at high speed with little attenuation, ensuring high reliability of communication.

[0071] <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 form a solution or a slurry. Here, the solution refers to a state in which the above-mentioned modified hydrogenated block copolymer is dissolved in an organic solvent. That is, it represents a state in which the modified hydrogenated block copolymer is molecularly dispersed in the organic solvent. Also, the slurry refers to a suspension in which particles of the modified hydrogenated block copolymer are mixed in an organic solvent. Generally, polyolefins have poor solubility in organic solvents and, even if they dissolve, they gel and are not suitable for coating. However, the modified hydrogenated block copolymer of the present invention exhibits specific properties in this regard.

[0072] Examples of the organic solvent in which the modified hydrogenated block copolymer of the present invention can be dissolved include aromatic solvents, aliphatic solvents, and alicyclic solvents. Examples of aromatic solvents include benzene, toluene, xylene, ethylbenzene, chlorobenzene, and bromonaphthalene. Examples of aliphatic solvents include hexane, heptane, octane, nonane, and decane. Examples of alicyclic solvents include cyclopentane, cyclohexane, cycloheptane, and cyclodecane. These may be used alone or in combination of two or more. Among these, from the viewpoints of handleability and ease of distillation, toluene and cyclohexane are preferred.

[0073] Also, organic solvents other than those described above can be added as long as the effects of the present invention are not inhibited. Examples of other organic solvents that can be used include ketones such as acetone, methyl ethyl ketone, cyclohexanone, acetophenone, and benzophenone; alcohols such as methanol, ethanol, isopropyl alcohol, and butanol; phenols such as phenol, cresol, and naphthol; ethers such as ethylene glycol monomethyl ether; and amides such as N,N-dimethylformamide and N,N-dimethylacetamide.

[0074] The concentration of the modified hydrogenated block copolymer in the above solution or slurry is preferably 1 to 30% by mass. If the concentration of the modified hydrogenated block copolymer is at least the above lower limit, the solution viscosity becomes appropriate and is suitable for coating work. Also, if it is at most the above upper limit, the solution viscosity is appropriate and gelation does not occur. The concentration of the modified hydrogenated block copolymer in the above solution or slurry is more preferably 5 to 10% by mass.

[0075] <Other components> 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, photocurable resins, curing accelerators, ultraviolet light absorbers, antioxidants, coupling agents, plasticizers, fluxes, flame retardants, colorants, dispersants, emulsifiers, low elasticizing agents, diluents, defoaming agents, ion trap agents, inorganic fillers, and organic fillers.

[0076] <Laminate of modified hydrogenated block copolymer> The modified hydrogenated block copolymer of the present invention has good adhesion strength to substrates such as metals, glasses, and plastics, and can provide a non-sticky adhesive surface, and a laminate with a substrate such as a metal, glass, or plastic can be obtained. The lamination method is not particularly limited, and known lamination methods such as melt coextrusion molding, thermal lamination, and insert injection molding can be used.

[0077] The above-mentioned melt coextrusion molding is a method of melt coextruding the modified hydrogenated block copolymer of the present invention with one or more other thermoplastic resins, whereby a laminate containing the modified hydrogenated block copolymer can be produced.

[0078] Examples of the other thermoplastic resin include ethylene-α-olefin copolymers such as ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, and ethylene-(meth)acrylate copolymer; polyolefin resins such as polyethylene, polypropylene, and polybutene-1 resin; polyphenylene ether resins, polyamide resins such as nylon 6 and nylon 66; aramid resins, aromatic polyester resins such as polyethylene terephthalate and polybutylene terephthalate; aliphatic polyester resins such as polylactic acid, polybutylene succinate, and polycaprolactone; polycarbonate resins; polyarylate resins; modified polyphenylene oxide resins; polysulfone resins; polyphenylene sulfide resins; polyethersulfone resins; polyetherketone resins; polyetheretherketone resins; polyimide resins; polyoxymethylene resins such as polyoxymethylene homopolymer and polyoxymethylene copolymer; polymethyl methacrylate resins; silicon-containing soft polymers such as dimethylpolysiloxane, diphenylpolysiloxane, and dihydroxypolysiloxane; vinyl aromatic polymers such as polystyrene; ethylene-based elastomers such as ethylene-propylene copolymer rubber (EPM), ethylene-propylene-nonconjugated diene copolymer rubber (EPDM), ethylene-butene copolymer rubber (EBM), and ethylene-propylene-butene copolymer rubber; styrene-based elastomers such as styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene / butylene-styrene block copolymer, and styrene-ethylene / propylene-styrene block copolymer; polybutadiene; other hydrogenated vinyl aromatic block copolymers including hydrogenated vinyl aromatic polymers and hydrogenated styrene / butadiene or styrene / isoprene block copolymers; cycloolefin (co)polymers. These may be used alone or in combination of two or more.

[0079] The above-mentioned thermal lamination process is a method of thermally laminating the modified hydrogenated block copolymer of the present invention onto a lamination substrate such as metal, paper, ceramics, thermoplastic resin, or thermosetting resin. By this method, a laminate containing the modified hydrogenated block copolymer can be produced. The above thermal lamination process is a method in which a film made of a previously manufactured modified hydrogenated block copolymer is brought into contact with the surface of a film or sheet serving as a lamination substrate, and these are heated and fused together. Specifically, it is a method of thermally fusing a plurality of films or sheets by passing them through a heating roll in a stacked state.

[0080] Known methods can be used to form a film from the modified hydrogenated block copolymer. Specifically, the T-die melt extrusion casting film forming method, inflation film forming method, calendar film forming method, and extrusion lamination forming method can be used. At this time, it can be formed as a single-layer film, or a multilayer film can be formed by the coextrusion forming method. Among them, the T-die melt extrusion casting film forming method, which is excellent in formability and easy to adjust, is preferred.

[0081] In the T-die melt extrusion casting film forming method, the modified hydrogenated block copolymer is melt-extruded at a temperature of 200 to 300°C from a T-shaped slit die with a slit width of about 0.1 to 2 mm attached to the tip of a single-screw or twin-screw extruder. Then, the extruded film is brought into contact with the surface of a cooling roll set at 20 to 80°C for cooling, and the film is obtained by winding it up. If necessary, it is also possible to perform corona treatment on the film surface.

[0082] The obtained film is arranged so as to be overlapped with a lamination substrate such as metal, paper, ceramics, thermoplastic resin, or thermosetting resin, and is sandwiched while applying pressure with a heating metal roll and a rubber roll, and thermal lamination can be achieved by thermocompression bonding. When the film made of the modified hydrogenated block copolymer to be used has a multilayer structure, the layer made of the modified hydrogenated block copolymer needs to be arranged so as to be in contact with the laminate substrate.

[0083] The temperature of the heating roll during the thermal lamination process is set as required, but it is necessary that it is equal to or higher than the glass transition point of the modified hydrogenated block copolymer. Although it also depends on the processing speed of the thermal lamination, the thickness of the film and the laminate substrate, and the crimping pressure, it is preferable to set it 10 to 50 °C higher than the glass transition point of the modified hydrogenated block copolymer. If the set temperature is 10 °C or higher than the glass transition point, sufficient adhesive strength can be obtained by the thermal lamination process. Also, if it is 50 °C or lower than the glass transition point, the film made of the modified hydrogenated block copolymer will not melt or stick to the roll.

[0084] The crimping pressure during the thermal lamination process is preferably 1 to 40 kg / m as the line pressure between the rolls. If the crimping pressure is equal to or higher than the lower limit, sufficient adhesive strength can be obtained by the thermal lamination process. Also, if the crimping pressure is equal to or lower than the upper limit, wrinkles will not occur and a nice appearance can be obtained. The processing speed during the thermal lamination process is preferably 0.5 to 50 m / min in terms of the balance between the adhesive strength and productivity. If the processing speed is equal to or higher than the lower limit, the productivity is sufficient and it is economically preferable. Also, if the processing speed is equal to or lower than the upper limit, sufficient adhesive strength can be obtained.

[0085] Also, a laminate can be obtained by applying a solution or slurry of the modified hydrogenated block copolymer of the present invention to a substrate such as metal, glass or plastic, and then removing the solvent. As the coating method, in addition to a bar coater, a blade coater, a die coater, a gravure roll coater, a spray coat, etc., it is also possible to coat with a brush.

[0086] It is also possible to distill off the solvent from the coated surface after coating. Usually, it is preferably by blowing hot air, but it is also possible to combine reduced pressure treatment and heating, or to perform pressure pressing simultaneously.

[0087] Examples of the base material, which is the material to be coated to obtain the above laminate, include metals and alloys such as copper, aluminum, iron, stainless steel, nickel, zinc, titanium, tungsten, etc.; glasses such as glass plates, glass fiber mats, glass fiber cloths, glass wool, etc.; plastics such as polyethylene, polypropylene, polybutene, ethylene-α-olefin copolymers, propylene-α-olefin copolymers, ethylene-acrylic ester copolymers, ethylene-vinyl monomer copolymers, polyamides, ethylene-vinyl acetate copolymers (EVOH), etc. These may be in the form of plates or films, or may have other shapes, and may be single materials or composite materials, and may be single layers or laminated layers.

[0088] Among these base materials, copper is preferable from the viewpoints of electrical conductivity and economy for electronic members such as circuit boards, iron and stainless steel are preferable from the viewpoints of economy and rigidity for handrails and plywood applications, aluminum is preferable from the viewpoints of light weight and workability for applications such as battery packaging, and polyamides and EVOH are preferable from the viewpoints of gas barrier property expression for food packaging applications.

[0089] In the laminate obtained by thermal lamination, the thickness of the layer containing the modified hydrogenated block copolymer is preferably 5 to 500 μm. If the thickness of the above layer is 5 μm or more, the strength of the layer becomes sufficient, and as a result, the adhesive strength of the laminate becomes sufficient. Also, if the thickness of the above layer is 500 μm or less, the heat transfer during thermal lamination becomes sufficient, and the rigidity of the layer containing the modified hydrogenated block copolymer does not increase, and as a result, the adhesive strength of the laminate becomes sufficient, and the flexibility of the laminate is not lost.

[0090] In the laminate obtained by coating, the thickness of the layer containing the modified hydrogenated block copolymer is preferably 1 to 100 μm. If the thickness of the above layer is 1 μm or more, the adhesion strength of the coating film will not decrease. Also, if the thickness of the above layer is 100 μm or less, the thickness can be easily controlled during coating, and there is no impact on productivity.

[0091] <Use> The modified hydrogenated block copolymer of the present invention is transparent, has heat resistance, is excellent in solubility in organic solvents, and has the effect of being excellent in adhesion to substrates such as metals, glass, and plastics. Also, the solution containing the modified hydrogenated block copolymer of the present invention also has the effect of providing a laminate excellent in adhesion to substrates such as metals, glass, and plastics. Therefore, it can be applied to various fields such as adhesives, paints, civil engineering and building materials, and insulating materials for electrical and electronic components. In particular, it is useful as an insulating casting, laminated material, encapsulating material, etc. in the electrical and electronic fields.

[0092] As an example of the use of the modified hydrogenated block copolymer of the present invention or a solution or slurry using the same, laminates for electrical and electronic circuits such as copper foil laminates, flexible printed circuit boards, multilayer printed wiring boards, and capacitors; adhesives such as film adhesives and liquid adhesives; semiconductor encapsulating materials, underfill materials, interchip fills for 3D-LSI, insulating sheets, prepregs, and heat dissipation substrates can be mentioned.

[0093] <Laminate containing a conductive metal layer> The modified hydrogenated block copolymer of the present invention, a solution or slurry using the same can also be suitably used as a laminate containing a conductive metal layer such as the above-mentioned laminate for electrical and electronic circuits. This laminate containing a conductive metal layer is obtained by laminating a layer containing the modified hydrogenated block copolymer of the present invention and a conductive metal layer. As long as it is a laminate obtained by laminating a layer containing the modified hydrogenated block copolymer of the present invention and a conductive metal layer, in addition to the above electrical and electronic circuits, it includes laminates such as circuits having capacitors. In the laminate containing a conductive metal layer, a layer composed of two or more modified hydrogenated block copolymers may be formed, and the modified hydrogenated block copolymer of the present invention may be used in at least one layer. Further, two or more conductive metal layers may be formed.

Examples

[0094] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the following examples and comparative examples, various physical properties were measured by the following methods.

[0095] <Molecular weight> · Apparatus: GPC HLC-832GPC / HT manufactured by Tosoh Corporation · Detector: 1A infrared spectrophotometer manufactured by MIRAN (measurement wavelength, 3.42 μm) · Column: Three AD806M / S columns manufactured by Showa Denko K.K. (For column calibration, measurements were performed on monodisperse polystyrene (0.5 mg / ml solutions of A500, A2500, F1, F2, F4, F10, F20, F40, F288) manufactured by Tosoh, and the elution volume and the logarithmic value of the molecular weight were approximated by a cubic equation. · Measurement temperature: 135 °C · Concentration: 20 mg / 10 mL · Injection volume: 0.2 ml · Solvent: o-dichlorobenzene · Flow rate: 1.0 ml / min

[0096] <Ratio of polymer blocks> [Measurement by carbon NMR] · Apparatus: "AVANCE400 spectrometer" manufactured by Bruker · Solvent: o-dichlorobenzene-h4 / p-dichlorobenzene-d4 mixed solvent · Concentration: 0.3 g / 2.5 mL · Measurement: 13 C-NMR · Resonance frequency: 400 MHz · Flip angle: 45 degrees · Data acquisition time: 1.5 seconds · Pulse repetition time: 15 seconds · Number of integrations: 3600 · Measurement temperature: 100 °C · 1 H irradiation: Complete decoupling

[0097] <Degree of hydrogenation of hydrogenated aromatic vinyl polymer block units, degree of hydrogenation of hydrogenated conjugated diene polymer block units> [Measurement by proton NMR] · Apparatus: "AVANCE400 spectrometer" manufactured by Bruker · Solvent: Tetrachloroethane · Concentration: 0.045 g / 1.0 mL · Measurement: 1 H-NMR · Resonance frequency: 400 MHz · Flip angle: 45 degrees · Data acquisition time: 4 seconds · Pulse repetition time: 10 seconds · Number of integrations: 64 · Measurement temperature: 80 °C · Degree of hydrogenation of hydrogenated aromatic vinyl polymer block units: Reduction rate of integral value at 6.8 - 7.5 ppm · Degree of hydrogenation of hydrogenated conjugated diene polymer block units: Reduction rate of integral value at 5.7 - 6.4 ppm

[0098] <Modification rate of modified hydrogenated block copolymer> [Measurement by proton NMR] · Apparatus: "AVANCE400 spectrometer" manufactured by BRUKER · Solvent: o-Dichlorobenzene-d2 · Concentration: 20 mg / 0.62 mL · Measurement: 1 H-NMR · Resonance frequency: 400 MHz · Flip angle: 45 degrees · Data acquisition time: 4 seconds · Pulse repetition time: 10 seconds · Number of integrations: 64 · Measurement temperature: 120 °C ·Modification rate of modified hydrogenated block copolymer: After subjecting the modified hydrogenated block copolymer to methyl esterification treatment, the signal at 3.42 - 3.94 ppm was counted as dimethyl maleate, and it was calculated from 1 / 2 of its integral value.

[0099] <Transparency> Using a SE - 18D injection molding machine manufactured by Sumitomo Heavy Industries, Ltd., a flat plate of 2 mm × 40 mm × 80 mm was injection - molded at a molding temperature of 220°C and a mold temperature of 40°C. Using this plate, HAZE measurement was carried out according to the measurement method described in JIS K7105 (1981). The measured HAZE value was used as an evaluation of transparency. The evaluation results are shown in a table. Note that the lower the HAZE value, the better the transparency.

[0100] <Heat resistance> Three plates obtained above were stacked, and the Vicat softening temperature was measured by the method described in JIS K7206 (1999). The measured Vicat softening temperature value was used as an evaluation of heat resistance. The evaluation results are shown in a table. Note that the higher the Vicat softening temperature, the higher the heat resistance.

[0101] <Dielectric properties (dielectric constant · dielectric loss tangent)> A press sheet of 2 mm × 100 mm × 100 mm was prepared at a molding temperature of 240°C. Using this sheet as a test piece, the dielectric constant (ε’) and dielectric loss tangent (tanδ) were measured at a measurement frequency of 50 GHz, a temperature of 25°C, and a humidity of 40% using a vector network analyzer (KEYSIGHT PNA N5227A).

[0102] <Adhesion> As the aluminum plate, an aluminum plate of JISH4000 A5052P 1 mm × 70 mm × 150 mm was used. As the stainless - steel plate, a stainless - steel plate of JISG4305 SUS304 BA 0.5 mm × 70 mm × 150 mm was used. As the copper plate, a copper plate of JISH3100 C1100P 0.8 mm × 25 mm × 150 mm was used. As the polyamide plate, Novamid 1020C manufactured by DSM was used. Using the SE-18D injection molding machine manufactured by Sumitomo Heavy Industries, Ltd., a flat plate of 2 mm × 40 mm × 80 mm was injection molded at a molding temperature of 240°C and a mold temperature of 40°C, and this was used. As the EVOH plate, Eval F101B manufactured by Kuraray was used. Using the SE-18D injection molding machine manufactured by Sumitomo Heavy Industries, Ltd., a flat plate of 2 mm × 40 mm × 80 mm was injection molded at a molding temperature of 220°C and a mold temperature of 40°C, and this was used.

[0103] For the metal plate and resin plate to be used, after wiping the surface with acetone, the solution was applied with a wire bar coater so as to have a thickness of 50 μm, hot air at 80°C was blown to remove the solvent, and a vacuum treatment was performed at 50°C for 2 hours in a vacuum dryer. Thereafter, 100 squares with a width of 1 mm were cut on the coated surface with an NT cutter, and after sticking and then peeling off the Nichiban cloth adhesive tape LS NO. 123, the number of remaining squares out of the 100 squares was observed for adhesive evaluation. The evaluation results are shown in Table 1. The higher the number of remaining squares, the better the adhesiveness.

[0104] <Raw materials> [Hydrogenated block copolymer (a-1)] Zelas (trademark registered) MC930 manufactured by Mitsubishi Chemical Corporation · MFR (230°C, 2.16 kg): 1 g / 10 min · Hydrogenated aromatic vinyl polymer block unit: Hydrogenated polystyrene with a content rate of 65 mol% and a hydrogenation level of 99.5% or more · Hydrogenated conjugated diene polymer block unit: Hydrogenated polybutadiene with a content rate 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 with an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride.

[0105] [Organic peroxide] Perhexa 25B manufactured by NOF Corporation · 2,5-Dimethyl-2,5-di(t-butylperoxy)hexane

[0106] <Example 1> [Modified hydrogenated block copolymer (A-1)] 1.3 parts by mass of maleic anhydride and 0.0065 parts by mass of an organic peroxide were blended with 100 parts by mass of the hydrogenated block copolymer (a-1) and stirred well. Thereafter, using a twin-screw extruder (TEX25αIII manufactured by Nippon Steel Corporation), melt-kneading was carried out at a cylinder temperature of 280 °C, a screw rotation speed of 400 rpm, and a discharge rate of 10 kg / h, and the extruded molten strands were 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 min · 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 · Maleic anhydride modification rate: 1.2 mass%

[0107] 5 g of A-1 and 100 ml (86.2 g) of toluene were put into a 200 mL separable flask, heated to 60 °C and stirred for 1 hour. All of A-1 dissolved to form a colorless and transparent solution. Using A-1 and the solution of A-1, each of the above evaluations was carried out. The evaluation results are shown in Table 1.

[0108] <Example 2> [Modified hydrogenated block copolymer (A-2)] 1 part by mass of an organic peroxide was blended with 100 parts by mass of the obtained A-1 and stirred well. Thereafter, melt kneading was carried out 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.

[0109] A toluene solution was obtained in the same manner as in Example 1, except that A-2 was used instead of A-1. All of A-2 dissolved to form a colorless and transparent solution. Using A-2 and the solution of A-2, each of the above evaluations was carried out. The evaluation results are shown in Table 1.

[0110] <Comparative Example 1> [Hydrogenated block copolymer (a-1)] A toluene solution was obtained in the same manner as in Example 1, except that a-1 was used instead of A-1. All of a-1 dissolved to form a colorless and transparent solution. Using a-1 and the solution of a-1, each of the above evaluations was carried out. The evaluation results are shown in Table 1.

[0111] <Comparative Example 2> [Modified block copolymer (a-2)] As the maleic anhydride-modified product of a hydrogenated styrene-butadiene block copolymer, Tough Tech M1943 manufactured by Asahi Kasei Corporation was used. a-2 is a maleic anhydride-modified product of a block copolymer, but the aromatic vinyl polymer block unit of the raw material block copolymer is not hydrogenated. A toluene solution was obtained in the same manner as in Example 1, except that a-2 was used instead of A-1. All of a-2 dissolved to form a colorless and transparent solution. Using a-2 and the solution of a-2, each of the above evaluations was carried out. The evaluation results are shown in Table 1.

[0112] <Comparative Example 3> [Modified polyolefin (a-3)] As a propylene-butene copolymer, Mitsui Chemicals, Inc.'s Tafmer XM7070 was used and modified with maleic anhydride in the same manner as in Example 1 to obtain an acid-modified propylene-butene copolymer (a-3). A toluene solution was obtained in the same manner as in Example 1, except that a-3 was used instead of A-1. All of a-3 dissolved to form a colorless and transparent solution. Each of the above evaluations was performed using a-3 and the solution of a-3. Since a-3 has poor transparency and heat resistance, its dielectric properties were not evaluated. The evaluation results are shown in Table 1.

[0113] <Comparative Example 4> [Modified polyethylene (a-4)] As the acid-modified polyethylene, Modic M704 manufactured by Mitsubishi Chemical Corporation was used. In the same manner as in Example 1, except that a-4 was used instead of A-1, an attempt was made to dissolve it in toluene. However, the entire amount of a-4 did not dissolve and became a turbid gel-like state, and it could not be used for coating. Therefore, the adhesiveness could not be evaluated. Also, since a-4 has poor transparency and heat resistance, its dielectric properties were not evaluated. The evaluation results are shown in Table 1.

[0114] <Comparative Example 5> [Modified polypropylene (a-5)] As the acid-modified polypropylene, Modic P908 manufactured by Mitsubishi Chemical Corporation was used. In the same manner as in Example 1, except that a-5 was used instead of A-1, an attempt was made to dissolve it in toluene. However, a-5 did not dissolve and could not be used for coating. Therefore, the adhesiveness could not be evaluated. Also, since a-5 has poor transparency, its dielectric properties were not evaluated. The evaluation results are shown in Table 1.

[0115] <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 in which the aromatic vinyl polymer block unit is not hydrogenated and is not acid-modified. a-6 is for showing the levels of heat resistance and dielectric properties of conventional products, and only the heat resistance and dielectric properties were evaluated. The evaluation results are shown in Table 1.

[0116]

Table 1

[0117] <Example 3> Using a multilayer film forming machine manufactured by Labtech Engineering, a three-layer film was formed at 260 °C and a speed of 5 m / min, with a-1 of 50 μm as the surface layer, a-1 of 10 μm as the intermediate layer, and A-1 of 20 μm as the seal layer. Using a laminator manufactured by Tester Industry Co., Ltd., a film having a nylon / aluminum foil structure and the three-layer film obtained above were used. The seal layer of the three-layer film was set to contact the aluminum surface, and thermal lamination was performed at a roll temperature of 200 °C, a speed of 0.75 m / min, and a nip pressure of 0.3 MPa (linear pressure 1.5 kg / m). Thereafter, it was cut into strips with a width of 15 mm, and a 90-degree peel test was performed by the following method to measure the aluminum adhesion strength. The results are shown in Table 2.

[0118] [90-degree Peel Test] The 90-degree peel test is measured using a normal tensile testing machine and a jig for the 90-degree peel test. The strip test piece is fixed horizontally by the jig, and the end is peeled off slightly in advance. This peeled portion is grasped by the upper grasping portion of the tensile testing machine and pulled upward, so that it can be peeled at an angle of 90 degrees with respect to the direction of the strip test piece. Since the peel point moves horizontally as the peeling progresses, the jig fixing the strip test piece is slid horizontally so that the peel point is always located directly below the upper grasping portion and peeled. The tensile speed is 300 mm / min, and the measurement environment is a temperature of 23 °C and a humidity of 40% RH.

[0119] <Comparative Example 7> The aluminum adhesion strength was measured in the same manner as in Example 3 except that a-1 was used for the seal layer. The results are shown in Table 2.

[0120]

Table 2

[0121] From Table 1, it was found that the modified hydrogenated block copolymers of the present invention (Examples 1 and 2) have good transparency and heat resistance, excellent dielectric properties, and good adhesiveness to various substrates. On the other hand, it was found that the hydrogenated block copolymer before modification (Comparative Example 1) has good transparency and heat resistance and excellent dielectric properties, but its adhesiveness to the substrate is not sufficient. It was found that the modified block copolymer in which the aromatic vinyl polymer block unit is not hydrogenated (Comparative Example 2) has inferior transparency and heat resistance, and although it has excellent dielectric properties, almost no adhesiveness to the substrate can be obtained.

[0122] It was found that the modified polyolefin (Comparative Example 3) has inferior transparency and heat resistance, and its adhesiveness to the substrate is not sufficient. Since the modified polyethylene (Comparative Example 4) and the modified polypropylene (Comparative Example 5) do not dissolve in the solvent, the adhesiveness by coating could not be evaluated. The block copolymer (Comparative Example 6) represents the prior art. From the comparison with Comparative Example 6, it was found that the modified hydrogenated block copolymer of the present invention has good heat resistance and its dielectric properties are equal to or better than those of the prior art.

[0123] From Table 2, it was found that the laminate using the modified hydrogenated block copolymer of the present invention (Example 3) shows good adhesiveness to the aluminum foil by heat laminating the aluminum foil. On the other hand, it was found that the laminate using the hydrogenated block copolymer before modification (Comparative Example 7) hardly shows adhesiveness to the aluminum foil even after heat laminating the aluminum foil.

Claims

1. A modified hydrogenated block copolymer which is a modification of a hydrogenated block copolymer with an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride, wherein the hydrogenated block copolymer is a hydrogenated product of a copolymer containing a polymer block composed of aromatic vinyl monomer units and a polymer block composed of conjugated diene monomer units, the hydrogenated product of the polymer block composed of the aromatic vinyl monomer units is a hydrogenated aromatic vinyl polymer block unit having a hydrogenation level of 90% or more, and the hydrogenated product of the polymer block composed of the conjugated diene monomer units is a hydrogenated conjugated diene polymer block unit having a hydrogenation level of 95% or more, the content of the hydrogenated aromatic vinyl polymer block unit is 50 to 99 mol% based on the hydrogenated block copolymer, A modified hydrogenated block copolymer for electrical and electronic parts, having a weight average molecular weight (Mw) of 5,000 to 80,000.

2. The modified hydrogenated block copolymer for electrical and electronic parts according to 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.

3. The modified hydrogenated block copolymer for electrical and electronic parts according to claim 1 or 2, wherein the modification rate with the unsaturated carboxylic acid and / or the unsaturated carboxylic acid anhydride is 0.1 to 2% by mass.

4. The modified hydrogenated block copolymer for electrical and electronic parts according to any one of claims 1 to 3, wherein the unsaturated carboxylic acid and / or the unsaturated carboxylic acid anhydride is maleic anhydride.

5. A modified hydrogenated block copolymer solution or a modified hydrogenated block copolymer slurry for electrical and electronic parts, wherein the modified hydrogenated block copolymer for electrical and electronic parts according to any one of claims 1 to 4 is dissolved or suspended in an organic solvent at a concentration of 1 to 30% by mass.

6. A modified hydrogenated block copolymer-containing laminate for electrical and electronic parts, wherein the modified hydrogenated block copolymer for electrical and electronic parts according to any one of claims 1 to 4 is laminated on a substrate.

7. The modified hydrogenated block copolymer-containing laminate for electrical and electronic parts according to claim 6, wherein the modified hydrogenated block copolymer for electrical and electronic parts is melt coextruded with one or more other thermoplastic resins.

8. The modified hydrogenated block copolymer for electrical and electronic components is thermally laminated onto metal, paper, ceramics, a thermoplastic resin, or a thermosetting resin. The laminated body containing the modified hydrogenated block copolymer for electrical and electronic components according to claim 6.

9. The laminated body containing the modified hydrogenated block copolymer for electrical and electronic components according to claim 8, wherein the thickness of the layer containing the modified hydrogenated block copolymer for electrical and electronic components is 5 to 500 μm.

10. A method for manufacturing a modified hydrogenated block copolymer for electrical and electronic components according to any one of claims 1 to 4, The method for manufacturing a modified hydrogenated block copolymer for electrical and electronic components, wherein the hydrogenated block copolymer is graft-modified by any method of melt kneading, reaction in solution, or solid-phase grafting.

11. A method for manufacturing a modified hydrogenated block copolymer for electrical and electronic components according to any one of claims 1 to 4, The method for manufacturing a modified hydrogenated block copolymer for electrical and electronic components, wherein the hydrogenated block copolymer is graft-modified with an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride.

12. A method for manufacturing a laminated body containing a modified hydrogenated block copolymer for electrical and electronic components, wherein a solution or slurry of the modified hydrogenated block copolymer for electrical and electronic components according to claim 5 is applied to a substrate, and then the solvent is removed to obtain the laminated body.

13. The method for manufacturing a laminated body containing a modified hydrogenated block copolymer for electrical and electronic components according to claim 12, wherein the thickness of the layer containing the modified hydrogenated block copolymer for electrical and electronic components is 1 to 100 μm.

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