THERMOPLASTIC POLYMER COMPOSITION AND MOLDED ARTICLE

Abstract

To provide a thermoplastic polymer composition, which can be adhered to a synthetic resin, a ceramic or a metal without performing a primer treatment or the like, is able to be handled as a molded article, exhibits an excellent adhesive property in a broad temperature range from a low temperature to room temperature and flexibility, and has high thermal creep resistance, and a molded article using the thermoplastic polymer composition.

A thermoplastic polymer composition, which contains from 10 to 100 parts by weight of a polar group-containing polypropylene-based resin (B) based on 100 parts by weight of a hydrogenated block copolymer (A) in which block copolymer containing a polymer block (S) including an aromatic vinyl compound unit and a polymer block (D) including a conjugated diene compound unit is hydrogenated, in which the hydrogenated block copolymer (A) is a mixture containing a hydrogenated block copolymer (A1) having at least one tan local maximum value in a range from 60 to 40 C., in which a block copolymer represented by formula (i) or (ii) shown below is hydrogenated:

(S-D).sub.n (i)

(D-S).sub.n-D (ii)

(in the formulae above, S is a polymer block including an aromatic vinyl compound unit, D is a polymer block including a conjugated diene compound unit, and n is an integer from 1 to 5); and a hydrogenated block copolymer (A2) in which a block copolymer represented by formula (iii) shown below is hydrogenated:

(S-D).sub.m-S (iii)

(in the formula above, S is a polymer block including an aromatic vinyl compound unit, D is a polymer block including a conjugated diene compound unit, and m is an integer from 1 to 5); and a weight ratio of the hydrogenated block copolymer (A1) to the hydrogenated block copolymer (A2) is from 20:80 to 99:1.

Claims

1. A thermoplastic polymer composition comprising from 10 to 100 parts by weight of a polar group-containing polypropylene-based resin (B) based on 100 parts by weight of a hydrogenated block copolymer (A) in which a block copolymer containing a polymer block (S) including an aromatic vinyl compound unit and a polymer block (D) including a conjugated diene compound unit is hydrogenated, wherein the hydrogenated block copolymer (A) is a mixture containing: a hydrogenated block copolymer (A1) having at least one tan local maximum value in a range from 60 to 40 C., in which a block copolymer represented by formula (i) or (ii) shown below is hydrogenated:
(S-D).sub.n (i)
(D-S).sub.n-D, (ii) wherein S is a polymer block including an aromatic vinyl compound unit, D is a polymer block including a conjugated diene compound unit, and n is an integer from 1 to 5; and a hydrogenated block copolymer (A2) in which a block copolymer represented by formula (iii) shown below is hydrogenated:
(S-D).sub.m-S, (iii) wherein S is a polymer block including an aromatic vinyl compound unit, D is a polymer block including a conjugated diene compound unit, and m is an integer from 1 to 5, and wherein a weight ratio of the hydrogenated block copolymer (A1) to the hydrogenated block copolymer (A2) is from 20:80 to 99:1.

2. The thermoplastic polymer composition as claimed in claim 1, wherein at least a part of the hydrogenated block copolymer (A2) is a hydrogenated block copolymer (A2) in which a block copolymer represented by formula (iv) shown below is hydrogenated: (iv) (S-D2)m-S, wherein S is a polymer block including an aromatic vinyl compound unit, D2 is a polymer block including a conjugated diene compound unit, in which a total amount of a 1,2-bonding content and a 3,4-bonding content is 40% by mole or more based on a total content of whole bonding forms of the conjugated diene, and m is an integer from 1 to 5.

3. The thermoplastic polymer composition as claimed in claim 2, wherein a content ratio of the hydrogenated block copolymer (A2) is from 20 to 100% by weight in the hydrogenated block copolymer (A2).

4. The thermoplastic polymer composition as claimed in claim 1, wherein the polymer block (D) including a conjugated diene compound unit contained in the hydrogenated block copolymer (A1) is a polymer block containing a conjugated diene compound in which a total amount of a 1, 2-bonding amount and a 3,4-bonding amount is less than 40% by mole based on a total amount of whole bonding forms of the conjugated diene.

5. The thermoplastic polymer composition as claimed in claim 1, wherein the hydrogenated block copolymer (A1) is a hydrogenated block copolymer in which a diblock copolymer represented by a formula shown below is hydrogenated:
S-D, wherein S and D have the same meanings as defined above, respectively.

6. The thermoplastic polymer composition as claimed in claim 1, wherein the conjugated diene compound unit is an isoprene unit or a mixture unit of isoprene and butadiene.

7. The thermoplastic polymer composition as claimed in claim 1, wherein the polar group-containing polypropylene-based resin (B) is a carboxylic acid-modified polypropylene-based resin.

8. The thermoplastic polymer composition as claimed in claim 1, further comprising from 10 to 100 parts by weight of a polyvinyl acetal resin (C).

9. The thermoplastic polymer composition as claimed in claim 8, wherein the polyvinyl acetal resin (C) is a polyvinyl butyral resin.

10. A molded article using the thermoplastic polymer composition as claimed in claim 1.

11. The molded article as claimed in claim 10, wherein the thermoplastic polymer composition is adhered to at least one selected from a ceramic, a metal and a synthetic resin.

12. The molded article as claimed in claim 11, wherein the thermoplastic polymer composition is adhered to at least two selected from a ceramic, a metal and a synthetic resin.

Description

EXAMPLES

[0155] The invention will be described more specifically with reference to the examples and the like, but the invention should not be construed as being limited thereto.

[0156] Each component used in the examples and comparative examples is shown below. Moreover, the weight average molecular weight, molecular weight distribution, hydrogenation rate of the hydrogenated block copolymer (A), the total amount of a 1,2-bonding content and a 3,4-bond content contained in the conjugated diene block, and the tan are determined in the manner shown below.

Weight Average Molecular Weight and Molecular Weight Distribution

[0157] The weight average molecular weight (Mw) and number average molecular weight (Mn) were determined by gel permeation chromatography (GPC) measurement and calculated in terms of standard polystyrene, and then the molecular weight distribution (Mw/Mn) was calculated.

Hydrogenation Rate

[0158] The hydrogenation rate was determined by measuring an iodine value of the block copolymer before and after the hydrogenation reaction. Total Amount of 1,2-Bonding Content and 3,4-Bonding Content

[0159] It was calculated from a ratio of an integrated value of the peaks present in 4.2 to 5.0 ppm derived from the 1,2-bonding unit and the 3,4-bonding unit and an integrated value of the peaks present in 5.0 to 5.45 ppm derived from the 1,4-bonding unit. tan

[0160] Each hydrogenated block copolymer was molded into a sheet having a thickness of 1 mm, set to be a width of 1 cm and a length of 2 cm in Rheovibron (produced by Orientec Co., Ltd.), and tan was measured by increasing temperature from 150 to 200 C. at a rate of 3 C./minute while applying tensile strain at a frequency of 11 Hz, thereby determining the temperature at the local maximum value derived from the conjugated diene block (D).

[Hydrogenated Block Copolymer (A)]

Hydrogenated Block Copolymer (A1-1)

[0161] Into a dried pressure vessel purged with nitrogen, 80 L of cyclohexane as a solvent and 0.16 L of sec-butyllithium (10% by weight cyclohexane solution) as an initiator were charged. After increasing the temperature to 50 C., 8.2 L of styrene was added to allow polymerization for 3 hours. Subsequently, 18 L of isoprene was added thereto to allow polymerization for 4 hours. The reaction solution obtained was poured into 80 L of methanol, and the solid deposited was separated by filtration and dried at 50 C. for 20 hours to obtain a polystyrene-polyisoprene diblock copolymer.

[0162] Then, 10 kg of the polystyrene-polyisoprene diblock copolymer was dissolved in 200 L of cyclohexane, and after adding palladium carbon (palladium supporting amount: 5% by weight) as a hydrogenation catalyst in an amount of 5% by weight based on the copolymer, the reaction was performed under conditions of a hydrogen pressure of 2 MPa and 50 C. for 10 hours. After allowing to cooling and depressurization, the palladium carbon was removed by filtration, and the filtrate was concentrated and then vacuum-dried to obtain a hydrogenated product of the polystyrene-polyisoprene diblock copolymer (hereinafter referred to as Hydrogenated block copolymer (A1-1)). Hydrogenated block copolymer (A1-1) obtained had a weight average molecular weight of 133,000, a styrene content of 37.5% by weight, a hydrogenation rate of 99%, a molecular weight distribution of 1.04, a total amount of a 1,2-bonding content and a 3,4-bonding content contained in the polyisoprene block of 5% by mole, and a tan local maximum value of 44 C.

Hydrogenated Block Copolymer (A1-2)

[0163] Into a dried pressure vessel purged with nitrogen, 80 L of cyclohexane as a solvent and 3.0 L of sec-butyllithium (10% by weight cyclohexane solution) as an initiator were charged. After increasing the temperature to 50 C., 14.6 L of styrene was added to allow polymerization for 3 hours. Subsequently, 130 L of isoprene was added thereto to allow polymerization for 4 hours. The reaction solution obtained was poured into 80 L of methanol, and the solid deposited was separated by filtration and dried at 50 C. for 20 hours to obtain a polystyrene-polyisoprene diblock copolymer.

[0164] Then, 10 kg of the polystyrene-polyisoprene diblock copolymer was dissolved in 200 L of cyclohexane, and after adding palladium carbon (palladium supporting amount: 5% by weight) as a hydrogenation catalyst in an amount of 5% by weight based on the copolymer, the reaction was performed under conditions of a hydrogen pressure of 2 MPa and 50 C. for 10 hours. After allowing to cooling and depressurization, the palladium carbon was removed by filtration, and the filtrate was concentrated and then vacuum-dried to obtain a hydrogenated product of the polystyrene-polyisoprene diblock copolymer (hereinafter referred to as Hydrogenated block copolymer (A1-2)). Hydrogenated block copolymer (A1-2) obtained had a weight average molecular weight of 43,000, a styrene content of 13% by weight, a hydrogenation rate of 98%, a molecular weight distribution of 1.04, a total amount of a 1,2-bonding content and a 3,4-bonding content contained in the polyisoprene block of 5% by mole, and a tan local maximum value of 51 C.

Hydrogenated Block Copolymer (A1-3)

[0165] Into a dried pressure vessel purged with nitrogen, 80 L of cyclohexane as a solvent and 0.46 L of sec-butyllithium (10% by weight cyclohexane solution) as an initiator were charged, and 0.25 L (corresponding to 5.4 times in a stoichiometric ratio to lithium atom in the initiator) of tetrahydrofuran as an organic Lewis base was charged therein. After increasing the temperature to 50 C., 3.5 L of styrene was added to allow polymerization for 3 hours. Subsequently, 34 L of butadiene was added thereto to allow polymerization for 4 hours. The reaction solution obtained was poured into 80 L of methanol, and the solid deposited was separated by filtration and dried at 50 C. for 20 hours to obtain a polystyrene-polybutadiene diblock copolymer.

[0166] Then, 10 kg of the polystyrene-polybutadiene diblock copolymer was dissolved in 200 L of cyclohexane, and after adding palladium carbon (palladium supporting amount: 5% by weight) as a hydrogenation catalyst in an amount of 5% by weight based on the copolymer, the reaction was performed under conditions of a hydrogen pressure of 2 MPa and 50 C. for 10 hours. After allowing to cooling and depressurization, the palladium carbon was removed by filtration, and the filtrate was concentrated and then vacuum-dried to obtain a hydrogenated product of the polystyrene-polybutadiene diblock copolymer (hereinafter referred to as Hydrogenated block copolymer (A1-3)). Hydrogenated block copolymer (A1-3) obtained had a weight average molecular weight of 70,500, a styrene content of 13% by weight, a hydrogenation rate of 98%, a molecular weight distribution of 1.05, a total amount of a 1,2-bonding content and a 3,4-bonding content contained in the polybutadiene block of 40% by mole, and a tan local maximum value of 43 C.

Hydrogenated Block Copolymer (A1-4)

[0167] Into a dried pressure vessel purged with nitrogen, 80 L of cyclohexane as a solvent and 1.1 L of sec-butyllithium (10% by weight cyclohexane solution) as an initiator were charged. After increasing the temperature to 50 C., 7.5 L of styrene was added to allow polymerization for 3 hours. Subsequently, a mixed solution of 13 L of isoprene and 15 liter of butadiene was added thereto to allow polymerization for 4 hours. The reaction solution obtained was poured into 80 L of methanol, and the solid deposited was separated by filtration and dried at 50 C. for 20 hours to obtain a polystyrene-poly(isoprene/butadiene) diblock copolymer.

[0168] Then, 10 kg of the polystyrene-poly(isoprene/butadiene) diblock copolymer was dissolved in 200 L of cyclohexane, and after adding palladium carbon (palladium supporting amount: 5% by weight) as a hydrogenation catalyst in an amount of 5% by weight based on the copolymer, the reaction was performed under conditions of a hydrogen pressure of 2 MPa and 50 C. for 10 hours. After allowing to cooling and depressurization, the palladium carbon was removed by filtration, and the filtrate was concentrated and then vacuum-dried to obtain a hydrogenated product of the polystyrene-poly(isoprene/butadiene) diblock copolymer (hereinafter referred to as Hydrogenated block copolymer (A1-4)). Hydrogenated block copolymer (A1-4) obtained had a weight average molecular weight of 46,000, a styrene content of 28% by weight, a hydrogenation rate of 98%, a molecular weight distribution of 1.05, a total amount of a 1,2-bonding content and a 3,4-bonding content contained in the poly(isoprene/butadiene) block of 5% by mole, and a tan local maximum value of 44 C.

Hydrogenated Block Copolymer (A1-1)

[0169] Into a dried pressure vessel purged with nitrogen, 80 L of cyclohexane as a solvent and 0.35 L of sec-butyllithium (10% by weight cyclohexane solution) as an initiator were charged, and 0.52 L (corresponding to 15 times in a stoichiometric ratio to lithium atom in the initiator) of tetrahydrofuran as an organic Lewis base was charged therein. After increasing the temperature to 50 C., 4.2 L of styrene was added to allow polymerization for 3 hours. Subsequently, 22 L of isoprene was added thereto to allow polymerization for 4 hours. The reaction solution obtained was poured into 80 L of methanol, and the solid deposited was separated by filtration and dried at 50 C. for 20 hours to obtain a polystyrene-polyisoprene diblock copolymer.

[0170] Then, 10 kg of the polystyrene-polyisoprene diblock copolymer was dissolved in 200 L of cyclohexane, and after adding palladium carbon (palladium supporting amount: 5% by weight) as a hydrogenation catalyst in an amount of 5% by weight based on the copolymer, the reaction was performed under conditions of a hydrogen pressure of 2 MPa and 50 C. for 10 hours. After allowing to cooling and depressurization, the palladium carbon was removed by filtration, and the filtrate was concentrated and then vacuum-dried to obtain a hydrogenated product of the polystyrene-polyisoprene diblock copolymer (hereinafter referred to as Hydrogenated block copolymer (A1-1)). Hydrogenated block copolymer (A1-1) obtained had a weight average molecular weight of 100,000, a styrene content of 20% by weight, a hydrogenation rate of 90%, a molecular weight distribution of 1.04, a total amount of a 1,2-bonding content and a 3,4-bonding content contained in the polyisoprene block of 60% by mole, and a tan local maximum value of 1.5 C.

Hydrogenated Block Copolymer (A2-1)

[0171] Into a dried pressure vessel purged with nitrogen, 80 L of cyclohexane as a solvent and 0.13 L of sec-butyllithium (10% by weight cyclohexane solution) as an initiator were charged. After raising the temperature to 50 C., 1.5 L of styrene was added to allow polymerization for 3 hours. Subsequently, 27 L of isoprene was added thereto to allow polymerization for 4 hours, and 1.5 L of styrene was further added thereto to allow polymerization for 3 hours. The reaction solution obtained was poured into 80 L of methanol, and the solid deposited was separated by filtration and dried at 50 C. for 20 hours to obtain a polystyrene-polyisoprene-polystyrene triblock copolymer.

[0172] Then, 10 kg of the polystyrene-polyisoprene-polystyrene triblock copolymer was dissolved in 200 L of cyclohexane, and after adding palladium carbon (palladium supporting amount: 5% by weight) as a hydrogenation catalyst in an amount of 5% by weight based on the copolymer, the reaction was performed under conditions of a hydrogen pressure of 2 MPa and 50 C. for 10 hours. After allowing to cooling and depressurization, the palladium carbon was removed by filtration, and the filtrate was concentrated and them vacuum-dried to obtain a hydrogenated product of the polystyrene-polyisoprene-polystyrene triblock copolymer (hereinafter referred to as Hydrogenated block copolymer (A2-1)). Hydrogenated block copolymer (A2-1) obtained had a weight average molecular weight of 183,000, a styrene content of 13% by weight, a hydrogenation rate of 98%, a molecular weight distribution of 1.01, a 1,4-bonding content contained in the polyisoprene block of 5% by mole, and a tan local maximum value of 51 C.

Hydrogenated Block Copolymer (A2-2)

[0173] Into a dried pressure vessel purged with nitrogen, 80 L of cyclohexane as a solvent and 0.23 L of sec-butyllithium (10% by weight cyclohexane solution) as an initiator were charged, and 0.13 L (corresponding to 5.4 times in a stoichiometric ratio to lithium atom in the initiator) of tetrahydrofuran as an organic Lewis base was charged therein. After increasing the temperature to 50 C., 1.7 L of styrene was added to allow polymerization for 3 hours. Subsequently, 34 L of butadiene was added thereto to allow polymerization for 4 hours, and 1.7 L of styrene was further added thereto to allow polymerization for 3 hours. The reaction solution obtained was poured into 80 L of methanol, and the solid deposited was separated by filtration and dried at 50 C. for 20 hours to obtain a polystyrene-polybutadiene-polystyrene triblock copolymer.

[0174] Then, 10 kg of the polystyrene-polybutadiene-polystyrene triblock copolymer was dissolved in 200 L of cyclohexane, and after adding palladium carbon (palladium supporting amount: 5% by weight) as a hydrogenation catalyst in an amount of 5% by weight based on the copolymer, the reaction was performed under conditions of a hydrogen pressure of 2 MPa and 50 C. for 10 hours. After allowing to cooling and depressurization, the palladium carbon was removed by filtration, and the filtrate was concentrated and then vacuum-dried to obtain a hydrogenated product of the polystyrene-polybutadiene-polystyrene triblock copolymer (hereinafter referred to as Hydrogenated block copolymer (A2-2)). Hydrogenated block copolymer (A2-2) obtained had a weight average molecular weight of 141,000, a styrene content of 13% by weight, a hydrogenation rate of 98%, a molecular weight distribution of 1.05, a total amount of a 1,2-bonding content and a 3,4-bonding content contained in the polybutadiene block of 40% by mole, and a tan local maximum value of 43 C.

Hydrogenated Block Copolymer (A2-3)

[0175] Into a dried pressure vessel purged with nitrogen, 80 L of cyclohexane as a solvent and 0.29 L of sec-butyllithium (10% by weight cyclohexane solution) as an initiator were charged. After increasing the temperature to 50 C., 2.3 L of styrene was added to allow polymerization for 3 hours. Subsequently, 28 L of isoprene was added thereto to allow polymerization for 4 hours, and 2.3 L of styrene was further added thereto to allow polymerization for 3 hours. The reaction solution obtained was poured into 80 L of methanol, and the solid deposited was separated by filtration and dried at 50 C. for 20 hours to obtain a polystyrene-polyisoprene-polystyrene triblock copolymer.

[0176] Then, 10 kg of the polystyrene-polyisoprene-polystyrene triblock copolymer was dissolved in 200 L of cyclohexane, and after adding palladium carbon (palladium supporting amount: 5% by weight) as a hydrogenation catalyst in an amount of 5% by weight based on the copolymer, the reaction was performed under conditions of a hydrogen pressure of 2 MPa and 50 C. for 10 hours. After allowing to cooling and depressurization, the palladium carbon was removed by filtration, and the filtrate was concentrated and then vacuum-dried to obtain a hydrogenated product of the polystyrene-polyisoprene-polystyrene triblock copolymer (hereinafter referred to as Hydrogenated block copolymer (A2-3)). Hydrogenated block copolymer (A2-3) obtained had a weight average molecular weight of 96,000, a styrene content of 18% by weight, a hydrogenation rate of 99%, a molecular weight distribution of 1.03, a 1,4-bonding content contained in the polyisoprene block of 5% by mole, and a tan local maximum value of 47 C.

Hydrogenated Block Copolymer (A2-4)

[0177] Into a dried pressure vessel purged with nitrogen, 80 L of cyclohexane as a solvent and 0.55 L of sec-butyllithium (10% by weight cyclohexane solution) as an initiator were charged. After increasing the temperature to 50 C., 3.8 L of styrene was added to allow polymerization for 3 hours. Subsequently, a mixed solution of 13 L of isoprene and 15 liter of butadiene was added thereto to allow polymerization for 4 hours, and 3.8 L of styrene was further added thereto to allow polymerization for 3 hours. The reaction solution obtained was poured into 80 L of methanol, and the solid deposited was separated by filtration and dried at 50 C. for 20 hours to obtain a polystyrene-poly(isoprene/butadiene)-polystyrene triblock copolymer.

[0178] Then, 10 kg of the polystyrene-poly(isoprene/butadiene)-polystyrene triblock copolymer was dissolved in 200 L of cyclohexane, and after adding palladium carbon (palladium supporting amount: 5% by weight) as a hydrogenation catalyst in an amount of 5% by weight based on the copolymer, the reaction was performed under conditions of a hydrogen pressure of 2 MPa and 50 C. for 10 hours. After allowing to cooling and depressurization, the palladium carbon was removed by filtration, and the filtrate was concentrated and then vacuum-dried to obtain a hydrogenated product of the polystyrene-poly(isoprene/butadiene)-polystyrene triblock copolymer (hereinafter referred to as Hydrogenated block copolymer (A2-4)). Hydrogenated block copolymer (A2-4) obtained had a weight average molecular weight of 92,000, a styrene content of 28% by weight, a hydrogenation rate of 99%, a molecular weight distribution of 1.03, a total amount of a 1,2-bonding content and a 3,4-bonding content contained in the poly(isoprene/butadiene) block of 5% by mole, and a tan local maximum value of 44 C.

Hydrogenated Block Copolymer (A2-5)

[0179] Into a dried pressure vessel purged with nitrogen, 64 L of cyclohexane as a solvent and 0.15 L of sec-butyllithium (10% by weight cyclohexane solution) as an initiator were charged, and 0.3 L (corresponding to 15 times in a stoichiometric ratio to lithium atom in the initiator) of tetrahydrofuran as an organic Lewis base was charged therein. After increasing the temperature to 50 C., 2.3 L of styrene was added to allow polymerization for 3 hours. Subsequently, 23 L of isoprene was added thereto to allow polymerization for 4 hours, and 2.3 L of styrene was further added thereto to allow polymerization for 3 hours. The reaction solution obtained was poured into 80 L of methanol, and the solid deposited was separated by filtration and dried at 50 C. for 20 hours to obtain a polystyrene-polyisoprene-polystyrene triblock copolymer.

[0180] Then, 10 kg of the polystyrene-polyisoprene-polystyrene triblock copolymer was dissolved in 200 L of cyclohexane, and after adding palladium carbon (palladium supporting amount: 5% by weight) as a hydrogenation catalyst in an amount of 5% by weight based on the copolymer, the reaction was performed under conditions of a hydrogen pressure of 2 MPa and 50 C. for 10 hours. After allowing to cooling and depressurization, the palladium carbon was removed by filtration, and the filtrate was concentrated and then vacuum-dried to obtain a hydrogenated product of the polystyrene-polyisoprene-polystyrene triblock copolymer (hereinafter referred to as Hydrogenated block copolymer (A2-5)). Hydrogenated block copolymer (A2-5) obtained had a weight average molecular weight of 107,000, a styrene content of 21% by weight, a hydrogenation rate of 85%, a molecular weight distribution of 1.04, a total amount of a 1,2-bonding content and a 3,4-bonding content contained in the polyisoprene block of 60% by mole, and a tan local maximum value of 4.2 C.

[Polar Group-Containing Polypropylene-Based Resin (B)]

(B-1)

[0181] Using a batch mixer, 42 g of polypropylene Prime Polypro F327 (produced by Prime Polymer Co., Ltd.), 160 mg of maleic anhydride and 42 mg of 2,5-dimethyl-2,5-di(tertiary butylperoxy)hexane were melt-kneaded under the conditions of 180 C. and the number of revolution of a screw of 40 rpm to obtain Polar group-containing polypropylene-based resin (B-1). Polar group-containing polypropylene-based resin (B-1) obtained had MFR [230 C., load of 2.16 kg (21.18 N)] of 6 g/10 minutes, a maleic anhydride concentration of 0.3%, and a melting point of 138 C.

[0182] The maleic anhydride concentration is a value obtained by titrating Polar group-containing polypropylene-based resin (B-1) obtained with a methanol solution of potassium hydroxide, and hereinafter the same. The melting point is a value read from an endothermic peak of a differential scanning calorimetry curve when increasing a temperature in a rate of 10 C./minute.

[Polyvinyl Acetal Resin (C)]

(C-1)

[0183] To an aqueous solution prepared by dissolving 10 parts by weight of polyvinyl alcohol having an average polymerization degree of 500 and a saponification degree of 99% by mole, 7 parts by weight of n-butylaldehyde and 8.5 parts by weight of an aqueous 35% hydrochloric acid were added and stirred to perform an acetalization reaction, thereby depositing a resin. The resin was washed by a known method until the pH value reached 6. Then, the resin was suspended in an aqueous alkaline medium and post-treated with stirring. The resin was washed until the pH value reached 7 and dried until the volatile component was reduced to 0.3% or less to obtain Polyvinyl acetal resin (C-1) having an acetalization degree of 80% by mole.

[Other Component]

[0184] Tackifying resin: Regalite 1100 (produced by Eastman Chemical Co.)

[0185] Preparation of test pieces in the examples and comparative examples and measurement or evaluation of each physical property were performed as shown below.

(1) Measurement of Melt Flow Rate (MFR)

[0186] A sheet of the thermoplastic polymer composition prepared in each of the examples and comparative examples shown below was finely cut, and MFR was measured under the conditions of 230 C. and load of 2.16 kg (21.18 N) by the method in accordance with JIS K 7210. The MFR was used as an index of the moldability. As the value of MFR increases, the moldability becomes excellent.

(2) Measurement of Hardness

[0187] Sheets of the thermoplastic polymer composition prepared in each of the examples and comparative examples shown below were piled to a thickness of 6 mm, and Type A hardness was measured using a Type A Durometer in accordance with JIS K 6253.

(3) Tensile Break Strength and Tensile Elongation at Break

[0188] A dumbbell shape test piece (dumbbell shape No. 5) was prepared from a sheet of the thermoplastic polymer composition prepared in each of the examples and comparative examples shown below and tensile break strength and tensile elongation at break were measured at 23 C. and a tensile speed of 500 mm/minute by the method in accordance with JIS K 6251.

(4) Measurement of Adhesive Force

[0189] As to a laminate of PET/thermoplastic polymer composition/glass plate, a laminate of PET/thermoplastic polymer composition/aluminum plate and a laminate of PET/thermoplastic polymer composition/6-nylon, prepared by the method described below, peel strengths between the thermoplastic polymer composition layer and the glass plate, between the thermoplastic polymer composition layer and the aluminum plate and between the thermoplastic polymer composition layer and the 6-nylon were measured respectively under the conditions of a peel angle of 180, a tensile rate of 50 mm/minute and at an ambient temperature shown in Table 2 in accordance with JIS K 6854-2, thereby determining the adhesive force.

(5) Creep Test

[0190] The thermoplastic polymer composition was molded into a sheet having a thickness of 1 mm and cut into a size of 10 mm10 mm. The sheet was sandwiched between two steel plates each having a width of 10 mm and a length of 50 mm to pile so that an adhesive area of 10 mm10 mm was formed, followed by adhering them together at 180 C. and 0.01 MPa for 2 seconds. One end of the adhesive body obtained was grasped with a clip to be hung the adhesive body lengthwise, allowed to stand at 150 C. for 60 minutes, and after taking it out the displacement of the steel plates was measured to evaluate as an index of the thermal creep resistance.

(6) Storage Modulus

[0191] The thermoplastic polymer composition was molded into a sheet having a thickness of 1 mm, and set to be a width of 1 cm and a length of 2 cm in Rheovibron (produced by Orientec Co., Ltd.). Temperature was increased from 150 to 200 C. at a rate of 2 C./minute while applying tensile strain at a frequency of 11 Hz, and storage modules at 40 C. was measured to evaluate as an index of flexibility at low temperature. When the storage modules is less than 1.5 GPa, the flexibility is recognized, and when the storage modules is less than 0.5 GPa, the flexibility is excellent.

<Preparation of Laminate with Glass Plate>

[0192] Both surfaces of a glass plate having a length of 75 mm, a width of 25 mm and a thickness of 1 mm were cleaned with an aqueous solution of surfactant, methanol, acetone and distilled water as cleaning solutions in this order, and dried. The glass plate, a sheet of the thermoplastic polymer composition prepared in each of the examples and comparative examples shown below and a polyethylene terephthalate (PET) sheet having a thickness of 50 were piled in this order, and the resulting piled sheet was arranged in the central part of a metal spacer having an outer size of 200 mm200 mm, an inner size of 150 mm150 mm and a thickness of 2 mm.

[0193] The piled sheet and the metal spacer were sandwiched between polytetrafluoroethylene sheets, and further sandwiched with metal plates from the outside. The resulting piled product was subjected to compression molding using a compression molding machine at 160 C. and under a load of 20 kgf/cm.sup.2 (2N/mm.sup.2) for 3 minutes to obtain a laminate of PET/thermoplastic polymer composition/glass plate.

<Preparation of Laminate with Aluminum Plate>

[0194] A laminate of PET/thermoplastic polymer composition/aluminum plate was obtained by performing the same operations as in the preparation of the laminate with glass plate, except that both surfaces of an aluminum plate having a length of 75 mm, a width of 25 mm and a thickness of 1 mm were cleaned with an aqueous solution of surfactant and distilled water as cleaning solutions in this order, and dried.

<Preparation of Laminate with 6-Nylon>

[0195] A laminate of PET/thermoplastic polymer composition/6-nylon was obtained by performing the same operations as in the preparation of the laminate with glass plate, except that 6-nylon 1013B (produced by Ube Industries, Ltd.) was injection molded into a sheet form having a thickness of 1 mm and the sheet was cut into a size having a length of 75 mm, a width of 25 mm and a thickness of 1 mm and that the sheet was subjected to compression molding using a compression molding machine at 230 C. and under a load of 20 kgf/cm.sup.2 (2N/mm.sup.2) for 3 minutes.

<Examples 1 to 8 and Comparative Examples 1 to 7>

[0196] The raw materials shown in Table 1 were melt-kneaded in the proportions shown in Table 2 (weight ratio) using a twin-screw extruder under the conditions of 230 C. and screw revolution of 200 rpm, and then extruded in a strand form. The strand-formed material was cut to obtain pellets of the thermoplastic polymer composition. The pellets obtained were compression molded using a compression molding machine under the conditions of 230 C. and a load of 100 kgf/cm.sup.2 (9.8N/mm.sup.2) for 3 minutes, thereby obtaining a sheet of the thermoplastic polymer composition having a thickness of 1 mm was obtained.

[0197] According to the measuring methods described above, the MFR, hardness, tensile break strength and tensile elongation at break of the sheet of the thermoplastic polymer composition obtained were measured. Moreover, the adhesive force between the thermoplastic polymer composition obtained and the glass plate, the aluminum plate or the 6-nylon was measured according to the method described above. Furthermore, the thermal creep resistance and the flexibility at low temperature (storage modules) of the thermoplastic polymer composition obtained were measured according to the method described above. The results are shown in Table 2.

TABLE-US-00001 TABLE 1 St tan Local Hydrogenated Polymer Skeleton (before Content Hydrogenation Degree of Maximum Value Block Copolymer Hydrogenation).sup.(*.sup.1) Mw (%) Rate Mw/Mn Vinylation.sup.(*2) ( C.) A1-1 S-I 133,000 37.5 99 1.04 5 44 A1-2 S-I 43,000 13 98 1.04 5 51 A1-3 S-B 70,500 13 98 1.05 40 43 A1-4 S-I/B 46,000 28 98 1.05 5 44 A1-1 S-I 100,000 20 90 1.04 60 1.5 A2-1 S-I-S 183,000 13 98 1.01 5 51 A2-2 S-B-S 141,000 13 98 1.05 40 43 A2-3 S-I-S 96,000 18 99 1.03 5 47 A2-4 S-I/B-S 92,000 28 99 1.03 5 44 A2-5 S-I-S 107,000 21 85 1.04 60 4.2 .sup.(*.sup.1)S-I: Styrene-isoprene diblock copolymer S-B: Styrene-butadiene diblock copolymer S-I/B: Styrene-isoprene/butadiene diblock copolymer S-I-S: Styrene-isoprene-styrene triblock copolymer S-B-S: Styrene-butadiene-styrene triblock copolymer S-I/B-S: Styrene-isoprene/butadiene-styrene triblock copolymer .sup.(*.sup.2)Total amount of 1,2-bonding content and 3,4-bonding content (% by mole)

TABLE-US-00002 TABLE 2 Example Example Example Example Example Example Example Example 1 2 3 4 5 6 7 8 Component Contained Block Copolymer A1-1 pbw 50 50 A1-2 pbw 50 25 25 50 A1-3 pbw 50 A1-4 pbw 50 A1-1 pbw A2-1 pbw 50 25 25 50 A2-2 pbw 50 A2-3 pbw 50 A2-4 pbw 50 A2-5 pbw 50 50 50 Polar B-1 pbw 25 25 25 25 25 25 25 25 Group-containing Polypropylene-based Resin Polyvinyl Acetal C-1 pbw 20 20 Resin Tackifying Resin Regalite pbw 1100 Physical Property MFR g/10 minutes 4.5 5.3 5.6 1.0 0.5 4.3 4.6 0.8 [230 C., 2.16 kg] Hardness Type A 50 64 65 80 77 69 53 79 Tensile Break MPa 10.5 9.7 9 20 6.7 12.5 10.8 6.9 Strength Tensile Elongation at % 600 720 600 500 510 920 780 500 Break Adhesive Force to N/25 mm 116 45 42 70 200 100 120 200 Aluminum (23 C.) Adhesive Force to N/25 mm 96 94 130 100 200 150 100 200 Aluminum (40 C.) Adhesive Force to N/25 mm 70 50 60 50 126 70 75 130 6-nylon (23 C.) Initial Adhesive N/25 mm 0 0 0 0 0 0 100 180 Force to Glass (23 C., after 10 Minutes) Adhesive Force to N/25 mm 45 50 40 75 180 105 110 190 Glass (23 C., after 10 Days) Creep Test (150 C.) mm 1 1 3 1 0 1 1 0 Storage Modules GPa 0.07 0.07 0.08 0.3 1.1 0.85 0.07 1.1 (40 C.) Comparative Comparative Comparative Comparative Comparative Comparative Comparative Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Component Contained Block Copolymer A1-1 pbw 100 A1-2 pbw 50 50 A1-3 pbw A1-4 pbw A1-1 pbw 50 A2-1 pbw 50 50 50 A2-2 pbw A2-3 pbw 50 100 A2-4 pbw A2-5 pbw 100 50 Polar B-1 pbw 25 25 25 25 25 Group-containing Polypropylene-based Resin Polyvinyl Acetal C-1 pbw Resin Tackifying Resin Regalite pbw 100 1100 Physical Property MFR g/10 minutes 7 100< 10 5 5.8 5.2 0.3 [230 C., 2.16 kg] Hardness Type A 36 16 73 75 77 74 77 Tensile Break MPa 10.8 11 15 23 23 2 Strength Tensile Elongation % 1,200 1,100< 500 680 730 670 100 at Break Adhesive Force to N/25 mm 3 34 150 167 16 3 Unmeasurable Aluminum (23 C.) Adhesive Force to N/25 mm 3 20 Brittle Brittle 20 3 Unmeasurable Aluminum (40 C.) Fracture Fracture Adhesive Force to N/25 mm 5 5 100 104 20 7 Unmeasurable 6-nylon (23 C.) Initial Adhesive N/25 mm 2 20 0 0 0 0 Unmeasurable Force to Glass (23 C., after 10 Minutes) Adhesive Force to N/25 mm 3 20 120 175 15 0 Unmeasurable Glass (23 C., after 1 Days) Creep Test (150 C.) mm Fallen Fallen 1 0 Fallen Fallen 1 Storage Modules GPa 0.009 1.0 1.9 1.9 0.9 0.08 0.07 (40 C.)

[0198] In all of Examples 1 to 8, the flexibility is excellent in a broad temperature range, the good adhesive property to all of glass, aluminum and 6-nylon is achieved, and the moldability, mechanical properties and thermal creep resistance are excellent. In Examples 1, 2 and 4 to 8 each using an isoprene monomer or an isoprene/butadiene monomer in the conjugated diene block (D) of the hydrogenated block copolymer (A1), the displacement in the creep test is slight, and in particular, it can be seen that the thermal creep resistance is excellent. Moreover, in Examples 5 and 8 each using (A2) as the hydrogenated block copolymer (A2), the adhesive property to various adherends and the thermal creep resistance are particularly well balanced. Furthermore, in Examples 7 and 8 each containing the polyvinyl acetal resin (C-1), the adhesive force to glass was expressed immediately after the adhesion.

[0199] On the other hand, in Comparative Example 1 not containing the polar group-containing polypropylene-based resin (B), the adhesive property is not expressed. In Comparative Example 2 using the tackifying resin, the adhesive force is still insufficient, and particularly, the adhesive property to 6-nylon is poor. Moreover, the thermal creep resistance was poor and the steel plate had fallen during the creep test. Furthermore, since it is a sticky material, it is not suitable for use as a molded article. In Comparative Example 3 using (A1-1) in place of (A1) and in Comparative Example 4 in which the component (A) is only composed of the component (A2), embrittlement at low temperature is severe and the thermoplastic polymer composition had caused the brittle fracture during the adhesion test at 40 C., although the adhesive performance is obtained. In Comparative Examples 5 and 6 in which the component (A1) was not used but only the component (A2) was used similar to Comparative Example 4, the adhesive force was insufficient and in addition, the thermal creep resistance was poor and the steel plate had fallen during the creep test. In Comparative Example 7 not containing the component (A2), the tensile break strength is significantly low. Since the test piece is very brittle, the test piece was broken at the time of separation in the adhesive force measurement and the measurement could not be performed.

INDUSTRIAL APPLICABILITY

[0200] Since the thermoplastic polymer composition according to the invention is excellent in the flexibility in a broad temperature range and is excellent in the adhesive force, the joined body which is adhered using the composition can absorb a variety of impact due to the flexibility of the adhesive layer and, in addition, in the case where different materials are adhered, it absorbs the distortion stress which is generated based on the difference between the respective linear expansion coefficients. Therefore, the joined body is able to be used under severe conditions, for example, under low temperature, under high temperature or in an environment of violent temperature change.

[0201] Moreover, the thermoplastic polymer composition itself is able to be molded into an arbitrary molded article, for example, a film form, a sheet form or a three-dimensional form. Since the molded article is easy to handle different from a tacky material or a liquid adhesive, it is useful for improving productivity of the joined body.

[0202] Utilizing the characteristics described above, the thermoplastic polymer composition and molded article of the invention can be used in a wide range of various applications, for example, automobile parts, home appliances, computer parts, machine parts, packings, gaskets and hoses.

[0203] While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention.

[0204] This application is based on a Japanese patent application filed on Aug. 26, 2014 (Japanese Patent Application No. 2014-172062), and the contents thereof are incorporated herein by reference.