Adhesive composition and article

Abstract

Provided are: an adhesive composition having excellent adhesiveness to a resin material; and an article comprising a cured product of the adhesive composition. The adhesive composition according to the present invention contains a polyether polycarbonate diol having a number average molecular weight of 500-10000 and not having a specific reactive silicon group or a polyether polycarbonate polymer (A) having a specific reactive silicon group.

Description

Technical Field

[0001] The present invention relates to an adhesive composition and an article comprising a cured product of the adhesive composition. Background Art

[0002] In the automotive field, as environmental awareness increases and the trend of de-gasoline is advancing, lightweighting is required as a measure to improve fuel efficiency. Steel plates are usually used in the interior and exterior decorations of automobiles such as car bodies, front doors, and front bumpers. In order to meet the demand for lightweighting, reinforced plastics such as carbon fiber reinforced plastics and glass fiber reinforced plastics, and various resin materials such as polypropylene are increasingly used as automobile interior and exterior decoration parts instead of steel plates.

[0003] In such bonding of a resin material and a different material such as glass, the resin material is usually flame treated and then bonded using a primer.

[0004] However, since the primer contains a large amount of solvent, there is a problem of adversely affecting the environment. In view of such a problem, an adhesive composition having improved adhesion to a resin material without using a primer is required.

[0005] For example, Patent Document 1 discloses a curable material including a polyether polycarbonate polymer having a reactive silicon group, and it is believed that the cured product of this curable material has excellent strength and elongation.

[0006] Patent Document 2 discloses a polyurethane resin having a unit based on a polyoxyalkylene glycol and a unit based on a diisocyanate compound having a molecular weight of 120 to 400, and is considered to have strength characteristics and be excellent in low-temperature characteristics and transparency.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Publication No. 2021-59722

[0010] Patent Document 2: Japanese Patent Application Publication No. 2021-155705 Summary of the invention

[0011] Problem that the invention aims to solve

[0012] However, Patent Documents 1 and 2 do not investigate the adhesiveness to resin materials.

[0013] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an adhesive composition having excellent adhesion to a resin material and an article including a cured product of the adhesive composition.

[0014] Solutions for solving problems

[0015] The present inventors conducted intensive research to solve the aforementioned problems and found that the following adhesive composition can solve the aforementioned problems, thereby completing the present invention. The adhesive composition comprises a polyether polycarbonate diol having a number average molecular weight in a specific range and not having a specific reactive silicon group, or a polyether polycarbonate polymer having a specific reactive silicon group.

[0016] That is, the present invention is as follows.

[0017] [1] An adhesive composition comprising a polyether polycarbonate diol having a number average molecular weight of 500 to 10,000 and having no reactive silicon group represented by the following formula (1) or a polyether polycarbonate polymer (A) having a reactive silicon group represented by the following formula (1).

[0018] -SiX a R 3-a Formula (1)

[0019] In formula (1), X is a halogen atom, a hydroxyl group or a hydrolyzable group. R is a monovalent organic group having 1 to 20 carbon atoms and does not contain a hydrolyzable group. a is an integer of 1 to 3. When a is 1, two Rs may be the same or different from each other. When a is 2 or 3, multiple Xs may be the same or different from each other.

[0020] [2] The adhesive composition according to [1] above, comprising a main agent and a curing agent, wherein the main agent contains an isocyanate-terminated urethane prepolymer, and the curing agent contains a polyether polycarbonate diol having no reactive silicon group represented by the above formula (1).

[0021] [3] The adhesive composition according to [1] or [2] above, wherein the polyether polycarbonate diol having no reactive silicon group represented by the formula (1) is a ring-opening polymer of a polycarbonate diol and a cyclic ether and has a carbonate group and an oxyalkylene group, and the polycarbonate diol is a condensate of two or more alcohols and a carbonate compound.

[0022] [4] The adhesive composition according to any one of [1] to [3] above, wherein the content of carbonate groups in the polyether polycarbonate diol not having a reactive silicon group represented by the above formula (1) is 5% by mass or more relative to 100% by mass of the total of carbonate groups and oxyalkylene groups.

[0023] [5] The adhesive composition according to any one of [1] to [4] above, wherein the oxyalkylene group in the polyether polycarbonate diol having no reactive silicon group represented by the formula (1) is at least one selected from the group consisting of oxypropylene and oxyethylene.

[0024] [6] The adhesive composition according to any one of [1] to [5] above, wherein the polyether polycarbonate diol having no reactive silicon group represented by the formula (1) is a compound represented by the following formula (2).

[0025] HO-(R 1 O) s -(R 2 -OC(=O)-O) u -R 20 -(OR 1 ) t -OH Formula (2)

[0026] In formula (2), R 1 is an alkylene group having 2 to 4 carbon atoms, R 2 and R 20 is a chain hydrocarbon group having 3 to 20 carbon atoms or a cyclic hydrocarbon group having a ring structure having 6 to 20 carbon atoms. These groups may optionally have one or more substituents. When it is a cyclic hydrocarbon group, it may optionally contain an oxygen atom as an atom constituting the ring. When it contains an oxygen atom, adjacent atoms may not be oxygen atoms at the same time. s and t are the number of repetitions, u is the number of repetitions of 2 or more, (R 2 -OC(=O)-O) u Contains 2 or more (R 2 -OC(=O)-O) represented by the unit.

[0027] [7] The adhesive composition according to the above [1], wherein the polyether polycarbonate polymer (A) having a reactive silicon group represented by the above formula (1) has two or more terminal groups in one molecule, and the terminal groups are at least one group selected from the group consisting of a reactive silicon group represented by the above formula (1), an active hydrogen-containing group and an isocyanate group.

[0028] [8] The adhesive composition according to [7] above, wherein the polyether polycarbonate polymer (A) having a reactive silicon group represented by the formula (1) has a number average molecular weight of 800 to 3,500.

[0029] [9] The adhesive composition according to [7] or [8] above, further comprising an oxyalkylene polymer (B).

[0030]

[10] The adhesive composition according to [9] above, wherein the number average molecular weight of the oxyalkylene polymer (B) is 5,000 to 50,000.

[0031]

[11] An article comprising, in order, a first substrate, a cured product of the adhesive composition according to any one of [1] to

[10] above, and a second substrate, wherein at least one of the first substrate and the second substrate is formed of a resin material.

[0032]

[12] The article according to

[11] above, wherein the resin material is polyolefin.

[0033]

[13] The article according to

[11] above, wherein the resin material is polypropylene.

[0034]

[14] The article according to any one of

[11] to

[13] above, wherein a surface of at least one of the first substrate and the second substrate that contacts the cured product of the adhesive composition is subjected to plasma treatment.

[0035] Effects of the Invention

[0036] According to the present invention, it is possible to provide an adhesive composition having excellent adhesiveness to a resin material and an article including a cured product of the adhesive composition. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 This is a cross-sectional view showing one embodiment of the article of the present invention. DETAILED DESCRIPTION

[0038] The definitions and meanings of the terms and symbols used in this specification are shown below.

[0039] In the present specification, any one considered to be preferred can be adopted, and it can be said that a combination of preferred ones is more preferred.

[0040] In this specification, the description of "XX~YY" means "above XX and below YY". In addition, in this specification, regarding the preferred numerical range (for example, the range of content, etc.), the lower limit and upper limit described in stages can be independently combined. For example, according to the description of "preferably 10 to 90, more preferably 30 to 60", the "preferred lower limit (10)" and the "more preferred upper limit (60)" can be combined to "10 to 60". In addition, in the numerical range described in this specification, the upper limit or lower limit of the numerical range can be replaced with the value shown in the examples.

[0041] In this specification, "condensate" means "condensate obtained by polycondensation by transesterification reaction".

[0042] The "unit" constituting a polymer refers to an atomic group formed by polymerization of a monomer.

[0043] The "oxyalkylene polymer" is a polymer having an oxyalkylene group.

[0044] The “isocyanate group-terminated urethane prepolymer” refers to a compound having isocyanate groups at at least a part of the ends of the molecular chain, which is obtained by reacting a polyisocyanate compound with a compound having two or more active hydrogen-containing groups in one molecule so that the isocyanate groups are in excess relative to the active hydrogen-containing groups.

[0045] The terminal group in the polyether polycarbonate diol refers to an atomic group including an oxygen atom closest to the molecular terminal among oxygen atoms in the main chain of the polymer.

[0046] The terminal group in the reactive silicon group-containing polyether polycarbonate polymer refers to an atomic group containing an oxygen atom closest to the molecular terminal among oxygen atoms in the main chain of the polymer.

[0047] The terminal group in the oxyalkylene polymer refers to an atomic group including an oxygen atom closest to the molecular terminal among oxygen atoms in the polyoxyalkylene chain.

[0048] <Adhesive Composition>

[0049] The adhesive composition of the present invention comprises a polyether polycarbonate diol having a number average molecular weight of 500 to 10,000 and having no reactive silicon group represented by the following formula (1) or a polyether polycarbonate polymer (A) having a reactive silicon group represented by the following formula (1).

[0050] -SiX a R 3-a Formula (1)

[0051] In formula (1), X is a halogen atom, a hydroxyl group or a hydrolyzable group. R is a monovalent organic group having 1 to 20 carbon atoms and does not contain a hydrolyzable group. a is an integer of 1 to 3. When a is 1, two Rs may be the same or different from each other. When a is 2 or 3, multiple Xs may be the same or different from each other.

[0052] The adhesive composition of the present invention contains a polyether polycarbonate diol having no reactive silicon group represented by the above formula (1) (hereinafter, also referred to as polyether polycarbonate diol) or a polyether polycarbonate polymer (A) having a reactive silicon group represented by the above formula (1) (hereinafter, also referred to as polyether polycarbonate polymer (A) having a reactive silicon group), thereby having excellent adhesion to resin materials.

[0053] (Polyether polycarbonate diol)

[0054] The number average molecular weight (Mn) of the polyether polycarbonate diol is 500 to 10,000, preferably 500 to 5,000, more preferably 500 to 4,000, further preferably 500 to 3,000, and particularly preferably 700 to 2,500. When the Mn of the polyether polycarbonate diol is at least the lower limit of the aforementioned range, the breaking strength and breaking elongation of the resin cured using the polyether polycarbonate diol become good, and when it is at most the upper limit of the aforementioned range, the adhesion to the resin material becomes good, the viscosity becomes low, and the handling becomes easy.

[0055] The Mw / Mn of the polyether polycarbonate diol is preferably 1.0 to 3.0, more preferably 1.0 to 2.5, and even more preferably 1.0 to 2.0. When the Mw / Mn of the polyether polycarbonate diol is below the upper limit of the above range, the proportion of the high molecular weight component, which is the main factor for high viscosity, is reduced, thereby reducing the viscosity and facilitating the handling of the composition.

[0056] The number average molecular weight (Mn) and weight average molecular weight (Mw) of the polyether polycarbonate diol are polystyrene-equivalent molecular weights measured by gel permeation chromatography (GPC) using a calibration curve prepared using standard polystyrene samples with known molecular weights as described in Examples below.

[0057] The hydroxyl value of the polyether polycarbonate diol is preferably 40 mgKOH / g or more, more preferably 45 mgKOH / g or more, particularly preferably 50 mgKOH / g or more, and preferably 500 mgKOH / g or less, more preferably 300 mgKOH / g or less, particularly preferably 200 mgKOH / g or less. When the hydroxyl value of the polyether polycarbonate diol is above the lower limit, the viscosity is easy to handle, and when it is below the upper limit, the breaking strength and breaking elongation of the cured product are further improved.

[0058] The hydroxyl value of the polyether polycarbonate diol is a value calculated by a method using an acetylating agent in accordance with JIS K1557:2007.

[0059] The viscosity of the polyether polycarbonate diol at 25° C. is preferably 3000 mPa·s or less, more preferably 2000 mPa·s or less, and even more preferably 1000 mPa·s or less, from the viewpoint of good workability in mixing the composition.

[0060] The viscosity of the polyether polycarbonate diol at 25° C. is a value measured using an E-type viscometer. Specifically, it is measured by the method described in the examples described below.

[0061] From the viewpoint of improving the adhesiveness to the resin material, the polyether polycarbonate diol is preferably a ring-opening polymer obtained by ring-opening polymerization of a polycarbonate diol and a cyclic ether described below. The polyether polycarbonate diol is preferably a diol having a carbonate group and an oxyalkylene group.

[0062] From the viewpoint of improving the adhesion to the resin material, cost, and availability, the oxyalkylene group in the polyether polycarbonate diol is preferably at least one selected from the group consisting of oxypropylene and oxyethylene, and more preferably oxypropylene.

[0063] For the content of the carbonate group in the polyether polycarbonate diol, from the viewpoint that makes the adhesiveness of resin material better, with respect to the total 100 quality % of carbonate group and oxyalkylene group, be preferably more than the 5 quality %, more preferably more than the 8 quality %, more preferably more than the 12 quality %.As the upper limit of the content of aforementioned carbonate group, from the viewpoint that the molecular bond of intramolecular carbonate group reduces thereby viscosity downgrades, the processing of composition becomes easy and the compatibility with other polymers improves, be preferably below the 22 quality %, more preferably below the 20 quality %, more preferably below the 18 quality %.

[0064] In addition, the content of the carbonate group is a value calculated based on the method described in the examples described later.

[0065] [Polycarbonate diol]

[0066] The polycarbonate diol is preferably a condensate of two or more alcohols and a carbonate compound from the viewpoint of being able to suppress crystallization at room temperature (23° C.) and suppressing phase separation when a cyclic ether is added.

[0067] Examples of the alcohol include ethylene glycol, 1,3-propylene glycol, 1,4-butanediol (1,4-BD), 1,5-pentanediol (1,5-PD), 1,6-hexanediol (1,6-HD), 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, 1,18-octadecanediol, and 1,20-eicosandiol; and diols having no side chain, such as 2-methyl-1,8-octanediol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 2-ethyl-1,6-hexanediol, 2-methyl-1,4-butanediol, and 2-methyl-1,3 diols having side chains such as propylene glycol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, and 2,4-diethyl-1,5-pentanediol; cyclic diols such as 1,3-cyclohexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, isosorbide, 2-bis(4-hydroxycyclohexyl)-propane, 2,7-norbornanediol, 2,3-norbornanediol, tetrahydrofuran-2,2-dimethanol, 2,5-bis(hydroxymethyl)-1,4-dioxane, and 5,5-bis(hydroxymethyl)-2-phenyl-1,3-dioxane; and diols having aromatic rings such as p-xylene glycol, p-tetrachloroxylene glycol, 1,4-bis(hydroxyethoxy)benzene, and 2,2-bis[(4-hydroxyethoxy)phenyl]propane. These may be used alone or in combination of two or more.

[0068] Among these, from the viewpoint of suppressing phase separation and further improving the breaking strength and breaking elongation of the cured product, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,4-butanediol, and 2-methyl-1,3-propanediol are preferred, and 1,5-pentanediol and 1,6-hexanediol are more preferred.

[0069] Examples of the carbonate compound include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, diphenyl carbonate, ethylene carbonate, trimethylene carbonate, propylene carbonate, 1,2-butylene carbonate, and 2,2-dimethyltrimethylene carbonate (neopentylene carbonate). These may be used alone or in combination of two or more.

[0070] Among these, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and ethylene carbonate are preferred from the viewpoint of reactivity with the above-mentioned alcohol and cyclic ether.

[0071] [Cyclic ether]

[0072] Examples of cyclic ethers include cyclic ethers having 2 carbon atoms in the ring, such as ethylene oxide (hereinafter sometimes referred to as "EO"), propylene oxide (hereinafter sometimes referred to as "PO"), 1,2-butylene oxide, 2,3-butylene oxide, cyclic ethers having 3 carbon atoms in the ring, such as oxetane, and cyclic ethers having 4 carbon atoms in the ring, such as tetrahydrofuran. The cyclic ether may have a substituent. Among these, cyclic ethers having 2 carbon atoms in the ring and having a substituent are preferred, and cyclic ethers having a total of 2 to 8 carbon atoms in the substituent and the carbon atoms constituting the ring are more preferred, and cyclic ethers having 2 carbon atoms in the ring, such as ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, are further preferred, and ethylene oxide or propylene oxide is particularly preferred.

[0073] These may be used alone or in combination of two or more.

[0074] From the viewpoint of improving the adhesiveness to the resin material, the polyether polycarbonate diol is more preferably a compound represented by the following formula (2).

[0075] HO-(R 1 O) s -(R 2 -OC(=O)-O) u -R 20 -(OR 1 ) t -OH Formula (2)

[0076] In formula (2), R 1 is an alkylene group having 2 to 4 carbon atoms, R 2 and R 20 is a chain hydrocarbon group having 3 to 20 carbon atoms or a cyclic hydrocarbon group having a ring structure having 6 to 20 carbon atoms. These groups may optionally have one or more substituents. When it is a cyclic hydrocarbon group, it may optionally contain an oxygen atom as an atom constituting the ring. When it contains an oxygen atom, adjacent atoms may not be oxygen atoms at the same time. s and t are the number of repetitions, u is the number of repetitions of 2 or more, (R 2 -OC(=O)-O) u Contains 2 or more (R 2 -OC(=O)-O) represented by the unit.

[0077] R in formula (2) 1 The carbon number of the alkylene group is 2 to 4, preferably 2 or 3, and particularly preferably 3.

[0078] (R 1 O) s OR 1 ) t Each may contain two or more kinds of oxyalkylene groups. When containing two or more kinds of oxyalkylene groups, a combination of an oxypropylene group and an oxyethylene group is preferred.

[0079] (R 1 O) s When composed of two or more oxyalkylene groups, the arrangement may be random, block, or a combination of the two. 1 ) t When composed of two or more oxyalkylene groups, the arrangement thereof may be random, block, or a combination of both.

[0080] R in formula (2) 2 and R 20 is a chain hydrocarbon group having 3 to 20 carbon atoms or a cyclic hydrocarbon group having a ring structure having 6 to 20 carbon atoms. These groups may optionally have one or more substituents. When they are cyclic hydrocarbon groups, they may optionally contain oxygen atoms as atoms constituting the ring. When they contain oxygen atoms, adjacent atoms may not be oxygen atoms at the same time. u is a repetition number of 2 or more, (R 2 -OC(=O)-O) u Contains 2 or more (R 2 -OC(=O)-O) represented by the unit.

[0081] R 2 The carbon number of the chain hydrocarbon group is 3 to 20, preferably 3 to 18, and more preferably 4 to 16. 2 The chain hydrocarbon group is preferably a linear or branched alkylene group, and is preferably unsubstituted.

[0082] R 2 In the case of a cyclic hydrocarbon group which may have a substituent, R 2 For example, -R 21 -R 22 -R 21 - the group shown. 21 represents a single bond or an alkylene group having 1 to 6 carbon atoms. 22 It represents an alicyclic hydrocarbon group having 3 to 9 carbon atoms and having a monocyclic structure which may have a substituent, an alicyclic hydrocarbon group having 4 to 16 carbon atoms and having a polycyclic structure which may have a substituent, or an aromatic hydrocarbon group having 6 to 18 carbon atoms and having a substituent. One or more carbon atoms constituting the ring in the alicyclic hydrocarbon group may be substituted with an oxygen atom. However, adjacent carbon atoms are not substituted with oxygen atoms at the same time.

[0083] R 21 The alkylene group having 1 to 6 carbon atoms may be a straight chain or a branched chain. 21 In the case of an alkylene group having 1 to 6 carbon atoms, the number of carbon atoms is preferably 1 to 4, more preferably 1 or 2. 21, examples include a single bond, methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, isopropylene, isobutylene and tert-butylene, preferably a single bond, methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene and tert-butylene, and more preferably a single bond, methylene and ethylene.

[0084] R 22 In the case of an unsubstituted monocyclic carbon number 3-9 divalent alicyclic saturated hydrocarbon group, R 22 The number of carbon atoms in R is preferably 4 to 8, more preferably 5 to 8, and further preferably 5 or 6, for better stability against heat and light. 22 Examples of the unsubstituted divalent alicyclic saturated hydrocarbon group having 3 to 9 carbon atoms and having a monocyclic structure include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene and cyclononylene, and cyclopentylene and cyclohexylene are preferred.

[0085] R 22 In the case of an unsubstituted divalent alicyclic saturated hydrocarbon group having 4 to 16 carbon atoms and having a polycyclic structure, R 22 The carbon number of R is preferably 4 to 15, more preferably 6 to 12. 22 A group having 2 or 3 ring structures is preferred, and a group having 2 ring structures is more preferred.

[0086] R 22 In the case of an unsubstituted divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, R 22 The carbon number of the group is preferably 6 to 14, more preferably 6 to 12. Examples of the unsubstituted divalent aromatic hydrocarbon group having 6 to 18 carbon atoms include phenylene and biphenylene, and phenylene is preferred.

[0087] R 22 In the case of a substituted C 3-9 divalent alicyclic saturated hydrocarbon group having a monocyclic structure, the monocyclic structure is the same as the unsubstituted C 3-9 divalent alicyclic saturated hydrocarbon group having a monocyclic structure described above.

[0088] R 22 In the case of a C4-16 divalent alicyclic saturated hydrocarbon group having a polycyclic structure having a substituent, the polycyclic structure is the same as the unsubstituted C4-16 divalent alicyclic saturated hydrocarbon group having a polycyclic structure.

[0089] R 22 In the case of a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms and having a substituent, the aromatic hydrocarbon group is the same as in the case of the above-mentioned unsubstituted divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.

[0090] R 22The carbon number of represents the number of carbon atoms constituting the ring only, excluding the carbon number of the substituent.

[0091] R 2 In the case of a chain hydrocarbon group having a substituent, examples of the substituent include a halogen atom and an alkoxy group. The halogen atom is preferably a chlorine atom. The alkoxy group is preferably a methoxy group and an ethoxy group. The number of the substituents is preferably 1 to 4, more preferably 1 to 2.

[0092] R 2 In the case of a cyclic hydrocarbon group having a substituent, examples of the substituent include an alkyl group having 1 to 8 carbon atoms, a halogen atom, and an alkoxy group.

[0093] Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, and octyl. Among them, methyl, ethyl, n-propyl, isopropyl, n-butyl, and tert-butyl are preferred, and methyl, ethyl, and tert-butyl are more preferred.

[0094] The halogen atom is preferably a chlorine atom. The alkoxy group is preferably a methoxy group or an ethoxy group. The number of substituents is preferably 1 to 4, more preferably 1 to 2.

[0095] R 22 In the case where one or more carbon atoms constituting the ring are substituted with oxygen atoms, the ratio of the number of oxygen atoms to the total number of atoms constituting the ring is preferably 5 to 50%, more preferably 10 to 30%.

[0096] In formula (2), s and t are repetition numbers, and are preferably integers of 1 or more.

[0097] s and t in the formula (2) are appropriately adjusted according to the Mn of the polycarbonate diol as a raw material of the polyether polycarbonate diol so that the Mn of the polyether polycarbonate diol falls within the above range.

[0098] s and t in the formula (2) may be the same value or different values, but are preferably substantially the same values ​​from the viewpoint of facilitating setting of production conditions.

[0099] In formula (2), (R 2 -OC(=O)-O) u Contains R 2 Two or more different units. 2 -OC(=O)-O) u It may contain more than 3 types of units.

[0100] Composition (R 2 -OC(=O)-O) uThe arrangement of two or more types of units may be random, block, or a combination of both.

[0101] The content of the polyether polycarbonate diol in the adhesive composition is preferably 10 to 70% by mass, more preferably 15 to 65% by mass, further preferably 18 to 60% by mass, and further preferably 20 to 40% by mass, relative to the total amount of the adhesive composition. When the content of the polyether polycarbonate diol is above the lower limit, the adhesion to the resin material becomes better, and when it is below the upper limit, the viscosity of the composition decreases, the preparation and coating become easier, and the compatibility with the polyisocyanate compound or isocyanate group-terminated urethane prepolymer described later becomes better.

[0102] (Method for producing polyether polycarbonate diol)

[0103] The method for producing the polyether polycarbonate diol is not particularly limited, and examples thereof include a method in which a cyclic ether is subjected to ring-opening addition reaction using a polycarbonate diol as an initiator in the presence of a catalyst to obtain the polyether polycarbonate diol.

[0104] Examples of the polycarbonate diol include condensates of two or more alcohols and carbonate compounds. Examples of the alcohol and carbonate compound include those listed in the section [Polycarbonate diol].

[0105] The polycarbonate diols may be used alone or in combination of two or more.

[0106] Examples of the cyclic ether include the same compounds as those mentioned above. Examples of the cyclic ether for ring-opening addition polymerization include ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran. From the viewpoint of improving the adhesion to the resin material, propylene oxide is more preferably contained.

[0107] As the catalyst for the ring-opening addition polymerization of the cyclic ether in the initiator, a conventionally known catalyst can be used. For example, an alkali catalyst such as potassium hydroxide, a transition metal compound-porphyrin complex catalyst such as a complex obtained by reacting an organoaluminum compound with porphyrin, a composite metal cyanide complex catalyst (hereinafter, also referred to as a "DMC catalyst"), and a catalyst formed from a phosphazene compound can be cited.

[0108] The amount of the catalyst added is not particularly limited as long as it is an amount required for the ring-opening polymerization of the cyclic ether, but is preferably as small as possible, such as 0.001 to 10 parts by mass, more preferably 0.002 to 5 parts by mass, and even more preferably 0.05 to 3 parts by mass, relative to 100 parts by mass of the obtained polyether polycarbonate diol.

[0109] [One-component curable urethane adhesive composition and two-component curable urethane adhesive composition]

[0110] The adhesive composition of the present invention includes a one-component curable urethane adhesive composition and a two-component curable urethane adhesive composition. The one-component curable urethane adhesive composition contains the aforementioned polyether polycarbonate diol and contains a polyisocyanate compound or an isocyanate-terminated urethane prepolymer. The two-component curable urethane adhesive composition includes a main agent and a curing agent, wherein the main agent contains an isocyanate-terminated urethane prepolymer, and the curing agent contains the aforementioned polyether polycarbonate diol.

[0111] (Two-component curing urethane adhesive composition)

[0112] The two-component curable urethane adhesive composition comprises: a main agent containing an isocyanate group-terminated urethane prepolymer, and a curing agent containing the above-mentioned polyether polycarbonate diol.

[0113] <Main agent>

[0114] The isocyanate-terminated urethane prepolymer contained in the main agent is obtained by reacting a polyisocyanate compound with a compound having two or more active hydrogen-containing groups in one molecule (hereinafter referred to as "active hydrogen compound") so that the isocyanate group is in excess relative to the active hydrogen-containing group. Examples of the active hydrogen-containing group include hydroxyl, amino, and imino groups.

[0115] Examples of the active hydrogen compound include polyols having two or more hydroxyl groups in one molecule and polyamines having two or more amino groups in one molecule. Polyols are preferred, and the aforementioned polyether polycarbonate diols may also be used.

[0116] [Polyol]

[0117] The number average molecular weight (Mn) of the polyol preferably contains a trifunctional component and a bifunctional component from the viewpoint that the viscosity of the urethane prepolymer obtained by the reaction with the polyisocyanate compound has appropriate fluidity at room temperature (25°C). As the trifunctional component, Mn is preferably 1000 to 10000, more preferably 2000 to 8000. As the bifunctional component, Mn is preferably 500 to 5000, more preferably 1000 to 3000.

[0118] The Mn of the polyol is a value obtained by the same method as the method for measuring the Mn of the polyether polycarbonate diol. When the Mn of the polyol is within the above range, the viscosity is lower and better reactivity with an isocyanate group can be obtained.

[0119] When the polyol is a compound having two or more hydroxyl groups, its molecular weight and skeleton are not particularly limited. As polyols, for example, polyether polyols, polyester polyols, polymer polyols, poly(meth)acrylic acid polyols, polycarbonate polyols, castor oil polyols, polyolefin polyols can be cited, and the substances described in

[0016] to

[0028] of Japanese Patent Publication No. 2020-37689 can be used without particular limitation. These can be used alone or in combination of two or more.

[0120] In addition, as the polyol, a polymer polyol in which a polymer having a unit based on a (meth) acrylic acid ester monomer is dispersed in a polyether polyol may be used. The polymer polyol may be a commercially available product, for example, the "ULTIFLOW (registered trademark)" series, the "Shapurflow (registered trademark)" series (all manufactured by Sanyo Chemical Industries, Ltd.), and the "EXCENOL (registered trademark)" series (manufactured by AGC Corporation) may be cited.

[0121] It should be noted that in the present specification, (meth)acrylic acid refers to acrylic acid and / or methacrylic acid, and (meth)acrylate refers to acrylate and / or methacrylate.

[0122] [Polyisocyanate compound]

[0123] The polyisocyanate compound is an organic compound having two or more isocyanate groups in one molecule. The number of isocyanate groups in one molecule is preferably 2 to 4. The polyisocyanate compound may be used alone or in combination of two or more.

[0124] Examples of the polyisocyanate compound include linear or branched aliphatic diisocyanate compounds such as tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dodecamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, and 3-methylpentane-1,5-diisocyanate;

[0125] Norbornane diisocyanate (NBDI), isophorone diisocyanate (IPDI), hydrogenated xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane diisocyanate (H 12 MDI) and other alicyclic diisocyanate compounds;

[0126] Aromatic polyisocyanate compounds such as toluene diisocyanate (TDI), 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diisocyanate, α, α, α', α'-tetramethylxylylene diisocyanate, 4,4'-dibenzyl diisocyanate, o-toluene diisocyanate, 1,5-naphthalene diisocyanate, dialkyl diphenylmethane diisocyanate, and tetraalkyl diphenylmethane diisocyanate;

[0127] Isocyanurate modified products of the above-mentioned diisocyanate compounds; biuret modified products of the above-mentioned diisocyanate compounds; allophanate modified products of the above-mentioned diisocyanate compounds; carbodiimide modified products of the above-mentioned diisocyanate compounds; trifunctional or higher isocyanate group-terminated urethane prepolymers (addition modified products) obtained by reacting the above-mentioned diisocyanate compounds with a polyol having more than three hydroxyl groups in one molecule; water-dispersible polyisocyanate compounds such as water-dispersible isocyanates and blocked isocyanates; triphenylmethane triisocyanate; and other polyisocyanate compounds having more than three isocyanate groups in one molecule.

[0128] Examples of commercially available isocyanurate-modified products include DURANATE TPA-100, DURANATE TKA-100 (manufactured by Asahi Kasei Corporation), and CORONATE HX (manufactured by Tosoh Corporation).

[0129] Examples of commercially available products of the biuret-modified body include DURANATE 24A-100 and DURANATE 22A-75P (manufactured by Asahi Kasei Corporation).

[0130] Examples of commercially available products of tri- or higher-functional isocyanate group-terminated urethane prepolymers include CORONATE L, CORONATE L-55E, and CORONATE L-45E (all manufactured by Tosoh Corporation).

[0131] Examples of commercially available water-dispersible isocyanates include DURANATE WB40-100, DURANATE WB40-80D, DURANATE WT20-100, DURANATE WL70-100, DURANATE WE50-100, and DURANATE WR80-70P (manufactured by Asahi Kasei Corporation), and Aquanate 105, Aquanate 130, Aquanate 140, Aquanate 200, and Aquanate 210 (manufactured by Tosoh Corporation).

[0132] Commercially available products of blocked isocyanates include, for example, SU-268A, NBP-211, Meikanate CX, Meikanate TP-10, and DM-6400 (all manufactured by Meisei Chemical Industries, Ltd.); WM44-L70G (manufactured by Asahi Kasei Corporation); Aqua BI200 and Aqua BI220 (both manufactured by Baxenden Chemicals); TAKELAC W and TAKELAC WPB (both manufactured by Mitsui Chemicals, Inc.); BURNOCK (manufactured by DIC Corporation); Elastron (manufactured by Daiichi Kogyo Co., Ltd.); and the like.

[0133] The content of the isocyanate group in the polyisocyanate compound is preferably 20% by mass or more, more preferably 25% by mass or more, particularly preferably 30% by mass or more, and is preferably 50% by mass or less, more preferably 45% by mass or less, and further preferably 40% by mass or less, from the viewpoint of obtaining good reactivity with the polyol.

[0134] Specifically, preferred polyisocyanate compounds containing isocyanate groups in the above preferred range include aliphatic diisocyanate compounds, alicyclic diisocyanate compounds, and aromatic polyisocyanate compounds, and examples thereof include MDI (isocyanate group content: 33.6% by mass), polymeric MDI (isocyanate group content: 31.0% by mass), crude MDI (a mixture of MDI and triphenylmethane triisocyanate), and IPDI (isocyanate group content: 37.8% by mass).

[0135] When obtaining the isocyanate group-terminated urethane prepolymer, the molar ratio of the isocyanate group in the polyisocyanate compound to the hydroxyl group in the polyol (isocyanate group / hydroxyl group) is preferably 110 or more and 600 or less.

[0136] The molar ratio is preferably 120 or more, more preferably 125 or more, particularly preferably 130 or more, and is preferably 500 or less, more preferably 400 or less, particularly preferably 300 or less. When the molar ratio is within the above range, an isocyanate group-terminated urethane prepolymer having an appropriate molecular chain length can be produced, so the productivity is further improved.

[0137] The molecular weight of the polyisocyanate compound is not particularly limited, but is preferably 120 to 400, more preferably 130 to 390, and particularly preferably 140 to 380. When the molecular weight of the polyisocyanate compound is within the above range, good reactivity with the polyol can be obtained.

[0138] [Method for producing isocyanate-terminated urethane prepolymer]

[0139] The isocyanate group-terminated urethane prepolymer can be produced by reacting a polyol with a polyisocyanate compound.

[0140] In the production of the isocyanate group-terminated urethane prepolymer, a catalyst may be used as required. Examples of the catalyst include tertiary amine compounds, tin compounds, non-tin compounds, etc. The catalyst may be used alone or in combination of two or more.

[0141] Examples of the tertiary amine compound include triethylamine, triethylenediamine, and 1,8-diazabicyclo[5.4.0]-7-undecene (DBU).

[0142] Examples of the tin compound include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, and 2-ethyltin hexanoate.

[0143] As non-tin compounds, there can be cited titanium compounds such as dibutyltitanium dichloride, tetrabutyl titanate, butoxytitanium trichloride; lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, lead naphthenate; iron compounds such as iron 2-ethylhexanoate, iron acetylacetonate; cobalt compounds such as cobalt benzoate, cobalt 2-ethylhexanoate; zinc compounds such as zinc naphthenate, zinc 2-ethylhexanoate; zirconium compounds such as zirconium naphthenate; and the like.

[0144] When a catalyst is used, the amount of the catalyst used is not particularly limited, but is preferably 0.001 parts by mass or more, more preferably 0.002 parts by mass or more, and particularly preferably 0.003 parts by mass or more, relative to 100 parts by mass of the total of the polyol and the polyisocyanate compound. In addition, it is preferably 1.0 parts by mass or less, more preferably 0.2 parts by mass or less, and particularly preferably 0.05 parts by mass or less.

[0145] In the production of the isocyanate group-terminated urethane prepolymer, a solvent may be used as necessary.

[0146] Examples of the solvent include ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, aromatic hydrocarbons such as toluene and xylene, etc. The solvent may be used alone or in combination of two or more.

[0147] When a solvent is used, the amount of the solvent used is not particularly limited, but is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, particularly preferably 50 parts by mass or more, relative to 100 parts by mass of the total of the polyol and the polyisocyanate compound, and is preferably 500 parts by mass or less, more preferably 450 parts by mass or less, particularly preferably 400 parts by mass or less.

[0148] As a method for producing the isocyanate group-terminated urethane prepolymer, for example, the method described below can be mentioned.

[0149] Production method 1: A method of simultaneously adding a polyol, a polyisocyanate compound, an optional catalyst, and an optional solvent

[0150] Production method 2: A method of adding a polyol, an optional catalyst, and an optional solvent and then dropping a polyisocyanate compound thereinto

[0151] In the case of the production method 2, the low molecular weight components in the raw materials are reacted preferentially, so that the molecular weight distribution can be made narrower and the reaction can be easily controlled.

[0152] The reaction temperature is preferably 50° C. or higher, more preferably 60° C. or higher, particularly preferably 65° C. or higher, and preferably lower than 100° C., more preferably 95° C. or lower, particularly preferably 80° C. or lower. When the reaction temperature is within the above range, side reactions other than the urethane reaction are easily suppressed, so that the desired isocyanate group-terminated urethane prepolymer is easily obtained.

[0153] After the reaction is completed, a reaction terminator may be added to deactivate the catalyst. As the reaction terminator, for example, acetylacetone may be mentioned. Two or more reaction terminators may be used in combination.

[0154] The Mn of the isocyanate-terminated urethane prepolymer is not particularly limited, but is preferably 2500 or more, more preferably 3000 or more, and particularly preferably 4000 or more, and is preferably 50000 or less, more preferably 40000 or less, and particularly preferably 30000 or less. When the Mn is within the above range, an adhesive composition having excellent coating properties can be obtained, and the viscosity during synthesis can be adjusted.

[0155] The Mn of the isocyanate group-terminated urethane prepolymer is a value obtained by the same method as the method for measuring the Mn of the above-mentioned polyether polycarbonate diol.

[0156] For the isocyanate-terminated urethane prepolymer, from the viewpoint of having better adhesion to the resin material, it is preferred to react a polyether polyol with an aromatic polyisocyanate compound to form a urethane prepolymer, or to react the aforementioned polyether polycarbonate diol with an aromatic polyisocyanate compound to form a urethane prepolymer. As the aromatic polyisocyanate compound, the same compounds as those exemplified above can be used.

[0157] The content of the isocyanate group-terminated urethane prepolymer in the adhesive composition is preferably 18 to 90% by mass, more preferably 20 to 80% by mass, further preferably 22 to 70% by mass, and further preferably 22 to 50% by mass, relative to the total amount of the adhesive composition. When the content of the isocyanate group-terminated urethane prepolymer is above the lower limit, it is easy to improve the adhesiveness, and the breaking strength and elongation at break of the cured product. In addition, when it is below the upper limit, good compatibility with other polymers can be obtained.

[0158] <Curing Agent>

[0159] The curing agent contains the aforementioned polyether polycarbonate diol.

[0160] From the viewpoint of promoting the effect when the main agent and the curing agent are mixed, the curing agent may contain a catalyst in addition to the above-mentioned polyether polycarbonate diol.

[0161] Examples of the catalyst include the above-mentioned tertiary amine compounds, tin compounds, and non-tin compounds that can be used in the production of the isocyanate group-terminated urethane prepolymer. The catalyst can be used alone or in combination of two or more.

[0162] When the catalyst is added, the amount thereof is not particularly limited, but is preferably 0.00001 parts by mass or more, more preferably 0.00005 parts by mass or more, particularly preferably 0.0001 parts by mass or more, and is preferably 1.0 parts by mass or less, more preferably 0.2 parts by mass or less, particularly preferably 0.05 parts by mass or less, relative to 100 parts by mass of the polyether polycarbonate diol.

[0163] In the two-component curable urethane adhesive composition, the isocyanate index representing the molar ratio of the isocyanate groups in the isocyanate group-terminated urethane prepolymer to the hydroxyl groups in the polyether polycarbonate diol (isocyanate groups / hydroxyl groups) is preferably 80 or more and 150 or less.

[0164] The isocyanate index is more preferably 85 or more, further preferably 90 or more, particularly preferably 95 or more, and more preferably 140 or less, further preferably 130 or less, particularly preferably 120 or less. When the isocyanate index is within the above preferred range, the fracture strength and elongation at break of the cured product obtained by curing the two-component curing type urethane adhesive composition are likely to become better. It should be noted that the isocyanate index is a value 100 times the ratio of the molar number of isocyanate groups of the isocyanate group-terminated urethane prepolymer to the total molar number of hydroxyl groups of the polyether polycarbonate diol.

[0165] The main agent and curing agent in the two-component curable urethane adhesive composition may further contain a solvent, additives described below, and the like.

[0166] As the solvent, the above-mentioned solvents which can be used as needed in the production of the isocyanate group-terminated urethane prepolymer are preferred.

[0167] When a solvent is contained, the amount thereof is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, particularly preferably 50 parts by mass or more, and is preferably 500 parts by mass or less, more preferably 450 parts by mass or less, particularly preferably 400 parts by mass or less, relative to 100 parts by mass of the isocyanate group-terminated urethane prepolymer.

[0168] The total ratio of the main agent and the curing agent in the two-component curing type urethane adhesive composition is preferably 50% by mass or more and 100% by mass or less. The total ratio of the main agent and the curing agent is more preferably 55% by mass or more, further preferably 60% by mass or more, and more preferably less than 100% by mass, further preferably 99.5% by mass or less, and further preferably 95% by mass or less.

[0169] (Method for producing two-component curable urethane adhesive composition)

[0170] The method for producing the two-component curing type urethane adhesive composition can be applied to a known method. For example, the main agent can be produced by uniformly stirring and mixing the components contained in the main agent, specifically the aforementioned isocyanate-terminated urethane prepolymer, and the solvent contained as required, and one or more of the additives described below. In addition, the curing agent can be produced by uniformly stirring and mixing the components contained in the curing agent, specifically the aforementioned polyether polycarbonate diol, the catalyst component contained as required, the solvent, and one or more of the additives described below.

[0171] For stirring and mixing, a known stirring and mixing machine such as a plastomill equipped with a heating device, a kneader, a Banbury mixer, a roll, etc. can be used. The stirring and mixing is preferably performed in an inert gas atmosphere such as nitrogen or in a reduced pressure dehydration atmosphere.

[0172] It should be noted that there is no particular limitation on the order in which the above components are added.

[0173] The base agent and the curing agent may be contained in different containers. Various containers such as tubes and bottles may be used as the container.

[0174] [Additives that can be compounded in the two-component curing type urethane adhesive composition]

[0175] The two-component curable urethane adhesive composition may contain additives such as a hydrolysis inhibitor, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a plasticizer, an antistatic agent, a leveling agent, and other optional components as necessary within a range not impairing the effects of the present invention.

[0176] -Hydrolysis Inhibitors-

[0177] Examples of the hydrolysis inhibitor include carbodiimide-based, isocyanate-based, oxazoline-based, and epoxy-based. The hydrolysis inhibitor may be used alone or in combination of two or more. Among these, carbodiimide-based is preferred from the viewpoint of the hydrolysis inhibition effect.

[0178] --Carbodiimide Series--

[0179] The carbodiimide hydrolysis inhibitor is a compound having one or more carbodiimide groups in one molecule. Examples of the monocarbodiimide compound include dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, diphenylcarbodiimide, and naphthylcarbodiimide.

[0180] The polycarbodiimide compound can be produced by subjecting diisocyanate to a decarboxylation condensation reaction in the presence of a carbodiimidization catalyst.

[0181] Examples of the diisocyanate include MDI, 3,3'-dimethoxy-4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, 3,3'-dimethyl-4,4'-diphenyl ether diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1-methoxyphenyl-2,4-diisocyanate, IPDI, 4,4'-dicyclohexylmethane diisocyanate, and tetramethylxylylene diisocyanate.

[0182] Examples of the carbodiimidization catalyst include phosphole oxides such as 1-phenyl-2-phosphole-1-oxide, 3-methyl-2-phosphole-1-oxide, 1-ethyl-3-methyl-2-phosphole-1-oxide, 1-ethyl-2-phosphole-1-oxide, and 3-phosphole isomers thereof.

[0183] --Isocyanate Series--

[0184] Examples of the isocyanate hydrolysis inhibitor include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, 1,5-naphthalene ...2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'- Isocyanate, 1,5-tetrahydronaphthalene diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, IPDI, 4,4'-dicyclohexylmethane diisocyanate, 3,3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate.

[0185] --Oxazoline Series--

[0186] Examples of the oxazoline hydrolysis inhibitor include 2,2'-o-phenylenebis(2-oxazoline), 2,2'-m-phenylenebis(2-oxazoline), 2,2'-p-phenylenebis(2-oxazoline), 2,2'-p-phenylenebis(4-methyl-2-oxazoline), 2,2'-m-phenylenebis(4-methyl-2-oxazoline), 2,2'-p-phenylenebis(4,4'-dimethyl-2-oxazoline, oxazoline), 2,2'-m-phenylenebis(4,4'-dimethyl-2-oxazoline), 2,2'-ethylenebis(2-oxazoline), 2,2'-tetramethylenebis(2-oxazoline), 2,2'-hexamethylenebis(2-oxazoline), 2,2'-octamethylenebis(2-oxazoline), 2,2'-ethylenebis(4-methyl-2-oxazoline), 2,2'-diphenylenebis(2-oxazoline).

[0187] --Epoxy Series--

[0188] Examples of epoxy hydrolyzing agents include diglycidyl ethers of aliphatic diols such as 1,6-hexanediol, neopentyl glycol, and polyalkylene glycol; polyglycidyl ethers of aliphatic polyols such as sorbitol, sorbitan, polyglycerol, pentaerythritol, diglycerol, glycerol, and trimethylolpropane; polyglycidyl ethers of alicyclic polyols such as cyclohexanedimethanol; diglycidyl esters or polyglycidyl esters of aliphatic or aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, trimellitic acid, adipic acid, and sebacic acid; and resorcinol, bis(p-hydroxyphenyl)methane, 2,2-bis( Diglycidyl ethers or polyglycidyl ethers of polyphenols such as (p-hydroxyphenyl)propane, tris(p-hydroxyphenyl)methane, 1,1,2,2-tetra(p-hydroxyphenyl)ethane; N-glycidyl derivatives of amines such as N,N-diglycidyl aniline, N,N-diglycidyl toluidine, N,N,N',N'-tetraglycidyl-bis(p-aminophenyl)methane; triglycidyl derivatives of aminophenol; triglycidyl tris(2-hydroxyethyl) isocyanurate; triglycidyl isocyanurate; epoxy resins such as o-cresol type epoxy resin and phenol novolac type epoxy resin.

[0189] The amount of the hydrolysis inhibitor added is not particularly limited, but is preferably 5 parts by mass or less, more preferably 4.5 parts by mass or less, and particularly preferably 3 parts by mass or less, based on 100 parts by mass of the isocyanate group-terminated urethane prepolymer.

[0190] -Antioxidants-

[0191] Examples of the antioxidant include free radical scavengers such as phenolic compounds and amine compounds, and peroxide decomposers such as sulfur compounds and phosphorus compounds. The antioxidant may be used alone or in combination of two or more.

[0192] --Phenolic compounds--

[0193] Examples of the phenolic compound include 2,6-di-tert-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-tert-butyl-4-ethylphenol, stearyl-β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-butylenebis(3-methyl-6-tert-butylphenol), 3,9-bis[1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]2,4,8,10-tetraoxaspiro[5,5]undecane, and phenylpropionic acid. 3,5-bis(1,1-dimethylethyl)-4-hydroxy-, C7-C9 side chain alkyl ester (product name Irganox1135 of BASF), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tetrakis-[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane, bis[3,3'-bis-(4'-hydroxy-3'-tert-butylphenyl)butanoic acid]diol ester, 1,3,5-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)-S-triazine-2,4,6-(1H,3H,5H)trione, tocopherol.

[0194] --Amine compounds--

[0195] Examples of the amine compound include bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, a polycondensate of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidinylethanol, N,N',N",N"'-tetrakis-(4,6-bis-(butyl-(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl)amino)-triazine-2-yl)-4,7-diazadecane-1,10-diamine, and a polycondensate of dibutylamine·1,3,5-triazine·N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidinyl)butylamine.

[0196] --Sulfur compounds--

[0197] Examples of the sulfur-based compound include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, and distearyl 3,3'-thiodipropionate.

[0198] --Phosphorus compounds--

[0199] Examples of the phosphorus compound include triphenyl phosphite, diphenyl isodecyl phosphite, 4,4'-butylene-bis(3-methyl-6-tert-butylphenyl ditridecyl)phosphite, cycloneopentanatetraylbis(octadecylphosphite), tris(nonylphenyl)phosphite, tris(monononylphenyl)phosphite, tris(dinonylphenyl)phosphite, diisodecyl pentaerythritol diphosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3 ,5-di-tert-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene, tris(2,4-di-tert-butylphenyl) phosphite, cycloneopentanetratetraylbis(2,4-di-tert-butylphenyl) phosphite, cycloneopentanetratetraylbis(2,6-di-tert-butyl-4-methylphenyl) phosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite.

[0200] By using an antioxidant, thermal degradation of the isocyanate group-terminated urethane prepolymer can be prevented.

[0201] The amount of the antioxidant added is not particularly limited, but is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and particularly preferably 2 parts by mass or less, based on 100 parts by mass of the isocyanate group-terminated urethane prepolymer.

[0202] As the antioxidant, from the viewpoint of stability and antioxidant effect, it is preferred to use one or more phenolic compounds as free radical scavengers. It is also possible to use one or more phenolic compounds as free radical scavengers in combination with one or more phosphorus compounds as peroxide decomposers. In addition, it is also possible to use a phenolic compound as a free radical scavenger and a phosphorus compound as a peroxide decomposer in combination as an antioxidant, and use these antioxidants in combination with the aforementioned hydrolysis inhibitor.

[0203] -UV absorber-

[0204] Examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, salicylic acid compounds, oxalylanilide compounds, cyanoacrylate compounds, and triazine compounds. The ultraviolet absorber may be used alone or in combination of two or more.

[0205] The amount of the ultraviolet absorber added is not particularly limited, but is preferably 3 parts by mass or less, more preferably 2.5 parts by mass or less, and particularly preferably 2 parts by mass or less, based on 100 parts by mass of the isocyanate group-terminated urethane prepolymer.

[0206] -Light Stabilizer-

[0207] Examples of the light stabilizer include hindered amine compounds and hindered piperidine compounds. The light stabilizer may be used alone or in combination of two or more.

[0208] The amount of the light stabilizer added is not particularly limited, but is preferably 2 parts by mass or less, more preferably 1.5 parts by mass or less, and particularly preferably 1 part by mass or less, based on 100 parts by mass of the isocyanate group-terminated urethane prepolymer.

[0209] - Fillers -

[0210] As fillers, there may be mentioned, for example, inorganic or organic fillers, such as, in particular, natural, heavy or precipitated calcium carbonate, optionally coated with fatty acids, in particular stearic acid, barite, talc, quartz powder, silica sand, dolomite, wollastonite, kaolin, calcined kaolin, mica (potassium aluminum silicate), zeolites, molecular sieves, aluminum oxide, aluminum hydroxide, magnesium hydroxide, silicon dioxide including finely divided silicon dioxide from a thermal decomposition process, industrially produced carbon black, graphite, metal powders, for example aluminum, copper, iron, silver or steel, PVC powder or hollow spheres and flame-retardant fillers, for example hydroxides or hydrates, in particular aluminum hydroxides or hydrates, preferably aluminum hydroxide.

[0211] The amount of the filler added is not particularly limited, but is preferably 80 parts by mass or less, more preferably 70 parts by mass or less, and particularly preferably 60 parts by mass or less, based on 100 parts by mass of the isocyanate group-terminated urethane prepolymer.

[0212] -Plasticizers-

[0213] Examples of the plasticizer include di(2-ethylhexyl) phthalate, dibutyl phthalate, dilauryl phthalate, dioctyl adipate, diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), diisodecyl adipate, tributyl phosphate, trioctyl phosphate, propylene glycol adipate polyester, butylene glycol adipate polyester, epoxidized soybean oil, chlorinated paraffin, and liquid paraffin.

[0214] The amount of the plasticizer added is not particularly limited, but is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and particularly preferably 25 parts by mass or less, based on 100 parts by mass of the isocyanate group-terminated urethane prepolymer.

[0215] -Antistatic Agent-

[0216] Examples of the antistatic agent include inorganic salts, polyol compounds, ionic liquids, surfactants, etc. The antistatic agent may be used alone or in combination of two or more.

[0217] Among these, ionic liquids are preferred. It should be noted that "ionic liquid" is also called room-temperature molten salt, and is a salt having fluidity at 25°C.

[0218] --Inorganic salts--

[0219] Examples of the inorganic salt include sodium chloride, potassium chloride, lithium chloride, lithium perchlorate, ammonium chloride, potassium chlorate, aluminum chloride, cupric chloride, ferrous chloride, ferric chloride, ammonium sulfate, potassium nitrate, sodium nitrate, sodium carbonate, and sodium thiocyanate.

[0220] --Polyol Compounds--

[0221] Examples of the polyol compound include propylene glycol, butylene glycol, hexylene glycol, polyethylene glycol, trimethylolpropane, and pentaerythritol.

[0222] --Ionic Liquids--

[0223] Examples of the ionic liquid include 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-methylpyridinium bis(trifluoromethylsulfonyl)imide, 1-butylpyridinium bis(trifluoromethylsulfonyl)imide, 1-hexylpyridinium bis(trifluoromethylsulfonyl)imide, 1-octylpyridinium bis(trifluoromethylsulfonyl)imide, 1-hexyl-4-methylpyridinium bis(trifluoromethylsulfonyl)imide, 1-hexyl-4-methylpyridinium hexafluorophosphate, 1-octyl-4-methylpyridinium bis(trifluoromethylsulfonyl)imide, and the like. Ionic liquids containing pyridinium ions such as 1-octyl-4-methylpyridinium bis(fluorosulfonyl)imide, 1-methylpyridinium bis(perfluoroethylsulfonyl)imide, and 1-methylpyridinium bis(perfluorobutylsulfonyl)imide; ionic liquids containing ammonium ions such as trimethylheptylammonium bis(trifluoromethanesulfonyl)imide, N,N-diethyl-N-methyl-N-propylammonium bis(trifluoromethanesulfonyl)imide, N,N-diethyl-N-methyl-N-pentylammonium bis(trifluoromethanesulfonyl)imide, N,N-diethyl-N-methyl-N-heptylammonium bis(trifluoromethanesulfonyl)imide, and tri-n-butylmethylammonium bis(trifluoromethanesulfonyl)imide; and other ionic liquids such as pyrrolidinium salts, phosphonium salts, and sulfonium salts.

[0224] --Surfactant--

[0225] Examples of the surfactant include nonionic low molecular surfactants such as glycerol fatty acid esters, polyoxyalkylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkylamines, polyoxyethylene alkylamine fatty acid esters, and fatty acid diethanolamides; anionic low molecular surfactants such as alkyl sulfonates, alkylbenzene sulfonates, and alkyl phosphates; cationic low molecular surfactants such as tetraalkylammonium salts and trialkylbenzylammonium salts; amphoteric low molecular surfactants such as alkyl betaines and alkyl imidazolium betaines; nonionic high molecular surfactants such as polyether ester amide type, ethylene oxide-epichlorohydrin type, and polyether ester type; anionic high molecular surfactants such as polystyrene sulfonic acid type; cationic high molecular surfactants such as acrylate polymer type containing a quaternary ammonium salt group; and amphoteric high molecular surfactants such as amino acid type amphoteric surfactants such as higher alkyl aminopropionates, and betaine type amphoteric surfactants such as higher alkyl dimethyl betaine and higher alkyl dihydroxyethyl betaine.

[0226] The amount of the antistatic agent added is not particularly limited, but is preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, and particularly preferably 0.05 parts by mass or more, relative to 100 parts by mass of the isocyanate-terminated urethane prepolymer, and is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and particularly preferably 3 parts by mass or less.

[0227] -Leveling agent-

[0228] As the leveling agent, for example, an acrylic leveling agent, a fluorine leveling agent, and a silicone leveling agent can be cited. The leveling agent can be used alone or in combination of two or more. Among these, an acrylic leveling agent is preferred.

[0229] The amount of the leveling agent added is not particularly limited, but is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, particularly preferably 0.1 parts by mass or more, relative to 100 parts by mass of the isocyanate group-terminated urethane prepolymer, and is preferably 2 parts by mass or less, more preferably 1.5 parts by mass or less, particularly preferably 1 part by mass or less.

[0230] -Other optional ingredients-

[0231] As other optional components, for example, there can be mentioned catalysts, other resins other than isocyanate-terminated urethane prepolymers, metal powder, colorants (pigments, etc.), foil-like materials, conductive agents, silane coupling agents, lubricants, preservatives, heat stabilizers, weather stabilizers, inhibitors, and defoaming agents.

[0232] (How to use)

[0233] The two-component curable urethane adhesive composition can be used by mixing the main agent and the curing agent.

[0234] The two-component curable urethane adhesive composition can be cured under the conditions of, for example, 5 to 90° C. and a relative humidity of 5 to 95%. The temperature during mixing is preferably 30° C. or higher, more preferably 35° C. or higher, particularly preferably 40° C. or higher, and is lower than 90° C., more preferably 80° C. or lower, particularly preferably 60° C. or lower. If the temperature is within the above range, side reactions other than the urethane reaction can be easily suppressed.

[0235] (One-component curing urethane adhesive composition)

[0236] The one-component curable urethane adhesive composition contains the aforementioned polyether polycarbonate diol and the aforementioned polyisocyanate compound or the aforementioned isocyanate group-terminated urethane prepolymer. The one-component curable urethane adhesive composition may contain the aforementioned additives as necessary.

[0237] The one-component curable urethane adhesive composition can be produced by a known method, for example, a method of mixing the polyether polycarbonate diol and the polyisocyanate compound, or a method of mixing the polyether polycarbonate diol and the isocyanate group-terminated urethane prepolymer.

[0238] The mixing may be performed using a known stirring mixer such as a plastomill equipped with a heating device, a kneader, a Banbury mixer, or a roll. The mixing may be performed preferably in an inert gas atmosphere such as nitrogen or in a reduced pressure dehydration atmosphere.

[0239] It should be noted that there is no particular restriction on the order in which the aforementioned components are added.

[0240] In the method for producing a one-component curable urethane adhesive composition, for example, the polyether polycarbonate diol may be reacted with the polyisocyanate compound to obtain an isocyanate-terminated prepolymer, and then the prepolymer may be reacted with a chain extender. Alternatively, the prepolymer may be reacted with the chain extender and then reacted with a polyisocyanate compound.

[0241] Alternatively, the polyether polycarbonate diol may be reacted with the polyisocyanate compound to obtain an isocyanate-terminated prepolymer, and the prepolymer may be reacted with a polyfunctional alcohol. Alternatively, the polyether polycarbonate diol may be reacted with the polyisocyanate compound to obtain a hydroxyl-terminated prepolymer, and the prepolymer may be reacted with a polyisocyanate compound.

[0242] Examples of the chain extender include straight-chain diols such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol; 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2,4-heptanediol, 1,4-dimethylolhexane, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, dimer glycol, neopentyl glycol and other diols with branched chains; diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol and other diols with ether groups; 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol , 1,4-dihydroxycyclohexane, 1,4-dihydroxyethylcyclohexane and other diols with alicyclic structures; diols with aromatic groups such as benzyl alcohol, 1,4-dihydroxyethylbenzene, 4,4'-methylenebis(hydroxyethylbenzene); polyols such as glycerol, trimethylolpropane, pentaerythritol; hydroxylamines such as N-methylethanolamine, N-ethylethanolamine; ethylenediamine, 1,3-diaminopropane, hexamethylenediamine, triethylenetetramine, diethylene Polyamines such as 1,2-diaminopiperazine, 1,2-diaminopiperazine, 1,2-diaminobenzene ...

[0243] Among these, ethylene glycol, propylene glycol, 1,4-butanediol, and 1,6-hexanediol are preferred, and 1,4-butanediol is more preferred, from the viewpoint of versatility and reactivity with an isocyanate group.

[0244] Examples of the polyfunctional alcohol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, glycerol, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, 1,2,6-hexanetriol, diglycerol, dipentaerythritol, and polyoxyalkylene glycols and polyoxyalkylene triols having a hydroxyl value-converted molecular weight of 6,000 or less.

[0245] A reaction catalyst may be used when reacting the polyether polycarbonate diol with the polyisocyanate compound. When a reaction catalyst is used when reacting the polyether polycarbonate diol with the polyisocyanate compound, examples of the reaction catalyst include organic tin compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, and 2-ethylhexanoic acid tin; iron compounds such as ferric acetylacetonate and ferric chloride; tertiary amine catalysts such as triethylamine and triethylenediamine; and other known urethanization reaction catalysts. These may be used alone or in combination of two or more.

[0246] Among these, organic tin compounds are preferred from the viewpoint of better reactivity.

[0247] When a reaction catalyst is used when reacting the polyether polycarbonate diol and the polyisocyanate compound, the amount of the reaction catalyst added is not particularly limited, but is preferably 0.00001 to 5 parts by mass, more preferably 0.00005 to 0.1 parts by mass, and particularly preferably 0.0001 to 0.05 parts by mass, based on 100 parts by mass of the polyether polycarbonate diol.

[0248] When the amount of the reaction catalyst added is 0.00001 parts by mass or more, the reactivity is more excellent, and when it is 5 parts by mass or less, impurities derived from the catalyst can be further reduced.

[0249] [Polyether polycarbonate polymer having reactive silicon groups (A)]

[0250] The polyether polycarbonate polymer (A) having a reactive silicon group has a number average molecular weight of 500 to 10,000 and has a reactive silicon group represented by the following formula (1).

[0251] -SiX a R 3-a Formula (1)

[0252] In formula (1), X is a halogen atom, a hydroxyl group or a hydrolyzable group. R is a monovalent organic group having 1 to 20 carbon atoms and does not contain a hydrolyzable group. a is an integer of 1 to 3. When a is 1, two Rs may be the same or different from each other. When a is 2 or 3, multiple Xs may be the same or different from each other.

[0253] For the polyether polycarbonate polymer (A) having a reactive silicon group, from the viewpoint of making the adhesion to the resin material better, it is preferred to obtain a polyether polycarbonate diol as a ring-opening polymer by ring-opening polymerization of a polycarbonate diol and a cyclic ether, convert the hydroxyl group at the end of the polyether polycarbonate diol into a group that can react with a silylating agent, and react the converted group with a silylating agent to introduce a reactive silicon group. As the cyclic ether, the same compound as above can be used, and the preferred embodiment is also the same. In addition, the preferred embodiment of the polyether polycarbonate diol is also the same as above.

[0254] The polyether polycarbonate polymer (A) having a reactive silicon group is preferably a polymer having a reactive silicon group, a carbonate group, and an oxyalkylene group.

[0255] From the viewpoint of improving the adhesiveness to the resin material, the oxyalkylene group in the polyether polycarbonate polymer (A) having a reactive silicon group is preferably at least one selected from the group consisting of oxypropylene groups and oxyethylene groups, and more preferably an oxypropylene group.

[0256] The polyether polycarbonate polymer (A) having a reactive silicon group preferably has two or more terminal groups in one molecule, and more preferably has two terminal groups. The terminal group is preferably at least one group selected from the group consisting of a reactive silicon group represented by the above formula (1), an active hydrogen-containing group, and an isocyanate group.

[0257] Examples of the active hydrogen-containing group include a hydroxyl group, a carboxyl group, an amino group, a monovalent functional group obtained by removing one hydrogen atom from a primary amine, a hydrazide group, and a mercapto group. Among them, a hydroxyl group is preferred.

[0258] The polyether polycarbonate polymer (A) having a reactive silicon group preferably has at least a part of terminal groups in one molecule being reactive silicon groups represented by the above formula (1), and more preferably has one or more reactive silicon groups represented by the above formula (1) as the terminal groups.

[0259] It should be noted that the polyether polycarbonate polymer (A) having a reactive silicon group may also have a reactive silicon group other than the group represented by the above formula (1), but from the viewpoint of improving the tensile properties of the cured product of the curable composition, it is preferred that the reactive silicon group is only the group represented by the above formula (1).

[0260] The reactive silicon group represented by the formula (1) is a crosslinking site of the polyether polycarbonate polymer (A) having a reactive silicon group, and can form a crosslinking structure based on a siloxane bond.

[0261] In formula (1), X is a halogen atom, a hydroxyl group or a hydrolyzable group. The hydrolyzable group is a group that can form a silanol group (-Si-OH) by hydrolysis, and examples thereof include alkoxy, acyloxy, ketoximate, amino, amide, acid amide, aminooxy, sulfanyl, and alkenyloxy. The number of carbon atoms in the alkyl or alkenyl group that can be included in the hydrolyzable group is preferably 1 to 6, and more preferably 1 to 3.

[0262] From the viewpoint of stable hydrolyzability, X is preferably an alkoxy group, more preferably an alkoxy group having 1 to 3 carbon atoms, and still more preferably a methoxy group, an ethoxy group or an isopropoxy group. From the viewpoint of accelerating curing by forming a crosslinked structure based on siloxane bonds, a methoxy group or an ethoxy group is particularly preferred.

[0263] R is a monovalent organic group having 1 to 20 carbon atoms and does not contain a hydrolyzable group. Examples of the organic group include a hydrocarbon group, a halogenated hydrocarbon group, and a triorganosiloxane group. The organic group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms.

[0264] R is preferably an alkyl group, a cycloalkyl group, an aryl group, a 1-chloroalkyl group or a triorganosiloxane group, more preferably a linear or branched alkyl group having 1 to 4 carbon atoms, a cyclohexyl group, a phenyl group, a benzyl group, a 1-chloroalkyl group, a trimethylsiloxane group, a triethylsiloxane group or a triphenylsiloxane group, and still more preferably an alkyl group having 1 to 3 carbon atoms or a 1-chloroalkyl group having 1 to 3 carbon atoms. Among these, a methyl group or an ethyl group is preferred from the viewpoint of good curability of the polyether polycarbonate polymer (A) having a reactive silicon group and good stability of the adhesive composition, a 1-chloromethyl group is preferred from the viewpoint of good curing speed of the adhesive composition, and a methyl group is preferred from the viewpoint of easy availability.

[0265] a is an integer of 1 to 3. When a is 1, two Rs may be the same or different from each other. When a is 2 or 3, a plurality of Xs may be the same or different from each other.

[0266] a is preferably 2 or 3, more preferably 2.

[0267] As the reactive silicon group represented by formula (1), for example, trimethoxysilyl, triethoxysilyl, triisopropoxysilyl, tri(2-propyleneoxy)silyl, triacetoxysilyl, dimethoxymethylsilyl, diethoxymethylsilyl, dimethoxyethylsilyl, diisopropoxymethylsilyl, chloromethyldimethoxysilyl, chloromethyldiethoxysilyl can be cited. Among these, from the viewpoint of tensile properties and mechanical strength of the cured product, trimethoxysilyl, triethoxysilyl, dimethoxymethylsilyl or diethoxymethylsilyl is preferred, and dimethoxymethylsilyl or trimethoxysilyl is more preferred.

[0268] The number of reactive silicon groups in the polyether polycarbonate polymer (A) having reactive silicon groups is more than 0.5 per molecule on average, preferably 6.0 or less, more preferably 1.2 to 3.8, and even more preferably 1.4 to 2.0, from the viewpoint of tensile properties and mechanical strength of the cured product.

[0269] It should be noted that the average number of reactive silicon groups per molecule can be calculated based on H 1 -NMR or the input equivalent (molar ratio) of the compound.

[0270] (Molecular weight)

[0271] The polyether polycarbonate polymer (A) having a reactive silicon group has an Mn of 500 to 10000, preferably 500 to 5000, more preferably 600 to 4000, and even more preferably 800 to 3500. When Mn is at least the lower limit, the tensile properties and mechanical strength of the resin cured using the polymer are improved, and when Mn is at most the upper limit, the adhesiveness to the resin material is improved and the handling is easy.

[0272] From the viewpoint of low viscosity and easy handling of the adhesive composition, the molecular weight distribution, Mw / Mn, of the polyether polycarbonate polymer (A) having a reactive silicon group is preferably 1.0 to 3.0, more preferably 1.0 to 2.5, and even more preferably 1.0 to 2.0.

[0273] In addition, Mn and Mw of the polyether polycarbonate polymer (A) having a reactive silicon group are values ​​obtained by the same method as the method for measuring Mn and Mw of the above-mentioned polyether polycarbonate diol.

[0274] The Mn and Mw / Mn of the polyether polycarbonate polymer (A) having a reactive silicon group can be controlled by the type of catalyst and polymerization conditions (temperature, stirring conditions, pressure, etc.).

[0275] When two or more polyether polycarbonate polymers (A) having a reactive silicon group are used, the above-mentioned Mn and Mw / Mn are preferably applied to each of the two or more polymers.

[0276] (Method for producing polyether polycarbonate polymer (A) having reactive silicon groups)

[0277] The polyether polycarbonate polymer (A) having a reactive silicon group can be produced, for example, by a method of reacting a silylating agent with the above-mentioned polyether polycarbonate diol.

[0278] The method for reacting the polyether polycarbonate diol with the silylating agent may be a known method. For example, there may be mentioned a method of reacting the hydroxyl group in the polyether polycarbonate diol with a silylating agent having an isocyanate group to form a carbamate (method 1); a method of introducing an isocyanate group into the hydroxyl group of the polyether polycarbonate diol, and then reacting the carbamate using a silylating agent having a functional group capable of reacting with the isocyanate group and a reactive silicon group represented by formula (1) (method 2).

[0279] As the silylating agent with isocyanate group in method 1, for example, the isocyanate silane compound described in Japanese Patent Application Laid-Open No. 2011-178955 can be cited. Specifically, 1-isocyanate methyl dimethoxymethyl silane, 1-isocyanate methyl diethoxy ethyl silane, 3-isocyanate propyl methyl dimethoxy silane, 3-isocyanate propyl ethyl diethoxy silane, 3-isocyanate propyl methyl diethoxy silane, 3-isocyanate propyl trimethoxy silane, 3-isocyanate propyl triethoxy silane, isocyanate methyl trimethoxy silane, isocyanate methyl triethoxy silane can be cited. The silylating agent can be used alone or in combination of two or more. Among these, 1-isocyanatemethyldimethoxymethylsilane, 3-isocyanatepropylmethyldimethoxysilane, 3-isocyanatepropyltrimethoxysilane, and isocyanatemethyltrimethoxysilane are preferred.

[0280] From the viewpoint of good reactivity of the silylation reaction, the hydroxyl group of the polyether polycarbonate diol to be reacted with the silylating agent having an isocyanate group is preferably a hydroxyl group derived from propylene oxide.

[0281] The reaction can be carried out in the presence of a carbamate catalyst. The carbamate catalyst is not particularly limited, and a known carbamate catalyst can be used appropriately. For example, metal catalysts such as organic tin compounds such as dibutyltin dilaurate and dioctyltin dilaurate, bismuth compounds, and base catalysts such as organic amines can be cited. The reaction temperature is preferably 20 to 200°C, more preferably 50 to 150°C. In addition, the carbamate reaction is preferably carried out under an inert gas atmosphere. As the inert gas, nitrogen is preferred.

[0282] In method 2, for example, a polyisocyanate compound is used to subject the hydroxyl groups of the polyether polycarbonate diol to a urethanization reaction to introduce an isocyanate group, and then the isocyanate group is reacted with a silylating agent having a functional group capable of reacting therewith and a reactive silicon group represented by formula (1). According to this method, two or more urethanate bonds and a silylating agent residue formed by reaction with the isocyanate group are introduced into the terminal of the polyether polycarbonate diol.

[0283] As the polyisocyanate compound in method 2, for example, there can be mentioned aromatic polyisocyanates such as naphthalene-1,5-diisocyanate, polyphenylene polymethylene polyisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate, and 2,4,4-trimethyl-hexamethylene diisocyanate; alicyclic polyisocyanates such as isophorone diisocyanate and 4,4'-methylenebis(cyclohexyl isocyanate); and urethane modified products, biuret modified products, allophanate modified products, carbodiimide modified products, and isocyanurate modified products obtained therefrom. The polyisocyanate compound may be used alone or in combination of two or more. Among these, those having two isocyanate groups are preferred, and hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, and 2,6-toluene diisocyanate are more preferred.

[0284] Examples of the functional group reactive with an isocyanate group of the silylating agent having a functional group reactive with an isocyanate group and a reactive silicon group represented by formula (1) in method 2 include a hydroxyl group, a carboxyl group, a mercapto group, an amino group, and an amino group in which one hydrogen atom is substituted by an alkyl group having 1 to 6 carbon atoms. Among these, groups having one or two active hydrogen atoms are preferred, and a hydroxyl group, a mercapto group, an amino group, a methylamino group, an ethylamino group, and a butylamino group are preferred, and a hydroxyl group, an amino group, a methylamino group, an ethylamino group, and a butylamino group are more preferred.

[0285] The functional group capable of reacting with an isocyanate group is preferably bonded to the reactive silicon group represented by formula (1) via a divalent organic group having 1 to 20 carbon atoms. The organic group is preferably a divalent hydrocarbon group having 1 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 1 to 10 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 1 to 10 carbon atoms, a linear hydrocarbon group having 1 to 12 carbon atoms, further preferably a linear hydrocarbon group having 1 to 8 carbon atoms, and particularly preferably a linear hydrocarbon group having 1 to 6 carbon atoms.

[0286] In method 1, the number of moles of reactive silicon groups introduced via urethane bonds to 1 mol of hydroxyl groups of the polyether polycarbonate diol and the number of moles of reactive silicon groups introduced via urethane bonds to 1 mol of hydroxyl groups of the polyether polycarbonate diol in method 2, that is, the silylation rate of the polyether polycarbonate polymer (A) having reactive silicon groups, are preferably 50 to 100%, more preferably 60 to 100%, further preferably 70 to 100%, and further preferably 80 to 100% from the viewpoint of better tensile properties and mechanical strength of the cured resin.

[0287] The silylation rate can be appropriately adjusted by the amount of the silylating agent used and the reaction conditions of the silylation reaction.

[0288] The silylation rate can be measured by NMR analysis. When the reaction rate of the silylating agent is assumed to be substantially 100%, a calculated value (theoretical value) based on the charged amounts of the polyether polycarbonate diol and the silylating agent may be used as the value of the silylation rate.

[0289] In methods 1 and 2, the amount of the silylating agent added is 1 mol per 1 mol of the group capable of introducing a reactive silicon group at the terminal of the polyether polycarbonate diol. When the silylation rate is 100%, there is 1 reactive silicon group per terminal group in the polyether polycarbonate diol.

[0290] The content of the polyether polycarbonate polymer (A) having a reactive silicon group in the adhesive composition is preferably 10 to 80% by mass, more preferably 12 to 70% by mass, and even more preferably 15 to 60% by mass, relative to the total amount of the adhesive composition, from the viewpoint of improving adhesion to the substrate and tensile properties and mechanical strength of the cured product.

[0291] [Oxyalkylene polymer (B)]

[0292] When the adhesive composition of the present invention contains the polyether polycarbonate polymer (A) having a reactive silicon group, it preferably further contains an oxyalkylene polymer (B) from the viewpoint of further improving the tensile properties and mechanical strength of the cured product.

[0293] The oxyalkylene polymer (B) has two or more terminal groups and has a reactive silicon group represented by formula (1). The oxyalkylene polymer (B) does not have a carbonate group.

[0294] In the adhesive composition, the reactive silicon group of the oxyalkylene polymer (B) may be the same as or different from the reactive silicon group of the polyether polycarbonate polymer (A) having a reactive silicon group.

[0295] The oxyalkylene polymer (B) may be used alone or in combination of two or more.

[0296] The oxyalkylene polymer (B) can be produced by reacting a precursor polymer (b) having a terminal group into which a reactive silicon group can be introduced with a silylating agent.

[0297] The terminal groups of the precursor polymer (b) are each independently preferably an unsaturated group or an active hydrogen-containing group.

[0298] As the unsaturated group, for example, there can be mentioned a vinyl group (CH2=CH-), an ethynyl group (CH≡C-), preferably an allyl group (CH2=CH-CH2-), an acryloyl group (CH2=CH-C(=O)-), a methacryloyl group (CH2=C(CH3)-C(=O)-), a methallyl group (CH2=C(CH3)-CH2-), a propynyl group (CH≡C-CH2-), and more preferably an allyl group.

[0299] Examples of the active hydrogen-containing group include a hydroxyl group, a carboxyl group, an amino group, a monovalent functional group obtained by removing one hydrogen atom from a primary amine, a hydrazide group, and a mercapto group.

[0300] The precursor polymer (b) is preferably obtained by addition-polymerizing an alkylene oxide in an initiator having two or more active hydrogen-containing groups. That is, the oxyalkylene polymer (B) and the precursor polymer (b) contain units derived from an alkylene oxide.

[0301] The precursor polymer (b) is preferably a precursor polymer (b1) containing a polyoxyalkylene chain and having two or more active hydrogen-containing groups as terminal groups; or a precursor polymer (b2) containing a polyoxyalkylene chain and having two or more unsaturated groups as terminal groups.

[0302] The precursor polymer (b1) can be produced by subjecting an alkylene oxide to ring-opening addition polymerization in an initiator having two or more active hydrogen-containing groups in the presence of a catalyst.

[0303] The active hydrogen-containing group of the initiator is preferably a hydroxyl group. Examples of the initiator include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, polypropylene glycol having a hydroxyl value converted molecular weight of 50 to 8000, glycerol, polyoxypropylene triol having a hydroxyl value converted molecular weight of 50 to 8000, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, 1,2,6-hexanetriol, diglycerol, and dipentaerythritol. One initiator may be used alone or two or more in combination.

[0304] Examples of the alkylene oxide (cyclic ether) and catalyst used in the ring-opening addition polymerization include the cyclic ethers and catalysts described above in the explanation of the production of the polyether polycarbonate diol. The cyclic ether and catalyst used in the production of the precursor polymer (b1) may be the same as or different from those used in the production of the polyether polycarbonate diol.

[0305] Precursor polymer (b2) is obtained by reacting a compound having a functional group and an unsaturated group that can react with a group containing active hydrogen with a precursor polymer (b1), and by introducing an unsaturated group by means of an ether bond or a carbamate bond, etc. In addition, when the terminal group of the precursor polymer (b1) is a hydroxyl group, it can be manufactured by a known method of reacting with a halogenated hydrocarbon containing an unsaturated group such as allyl chloride, methylallyl chloride, or bromopropyne after the hydroxyl group is subjected to metal oxidation to form an alkoxide. In addition, it can also be manufactured by a known method of reacting with a halogenated hydrocarbon containing an unsaturated group after the hydroxyl group of the precursor polymer (b1) is subjected to metal oxidation to form an alkoxide, and then reacting with an epoxy compound having an unsaturated group such as allyl glycidyl ether.

[0306] The method for introducing a reactive silicon group into the active hydrogen-containing group at the terminal of the precursor polymer (b1) to obtain the oxyalkylene polymer (B) can be the same method as the method for introducing a reactive silicon group into the hydroxyl group at the terminal of the polyether polycarbonate diol. In addition, as a method for introducing a reactive silicon group into the unsaturated group at the terminal of the precursor polymer (b2) to obtain the oxyalkylene polymer (B), for example, there can be mentioned a method of reacting the precursor polymer (b2) having an unsaturated group at the terminal with a silylating agent capable of addition reaction with the unsaturated group (method 3).

[0307] Examples of the silylating agent capable of undergoing addition reaction with the unsaturated group in method 3 include hydrosilane compounds (e.g., HSiX a R 3-a(X, R and a are the same as those in formula (1).)) Compounds having reactive silicon groups and mercapto groups. Specifically, trimethoxysilane, triethoxysilane, triisopropoxysilane, tri(2-propyleneoxy)silane, triacetoxysilane, dimethoxymethylsilane, diethoxymethylsilane, dimethoxyethylsilane, diisopropoxymethylsilane, (α-chloromethyl)dimethoxysilane, (α-chloromethyl)diethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane. Silylating agents may be used alone or in combination of two or more. Among these, trimethoxysilane, triethoxysilane, dimethoxymethylsilane, diethoxymethylsilane are preferred from the viewpoint of high reactivity and good curability, and dimethoxymethylsilane or trimethoxysilane are more preferred.

[0308] From the viewpoint of obtaining better tensile properties and mechanical strength of the cured product, the ratio of the reactive silicon group introduced into the unsaturated group or the active hydrogen-containing group as the terminal group of the precursor polymer (b), i.e., the silylation rate of the oxyalkylene polymer (B) is preferably 50 to 100%, more preferably 55 to 100%, and still more preferably 60 to 100%.

[0309] From the viewpoint of the viscosity for easy handling of the adhesive composition, the Mn of the oxyalkylene polymer (B) is preferably 5,000 to 50,000, more preferably 10,000 to 40,000, and even more preferably 12,000 to 30,000.

[0310] From the viewpoint of the viscosity for easy handling of the adhesive composition, Mw / Mn of the oxyalkylene polymer (B) is preferably 1.0 to 1.8, more preferably 1.0 to 1.7, and even more preferably 1.0 to 1.5.

[0311] In addition, Mn and Mw of an oxyalkylene polymer (B) are values ​​obtained by the same method as the measurement method of Mn and Mw of the polyether polycarbonate polymer (A) having a reactive silicon group described above.

[0312] The oxyalkylene polymer (B) has, for example, an unsaturated group, an active hydrogen-containing group, or an isocyanate group as a terminal group other than the reactive silicon group represented by formula (1). Examples and preferred embodiments of the unsaturated group and the active hydrogen-containing group are as described above.

[0313] When the adhesive composition of the present invention includes a polyether polycarbonate polymer (A) having a reactive silicon group, other components may be included in addition to the oxyalkylene polymer (B) contained as required. Other components may be applied with known additives according to the purpose of the adhesive composition, such as, tackifiers, curing catalysts, fillers, plasticizers, thixotropy imparting agents, antioxidants, ultraviolet light absorbers, light stabilizers, dehydrating agents, adhesion promoters, amine compounds, oxygen-curable compounds, light-curable compounds, epoxy compounds, acrylic compounds, acrylic silicon. Each of these components may also be used in combination of two or more. For example, the known substances described in International Publication No. 2013 / 180203, International Publication No. 2014 / 192842, International Publication No. 2016 / 002907, Japanese Patent Publication No. 2014-88481, Japanese Patent Publication No. 2015-10162, Japanese Patent Publication No. 2015-105293, Japanese Patent Publication No. 2017-039728, and Japanese Patent Publication No. 2017-214541 can be appropriately combined and used. Other components are blended within the range that does not hinder the effect of the present invention.

[0314] As acrylic silicon, vinyl polymers having a reactive silicon group represented by the above formula (1) in the molecule can be cited. The reactive silicon group of acrylic silicon can be introduced into the end of the main chain, can be introduced into the side chain, or can be introduced into both the end of the main chain and the side chain. The average number of reactive silicon groups per molecule of acrylic silicon is preferably 0.8 or more. From the aspect of breaking strength, it is preferably 1.0 or more, and more preferably 1.2 or more. From the aspect of good elongation at break, it is preferably 4.0 or less, and more preferably 3.0 or less. As monomers constituting the main chain of acrylic silicon, for example, previously known monomers recorded in Japanese Patent Gazette No. 3-14068, Japanese Patent Gazette No. 6-211922, and Japanese Patent Gazette No. 11-130931 can be used. As the monomer containing reactive silicon group and unsaturated group copolymerized with the above-mentioned monomer, vinyldimethoxymethylsilane, vinyldiethoxymethylsilane, vinylmethyldichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, tri(2-methoxyethoxy)vinylsilane, (methyl)acrylate-3-(dimethoxymethylsilyl)propyl ester, (methyl)acrylate-3-(trimethoxysilyl)propyl ester, (methyl)acrylate-3-(triethoxysilyl)propyl ester can be exemplified. These can be used alone or in combination of two or more.

[0315] As the polymerization method, a polymerization method using a radical polymerization initiator based on solution polymerization, emulsion polymerization, suspension polymerization or bulk polymerization and living radical polymerization can be exemplified. As the living radical polymerization method, a method using a cobalt porphyrin complex as shown in the Journal of the American Chemical Society (J.Am.Chem.Soc.), 1994, Vol. 116, p. 7943, a method using a nitroxide radical as shown in the Japanese Unexamined Patent Publication No. 2003-500378, and an atom transfer radical polymerization (ATRP method) using an organic halide and a halogenated sulfonyl compound as an initiator and a transition metal complex as a catalyst as shown in the Japanese Unexamined Patent Publication No. 11-130931 can be exemplified. The polymer obtained by living radical polymerization has a tendency to have a narrow molecular weight distribution and low viscosity.

[0316] In order to improve the adhesion to the polyolefin substrate, the adhesion can be further improved by adding chlorinated polyolefin (for example, Superchlon 814HS manufactured by Nippon Paper Industries, Ltd.). When adding chlorinated polyolefin, it is preferably used in combination with acrylic silicone from the viewpoint of compatibility.

[0317] When the adhesive composition contains an oxyalkylene polymer (B), the content thereof is preferably 20 to 90% by mass, more preferably 25 to 80% by mass, and even more preferably 30 to 70% by mass relative to the total amount of the adhesive composition from the viewpoint of better tensile properties and mechanical strength of the cured product. When the adhesive composition contains a polyether polycarbonate polymer (A) having a reactive silicon group and an oxyalkylene polymer (B), the content of the oxyalkylene polymer (B) is preferably 5 to 90% by mass, more preferably 25 to 80% by mass, and even more preferably 30 to 70% by mass relative to the total amount of the polyether polycarbonate polymer (A) having a reactive silicon group and the oxyalkylene polymer (B) from the viewpoint of better adhesion to the resin material.

[0318] In order to promote crosslinking caused by the formation of siloxane bonds based on reactive silicon groups, the adhesive composition preferably contains a curing catalyst. The content of the curing catalyst in the adhesive composition is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 6 parts by mass, and even more preferably 0.5 to 4 parts by mass, relative to 100 parts by mass of the polyether polycarbonate polymer (A) having reactive silicon groups, from the viewpoint of obtaining a uniform cured product by moderate crosslinking promotion.

[0319] The adhesive composition may be a one-component type in which all the ingredients are pre-mixed and sealed and stored, and cured by moisture in the air after construction, or a two-component type in which a main agent composition containing a polyether polycarbonate polymer (A) having a reactive silicon group and an oxyalkylene polymer (B) as required and a curing agent composition containing a curing catalyst are stored separately, and the curing agent composition and the main agent composition are mixed before use. From the viewpoint of ease of construction, a one-component type is preferred.

[0320] In the case of a one-component adhesive composition, it is preferred that the adhesive composition does not contain water. It is preferred that the compounding components containing water be dehydrated and dried in advance, or dehydrated by reducing pressure or the like during compounding and kneading.

[0321] In the case of a two-component type, the main agent composition is unlikely to gel even if it contains a small amount of water. However, from the viewpoint of good storage stability, it is preferred that the compounding components be dehydrated and dried in advance.

[0322] From the viewpoint of good storage stability, a dehydrating agent may be added to the one-component adhesive composition and the two-component main agent composition.

[0323] Since the adhesive composition of the present invention has excellent adhesiveness to resin materials, it can be used for bonding resin materials to each other or bonding a resin material to glass, rubber, or metal.

[0324] <Items>

[0325] The article of the present invention comprises a first substrate, a cured product of the adhesive composition, and a second substrate in this order, and at least one of the first substrate and the second substrate is formed of a resin material.

[0326] Figure 1 This is a cross-sectional view showing one embodiment of the article of the present invention. Figure 1 The article 10 has a cured product (adhesive layer) 2 of an adhesive composition provided on a first substrate 1, and a second substrate 3 provided on the adhesive layer 2. At least one of the first substrate 1 and the second substrate 3 is formed of a resin material. When the first substrate 1 is formed of a resin material, the second substrate 3 may be a substrate formed of a resin material or a substrate formed of a material other than a resin material. Examples of materials other than resin materials include glass and metal.

[0327] In addition, it is preferred that the surface on the adhesive layer 2 side of at least one of the first substrate 1 and the second substrate 3 is plasma treated, and the surface on the adhesive layer 2 side of the first substrate 1 and the surface on the adhesive layer 2 side of the second substrate 3 may both be plasma treated.

[0328] From the viewpoint of further exerting the effects of the present invention, it is preferred that both the first substrate and the second substrate are formed of a resin material.

[0329] Examples of the resin material constituting the first substrate and the second substrate include polyolefins such as polypropylene, polyethylene, ethylene-propylene copolymers, and cycloolefin polymers; polyesters such as polyethylene terephthalate and polybutylene terephthalate; polymethyl methacrylate; polycarbonate; polystyrene; acrylonitrile-styrene copolymers; polyvinyl chloride; polyacetate; acrylonitrile-butadiene-styrene copolymers; and polyamide. The resin material may be used alone or in combination of two or more.

[0330] From the viewpoint of versatility and weight reduction, the resin material is preferably polyolefin, more preferably polypropylene.

[0331] From the viewpoint of further exerting the effects of the present invention, it is preferred that at least one of the first substrate and the second substrate has its surface plasma-treated, and it is more preferred that both the first substrate and the second substrate have their surfaces plasma-treated.

[0332] It is presumed that the functional groups generated on the surface of the substrate by plasma treatment of the surface of the substrate are bonded to the carbonate groups of the polymer in the adhesive composition of the present invention, thereby improving the adhesion to the substrate (resin material).

[0333] Furthermore, the adhesive composition of the present invention has excellent adhesiveness to a resin material, and thus can exhibit excellent adhesiveness without forming a primer on the surface of a substrate formed of a resin material.

[0334] Plasma treatment is a method of performing surface treatment by plasma discharge.

[0335] The plasma treatment is not particularly limited, and examples thereof include atmospheric pressure plasma treatment and vacuum plasma treatment.

[0336] The plasma gas (process gas) used in the plasma treatment is not particularly limited, and examples thereof include nitrogen gas, helium gas, argon gas, and mixed gas obtained by mixing these gases with one or more of oxygen gas, carbon dioxide gas, and hydrogen gas.

[0337] The speed of the plasma treatment is preferably 10 to 1500 mm / sec, more preferably 50 to 1000 mm / sec.

[0338] When the plasma treatment is performed using a plasma discharge nozzle, the distance between the plasma discharge nozzle and the surface of the substrate is preferably 1 to 100 mm, more preferably 5 to 50 mm.

[0339] The thickness of each of the first substrate and the second substrate is preferably 0.5 to 20 mm, more preferably 1 to 15 mm.

[0340] The method for coating the adhesive composition of the present invention on the first substrate is not particularly limited, and examples thereof include dip coating, coating using a double roll coater, a slit coater, an air knife coater, a wire bar coater, a slide hopper, spray coating, a knife coater, a doctor coater, a squeeze coater, a reverse roll coater, a transfer roll coater, an extrusion coater, a curtain coater, a dip coater, a die coater, a gravure roll coating method, a screen printing method, a spray coating method, a spin coating method, and an inkjet method.

[0341] The thickness of the adhesive layer to be formed is not particularly limited, but is preferably 0.1 to 10 mm.

[0342] By bonding the second substrate to the adhesive composition applied to the first substrate, an article having the first substrate, the cured product of the adhesive composition, and the second substrate in this order is obtained.

[0343] The method of laminating the second substrate to the adhesive composition is not particularly limited, and for example, a method of pressing can be mentioned. In addition, in order to cure the adhesive composition, a heat treatment or the like may be performed after laminating the second substrate.

[0344] The article of the present invention has excellent adhesiveness and is therefore suitable for automobile interior and exterior components such as automobile bodies, front doors, rear doors, back doors, front bumpers, rear bumpers, and side sill moldings.

[0345] Example

[0346] Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to the following examples, and various modifications can be made within the scope not departing from the gist of the present invention.

[0347] (Evaluation method)

[0348] [Number of hydroxyl groups per molecule]

[0349] The number of hydroxyl groups per molecule is defined as the number of hydroxyl groups of the initiator.

[0350] [Hydroxy value]

[0351] The hydroxyl values ​​(OHV) of the polyether polycarbonate diols (a1), (a2) (hereinafter, also referred to as diols (a1), (a2)), polyoxyalkylene diols (b1), (b2) (hereinafter, also referred to as diols (b1), (b2)), and polyol (c1) obtained in the synthesis examples described below were measured in accordance with JIS K1557:2007.

[0352] [Number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of polyether polycarbonate diols (a1), (a2), polyoxyalkylene diols (b1), (b2), polymers A1, A2, B1, B2, and isocyanate-terminated urethane prepolymer P1]

[0353] The number average molecular weight (Mn) and weight average molecular weight (Mw) of the diols (a1), (a2), (b1), (b2), polymers A1, A2, B1, B2, and isocyanate-terminated urethane prepolymer P1 obtained in the synthesis examples described below were analyzed using gel permeation chromatography (GPC) (HLC-8320GPC, manufactured by Tosoh Techno-System, Inc.) using an RI detector. As columns, two TSK-GEL Super HZ4000 (4.6 mm × 150 mm) and two Super HZ2500 (4.6 mm × 150 mm) were connected in series in sequence and used. Tetrahydrofuran was used as an eluent at a flow rate of 0.35 ml / min, and the column temperature was set to 40° C. Each sample was measured, and the obtained spectrum was analyzed using a calibration curve prepared using a standard polystyrene with a known molecular weight, thereby calculating Mn and Mw. That is, Mn and Mw of diols (a1), (a2), (b1), and (b2) are polystyrene-equivalent molecular weights, and molecular weight distribution (Mw / Mn) is a value calculated from Mw and Mn.

[0354] [Content of Carbonate Groups in Polyether Polycarbonate Diol]

[0355] The content of carbonate groups in polyether polycarbonate diol (G (PCD+PO) , mass %) is calculated by the following formula 1.

[0356] G (PCD+PO) =(A×60) / (Mn (PCD+PO) )×100···Formula 1

[0357] The symbols in Formula 1 have the following meanings: "60" is the formula weight per carbonate group present in one molecule of the polycarbonate diol of the initiator.

[0358] A: The number of carbonate groups in one molecule of the polycarbonate diol of the initiator

[0359] G(PCD+PO) : The content ratio of carbonate groups in polyether polycarbonate diol (mass %)

[0360] Mn (PCD+PO) :Mn of polyether polycarbonate diol

[0361] [Viscosity]

[0362] The viscosity (unit: mPa·s) at 25° C. of diols (a1), (a2), (b1), (b2), and polyol (c1) obtained in the synthesis examples described below was measured using an E-type viscometer (product name: VISCOMETER TV-22, manufactured by Toki Sangyo Co., Ltd.).

[0363] [Silylation rate]

[0364] The silylation rate is defined as the charge equivalent (molar ratio) of the silylation agent relative to the amount of hydroxyl groups which are terminal groups of the polyether polycarbonate diol or the polyoxyalkylene glycol.

[0365] [Average number of reactive silicon groups per molecule]

[0366] The average number of reactive silicon groups per molecule is calculated by multiplying the number of terminal groups of the polyether polycarbonate diol or polyoxyalkylene diol by the silylation rate.

[0367] [Synthesis of polyether polycarbonate diol]

[0368] (Synthesis example 1)

[0369] As an initiator, a polycarbonate diol (product name: PH-50, manufactured by UBE Corporation, hydroxyl value 218.6 mgKOH / g, Mw / Mn=1.80, Mn=600, composition ratio of 1,5-BD / 1,6-HD: 50 / 50 (molar ratio)) derived from two diol compounds, 1,5-pentanediol (1,5-PD) and 1,6-hexanediol (1,6-HD) was used.

[0370] Using 0.02 parts by mass of a zinc hexacyanocobaltate complex whose ligand is tert-butyl alcohol (hereinafter referred to as "TBA-DMC catalyst") as a ring-opening polymerization catalyst, 100 parts by mass of propylene oxide (PO) as a cyclic ether was subjected to ring-opening addition polymerization at 130° C. to obtain a polyether polycarbonate diol (a1) [transparent liquid, Mn=1370, Mw / Mn=1.28, viscosity (25° C.)=827 mPa·s, hydroxyl value=112.8 mgKOH / g, carbonate group content=18% by mass, 2 hydroxyl groups per 1 molecule].

[0371] (Synthesis example 2)

[0372] Using 0.04 parts by mass of TBA-DMC catalyst as a ring-opening polymerization catalyst relative to 100 parts by mass of polycarbonate diol (product name: PH-50, manufactured by UBE Corporation) as an initiator, 300 parts by mass of propylene oxide (PO) as a cyclic ether was subjected to ring-opening addition polymerization at 130° C. to obtain polyether polycarbonate diol (a2) [transparent liquid, Mn=2800, Mw / Mn=1.11, viscosity (25° C.)=873 mPa·s, hydroxyl value=56.8 mgKOH / g, carbonate group content=9% by mass, 2 hydroxyl groups per 1 molecule].

[0373] [Synthesis of polyoxyalkylene glycol]

[0374] (Synthesis example 3)

[0375] 400 g of polyoxypropylene glycol having a hydroxyl value converted molecular weight of 400 obtained by ring-opening polymerization of propylene oxide in propylene glycol was used as an initiator, and 600 g of propylene oxide (PO) was subjected to ring-opening addition polymerization in the presence of potassium hydroxide to obtain polyoxyalkylene glycol (b1) having two hydroxyl groups per molecule [transparent liquid, Mn=1280, Mw / Mn=1.04, viscosity (25°C)=150 mPa·s, hydroxyl value=111.0 mgKOH / g, and 2 hydroxyl groups per molecule].

[0376] (Synthesis Example 4)

[0377] 167 g of polyoxypropylene glycol having a hydroxyl value converted molecular weight of 2000 obtained by ring-opening polymerization of propylene oxide in propylene glycol was used as an initiator, and 833 g of propylene oxide (PO) was polymerized using a TBA-DMC catalyst to obtain a polyoxyalkylene glycol (b2) having two hydroxyl groups per molecule [transparent liquid, Mn=16980, Mw / Mn=1.05, viscosity (25°C)=7000mPa·s, hydroxyl value=9.4mgKOH / g, and two hydroxyl groups per molecule].

[0378] The forms of the diols (a1), (a2), (b1), and (b2) produced in the above-mentioned Synthesis Examples 1 to 4 are shown in Table 1 below.

[0379] [Table 1]

[0380]

[0381] [Synthesis of isocyanate-terminated urethane prepolymer]

[0382] (Synthesis Example 5)

[0383] In a reaction vessel equipped with a thermometer, a stirrer and a cooling tube, 113.4 g of a polyisocyanate compound (Millionate MT, manufactured by Tosoh Corporation, monomeric MDI, isocyanate group content 33.5% by mass) was added. Then, 140 g of a polyether polyol (EXCENOL 5030, manufactured by AGC Corporation, a polyoxypropylene polymer with glycerol as an initiator) and 420 g of a polyether polyol (EXCENOL-2020, manufactured by AGC Corporation, a polyoxypropylene polymer with propylene glycol as an initiator) were added, and the temperature was gradually raised. The reaction was carried out at an internal temperature of about 80° C. for about 4 hours to obtain an isocyanate group-terminated urethane prepolymer P1 (Mn=24000, Mw / Mn=1.85) having a terminal isocyanate group content of 2.6% by mass.

[0384] In the following examples, Examples 1 and 3 are embodiments, and Example 2 is a comparative example.

[0385] [Example 1]

[0386] (Preparation of main agent)

[0387] 60 g of the isocyanate-terminated urethane prepolymer P1 obtained above, 20 g of carbodiimide-modified MDI (Millionate MTL, manufactured by Tosoh Corporation, isocyanate content 28.9% by mass), 10 g of a plasticizer (DINP: diisononyl phthalate, manufactured by J-PLUS Co., Ltd.) and 20 g of calcium carbonate (NS#400, manufactured by Nitto Powder Chemical Industry Co., Ltd.) as a filler were placed in a reaction container and stirred at 1400 rpm / min for 10 minutes using a stirrer (vacuum stirring and degassing stirrer: V-mini300, manufactured by EME Co., Ltd.) to obtain a main agent 1.

[0388] (Manufacturing and Evaluation of Two-Component Curable Urethane Adhesive Composition)

[0389] The main agent 1 was filled into the box 1. On the other hand, 10.0 g of the polyol (c1) synthesized by the following steps as a curing agent, 36.3 g of the diol (a1), 0.2 g of triethylenediamine (TEDA; manufactured by Junsei Chemical Co., Ltd.) as a catalyst, and 43.5 g of calcium carbonate (NS#400, manufactured by Nitto Powder Chemical Industry Co., Ltd.) as a filler were placed in a reaction container, and stirred at 1400 rpm / min for 10 minutes using a stirrer (vacuum stirring and degassing stirrer: V-mini300, manufactured by EME Co., Ltd.), and the prepared mixture was filled into the box 2.

[0390] Boxes 1 and 2 are respectively arranged on an extrusion gun, and a mixing nozzle is installed at the front end. The film is extruded onto a release film in such a manner that the discharge amount from box 1 and the discharge amount from box 2 become a ratio of 1:1 (mass ratio), stretched in such a manner that the thickness becomes about 200 μm, and placed in an atmosphere of a temperature of 23° C. and a relative humidity of 50% for 72 hours to produce a sheet-like solidified product.

[0391] Here, the value of 100 times the number of isocyanate groups in the isocyanate-terminated urethane prepolymer P1 relative to the average number of hydroxyl groups in the polyol (c1) and the diol (a1) is taken as the isocyanate index of the two-component curable urethane adhesive composition. The discharge ratio of the box 1 to the box 2 can be changed by appropriately changing the diameter of the box 2.

[0392] (Synthesis of polyol (c1))

[0393] As a polyol (c1), 120 g of ethylenediamine was used as an initiator, 470 g of propylene oxide (PO) was polymerized, and then 410 g of ethylene oxide (EO) was further polymerized in the presence of potassium hydroxide, and then the neutralizing salt was removed to obtain a polyoxyalkylene polyol (c1) having EO units in a block form [transparent liquid, viscosity (25°C) = 1300 mPa·s, hydroxyl value = 451.0 mgKOH / g, EO unit content = 41% by mass, and 4 hydroxyl groups per 1 molecule].

[0394] [Gelation time]

[0395] As described above, the main agent and the curing agent were filled into boxes 1 and 2, and a mixing nozzle was set at the front end of each extrusion gun to discharge the main agent and the curing agent. The loss tangent (tan δ) of the obtained adhesive composition was measured using MCR301 (manufactured by Anton Paar) under nitrogen atmosphere, temperature 25°C, cone diameter 25mm, and frequency 1Hz, and the time when the adhesive composition was discharged from the mixing nozzle was set as the starting point, and the time when tan δ became 1 was set as the gelation time.

[0396] [Breaking strength, breaking elongation]

[0397] The obtained sheet-like cured product was measured for tensile strength at break (unit: MPa) and elongation at break (unit: %) at a tensile speed of 50 mm / min using a Tensilon tester (manufactured by A&D Company, Limited, product name: RTG-1310) in accordance with JIS K7312:1996.

[0398] [Tensile shear test]

[0399] The main agent and curing agent were mixed separately with a planetary mixer, and each was inserted into a specified box. On one surface of a glass fiber reinforced polypropylene test piece (made by Standard-Testpiece Co., Ltd.) with a length of 100mm×width of 25mm×thickness of 3mm, which was wiped with isopropyl alcohol and dried, two adhesive tapes with a thickness of 500μm were attached in a manner that was 12.5mm wide perpendicular to the edge of the front end of the test piece, and the following plasma treatment was implemented. On the plasma-treated surface of the glass fiber reinforced polypropylene test piece, the main agent and curing agent were applied in a manner that the discharge amount of the main agent and the discharge amount of the curing agent were 3:4 (mass ratio), and the plasma-treated surface of the glass fiber reinforced polypropylene test piece was overlapped on the coated surface, and the adhesive composition was pressed in a manner that it was 25mm in length×12.5mm in width×500μm in thickness. Thereafter, it was cured in an atmosphere of a temperature of 23°C and a relative humidity of 50% for 7 days to obtain a test piece. The obtained test piece was subjected to a tensile shear test at a temperature of 23°C and a tensile speed of 5 mm / min in accordance with JIS K6850:1999 using a Tensilon tester (manufactured by A&D Company, Limited, product name: RTG-1310) to measure the maximum point stress (Tmax, unit: N / mm 2 ) as the maximum value of tensile shear stress.

[0400] The peeled surface of the test piece after the shear test was visually observed, and the ratio of the area where the cured layer was cohesively broken and peeled off in the entire peeled surface was calculated as the cohesive failure rate (%).

[0401] It should be noted that the larger the value of the cohesive failure rate, the better the adhesiveness.

[0402] (Plasma Treatment)

[0403] The surface of one side of a glass fiber reinforced polypropylene test piece was subjected to plasma treatment under the following conditions. The contact angle of the treated test piece surface was measured, and it was confirmed that the contact angle was lower than that before the treatment.

[0404] Device name: PS-1200AW manufactured by Wedge

[0405] Gas type: Air

[0406] Distance from head to substrate: 10mm

[0407] Number of passes: 1

[0408] Processing speed: 40mm / sec or 160mm / sec

[0409] [Example 2 and Example 3]

[0410] Two-component curable urethane adhesive compositions of Examples 2 and 3 were prepared by the same procedure as in Example 1 except that the type and blending amount of each component used in the curing agent were changed as shown in Table 2.

[0411] Table 2 shows the isocyanate index, physical properties of the cured product (gel time, breaking strength, breaking elongation), and evaluation results of the tensile shear test (Tmax, cohesive failure rate) of each two-component curable urethane adhesive composition.

[0412] [Table 2]

[0413] Department 2

[0414]

[0415] It was confirmed that the adhesive compositions of Examples 1 and 3 had higher cohesive failure rates and better adhesion to resin materials than the adhesive composition of Example 2. In addition, it was found that the cured products of the adhesive compositions of Examples 1 and 3 had better breaking strength and breaking elongation.

[0416] [Synthesis of polymer]

[0417] (Synthesis Example 6)

[0418] The reactor containing the diol (a1) obtained in Synthesis Example 1 was replaced with nitrogen, and 3-isocyanatepropyltrimethoxysilane was added in a ratio of 0.97 (NCO / OH molar ratio) to 1 mol of hydroxyl group in the diol (a1) while the internal temperature was maintained at 50°C, and 2-ethylhexanoic acid bismuth (III) 2-ethylhexanoic acid solution (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added as a catalyst. The liquid temperature was raised to 80°C and maintained, and stirred. The reaction was carried out until the termination of the reaction between the hydroxyl group and the isocyanate group could be confirmed by analysis using a Fourier transform infrared spectrophotometer, and a polyether polycarbonate polymer (polymer A1) having a carbamate bond introduced into the main chain and a trimethoxysilyl group introduced into the terminal group was obtained. 0.06 parts by mass of 3-mercaptopropyltrimethoxysilane (KBM-803, manufactured by Shin-Etsu Chemical Co., Ltd.) was added as a storage stabilizer based on 100 parts by mass of the polymer A1 to obtain a composition containing the polymer A1.

[0419] (Synthesis Example 7)

[0420] A polyether polycarbonate polymer (polymer A2) having a urethane bond introduced in the main chain and a trimethoxysilyl group introduced in the terminal group was obtained by the same method as in Synthesis Example 6 except that the diol (a2) obtained in Synthesis Example 2 was used. As a storage stabilizer, 0.06 parts by mass of 3-mercaptopropyltrimethoxysilane (KBM-803, manufactured by Shin-Etsu Chemical Co., Ltd.) was added relative to 100 parts by mass of the polymer A2 to obtain a composition containing the polymer A2.

[0421] (Synthesis Example 8)

[0422] A polyoxypropylene polymer (polymer B1) having a urethane bond introduced in the main chain and a trimethoxysilyl group introduced in the terminal group was obtained by the same method as in Synthesis Example 6 except that the diol (b1) obtained in Synthesis Example 3 was used. 0.06 parts by mass of 3-mercaptopropyltrimethoxysilane (KBM-803, manufactured by Shin-Etsu Chemical Co., Ltd.) was added as a storage stabilizer relative to 100 parts by mass of the polymer B1 to obtain a composition containing the polymer B1.

[0423] (Synthesis Example 9)

[0424] A polyoxypropylene polymer (polymer B2) having a urethane bond introduced in the main chain and a trimethoxysilyl group introduced in the terminal group was obtained by the same method as in Synthesis Example 6 except that the diol (b2) obtained in Synthesis Example 4 was used. 0.06 parts by mass of 3-mercaptopropyltrimethoxysilane (KBM-803, manufactured by Shin-Etsu Chemical Co., Ltd.) was added as a storage stabilizer relative to 100 parts by mass of the polymer B2 to obtain a composition containing the polymer B2.

[0425] Table 3 below shows the properties of the polymers produced in Synthesis Examples 6 to 9.

[0426] [Table 3]

[0427]

[0428] [Preparation of Adhesive Composition]

[0429] An adhesive composition was prepared using a composition containing each polymer produced in the above-mentioned synthesis example and various additives.

[0430] The additives used are shown below.

[0431] (Bulking Agent)

[0432] Baiyanhua CCR: Colloidal calcium carbonate, product name of Shiraishi Calcium Co., Ltd.

[0433] Whiton (registered trademark) SB: Heavy calcium carbonate, product name of Shiraishi Calcium Co., Ltd.

[0434] (Dehydrating Agent)

[0435] ·KBM-1003: Vinyltrimethoxysilane, product name of Shin-Etsu Chemical Co., Ltd.

[0436] (Adhesion promoter)

[0437] ·KBM-403: 3-Glycidyloxypropyltrimethoxysilane, product name of Shin-Etsu Chemical Co., Ltd.

[0438] ·KBM-603: 3-(2-aminoethylamino)propyltrimethoxysilane, product name of Shin-Etsu Chemical Co., Ltd.

[0439] (Curing Catalyst)

[0440] ·NEOSTANN (registered trademark) U-830: Dioctyl bis-neodecanoyl tin oxide (Dioctyltin oxide), Nitto Kasei Co., Ltd. product name

[0441] In the following examples, Examples 4, 7, 8 and 10 are embodiments, and Examples 5, 6 and 9 are comparative examples.

[0442] (Example 4~Example 10)

[0443] The composition of the polymer and the additives containing the compounding amount (parts by mass) shown in Tables 4 to 6 were added and mixed with a planetary mixer to prepare an adhesive composition. The compounding amount of each component shown in Tables 4 to 6 is a value (unit: part by mass) relative to 100 parts by mass of the polymer. Using the obtained adhesive composition, a tensile shear test was performed. The results are shown in Tables 4 to 6.

[0444] [Tensile shear test]

[0445] A polypropylene test piece (manufactured by Engineering Test Service Co., Ltd.) with a length of 100 mm, a width of 25 mm, and a thickness of 2 mm, and a glass fiber reinforced polypropylene test piece (manufactured by Standard-Testpiece Co., Ltd.) with a length of 100 mm, a width of 25 mm, and a thickness of 3 mm, which were wiped with isopropyl alcohol and dried, were prepared, and one surface of each test piece was subjected to surface treatment under the above-mentioned plasma treatment conditions. According to JIS K6850:1999, a spacer with a thickness of 1 mm was arranged between the two test pieces, and the adhesive composition of Examples 4 to 10 was applied to the surface of one test piece (the surface subjected to plasma treatment) so as to have a length of 25 mm, a width of 25 mm, and a thickness of 1 mm, and the adhesive composition of Examples 4 to 10 was applied to the surface of the other test piece (the surface subjected to plasma treatment) and pressed to produce a test body. The produced test body was aged for 7 days in an atmosphere of a temperature of 23° C. and a relative humidity of 50%, and then the spacer was removed, and then aged for 7 days in an atmosphere of a temperature of 50° C. and a relative humidity of 65% to cure, thereby obtaining a test piece.

[0446] Each test piece was subjected to a tensile shear test using a Tensilon tester (temperature 23°C, tensile speed 5 mm / min). The maximum point stress (Tmax, unit: N / mm) which is the maximum value of the tensile shear stress at this time was measured. 2 ), and the elongation at the maximum stress (Emax, unit: mm). In addition, by visually observing the peeling surface of the test piece after the shear test, the ratio of the area of ​​the layer of the cured material (adhesive layer) in the whole peeling surface that is peeled due to cohesive failure is calculated as the cohesive failure rate (%). In addition, for the whole peeling surface, the ratio of the area where the adhesive layer is peeled at the interface and no resin remains on the test piece is calculated as the interface peeling rate (%). Furthermore, the ratio of the area where the adhesive remains very thinly on the surface of the test piece and the resin is broken and peeled is calculated as the thin layer cohesive failure rate (%).

[0447] It should be noted that the greater the value of the cohesive failure rate, the better the adhesiveness. In addition, the smaller the value of the interface peeling rate, the better the adhesiveness.

[0448] [Table 4]

[0449] [Table 4]

[0450]

[0451] It was confirmed that the adhesive composition of Example 4 had a higher cohesive failure rate and a lower interfacial peeling rate than the adhesive composition of Example 5, and therefore had excellent adhesiveness to the resin material.

[0452] [Table 5]

[0453] surface

[0454]

[0455] It was confirmed that the adhesive compositions of Examples 7 and 8 had higher cohesive failure rates and the same or lower interfacial peeling rates than the adhesive composition of Example 6, and therefore had excellent adhesiveness to resin materials.

[0456] [Table 6]

[0457] Table 6

[0458]

[0459] It was confirmed that the adhesive composition of Example 10 had a higher cohesive failure rate and a lower interface peeling rate than the adhesive composition of Example 9, and therefore had excellent adhesiveness to the resin material.

[0460] Description of Reference Numerals

[0461] 10 Items

[0462] 1. First substrate

[0463] 2. Cured product of adhesive composition (adhesive layer)

[0464] 3 Second substrate

Claims

1. An adhesive composition comprising a polyether polycarbonate diol having a number average molecular weight of 500 to 10,000 and not having a reactive silicon group represented by the following formula (1) or a polyether polycarbonate polymer (A) having a reactive silicon group represented by the following formula (1), -SiX a R 3-a Formula (1) In formula (1), X is a halogen atom, a hydroxyl group or a hydrolyzable group, R is a monovalent organic group having 1 to 20 carbon atoms and does not contain a hydrolyzable group, a is an integer of 1 to 3, when a is 1, two Rs may be the same or different from each other, and when a is 2 or 3, multiple Xs may be the same or different from each other. 2 . The adhesive composition according to claim 1 , comprising a main agent and a curing agent, wherein the main agent contains an isocyanate-terminated urethane prepolymer, and the curing agent contains a polyether polycarbonate diol having no reactive silicon group represented by the formula (1).

3. The adhesive composition according to claim 2, wherein The polyether polycarbonate diol having no reactive silicon group represented by the formula (1) is a ring-opening polymer of polycarbonate diol and a cyclic ether and has a carbonate group and an oxyalkylene group. The polycarbonate diol is a condensate of two or more alcohols and a carbonate compound.

4. The adhesive composition according to claim 3, wherein The content of carbonate groups in the polyether polycarbonate diol having no reactive silicon group represented by the formula (1) is 5% by mass or more based on 100% by mass of the total of carbonate groups and oxyalkylene groups.

5. The adhesive composition according to claim 3, wherein The oxyalkylene group in the polyether polycarbonate diol having no reactive silicon group represented by the formula (1) is at least one selected from the group consisting of oxypropylene and oxyethylene.

6. The adhesive composition according to claim 2, wherein The polyether polycarbonate diol having no reactive silicon group represented by the formula (1) is a compound represented by the following formula (2): HO-(R 1 O) s -(R 2 -O-C(=O)-O) u -R 20 -(OR 1 ) t -OH Formula (2) In formula (2), R 1 is an alkylene group having 2 to 4 carbon atoms, R 2 and R 20 is a chain hydrocarbon group having 3 to 20 carbon atoms or a cyclic hydrocarbon group having a ring structure having 6 to 20 carbon atoms, these groups may optionally have one or more substituents, when it is a cyclic hydrocarbon group, it may optionally contain an oxygen atom as an atom constituting the ring, when it contains an oxygen atom, adjacent atoms are not simultaneously oxygen atoms, s and t are the number of repetitions, u is the number of repetitions of 2 or more, (R 2 -OC(=O)-O) u Contains 2 or more (R 2 -OC(=O)-O) represented by the unit.

7. The adhesive composition according to claim 1, wherein The polyether polycarbonate polymer (A) having a reactive silicon group represented by the formula (1) has two or more terminal groups in one molecule, wherein the terminal groups are at least one group selected from the group consisting of a reactive silicon group represented by the formula (1), an active hydrogen-containing group and an isocyanate group.

8. The adhesive composition according to claim 7, wherein The number average molecular weight of the polyether polycarbonate polymer (A) having a reactive silicon group represented by the formula (1) is 800 to 3,500. 9 . The adhesive composition according to claim 7 , further comprising an oxyalkylene polymer (B).

10. The adhesive composition according to claim 9, wherein The number average molecular weight of the oxyalkylene polymer (B) is 5,000 to 50,000.

11. An article comprising a first substrate, a cured product of the adhesive composition according to claim 1, and a second substrate in this order, At least one of the first substrate and the second substrate is formed of a resin material.

12. The article according to claim 11, wherein The resin material is polyolefin.

13. The article of claim 11, wherein: The resin material is polypropylene.

14. The article of claim 11, wherein: A surface of at least one of the first substrate and the second substrate that contacts the cured product of the adhesive composition is plasma treated.

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