Ethylene-α-olefin copolymer having a hydroxyl group at its terminus and method for producing the same

Abstract

The object of the present invention is to provide a novel terminal hydroxyethylene-α-olefin copolymer that is liquid at room temperature and exhibits good compatibility with various resins. [Solution] The present invention provides a terminal hydroxyethylene-α-olefin copolymer (Z) having a hydroxyl group at the end of an ethylene-α-olefin copolymer (A) having a constituent unit (i) derived from ethylene and a constituent unit (ii) derived from an α-olefin having 3 to 10 carbon atoms, and satisfying the following requirements (Z1) and (Z2); (Z1) 1 Excluding saturated ends determined by 1H-NMR, more than 60% of all ends contain two or more hydroxyl groups; (Z2) The melting point measured by differential scanning calorimetry (DSC) is not observed.

Description

[Technical Field]

[0001] This invention relates to an ethylene-α-olefin copolymer having a hydroxyl group at its terminus and a method for producing the ethylene-α-olefin copolymer. [Background technology]

[0002] Among polyolefins, ethylene-α-olefin copolymers, when added in small amounts to polyolefin resins, exhibit the effect of improving properties such as impact resistance, durability, abrasion resistance, and flexibility. For example, as described in Patent Document 1, low molecular weight liquid ethylene-α-olefin copolymers impart excellent low-temperature properties and shear stability when added to hydrocarbon-based lubricants such as mineral oil. Generally, high affinity between the additive and the base material is important for exhibiting such properties. However, because the molecular structure of polyolefins is nonpolar, it has been difficult to add them to polar synthetic resins such as acrylic and ester resins. For this reason, functionalization of polyolefins has been practiced for a long time, employing methods such as radical grafting reactions using organic peroxides, and introducing functional groups through various organic reactions after controlling the terminals to unsaturated bond groups. In the latter method, since polyolefins are crystalline, they are mostly in a solid state, and the functional groups that can be introduced are limited. Patent Document 1 discloses that a liquid ethylene-α-olefin copolymer is used to adjust the viscosity of lubricating oil, but it does not describe the introduction of polar groups such as hydroxyl groups into the liquid ethylene-α-olefin copolymer. Patent Document 2 describes the control of vinyl groups at the ends of polyethylene, the introduction of functional groups starting from this control, and the synthesis of block polymers with different monomers. Because the main chain of the polymer is polyethylene, it has high crystallinity and the resulting polymer is solid. Furthermore, in Patent Document 2, it is necessary to perform epoxidation under extreme reaction conditions in order to dissolve the polyethylene. In Patent Document 3, a hydroxy-terminated ethylene-based random copolymer that is liquid at room temperature is disclosed. Since hydroxy groups are introduced by a hydroboration reaction using a terminal vinylidene ethylene-α-olefin copolymer, it is not possible to introduce a plurality of hydroxy groups into one polymer molecule. Therefore, further improvement is required from the viewpoint of imparting polarity.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0004] The present invention provides a terminal hydroxyethylene-α-olefin copolymer that exhibits good compatibility with various resins and has no observed melting point, and a method for producing the same.

Means for Solving the Problems

[0005] The present invention is based on the finding that by introducing a terminal having two or more hydroxy groups at the terminal of an ethylene-α-olefin copolymer having a constitutional unit (i) derived from ethylene and a constitutional unit (ii) derived from an α-olefin having 3 to 10 carbon atoms, an additive having excellent dispersibility in various synthetic resins including (meth)acrylic copolymers can be obtained. Each aspect of the present invention will be described below.

[0006] [1] At the terminal of an ethylene-α-olefin copolymer (A) having a constitutional unit (i) derived from ethylene and a constitutional unit (ii) derived from an α-olefin having 3 to 10 carbon atoms, it has a terminal having a hydroxy group, A terminal hydroxyethylene-α-olefin copolymer (Z) that satisfies the following requirements (Z1) and (Z2); (Z1) 1 Excluding saturated ends determined by 1H-NMR, more than 60% of all ends contain two or more hydroxyl groups; (Z2) The melting point measured by differential scanning calorimetry (DSC) is not observed. [2] A terminal hydroxyethylene-α-olefin copolymer (Z) as described in [1] above, which further satisfies the following requirements (Z3) to (Z5); (Z3) With respect to a total of 100 mol% of the content of constituent unit (i) and constituent unit (ii), the content of constituent unit (i) is 30 to 70 mol%, and the content of constituent unit (ii) is 30 to 70 mol%; (Z4) The number-average molecular weight (Mn) obtained by gel permeation chromatography (GPC) and converted to polystyrene equivalent is 300 to 10,000; (Z5) The ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) obtained by gel permeation chromatography (GPC) and converted to polystyrene equivalent (Mw / Mn) is between 1.5 and 5.0. [3] A terminal hydroxyethylene-α-olefin copolymer (Z) as described in [1] or [2] above, further satisfying the following requirement (Z6); (Z6) 1 At least 60% of all ends, excluding the saturated ends determined by 1H-NMR, must contain at least the following general formula (1). ―N(-R 1 -OH)(-R 2 -OH) General formula (1) (In the formula, R 1 , R 2 (It is a divalent organic group with 1 to 6 carbon atoms.) [4] A terminal hydroxyethylene-α-olefin copolymer (Z) as described in [1] or [2] above, further satisfying the following requirement (Z7); (Z7) 1More than 60% of all the terminals excluding the saturated terminals determined by 1H-NMR are terminals containing at least the following general formula (2). -S-CH2-R 3 General formula (2) (In the formula, R 3 is an organic group having 2 to 5 hydroxy groups.) [5] A method for producing a terminal hydroxyethylene-α-olefin copolymer (Z) that satisfies the following requirements (Z1) and (Z2), wherein an ethylene-α-olefin copolymer (A) having a structural unit (i) derived from ethylene and a structural unit (ii) derived from an α-olefin having 3 to 10 carbon atoms is reacted with a low molecular weight compound in one or more than two steps; (Z1) 1 More than 60% of all the terminals excluding the saturated terminals determined by 1H-NMR are terminals containing two or more hydroxy groups; (Z2) No melting point is observed by differential scanning calorimetry (DSC). [6] The method for producing the terminal hydroxyethylene-α-olefin copolymer (Z) according to the above [5], wherein the ethylene-α-olefin copolymer (A) satisfies the following requirements (A1) to (A3); (A1) Based on 100 mol% of the total content of the structural unit (i) and the structural unit (ii), the content of the structural unit (i) is 30 to 70 mol%, and the content of the structural unit (ii) is 30 to 70 mol%; (A2) Measured by gel permeation chromatography (GPC), the number average molecular weight (Mn) obtained in terms of polystyrene is 300 to 10,000; (A3) 1 Based on 100% of the total integrated intensity of the vinyl group terminal, vinylidene group terminal, 2-substituted olefin terminal and 3-substituted olefin terminal signals determined by 1H-NMR, the total integrated intensity of the vinyl group terminal and vinylidene group terminal is more than 70%. [7] A method for producing a terminalized hydroxyethylene-α-olefin copolymer (Z) according to [5] or [6] above, comprising converting both or either of the vinyl group terminals and vinylidene group terminals of an ethylene-α-olefin copolymer (A) to an epoxy-containing group, and then reacting the epoxy-containing group with a secondary amine having two hydroxyl groups, or reacting both or either of the vinyl group terminals and vinylidene group terminals of an ethylene-α-olefin copolymer (A) with a thiol compound having two or more hydroxyl groups to introduce a terminal having a hydroxyl group to the vinyl group terminal portion. [8] A method for producing the terminal hydroxyethylene-α-olefin copolymer (Z) described in [7] above, using a peroxide when converting either or both of the vinyl group and vinylidene group terminals to epoxy-containing groups. [9] A method for producing the terminal hydroxyethylene-α-olefin copolymer (Z) described in [7] or [8] above, wherein the secondary amine having a hydroxyl group is a compound represented by the following general formula (3). HN(-R 1 -OH)(-R 2 -OH) General formula (3) (In the formula, R 1 , R 2 These are R in the general formula (1) above. 1 , R 2 It is similar to this.

[10] A method for producing the terminal hydroxyethylene-α-olefin copolymer (Z) described in [7] above, wherein the thiol compound having a hydroxyl group is a compound represented by the following general formula (4). HS-R 3 General formula (4) (In the formula, R 3 R in the general formula (2) above is 3 It is similar to this.

[11] A resin composition comprising a (meth)acrylic resin or a thermosetting resin, and a terminal hydroxyethylene-α-olefin copolymer (Z) as described in any one of [1] to [4] above.

Advantages of the Invention

[0007] According to the present invention, it is possible to provide a terminal hydroxyethylene·α-olefin copolymer that exhibits good compatibility with various resins and has no observed melting point.

[0008] Hereinafter, the present invention will be described in more detail. In the present invention, "room temperature" means 25°C. In this specification, "~" indicating a numerical range is used to mean a range including the numerical values described before and after it as the lower limit value and the upper limit value. In this specification, when "~" indicating a numerical range is used, for example, when expressed as "M~N" (where M and N are numerical values satisfying M < N), unless otherwise specified, it means "M or more and N or less". Also, the unit described after either one of the numerical values before and after "~" is, unless otherwise specified, the unit of both the numerical values described before and after "~". Further, when the numerical range is described stepwise, the upper limit and the lower limit of each numerical range can be arbitrarily combined. In this specification, a combination of two or more preferred embodiments is a more preferred embodiment. In this specification, unless otherwise particularly limited, each component in the composition, or each structural unit in a polymer (polymer) such as a copolymer, may be included alone or in combination of two or more.

[0009] Terminal hydroxyethylene-α-olefin copolymer (Z) The terminal hydroxyethylene·α-olefin copolymer (Z) of the present invention has a structural unit (i) derived from ethylene and a structural unit (ii) derived from an α-olefin having 3 to 10 carbon atoms. Examples of the α-olefin having 3 to 10 carbon atoms of the structural unit (ii) include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, etc. Preferably, it is an α-olefin having 3 to 8 carbon atoms, more preferably an α-olefin having 3 to 5 carbon atoms, and even more preferably propylene. The content of these constituent units (i) and (ii) is arbitrary. Among these, it is preferable that the content of constituent unit (i) be 30 to 70 mol% (Requirement (Z3)), more preferably 35 to 65 mol%, more preferably 40 to 60 mol%, and even more preferably 45 to 55 mol%, based on a total of 100 mol%, and that the content of constituent unit (ii) be 30 to 70 mol% (Requirement (Z3)), more preferably 35 to 65 mol%, more preferably 40 to 60 mol%, and even more preferably 45 to 55 mol%. The combination of the lower and upper limits for the content of constituent unit (i) and constituent unit (ii) is arbitrary.

[0010] The terminal hydroxyethylene-α-olefin copolymer (Z) of the present invention is a copolymer that satisfies the following conditions (Z1) and (Z2). (Z1) 1 Excluding saturated ends determined by 1H-NMR, more than 60% of all ends contain two or more hydroxyl groups; (Z2) The melting point measured by differential scanning calorimetry (DSC) is not observed.

[0011] Regarding requirement (Z1) In the present invention, the terminal containing two or more hydroxyl groups is selected from all terminals of the terminal hydroxyethylene-α-olefin copolymer (Z), 1 The ends remaining after removing the saturated ends determined by 1H-NMR account for 60% or more of the total length (Requirement (Z1)). The upper limit is preferably 100%, more preferably 95%, and even more preferably 90%.

[0012] Regarding requirement (Z2) The terminal hydroxyethylene-α-olefin copolymer (Z) of the present invention does not exhibit a melting point as measured by differential scanning calorimetry (DSC). Here, "not observing the melting point (Tm)" means that the heat of fusion (ΔH) (unit: J / g) measured by differential scanning calorimetry (DSC) is not substantially measured. "Not substantially measuring the heat of fusion (ΔH)" means that no peak is observed in the differential scanning calorimetry (DSC) measurement, or the observed heat of fusion is 1 J / g or less.

[0013] Furthermore, the terminal hydroxyethylene-α-olefin copolymer (Z) of the present invention is preferably a copolymer that satisfies at least one of the following requirements (Z3) to (Z7). More preferably, it is a copolymer that satisfies at least two of the requirements (Z3) to (Z7), and even more preferably, it is a copolymer that satisfies at least three of the requirements (Z3) to (Z7). (Z3) With respect to a total of 100 mol% of the content of constituent unit (i) and constituent unit (ii), the content of constituent unit (i) is 30 to 70 mol%, and the content of constituent unit (ii) is 30 to 70 mol%; (Z4) The number-average molecular weight (Mn) obtained by gel permeation chromatography (GPC) and converted to polystyrene equivalent is 300 to 10,000; (Z5) The ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) obtained by gel permeation chromatography (GPC) and converted to polystyrene equivalent (Mw / Mn) is between 1.5 and 5.0. (Z6) 1 At least 60% of all ends, excluding the saturated ends determined by H-NMR, must contain at least the following general formula (1); ―N(-R 1 -OH)(-R 2 -OH) General formula (1) (In the formula, R 1 , R 2 (It is a divalent organic group with 1 to 6 carbon atoms.) (Z7) 1 At least 60% of all ends, excluding the saturated ends determined by 1H-NMR, must contain at least the following general formula (2). -S-CH2-R 3 General formula (2) (In the formula, R 3 (A hydroxyl group is an organic group that has 2 to 5 hydroxyl groups.) In the present invention, the terminal hydroxyethylene-α-olefin copolymer (Z) is preferably a copolymer that satisfies not only requirements (Z1) and (Z2) but also requirements (Z3) to (Z5) among the above embodiments. Furthermore, a copolymer that satisfies requirement (Z6) or requirement (Z7) is preferred. Requirements (Z4) through (Z7) are described below.

[0014] Regarding the requirements (Z4) The terminal hydroxyethylene-α-olefin copolymer (Z) is measured by gel permeation chromatography (GPC), and the number-average molecular weight (Mn) obtained in polystyrene terms is preferably 300 to 10,000, more preferably 400 to 8,000, more preferably 500 to 7,000, and particularly preferably 1,000 to 5,000. The combination of the lower and upper limits of the number-average molecular weight (Mn) is arbitrary.

[0015] Regarding the requirement (Z5) The terminal hydroxyethylene-α-olefin copolymer (Z) is measured by gel permeation chromatography (GPC), and the ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) obtained on a polystyrene basis (Mw / Mn) is preferably 1.5 to 5.0 (Requirement (Z5)), more preferably 1.55 to 4.7, more preferably 1.57 to 4.5, and among these, 1.60 to 4.3 is preferred. (Mw / Mn) can be determined by the method described in the examples. Note that the combination of the lower and upper limits of Mw / Mn is arbitrary.

[0016] Regarding requirement (Z6) Preferably, the terminal of the terminal hydroxyethylene-α-olefin copolymer (Z) contains two or more hydroxyl groups, and at least one of these terminals contains the following general formula (1) (requirement (Z6)). ―N(-R 1 -OH)(-R2 -OH) General formula (1) (In the formula, R 1 , R 2 (It is a divalent organic group with 1 to 6 carbon atoms.) In the general formula (1) above, R 1 , R 2 These are organic groups such as divalent hydrocarbon groups, each having 1 to 6 carbon atoms, and examples include alkylene groups such as methylene (-CH2-), ethylene (-CH2CH2-), and propylene (-CH2CH(-CH3)-).

[0017] An example of general formula (1) is the following: -N(-CH2OH)2 -N(-CH2CH2OH)2 -N [-CH2CH(-CH3)OH]2 Also, examples of terminals containing general formula (1) are as follows: -CH(-OH)-CH2-N(-CH2CH2OH)2 -C(-CH3)(-OH)-CH2-N(-CH2CH2OH)2

[0018] Regarding requirement (Z7) Furthermore, other preferred embodiments of such terminals include, 1 In some cases, more than 60% of all ends, excluding the saturated ends determined by 1H-NMR, contain at least the following general formula (2). -S-CH2-R 3 General formula (2) (In the formula, R 3 (It is an organic group that has 2 to 5 hydroxyl groups.)

[0019] An example of general formula (2) is the following: -S-CH2-CH(-OH)-CH2OH -S-CH2-CH(-CH2OH)-CH2CH2OH -S-CH2-CH(-OH)-CH2-O-CH2-CH(-OH)-CH2OH Furthermore, examples of terminals that include general formula (2) are as follows: -CH2-CH2-S-CH2-CH(-OH)-CH2OH -CH(-CH3)-CH2-S-CH2-CH(-OH)-CH2OH

[0020] Ends containing two or more hydroxyl groups, such as general formula (1) and general formula (2), are selected from all the ends of the terminal hydroxyethylene-α-olefin copolymer (Z). 1 It accounts for 60% or more of the total ends after removing the saturated ends determined by 1H-NMR (Requirement (Z1)). Preferably, it accounts for 65% or more of these ends. The upper limit is preferably 100%, more preferably 95%, and even more preferably 90%.

[0021] Method for producing terminal hydroxyethylene-α-olefin copolymer (Z) The terminal hydroxyethylene-α-olefin copolymer (Z) of the present invention is produced by introducing a terminal containing two or more hydroxyl groups to the terminal of an ethylene-α-olefin copolymer (A) having structural unit (i) and structural unit (ii). A preferred method involves converting either or both of the vinyl group ends and vinylidene group ends of an ethylene-α-olefin copolymer (A) into epoxy-containing groups, and then reacting these epoxy-containing groups with a low-molecular-weight compound having two or more hydroxyl groups.

[0022] The raw material is ethylene-α-olefin copolymer (A) The method for producing the ethylene-α-olefin copolymer (A) is not particularly limited, but for example, it can be produced by copolymerizing ethylene with at least one α-olefin having 3 to 10 carbon atoms in the presence of an olefin polymerization catalyst. Preferably, the method includes a step of polymerizing the olefin at a temperature of 20 to 130°C in the presence of an activator and at least one metallocene compound.

[0023] The polymerization temperature is preferably 25 to 130°C, more preferably 30 to 125°C, and more preferably 40 to 120°C. A polymerization temperature within this range is preferable because it allows the molecular weight of the resulting polymer to be controlled within the range specified in requirement (A2). Examples of activators include at least one compound (b) selected from organometallic compounds (b-1), organoaluminum oxy compounds (b-2), and compounds that react with metallocene compounds to form ion pairs (b-3). Examples of organometallic compounds (b-1) (excluding organoaluminum oxy compounds (b-2)) include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, and tri-n-octylaluminum, as well as organoaluminum compounds such as tricycloalkylaluminum, isobutylaluminum dichloride, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, methylaluminum dichloride, dimethylaluminum chloride, and diisobutylaluminum hydride. Examples of organoaluminum oxy compounds (b-2) include conventionally known aluminoxanes. Examples of compounds (b-3) that react with metallocene compounds to form ion pairs include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in Japanese Patent Publication No. 1-501950, Japanese Patent Publication No. 1-502036, Japanese Patent Publication No. 3-179005, Japanese Patent Publication No. 3-179006, Japanese Patent Publication No. 3-207703, Japanese Patent Publication No. 3-207704, U.S. Patent No. 5321106, International Publication No. 2015 / 122415, etc. The polymerization pressure is typically atmospheric pressure to 10 MPa gauge pressure, preferably atmospheric pressure to 8 MPa gauge pressure, and copolymerization can be carried out by batch, semi-continuous, or continuous methods. The reaction time (or average residence time if the copolymerization reaction is carried out continuously) varies depending on conditions such as catalyst concentration and polymerization temperature, and can be selected as appropriate, but is usually 1 minute to 3 hours, preferably 5 minutes to 2.5 hours. Furthermore, polymerization can be carried out in two or more stages with different reaction conditions. The molecular weight of the resulting ethylene-α-olefin copolymer (A) can also be adjusted by changing the hydrogen concentration in the polymerization system and the polymerization temperature. It can also be adjusted by the amount of catalyst component used. When hydrogen is added to the polymerization system, an appropriate amount is approximately 0.001 to 5,000 NL per 1 kg of the resulting ethylene-α-olefin copolymer. The amount of terminal unsaturation in the resulting ethylene-α-olefin copolymer (A) can be increased by minimizing the amount of hydrogenation.

[0024] The raw material ethylene-α-olefin copolymer (A) may contain biomass-derived monomers (ethylene, α-olefin). The monomers constituting the polymer may consist solely of biomass-derived monomers, or it may contain both biomass-derived monomers and fossil fuel-derived monomers. Biomass-derived monomers are monomers derived from any renewable natural raw materials and their residues, including fungi, yeasts, algae, and bacteria, which are of plant or animal origin, and which contain carbon 14 10 C isotopes -12 It contains a certain proportion, and the biomass carbon concentration (pMC) measured according to ASTM D 6866 is approximately 100 pMC. Biomass-derived monomers are obtained by conventionally known methods.

[0025] The raw material ethylene-α-olefin copolymer (A) may contain monomers derived from chemical recycling (ethylene, α-olefin). The monomers constituting the polymer may consist solely of monomers derived from chemical recycling, or they may contain monomers derived from chemical recycling, monomers derived from fossil fuels, and / or monomers derived from biomass. Monomers derived from chemical recycling can be obtained by conventionally known methods.

[0026] The raw material, ethylene-α-olefin copolymer (A), is not particularly limited, but those that satisfy the following requirements (A1) to (A3) are preferred. (A1) With respect to a total of 100 mol% of the content of constituent unit (i) and constituent unit (ii), the content of constituent unit (i) is 30 to 70 mol%, and the content of constituent unit (ii) is 30 to 70 mol%. Preferably, the content of constituent unit (i) is 35 to 65 mol%, more preferably 40 to 60 mol%, and even more preferably 45 to 55 mol%, and preferably the content of constituent unit (ii) is 35 to 65 mol%, more preferably 40 to 60 mol%, and even more preferably 45 to 55 mol%. Constituent unit (ii) is preferably an α-olefin having 3 to 8 carbon atoms, more preferably an α-olefin having 3 to 5 carbon atoms, and even more preferably propylene. The combination of the lower and upper limits of the content of constituent unit (i) and constituent unit (ii) is arbitrary. (A2) The number-average molecular weight (Mn) obtained by gel permeation chromatography (GPC) and converted to polystyrene equivalent is 300 to 10,000, preferably 400 to 8,000, more preferably 500 to 7,000, and particularly preferably 1,500 to 4,000. The combination of the lower and upper limits of the number-average molecular weight (Mn) is arbitrary. (A3) 1 The sum of the integrated intensities of the vinyl group endpoints and vinylidene group endpoints is greater than 70%, preferably greater than 75%, more preferably greater than 80%, even more preferably greater than 85%, and particularly preferably greater than 90%, relative to 100% of the sum of the integrated intensities of the vinyl group endpoints, vinylidene group endpoints, disubstituted olefin endpoints, and trisubstituted olefin endpoints determined by 1H-NMR. The upper limit is 100%, preferably 99%, and more preferably 98%.

[0027] In other words, the raw material, ethylene-α-olefin copolymer (A), has saturated and unsaturated ends, and the unsaturated ends include vinyl group ends, vinylidene group ends, disubstituted olefin ends, and trisubstituted olefin ends. Of these unsaturated ends, vinyl group ends and vinylidene group ends account for more than 70% of the total unsaturated ends (calculation is 1 If an ethylene-α-olefin copolymer (A) (as determined by 1H-NMR) is used as a raw material, it is preferable to introduce a terminal containing two or more hydroxyl groups to either or both of its vinyl group terminals and vinylidene group terminals, as a result, if the reaction proceeds quantitatively, it is possible to introduce terminals containing two or more hydroxyl groups to more than 70% of all terminals excluding the saturated terminal.

[0028] Method for epoxidizing vinyl and vinylidene group ends The method for converting the vinyl groups at the ends of the ethylene-α-olefin copolymer (A), and even unsaturated groups such as vinylidene groups, to epoxy-containing groups is not particularly limited, but the following methods can be given as examples. (1) Oxidation by peracids such as performic acid, peracetic acid, and perbenzoic acid (2) Oxidation with titanosilicate and hydrogen peroxide (3) Oxidation with rhenium oxide catalyst such as methyltrioxorhenium and hydrogen peroxide (4) Oxidation with a porphyrin complex catalyst such as manganese porphyrin or iron porphyrin and hydrogen peroxide or hypochlorite (5) Oxidation with Salen complex such as manganese Salen and hydrogen peroxide or hypochlorite (6) Oxidation with manganese-triazacyclononane (TACN) complex and other TACN complexes and hydrogen peroxide (7) Oxidation by hydrogen peroxide in the presence of a group VI transition metal catalyst such as a tungsten compound and a phase transfer catalyst. Of the methods (1) to (7) described above, methods (1) and (7) are particularly preferred in terms of activity.

[0029] In the oxidation by peracid described in (1) above, it is preferable to use bis(monoperoxyphthalate)magnesium hexahydrate (MMPP) and / or m-chloroperbenzoic acid (mCPBA) as the peracid.

[0030] Method for introducing two or more hydroxyl group-containing terminals to an epoxy-containing group To introduce two or more hydroxyl group-containing terminals to the ethylene-α-olefin copolymer having epoxy groups at its terminals obtained above, a preferred method is to react the epoxy group with a low-molecular-weight compound having two or more hydroxyl groups in one molecule. For example, a secondary amine having two hydroxyl groups in one molecule is a suitable low-molecular-weight compound. The low-molecular-weight compound having hydroxyl groups may be derived from biomass.

[0031] As a secondary amine having two hydroxyl groups in one molecule, the compound represented by the following general formula (3) is preferred. HN(-R 1 -OH)(-R 2 -OH) General formula (3) (In the formula, R 1 , R 2 These are R in the general formula (1) above. 1 , R 2 It is similar to this. Examples of compounds represented by general formula (3) include dimethanolamine, diethanolamine, di(n-propanol)amine, diisopropanolamine, dibutanolamine, dipentanolamine, and dihexanolamine, which may be used individually or in combination of two or more.

[0032] Method of hydroxylation by thiolene reaction of vinyl and vinylidene group termini As a thiol compound having two or more hydroxyl groups in one molecule, the compound represented by the following general formula (4) is preferred. HS-R 3 General formula (4) (In the formula, R 3 R in the general formula (2) above is 3 It is similar to this. Examples of thiol compounds represented by general formula (4) include the following: 1-Thioglycerol [HS-CH2-CH(-OH)-CH2(-OH)] 1-Thiodiglycerol [HS-CH2-CH(-OH)-CH2-O-CH2-CH(-OH)-CH2OH]

[0033] When using the thiol compound represented by general formula (4), it is obtained by reacting the starting material, ethylene-α-olefin copolymer (A), in the presence of a radical generator. The radical initiator is not particularly limited as long as it has the function of a thermal radical initiator or a photoradical initiator, but examples include the azo compound azobisisobutyronitrile (AIBN), the organic peroxide benzoyl peroxide, Kayaren 6 (manufactured by Kayaku Akzo Co., Ltd.), Perhexa 25B (registered trademark, manufactured by Nippon Oil & Fats Co., Ltd.), the benzophenone-based photoradical initiator benzophenone, orthobenzoylmethyl benzoate, 4-benzoyl-4'-methyldiphenyl sulfide, the acetophenone-based photopolymerization initiator acetophenone, benzyldimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and the benzoin ether-based photoradical initiator benzoin isobutyl ether, etc.

[0034] The amount of radical initiator used is preferably 0.0001 to 10 molar times, more preferably 0.0001 to 5 molar times, and most preferably 0.0001 to 1 molar time, relative to the ethylene-α-olefin copolymer (A). These radical initiators may be used individually or in combination of two or more.

[0035] The reaction between the ethylene-α-olefin copolymer (A) and the thiol compound can be carried out in the absence of a solvent or in the presence of a solvent. The solvent used is not particularly limited, but examples include aliphatic hydrocarbons such as n-hexane, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, and methyl propyl ketone, ethers such as tetrahydrofuran and 1,4-dioxane, and halogenated hydrocarbons such as chloroform, dichloroethane, trichloroethane, and perchloroethane. Aromatic hydrocarbons such as toluene and xylene are preferred, as long as the ethylene-α-olefin copolymer (A) is insoluble in the solvent. The amount of solvent used affects the solubility of the raw materials, but is preferably 0 to 100 times the mass of the ethylene-α-olefin copolymer (A), more preferably 0 to 50 times, and even more preferably 0 to 20 times.

[0036] In the reaction between the ethylene-α-olefin copolymer (A) and the thiol compound, the ratio is not particularly limited, but is usually carried out under conditions of excess thiol compound, and the excess thiol compound can also be used as a solvent. The ratio is preferably 0.1 to 100 molar times, more preferably 0.1 to 50 molar times, and even more preferably 0.1 to 10 molar times relative to the ethylene-α-olefin copolymer (A).

[0037] The reaction temperature is preferably 25 to 300°C, more preferably 25 to 250°C, and even more preferably 25 to 150°C. Depending on the compound and solvent used, the reaction temperature may exceed the boiling point, so an appropriate reaction apparatus such as an autoclave should be selected. The reaction time varies depending on the reaction conditions such as the amount of radical initiator used, the reaction temperature, and the reactivity of the polymers, but is usually in the range of several minutes to 50 hours.

[0038] After the reaction, the radical initiator, excess thiol compound, and reaction solvent can be removed by simple operations such as crystallization, extraction, and washing to obtain the terminal hydroxyethylene-α-olefin copolymer (Z).

[0039] The terminal hydroxyethylene ethylene-α-olefin copolymer (Z) of the present invention has many applications, including compositions with various synthetic resins, such as (meth)acrylic resins. Examples of synthetic resins include the following thermoplastic resins and thermosetting resins.

[0040] Thermoplastic resins include (meth)acrylic resins, polycarbonate resins, polyester resins, fluorinated aromatic polymer resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyamide-imide resins, polystyrene resins, polyamide resins, polyimide resins, polyacetal, acrylonitrile-butadiene-styrene copolymers, polyvinyl chloride resins, polyvinylidene chloride resins, polyvinyl acetate resins, and ethylene-(meth)acrylic acid ester copolymer resins.

[0041] Thermosetting resins include epoxy resins, amino resins, phenolic resins, thermosetting urethane resins, thermosetting polyimide resins, amino alkyd resins, urea resins, benzooxanzine resins, silicon resins, and unsaturated polyester resins.

[0042] The terminal hydroxyethylene-α-olefin copolymer (Z) of the present invention is preferably used in a composition with synthetic resins, such as (meth)acrylic resins or thermosetting resins. The composition of the terminal hydroxyethylene-α-olefin copolymer (Z) and synthetic resin of the present invention may optionally contain a crosslinking agent. Examples of crosslinking agents include epoxy compounds such as sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, neopentyl glycol diglycidyl ether, and resolcin diglycidyl ether; isocyanate compounds such as tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylolpropane toluene diisocyanate 3 adduct, and polyisocyanates; and trimethylol This includes aziridine compounds such as propane-tri-β-aziridinylpropionate, tetramethylolmethane-tri-β-aziridinylpropionate, N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), N,N'-hexamethylene-1,6-bis(1-aziridinecarboxamide), N,N'-toluene-2,4-bis(1-aziridinecarboxamide), trimethylolpropane-tri-β-(2-methylaziridine)propionate, and melamine compounds such as hexamethoxymethylolmelamine. Here, the epoxy compounds usually have two or more epoxy groups, the isocyanate compounds usually have two or more isocyanate groups (groups represented by -N=C=O), and the aziridine compounds usually have two or more aziridine groups. In one preferred and exemplary embodiment of the present invention, the crosslinking agent is an isocyanate compound. The crosslinking agent (C) may be used alone or in combination of multiple types. The mixing ratio of each component in a composition containing a synthetic resin, a terminal hydroxyethylene-α-olefin copolymer (Z), and an optional crosslinking agent is not particularly limited, but compositions with the following mixing ratios are preferred. When the total amount of synthetic resin, terminal hydroxyethylene-α-olefin copolymer (Z), and optional crosslinking agent is taken as 100% by mass, it is preferable that the amount of synthetic resin is 40% by mass or more and 99% by mass or less, the amount of terminal hydroxyethylene-α-olefin copolymer (Z) is 0.1% by mass or more and 60% by mass or less, and the amount of crosslinking agent (C) is 0% by mass or more and 10% by mass or less. More preferably, among these, it is preferable that the amount of synthetic resin is 47% by mass or more and 99% by mass or less, the amount of terminal hydroxyethylene-α-olefin copolymer (Z) is 0.5% by mass or more and 50% by mass or less, and the amount of crosslinking agent (C) is 0.5% by mass or more and 5% by mass or less.

[0043] [Additives] In addition to the (meth)acrylic resin (B), the terminal hydroxyethylene-α-olefin copolymer (Z), and the crosslinking agent (C) described above, the adhesive composition of the present invention may also contain, to the extent that it does not impair the effects of the present invention, at least one additive selected from organic solvents, antistatic agents, silane coupling agents, ultraviolet absorbers, antioxidants, tackifying resins, plasticizers, defoaming agents, fillers, stabilizers, softeners, and wettability modifiers.

[0044] Purpose The terminal hydroxyethylene-α-olefin copolymer (Z) of the present invention has many applications. For example, it is used as a modifier in synthetic resins. It is used in paints, primers, coatings, etc., and is also used as a modifier for these materials. It is used in various types of paints, including lacquer-based, urethane-based, acrylic-based, alkyd-based, epoxy-based, and polyester-based paints. As a primer, it is used as a compounding agent for synthetic resins, such as thermoplastic polyurethane resins / urea resins and thermosetting polyester resins / melamine resins / epoxy resins. Examples of modifiers include lubricating oil modifiers and surface modifiers. Examples of coating materials include fluorine-based and silicone-based materials. [Examples]

[0045] Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples at all. The physical property values were as follows.

[0046] <Weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) by GPC> The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the ethylene-propylene copolymer (A-1) produced in the synthesis example and the terminal hydroxyethylene-propylene copolymers (Z-a), terminal hydroxyethylene-propylene copolymer (Z-b), and graft-modified ethylene-propylene copolymer (X-1) used in the examples were determined by the following method.

[0047] 〔Pretreatment of sample〕 10 mg of the ethylene-propylene copolymer (A-1) produced in the synthesis example and 10 mg of the terminal hydroxyethylene-propylene copolymer (Z-a) produced in the example were dissolved in 10 ml of THF at room temperature, and then the solution was filtered through a 0.45 μm hydrophilic PTFE membrane filter cartridge to obtain an analytical sample.

[0048] 〔GPC analysis〕 Using gel permeation chromatography (GPC), the weight average molecular weight (Mw) and number average molecular weight (Mn) were calculated in terms of polystyrene molecular weight, and a molecular weight distribution curve was obtained. The molecular weight distribution (Mw / Mn) was calculated from the obtained weight average molecular weight (Mw) and number average molecular weight (Mn).

[0049] 〔Measurement conditions〕 Determined by the following high-speed GPC measuring device. Measuring device: HLC8320GPC manufactured by Tosoh Corporation Mobile phase: THF (manufactured by Wako Pure Chemical Industries, Ltd., without stabilizer, grade for liquid chromatography) Column: Two TSKgel Super Multipore HZ-M columns manufactured by Tosoh Corporation were connected in series. Sample concentration: 5 mg / mL Mobile phase flow rate: 0.35mL / min Measurement temperature: 40℃ Standard sample for calibration curve: PStQuick MP-M manufactured by Tosoh Corporation

[0050] < 1 H-NMR> [Measurement conditions] Measurement device: JEOL ECX400P nuclear magnetic resonance spectrometer Nucleus for measurement: 1 H (400MHz) Measurement mode: Single pulse Pulse width: 45° (5.25 μsec) Points: 32k Measurement range: 20 ppm (-4 to 16 ppm) Repeat time: 7.0 seconds Total number of times: 64 Measurement solvent: Deuterated chloroform Sample concentration: approx. 20 mg / 0.6 mL Measurement temperature: 25℃ Window function: exponential (BF: 0.12Hz) Chemical shift standard: Chloroform (7.26 ppm). After adding a drop of heavy water to the sample and vigorously stirring, the hydroxyl groups were deuterated, and then the measurement was performed.

[0051] [Concentration of terminals containing two or more hydroxyl groups] The measurement sample is terminal hydroxyethylene-propylene copolymer (Za). For terminal hydroxyethylene-propylene copolymer (Zb) and graft-modified ethylene-propylene copolymer (X-1), the peaks for hydrogen atoms 1-8 in the following formulas are... 1 The results were measured by 1H-NMR.

[0052] [ka]

[0053] In each formula, the dashed lines indicate bonds other than those of hydrogen atoms and represent the main chain of the ethylene-propylene copolymer. The peaks for each hydrogen atom (1-11) are observed near the following locations. Furthermore, since the disubstituted olefin ends and trisubstituted olefin ends in the unsaturated bonds of the ethylene-propylene copolymer (A-1) used as the raw material were hardly observed, these structures and the epoxy group-containing ends generated from these structures were not considered in the calculation formulas. • Peaks for hydrogen atoms 1 and 2: 3.5 ppm - 3.9 ppm • Peak for hydrogen atom 3: 3.0 ppm • Peak for hydrogen atom 4: 2.8 ppm • Peak for hydrogen atom 5: 2.2 - 2.9 ppm • Peak for hydrogen atom 6: 2.4 - 2.9 ppm • Peak for hydrogen atom 7: 5.9 ppm • Peak for hydrogen atom 8: 4.6 ppm The percentage of terminals with two or more hydroxyl groups is as follows:

[0054] [[If formula (1-a) is present]] -CH2-N-(CH2CH2OH)2 formula (1-a) The percentage of terminal cells containing two or more hydroxyl groups (%) = 100 × [(integrated intensity of signal 1 + integrated intensity of signal 2) / 5] / [(integrated intensity of signal 1 + integrated intensity of signal 2) / 5 + integrated intensity of signal 3 + {integrated intensity of signal 4 + integrated intensity of signal 5 - [6 × (integrated intensity of signal 1 + integrated intensity of signal 2) / 5]} / 2 + integrated intensity of signal 7 + integrated intensity of signal 8 / 2]

[0055] [[If formula (2-a) is present]] -CH2-S-CH2-CH(-OH)-CH2OH Formula (2-a) The percentage of terminal cells containing two or more hydroxyl groups (%) = 100 × [(integrated intensity of signal 1 + integrated intensity of signal 2) / 3] / [(integrated intensity of signal 1 + integrated intensity of signal 2) / 3] + integrated intensity of signal 7 + integrated intensity of signal 8 / 2]

[0056] [Calculation of the content of vinyl group and vinylidene group in the unsaturated end of ethylene-propylene copolymer (A-1)] For the ethylene-propylene copolymer (A-1) used as the measurement sample, the peaks for each hydrogen atom I to IV in the following equations are... 1 The results were measured by 1H-NMR.

[0057] [ka]

[0058] In each formula, dashed lines indicate bonding with atoms other than hydrogen atoms. The peaks for each hydrogen atom I-IV are observed in the vicinity of the following locations. • Peak of carbon atom I: 5.9 ppm • Peak of carbon atom I': 4.9 ppm • Peak of carbon atom II: 4.6 ppm • Peak of carbon atom III: 5.3 ppm • Peak of carbon atom IV: 4.9 ppm Furthermore, since it is not possible to distinguish between the peaks of IV and I', the integrated intensity of IV is calculated using the peak of I. The quantitative formula for the content of vinyl groups at the end of unsaturated ends is as follows: The percentage of vinyl groups at the unsaturated end (%) = 100 × integrated intensity of signal I / [integrated intensity of signal I + (integrated intensity of signal II / 2) + (integrated intensity of signal III / 2) + (integrated intensity of signal I' + integrated intensity of signal IV - integrated intensity of signal I × 2)] The percentage of vinylidene groups at the unsaturated end (%) = 100 × (integrated intensity of signal II / 2) / [integrated intensity of signal I + (integrated intensity of signal II / 2) + (integrated intensity of signal III / 2) + (integrated intensity of signal I' + integrated intensity of signal IV - integrated intensity of signal I × 2)]

[0059] [Calculation of ethylene and propylene content] the above 1 The spectra obtained by 1H-NMR measurements show ethylene and propylene units in the main chain. The ethylene and propylene content was calculated from the integrated intensity of each signal.

[0060] [ka]

[0061] In each formula, dashed lines indicate bonding with atoms other than hydrogen atoms. The peaks for each hydrogen atom, A through C, are observed in the following ranges. • Hydrogen atom peak: 0.95 ppm ~ 1.4 ppm • Hydrogen atom peak: 0.95 ppm ~ 1.4 ppm • Hydrogen atom peak: 1.4 ppm ~ 1.7 ppm Furthermore, since it is not possible to distinguish between peaks A and B, the integrated intensity of A is calculated using peak C. The quantitative formulas for ethylene and propylene content are as follows: Ethylene content (mol%) = 100 × [(Integrated intensity of signal: A + Integrated intensity of signal: B - 2 × Integrated intensity of signal: C) / 4] / {[(Integrated intensity of signal: A + Integrated intensity of signal: B - 2 × Integrated intensity of signal: C) / 4] + Integrated intensity of signal: C} Propylene content (mol%) = 100 × Integrated intensity of signal:U / {[(Integrated intensity of signal:A + Integrated intensity of signal:B - 2 × Integrated intensity of signal:U) / 4] + Integrated intensity of signal:U}

[0062] [Measuring melting point using DSC] Measurements were performed using a Seiko Instruments X-DSC-7000. Approximately 8 mg of sample was placed in a simple, sealable aluminum sample pan and placed in the DSC cell. The DSC cell was heated from room temperature to 150°C at a rate of 10°C / min under a nitrogen atmosphere, then held at 150°C for 5 minutes, and then cooled down to -100°C at a rate of 10°C / min (cooling process). Then, after holding at -100°C for 5 minutes, the temperature was raised to 150°C at a rate of 10°C / min. The melting point was defined as the temperature at which the enthalpy curve (DSC curve) obtained during the heating process showed a maximum value (however, a minimum value when the heat flow associated with endothermic heating was taken in the negative direction), and the total amount of heat absorbed during melting was defined as the heat of fusion. If no peak was observed in this enthalpy curve (DSC curve), or if the observed heat of fusion value was 1 J / g or less, the melting point (Tm) was considered not to have been observed. The melting point and heat of fusion were determined in accordance with JIS K7121.

[0063] <Raw materials> <<Terminal unsaturated ethylene-propylene copolymer (A-1)>>

[0064] [Synthesis Example 1] The raw material, ethylene-propylene copolymer (A-1), was synthesized by the following method. 500 mL of xylene was added to a 1.0 L glass reactor that had been thoroughly purged with nitrogen. The reactor was then maintained at 110°C, and while stirring the inside of the polymerizer at 600 rpm, ethylene, propylene, and nitrogen were continuously supplied at 78 L / h, 44 L / h, and 52 L / h, respectively, until the liquid and gas phases were saturated.

[0065] While ethylene and propylene were continuously supplied, 0.10 mL (0.10 mmol) of a toluene solution of triisobutylaluminum (1.0 mol / L), 2.5 mL (0.005 mmol) of a toluene solution of dimethylsilylbis(2-methyl-4-phenylindenyl)hafnium dichloride (0.002 mol / L), and then 2.0 mL (0.020 mmol) of a toluene solution of triphenylcarbenium tetrakis(pentafluorophenyl) borate (hereinafter also referred to as Ph3CB(C6F5)4) (0.01 mol / L) were added, and polymerization was carried out at 110°C for 16 minutes under normal pressure.

[0066] Polymerization was stopped by adding a small amount of isobutanol. The resulting polymerization reaction solution was washed with dilute hydrochloric acid, and the solvent in the resulting organic layer was removed by vacuum distillation to obtain ethylene-propylene copolymer (A-1). The copolymer (A-1) was dried under reduced pressure at 130°C for 10 hours to obtain 8.45 g of ethylene-propylene copolymer. The obtained copolymer (A-1) had Mw=3,800, Mn=2,200, Mw / Mn=1.73, ethylene content=50 mol%, and propylene content=50 mol%. 1 The vinyl group content and vinylidene group content in the unsaturated end, as measured by 1H-NMR, were 81% and 16%, respectively.

[0067] [Example 1] In a 300 mL round-bottom flask containing a stirring bar, 25.2 g of (A-1) obtained in Synthesis Example 1 was dissolved by adding 150 mL of dichloromethane. Subsequently, at room temperature, while stirring with a magnetic stirrer, 4.2 g of metachloroperbenzoic acid (approximately 30 wt% water content) was added and the mixture was reacted for 72 hours. After that, a small amount of saturated sodium bicarbonate solution and 25 wt% sodium thiosulfate solution were added to stop the reaction.

[0068] The resulting reaction solution was washed with saturated sodium bicarbonate solution, and the resulting organic layer was separated and dried over sodium sulfate. The solvent was then removed under reduced pressure to obtain 24.3 g of terminal epoxyethylene-propylene copolymer. Next, 20.0 g of terminal epoxyethylene-propylene copolymer was added to a 150 mL Schlenk tube containing a stirring bar.

[0069] Afterward, 5.9g of diethanolamine was added, and the mixture was dried at room temperature for 5 hours. Next, 20 mL of xylene was added, and the mixture was heated in an oil bath to 135°C and reacted for 8 hours. The reaction solution was cooled to room temperature, and 100 mL of toluene was added. The resulting organic layer was washed with water, dried over sodium sulfate, and then the solvent was removed under reduced pressure to obtain 20.2 g of terminal hydroxyethylene-propylene copolymer (Za). The properties of the obtained terminal hydroxyethylene-propylene copolymer (Za) are shown in Table 1.

[0070] [Comparative Example 1] A 2L stainless steel autoclave, thoroughly purged with nitrogen, was charged with 760mL of heptane and 120g of propylene. After raising the temperature of the system to 150°C, the total pressure was increased to 3MPa-G by supplying hydrogen at 0.85MPa and ethylene at 0.19MPa.

[0071] Next, triisobutylaluminum 0.4 mmol, [methylphenylmethylene (η 5 -cyclopentadienyl)(η 5 Polymerization was initiated by introducing 0.0002 mmol of -2,7-di-tert-butylfluorenyl) zirconium dichloride and 0.002 mmol of N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate under pressure with nitrogen and increasing the stirring speed to 400 rpm.

[0072] Subsequently, the total pressure was maintained at 3 MPa-G by continuously supplying only ethylene, and polymerization was carried out at 150°C for 5 minutes. After stopping the polymerization by adding a small amount of ethanol to the system, unreacted ethylene, propylene, and hydrogen were purged. The obtained polymerization solution was washed three times with 1000 mL of 0.2 mo / L hydrochloric acid, followed by three washes with 1000 mL of distilled water, dried with magnesium sulfate, and the solvent was removed by vacuum distillation to obtain crude ethylene-propylene copolymer. In a 500 mL glass reactor equipped with a stirrer, nitrogen inlet tube, water-cooled condenser, and thermometer, 120 g of crude ethylene-propylene copolymer, 15 g of 2-methyl-3-buten-2-ol, and 3 g of di-tert-butyl peroxide were added, and the reactor was purged with nitrogen for 1 hour to remove dissolved oxygen. Subsequently, the reactor temperature was raised to 160°C and the reaction was carried out for 3 hours. After that, the reactor temperature was raised to 180°C and the decomposition products of unreacted 2-methyl-3-buten-2-ol and di-tert-butyl peroxide were removed under reduced pressure (10 Torr) to obtain graft-modified ethylene-propylene copolymer (X-1).

[0073] [Example 2] 9.9 g of (A-1) obtained in Synthesis Example 1 and 7.1 mL of thioglycerol were added to a 300 mL round-bottom flask containing a stirring bar, and then dried at room temperature for 2 hours. Next, 240 mL of butyl acetate was added and the temperature was raised to 80°C. Subsequently, a solution of 0.67 g of 2,2'-azobis(isobutyronitrile) dissolved in 100 mL of butyl acetate was gradually added, and the mixture was reacted for 4 hours. Subsequently, the temperature was raised to 100°C and heated for 2 hours to decompose the unreacted 2,2'-azobis(isobutyronitrile). The reaction solution was cooled to room temperature, and 100 mL of hexane was added. After washing with water, the resulting organic layer was dried over sodium sulfate, and the solvent was removed by vacuum distillation to obtain 4.8 g of terminal hydroxyethylene α-olefin copolymer (Zb). The properties of the obtained terminal hydroxyethylene-propylene copolymer (Zb) are shown in Table 1.

[0074] [Table 1]

[0075] <<(Meth)acrylic resin (B)>> [Manufacturing Example B1] Synthesis of (meth)acrylic resin (B-1) In a temperature-controllable reactor equipped with a stirrer, 350 parts by mass of ethyl acetate as the polymerization solvent and 40 parts by mass of toluene were charged, the reactor was purged with nitrogen, and the temperature was raised to 75°C. Subsequently, to the resulting mixture of ethyl acetate and toluene, a mixture of 316 parts by mass of n-butyl acrylate, 43 parts by mass of ethyl acrylate, 50 parts by mass of vinyl acetate, 9 parts by mass of acrylic acid, 2 parts by mass of hydroxyethyl acrylate, and 2 parts by mass of benzoyl peroxide as a polymerization initiator was successively added, and the mixture was then reacted for 5 hours. Five hours after the completion of the additions, the resulting reaction mixture was diluted with 120 parts by mass of toluene to obtain an ethyl acetate / toluene solution containing (meth)acrylic resin with a solid content of 45%.

[0076] Here, the (meth)acrylic resin obtained in this manufacturing example B1 is referred to as (meth)acrylic resin (B-1). The peak temperature of the loss tangent (tanδ) due to the glass transition temperature, measured by the temperature dependence of dynamic viscoelasticity (frequency 1 Hz, -100 to 200°C) of (meth)acrylic resin (B-1) obtained by volatilizing the solvent from the resulting ethyl acetate / toluene solution, was -47°C. The composition of (meth)acrylic resin (B-1) was quantified by pyrolysis gas chromatography-mass spectrometry (pyrolysis GC-MS). The content of structural units derived from (meth)acrylate having an alkyl group with 1 to 12 carbon atoms was 80 mol%, and the content of structural units derived from (meth)acrylate containing a hydroxyl group was 0.5 mol%. The quantification by pyrolysis GC-MS was performed under the following conditions.

[0077] Pyrolysis apparatus: JAIJHP-5 manufactured by Nippon Analytical Engineering Co., Ltd. Thermal decomposition temperature: 590℃ GC device: Agilent 6890N Column: Agilent DB-5MS Column temperature: 40℃ Column flow rate: 0.9 mL / min (Mobile phase: Helium) MS device: JMS-Q1000GC manufactured by JEOL

[0078] <<Crosslinking agent (C-1)>> As the crosslinking agent (C-1), we used Takenate D-101E (an isocyanate compound, "Takenate" is a registered trademark of Mitsui Chemicals, Inc.).

[0079] [Example 3, Comparative Examples 2-3] In each of Example 3 and Comparative Examples 2-3, an ethyl acetate / toluene solution containing the above (meth)acrylic resin (B-1) and either a terminal hydroxyethylene-propylene copolymer (Za) or a graft-modified ethylene-propylene copolymer (X-1) were used. The crosslinking agent (C-1) was stirred and mixed at room temperature to obtain an ethyl acetate / toluene solution of the adhesive composition. Here, the ratio of the mass of (meth)acrylic resin (B-1) contained in the ethyl acetate / toluene solution of the adhesive composition to the mass of either the terminal hydroxyethylene-propylene copolymer (Za) or the graft-modified ethylene-propylene copolymer (X-1) and the mass of the crosslinking agent (C-1) was as shown in Table 2. In the evaluation of each physical property described below, an ethyl acetate / toluene solution obtained by adding toluene to the mixture obtained by the aforementioned stirring and mixing, and adjusting the mass ratio of ethyl acetate to toluene to 40 / 60 (hereinafter referred to as "ethyl acetate / toluene (40 / 60 mass%) solution of the adhesive composition") was used.

[0080] [Evaluation of adhesion] For each of the ethyl acetate / toluene (40 / 60% by mass) solutions of the adhesive compositions obtained in the examples and comparative examples, the following procedures were performed. An ethyl acetate / toluene (40 / 60% by mass) solution of the obtained adhesive composition was applied to release paper so that the film thickness after drying was 25 μm. After drying at 100°C for 10 minutes, a 50 μm PET film was pressed onto the applied surface to prepare an adhesive sheet having a base layer made of PET film and an adhesive layer made of the adhesive composition. The sheet was left at 50°C for 3 days to allow the adhesive composition to crosslink sufficiently.

[0081] The above adhesive sheet was cut into pieces 25 mm wide and 150 mm long to prepare test specimens. The release paper was peeled off the test specimens to expose the adhesive layer, and the exposed adhesive layer was brought into contact with a PP board in a 23°C atmosphere. The test specimens were then pressed down by rolling a 2 kg rubber roll back and forth twice. After standing for 20 minutes, the 180° peel strength was measured at a speed of 300 mm / min.

[0082] The adhesive properties were evaluated based on the obtained peel strength. The evaluation results are shown in Table 2. The meaning of the symbols in the table is as follows. ○: Peel strength of 3N / 25mm or more △: Peel strength less than 3N / 25mm, 1N / 25mm or more. ×: Peel strength less than 1N / 25mm Here, the symbol "○" indicates that the adhesive sheet and the PP board are bonded together with sufficient strength. The symbol "△" indicates that the adhesive sheet and the PP board are bonded together with a certain degree of strength. The symbol "×" indicates a state of poor adhesion (non-adhered state) between the adhesive sheet and the PP board. When the adhesive composition of the present invention is used as an adhesive for adhesive sheets or the like, a higher adhesive strength is preferable because it prevents the substrates from peeling apart.

[0083] [Low-temperature flexibility evaluation] Low-temperature flexibility was evaluated for each of the ethyl acetate / toluene (40 / 60 mass%) solutions of the adhesive compositions obtained in the examples and comparative examples, as follows. A 40 / 60% by mass ethyl acetate / toluene (40 / 60 mass) solution of the obtained adhesive composition was applied to release paper so that the film thickness after drying would be 25 μm. The mixture was dried at 100°C for 10 minutes, and the release paper was peeled off the resulting laminate to obtain a sheet made of the adhesive composition.

[0084] The dynamic viscoelasticity of the obtained adhesive composition sheet was measured at -20°C at a frequency of 1 Hz using a rheometer (ARES-G2, T.A. Instruments) with a parallel plate (8 mmφ) measuring fixture. Specifically, a sample made by molding the adhesive composition sheet into a disc shape with a diameter of 8 mm and a thickness of 0.4 mm was used. The sample was sandwiched between two parallel plates (8 mmφ) attached to the rheometer (with a gap of 0.4 mm between the parallel plates), and the loss modulus G'' and storage modulus G' were measured at -20°C at a frequency of 1 Hz. Low-temperature flexibility was evaluated from the obtained storage modulus G'. The evaluation results are shown in Table 2. The meaning of the symbols in the table is as follows. ○: Storage modulus G' is 0.1 MPa or higher and less than 0.5 MPa. △: Storage modulus G' is 0.5 MPa or higher and less than 1.0 MPa. ×: Storage modulus G' is 1.0 MPa or higher

[0085] Here, the symbol "○" indicates that the adhesive is sufficiently soft, and when the adhesive sheet obtained by combining it with the substrate is bent, the adhesive can adequately follow the movement of the substrate, making it extremely unlikely that the adhesive will peel off from the substrate (i.e., it is extremely unlikely that the adhesive will peel off due to insufficient followability when the substrate is bent).

[0086] The symbol "△" indicates that the adhesive is somewhat soft, and when the adhesive sheet obtained by combining it with the substrate is bent, the adhesive can follow the movement of the substrate to some extent, making it somewhat difficult for the adhesive to peel off from the substrate (i.e., it is somewhat difficult for the adhesive to peel off due to insufficient followability when the substrate is bent).

[0087] The symbol "×" indicates that the adhesive is hard, and when the adhesive sheet obtained by combining it with the substrate is bent, the adhesive cannot follow the movement of the substrate, making it prone to peeling of the adhesive from the substrate (i.e., it is prone to peeling of the adhesive due to insufficient conformity when the substrate is bent).

[0088] When the adhesive composition of the present invention is used as an adhesive for adhesive sheets, the lower the storage modulus G' at -20°C, the better the low-temperature flexibility. Therefore, when the adhesive composition of the present invention is combined with a substrate to form an adhesive sheet, the adhesive can follow the bending of the substrate, and peeling of the adhesive can be suppressed, which is preferable.

[0089] [Evaluation of bleed resistance] The bleed resistance was evaluated for each of the ethyl acetate / toluene (40 / 60 mass%) solutions of the adhesive compositions obtained in the examples and comparative examples, as follows. An ethyl acetate / toluene (40 / 60% by mass) solution of the obtained adhesive composition was applied to release paper so that the film thickness after drying would be 50 μm. After drying at 100°C for 10 minutes, a 50 μm PET film was pressed onto the applied surface to create an adhesive sheet having a base layer made of PET film and an adhesive layer made of the adhesive composition. The sheet was left at 50°C for 3 days to allow the adhesive composition to crosslink sufficiently.

[0090] The above adhesive sheet was cut to a width of 25 mm and a length of 150 mm to prepare test specimens. The release paper was peeled off the test specimens to expose the adhesive layer, and the exposed adhesive layer was brought into contact with a glass plate in an atmosphere of 23°C. The test specimens were then pressed down by passing a 2 kg rubber roll back and forth twice. After standing for 20 minutes, a 180° peel was performed at a speed of 300 mm / min, and the surface of the glass plate after peeling was observed visually. The bleed resistance was evaluated by visually observing the surface of the glass plate. The evaluation results are shown in Table 2. The meaning of the symbols in the table is as follows.

[0091] ○: No liquid deposits were found. ×: Liquid deposits were observed.

[0092] Here, the symbol "○" indicates that the adhesive is in a state of excellent bleed resistance. The symbol "×" indicates that the adhesive is in a state of poor bleed resistance. When the adhesive composition of the present invention is used as an adhesive for adhesive sheets or the like, it is preferable that it has excellent bleed resistance, as this prevents the substrates from peeling off from each other for a long period of time.

[0093] [Table 2]

Claims

1. An ethylene-α-olefin copolymer (A) having a constituent unit (i) derived from ethylene and a constituent unit (ii) derived from an α-olefin having 3 to 10 carbon atoms, has a hydroxyl group at one end. A terminal hydroxyethylene-α-olefin copolymer (Z) that satisfies the following requirements (Z1) and (Z2); (Z1) 1 More than 60% of all terminals, excluding the saturated terminal determined by 1H-NMR, contain two or more hydroxyl groups; (Z2) The melting point measured by differential scanning calorimetry (DSC) is not observed.

2. A terminal hydroxyethylene-α-olefin copolymer (Z) according to claim 1, further satisfying the following requirements (Z3) to (Z5); (Z3) With respect to a total of 100 mol% of the content of constituent unit (i) and constituent unit (ii), the content of constituent unit (i) is 30 to 70 mol%, and the content of constituent unit (ii) is 30 to 70 mol%; (Z4) The number-average molecular weight (Mn) obtained by gel permeation chromatography (GPC) and converted to polystyrene equivalent is 300 to 10,000; (Z5) The ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) obtained by gel permeation chromatography (GPC) and converted to polystyrene equivalent (Mw / Mn) is between 1.5 and 5.

0.

3. A terminal hydroxyethylene-α-olefin copolymer (Z) according to claim 1, further satisfying the following requirement (Z6); (Z6) 1 At least 60% of all terminals, excluding the saturated terminal determined by H-NMR, contain at least the following general formula (1). ―N(-R) 1 -OH)(-R 2 -OH) General formula (1) (In the formula, R 1 , R 2 (It is a divalent organic group with 1 to 6 carbon atoms.)

4. A terminal hydroxyethylene-α-olefin copolymer (Z) according to claim 1, further satisfying the following requirement (Z7); (Z7) 1 At least 60% of all terminals, excluding saturated terminals determined by H-NMR, contain at least the following general formula (2). -S-CH 2 -R 3 General form (2) (In the formula, R 3 (A hydroxyl group is an organic group having 2 to 5 hydroxyl groups.)

5. A method for producing a terminal hydroxyethylene-α-olefin copolymer (Z) that satisfies the following requirements (Z1) and (Z2), by reacting an ethylene-α-olefin copolymer (A) having a constituent unit (i) derived from ethylene and a constituent unit (ii) derived from an α-olefin having 3 to 10 carbon atoms with a low molecular weight compound in one or more steps; (Z1) 1 More than 60% of all terminals, excluding the saturated terminal determined by 1H-NMR, contain two or more hydroxyl groups; (Z2) The melting point measured by differential scanning calorimetry (DSC) is not observed.

6. A method for producing a terminal hydroxyethylene-α-olefin copolymer (Z) according to claim 5, wherein the ethylene-α-olefin copolymer (A) satisfies the following requirements (A1) to (A3); (A1) The content of component (i) is 30 to 70 mol% and the content of component (ii) is 30 to 70 mol% with respect to a total of 100 mol% of the content of component (i) and component (ii); (A2) The number-average molecular weight (Mn) obtained by gel permeation chromatography (GPC) and converted to polystyrene equivalent is 300 to 10,000; (A3) 1 The combined integrated intensity of the vinyl group endpoints and vinylidene group endpoints exceeds 70% of the combined integrated intensity of the signals for vinyl group endpoints, vinylidene group endpoints, disubstituted olefin endpoints, and trisubstituted olefin endpoints determined by 1H-NMR, which is 100%.

7. A method for producing a terminalized hydroxyethylene-α-olefin copolymer (Z) according to claim 5, comprising: converting both or either of the vinyl group ends and vinylidene group ends of the ethylene-α-olefin copolymer (A) to epoxy-containing groups; reacting the epoxy-containing groups with a secondary amine having two hydroxyl groups; or reacting both or either of the vinyl group ends and vinylidene group ends of the ethylene-α-olefin copolymer (A) with a thiol compound having two or more hydroxyl groups to introduce a terminal having a hydroxyl group to the vinyl group ends.

8. A method for producing a terminal hydroxyethylene-α-olefin copolymer (Z) according to claim 7, wherein a peroxide is used when converting both or either of the vinyl group and vinylidene group terminals to an epoxy-containing group.

9. A method for producing a terminal hydroxyethylene-α-olefin copolymer (Z) according to claim 7, wherein the secondary amine having a hydroxyl group is a compound represented by the following general formula (3). HN(-R) 1 -OH)(-R 2 -OH) General formula (3) (In the formula, R 1 , R 2 These are R in the general formula (1) above. 1 , R 2 (It is similar to this.)

10. A method for producing a terminal hydroxyethylene-α-olefin copolymer (Z) according to claim 7, wherein the thiol compound having a hydroxyl group is a compound represented by the following general formula (4). HS-R 3 General form (4) (In the formula, R 3 R in the above general formula (2) is 3 (It is similar to this.)

11. A resin composition comprising a (meth)acrylic resin or a thermosetting resin, and a terminal hydroxyethylene-α-olefin copolymer (Z) according to any one of claims 1 to 4.

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