Compound, method for producing the compound, adhesive composition, and adhesive tape

Abstract

The present invention provides a compound that can increase the adhesive strength of an adhesive composition, and in particular, can increase the adhesive strength even to low-polarity adherends. Furthermore, the present invention provides a method for producing the compound, an adhesive composition containing the compound, and an adhesive tape having an adhesive layer containing the adhesive composition. [Solution] A compound having a constituent unit (A) derived from a monomer (a) whose solvation free energy Δμ with polytetrafluoroethylene is -30 kcal / mol or less, and a constituent unit (B) derived from at least one monomer (b) selected from the group consisting of terpene monomers, vinyl monomers and conjugated diene monomers.

Description

Technical Field

[0001] The present invention relates to a compound that can be used in an adhesive composition. The present invention also relates to a method for producing the compound, an adhesive composition containing the compound, and an adhesive tape having an adhesive layer containing the adhesive composition.

Background Art

[0002] Conventionally, when fixing components in electronic devices, adhesive tapes are widely used. Specifically, for example, an adhesive tape is used to adhere a cover panel for protecting the surface of a portable electronic device to a touch panel module or a display panel module, or to adhere a touch panel module and a display panel module. For adhesive tapes used for fixing such electronic device components, in addition to high adhesiveness, functions such as heat resistance, thermal conductivity, and impact resistance are required according to the environment of the site where they are used (for example, Patent Documents 1 to 3).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

[0006] An object of the present invention is to provide a compound that can enhance the adhesive strength of an adhesive composition, and particularly can enhance the adhesive strength even with respect to a low-polarity adherend. Another object of the present invention is to provide a method for producing the compound, an adhesive composition containing the compound, and an adhesive tape having an adhesive layer containing the adhesive composition.

Means for Solving the Problems

[0007] The present invention relates to a compound having a structural unit (A) derived from a monomer (a) with a solvation free energy Δμ with polytetrafluoroethylene of -30 kcal / mol or less, and a structural unit (B) derived from at least one monomer (b) selected from the group consisting of terpene monomers, vinyl monomers, and conjugated diene monomers. The present invention will be described in detail below.

[0008] The present inventors have succeeded in producing a novel compound having a structural unit (A) derived from a monomer (a) with a solvation free energy Δμ with polytetrafluoroethylene of a certain value or less, and a structural unit (B) derived from at least one monomer (b) selected from the group consisting of terpene monomers, vinyl monomers, and conjugated diene monomers. The present inventors have found that by blending such a compound as a tackifier resin into an adhesive composition, the adhesive strength of the adhesive composition can be enhanced, and particularly the adhesive strength can be enhanced even with respect to a low-polarity adherend, and thus have completed the present invention.

[0009] The compound of the present invention has a constituent unit (A) derived from monomer (a) whose solvation free energy Δμ with polytetrafluoroethylene is -30 kcal / mol or less. Hereinafter, polytetrafluoroethylene will also be referred to as "PTFE". Having such a structural unit (A), the compound of the present invention can increase the adhesive strength of adhesive compositions, and in particular, it can greatly improve interaction with low-polarity adherends, thereby increasing adhesive strength even with low-polarity adherends. For this reason, the compound of the present invention is suitably used as a tackifying resin to be incorporated into adhesive compositions. Here, the solvation free energy Δμ with polytetrafluoroethylene refers to the change in standard free energy when monomer (a) is brought into contact with polytetrafluoroethylene. Therefore, the smaller the solvation free energy Δμ, the stronger the interaction between polytetrafluoroethylene and monomer (a). Furthermore, polytetrafluoroethylene is known as one of the least polar adherends, and it is thought that a strong interaction with such an adherend can greatly improve the interaction with a wide range of less polar adherends. From the above, it is considered that by having a constituent unit (A) derived from monomer (a) whose solvation free energy Δμ with polytetrafluoroethylene is below a certain value, the compound of the present invention can increase the adhesive strength to a wide range of less polar adherends.

[0010] The solvation free energy Δμ of monomer (a) with polytetrafluoroethylene is not particularly limited as long as it is -30 kcal / mol or less, but is preferably -40 kcal / mol or less, more preferably -50 kcal / mol or less, and even more preferably -60 kcal / mol or less. The lower limit of the solvation free energy Δμ of monomer (a) with polytetrafluoroethylene is not particularly limited, but the substantial lower limit is -300 kcal / mol, the preferred lower limit is -200 kcal / mol, and the more preferred lower limit is -100 kcal / mol.

[0011] The solvation free energy Δμ of monomer (a) with polytetrafluoroethylene can be calculated using molecular dynamics. The more specific calculation procedure involves 1) molecular modeling, 2) charge setting, 3) creation of the calculation system, 4) molecular dynamics calculation, and 5) calculation of the solvation free energy Δμ using the energy representation method.

[0012] 1) Molecular Modeling The chemical structures of PTFE and monomer (a) are drawn using molecular modeling software (Winmostar (ver. 10) or equivalent, manufactured by CrossAbility). At this time, the PTFE substrate is treated as a crystal, and the atomic positions are determined according to Reference 1 below. Reference 1: A crystal structure of ultra-dispersed form of polytetrafluoroethylene based on X-ray powder diffraction data, Powder Diffr., Vol. 19, No. 3, September 2004.

[0013] 2) Charge setting The charge of the drawn molecular model is calculated as follows: For monomer (a), the RESP charge is calculated using density functional calculations (conditions: functional B3LYP / basis set 6-31G**) with quantum chemistry calculation software (GAMESS (ver. 2018 R1) or equivalent, manufactured by the Gordon research group at Iowa State University). For the PTFE substrate, the Lowdin charge is calculated by performing an SCF calculation using first-principles calculation software (Quantum ESPRESSO Foundation, Quantum ESPRESSO, or equivalent). The SCF calculation is performed under the following conditions. &system ibrav = 0, nat = 45, nspin = 1, ntyp = 2, ecutwfc = 25., ecutrho = 225., occupations = 'fixed', nosym = .False., noinv = .False., tot_charge = 0., &images conv_thr = 1d-6, mixing_beta = 0.3, mixing_mode = 'plain', electron_maxstep = 100, diagonalization = 'david', ATOMIC_SPECIES C 12.011 C.pbe-rrkjus.UPF F 18.9984 F.pbe-n-van.UPF

[0014] 3) Creation of a calculation system For the molecular model of PTFE created, a PTFE crystal system is constructed with a total of 90 PTFE heptomers arranged in the x, y, and z axes, with 10, 3, and 3 heptomers respectively, using the heptomer as the basic cell. Then, excess atoms are removed. The Z axis is the direction of polymer elongation. A vacuum layer is inserted into the PTFE crystal system, and a model of monomer (a) is placed on the outermost XZ plane of the PTFE. At this time, the model of monomer (a) is positioned so that the closest approach distance from the outermost atom of the PTFE is 3 Å. The system used in the calculation of monomer (a) alone, described later, is created by making a cube consisting of a vacuum layer with a cell size of 999 nm on each side, and placing one monomer (a) inside this cube to create the system.

[0015] 4) Molecular dynamics calculation Molecular dynamics (MD) calculations will be performed using calculation software (GROMACS (ver. 5.0.7) or equivalent, manufactured by the University of Groningen). Dreiding will be used as the force field, and energy minimization calculations, equilibrium MD calculations, and the main calculations will be performed to calculate the coordinates, velocities, and energies of each molecular model. MD calculations will be performed on three types of systems: the interface system between monomer (a) and PTFE created in step 3), monomer (a) only, and the PTFE crystal system only, each under the following calculation conditions. [1] In the case of a system consisting only of PTFE crystals, and in the case of an interface system between monomer (a) and PTFE. Step 1: Energy Minimization Calculation Conditions: Integrator=steep, Emtol=100.0KJ / mol / nm Step2 Equilibration MD calculation Conditions: NVT ensemble (nose-hoover method), Temperature: 300K, Calculation time: 2000 (ps) Time step dt: 1fs Step3 Main calculation Conditions: NVT ensemble (nose-hoover method), Temperature: 300K, Calculation time: 500 (ps) Time step dt: 1fs [2] System consisting only of monomer (a) Step 1: Energy Minimization Calculation Conditions: Integrator=steep, Emtol=100.0KJ / mol / nm Step2 Equilibration MD calculation Conditions: NVT ensemble (nose-hoover method), Temperature: 300K, Calculation time: 10 (ps) Time step dt: 1fs Step3 Main calculation Conditions: NVT ensemble (nose-hoover method), Temperature: 300K, Calculation time: 25000 (ps) Time step dt: 1fs

[0016] 5) Calculation of solvation free energy Δμ using the energy notation method For monomer (a) only, PTFE crystal system only, and the interface system between monomer (a) and PTFE, the solvation free energy Δμ is calculated using the energy notation method with the data obtained from the molecular dynamics calculations in 4). The calculation software used is ERmod (ver. 0.3.6) (or an equivalent) manufactured by the Matsubayashi Laboratory at Osaka University. In the preparation of the systems in 3), the arrangement of PTFE and monomer (a) is performed with multiple initial arrangements, and calculations are performed for each, with the solvation free energy Δμ being calculated as the statistical average.

[0017] The compounds of the present invention may have the above-mentioned structural unit (A) in the side chain, in the main chain skeleton, or at the ends of the main chain skeleton. In particular, it is preferable that the compounds of the present invention have the above-mentioned structural unit (A) in the main chain skeleton or at the ends of the main chain skeleton, as this allows them to have suitable physical properties required when used as a tackifying resin.

[0018] Specifically, the above-mentioned constituent unit (A) is preferably at least one selected from the group consisting of constituent units (A-1) and (A-1') represented by the following formula.

[0019] [ka]

[0020] In the formula, R 1 The terms *,

[0021] In the above constituent unit (A-1) and the above constituent unit (A-1'), R 1 Each of these represents a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a polar functional group, an aliphatic hydrocarbon group having a polar functional group, or an aromatic hydrocarbon group having a polar functional group. The above aliphatic hydrocarbon group is not particularly limited and includes, for example, linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms. The above aromatic hydrocarbon group is not particularly limited and includes, for example, substituted or unsubstituted aryl groups having 1 to 20 carbon atoms. The above polar functional groups are not particularly limited and include, for example, amino groups, carboxyl groups, carbonyl groups, alkoxy groups, hydroxyl groups, nitrile groups, nitro groups, and the like. The aliphatic hydrocarbon group having the above polar functional group is not particularly limited, and for example, a group in which one or more hydrogens in the above aliphatic hydrocarbon group are substituted with the above polar functional group can be used. The aromatic hydrocarbon group having the above polar functional group is also not particularly limited, and for example, a group in which one or more hydrogens in the above aromatic hydrocarbon group are substituted with the above polar functional group can be used. Furthermore, in the compound of the present invention, multiple R components are contained in one structural unit (A-1). 1 These may be the same or different. Also, multiple Rs contained in different constituent units (A-1) 1 These may be the same or different. Similarly, multiple Rs contained within a single constituent unit (A-1') 1 These may be the same or different. Also, multiple Rs contained in different constituent units (A-1') 1 They may be the same or they may be different.

[0022] In the above constituent units (A-1) and (A-1'), n is an integer between 2 and 4, and n' is an integer between 2 and 5, but from the viewpoint of ease of obtaining raw materials, it is preferable that n and n' be 2 or 3. It is more preferable that n and n' be 3, as this can further increase the adhesive strength of the adhesive composition, and in particular, further increase the adhesive strength even for substrates with low polarity.

[0023] More specifically, the above-mentioned constituent units (A-1) and (A-1') include, for example, a constituent unit derived from dihydroxybenzene or its derivatives (when n and n' are 2), a constituent unit derived from trihydroxybenzene or its derivatives (when n and n' are 3), and so on. These constituent units may be used individually, or two or more may be used in combination. The above-mentioned dihydroxybenzene or its derivatives are not particularly limited, and examples include resorcinol, pyrocatechol, hydroquinone, dihydroxytoluene, dihydroxyxylene, dihydroxyphenylethylamine hydrochloride, dihydroxybenzoic acid, dihydroxyphenylacetic acid, dihydroxyhydrocinnamic acid, dihydroxyphenylpropionic acid, dihydroxyphenylalanine, dihydroxybenzaldehyde, dihydroxyacetophenone, diacetyldihydroxybenzene, dihydroxyphenyl-2-butanone, dihydroxyphenylmethyl acetate, benzyldihydroxyphenyl ketone, dihydroxybenzamide, dihydroxymethoxybenzene, dihydroxybenzyl alcohol, dihydroxyphenylethanol, dihydroxyphenyl glycol, dihydroxyphenylacetonitrile, dihydroxynitrobenzene, and the like. These dihydroxybenzenes or their derivatives may be used alone or in combination of two or more. Among them, pyrocatechol is preferred because it has less steric hindrance and readily interacts with the adherend. The above-mentioned trihydroxybenzene or its derivative is not particularly limited. For example, pyrogallol, 1,2,4-trihydroxybenzene, phloroglucinol, trihydroxytoluene, trihydroxydiphenylmethane, 6-hydroxy-L-DOPA, gallic acid, methyl gallate, butyl gallate, isobutyl gallate, isoamyl gallate, hexadecyl gallate, stearyl gallate, trihydroxyacetophenone, trihydroxyphenyl ethanone, trihydroxyphenyl butanone, trihydroxybenzaldehyde, trihydroxybenzamide, trihydroxynitrobenzene, etc. may be mentioned. These trihydroxybenzenes or their derivatives may be used alone or in combination of two or more. Among them, pyrogallol is preferred because it has less steric hindrance and easily interacts with the adherent body.

[0024] Further, as the above-mentioned structural unit (A), at least one selected from the group consisting of a structural unit (A-2), a structural unit (A-2'), a structural unit (A-3), a structural unit (A-3'), a structural unit (A-4) and a structural unit (A-4') represented by the following formula is also preferred.

[0025]

Chemical formula

[0026]

Chemical formula

[0027]

Chemical formula

[0028] In the formula, R 2 , R <A 3 and R 5 each represent a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a polar functional group, an aliphatic hydrocarbon group having a polar functional group, or an aromatic hydrocarbon group having a polar functional group. R 4R represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an aliphatic hydrocarbon group with a polar functional group, or an aromatic hydrocarbon group with a polar functional group, respectively. 6 and R 7 Each represents either a hydrogen atom or an aliphatic hydrocarbon group. m represents an integer between 1 and 4, and m' represents an integer between 1 and 5. l represents an integer between 2 and 4, and l' represents an integer between 2 and 5. k represents an integer between 1 and 4, and k' represents an integer between 1 and 5. * represents a linking part.

[0029] In the above constituent unit (A-2) and the above constituent unit (A-2'), R 2 Each of these represents a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a polar functional group, an aliphatic hydrocarbon group having a polar functional group, or an aromatic hydrocarbon group having a polar functional group. The above aliphatic hydrocarbon group is not particularly limited and includes, for example, linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms. The above aromatic hydrocarbon group is not particularly limited and includes, for example, substituted or unsubstituted aryl groups having 1 to 20 carbon atoms. The above polar functional groups are not particularly limited and include, for example, amino groups, carbonyl groups, alkoxy groups, hydroxyl groups, nitrile groups, nitro groups, and the like. The aliphatic hydrocarbon group having the above polar functional group is not particularly limited, and for example, a group in which one or more hydrogens in the above aliphatic hydrocarbon group are substituted with the above polar functional group can be used. The aromatic hydrocarbon group having the above polar functional group is also not particularly limited, and for example, a group in which one or more hydrogens in the above aromatic hydrocarbon group are substituted with the above polar functional group can be used. Furthermore, in the compound of the present invention, multiple R components are contained in one structural unit (A-2). 2 These may be the same or different. Also, multiple Rs contained in different constituent units (A-2) 2 These may be the same or different. Similarly, multiple Rs contained within a single constituent unit (A-2') 2These may be the same or different. Also, multiple Rs contained in different constituent units (A-2') 2 They may be the same or they may be different.

[0030] In the above constituent units (A-2) and (A-2'), m is an integer between 1 and 4, and m' is an integer between 1 and 5, but from the viewpoint of ease of obtaining raw materials, it is preferable that m and m' be 1 or 2. It is more preferable that m and m' be 1, as this can further increase the adhesive strength of the adhesive composition, and in particular, further increase the adhesive strength even to adherends with low polarity.

[0031] More specifically, the above-mentioned constituent units (A-2) and (A-2') include constituent units derived from benzoic acid, salicylic acid, dihydroxybenzoic acid, gallic acid, 2-methylbenzoic acid, 3-methylbenzoic acid, 4-methylbenzoic acid, 2-ethylbenzoic acid, 3-ethylbenzoic acid, 4-ethylbenzoic acid, 4-tert-butylbenzoic acid, 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, and their derivatives. These constituent units may be used individually or in combination of two or more. Among these, 4-vinylbenzoic acid is preferred because it has less steric hindrance and readily interacts with the adherend.

[0032] In the above constituent unit (A-3) and the above constituent unit (A-3'), R 3 Each of these represents a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a polar functional group, an aliphatic hydrocarbon group having a polar functional group, or an aromatic hydrocarbon group having a polar functional group. The above aliphatic hydrocarbon group is not particularly limited and includes, for example, linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms. The above aromatic hydrocarbon group is not particularly limited and includes, for example, substituted or unsubstituted aryl groups having 1 to 20 carbon atoms. The above polar functional groups are not particularly limited and include, for example, amino groups, carboxyl groups, carbonyl groups, hydroxyl groups, nitrile groups, nitro groups, and the like. The aliphatic hydrocarbon group having the above polar functional group is not particularly limited, and for example, a group in which one or more hydrogens in the above aliphatic hydrocarbon group are substituted with the above polar functional group can be used. The aromatic hydrocarbon group having the above polar functional group is also not particularly limited, and for example, a group in which one or more hydrogens in the above aromatic hydrocarbon group are substituted with the above polar functional group can be used. Furthermore, in the compound of the present invention, multiple Rs are contained in one structural unit (A-3). 3 These may be the same or different. Also, multiple Rs contained in different constituent units (A-3) 3 These may be the same or different. Similarly, multiple Rs contained within a single constituent unit (A-3') 3 These may be the same or different. Also, multiple Rs contained in different constituent units (A-3') 3 They may be the same or they may be different.

[0033] In the above constituent unit (A-3) and the above constituent unit (A-3'), R 4 Each of these represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an aliphatic hydrocarbon group having a polar functional group, or an aromatic hydrocarbon group having a polar functional group. The above aliphatic hydrocarbon group is not particularly limited and includes, for example, linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms. The above aromatic hydrocarbon group is not particularly limited and includes, for example, substituted or unsubstituted aryl groups having 1 to 20 carbon atoms. In the compound of the present invention, multiple R groups are contained in one structural unit (A-3). 4 These may be the same or different. Also, multiple Rs contained in different constituent units (A-3) 4 These may be the same or different. Similarly, multiple Rs contained within a single constituent unit (A-3') 4 These may be the same or different. Also, multiple Rs contained in different constituent units (A-3') 4They may be the same or they may be different.

[0034] In the above constituent units (A-3) and (A-3'), l is an integer between 2 and 4, and l' is an integer between 2 and 5, but from the viewpoint of ease of obtaining raw materials, it is preferable that l and l' be 2 or 3. It is more preferable that l and l' be 3, as this can further increase the adhesive strength of the adhesive composition, and in particular, it can further increase the adhesive strength even to adherends with low polarity.

[0035] More specifically, the above-mentioned constituent units (A-3) and (A-3') include, for example, constituent units derived from trialkoxybenzene or its derivatives (when l is 3). The above-mentioned trialkoxybenzene or its derivatives are not particularly limited, and examples include 1,2,3-trimethoxybenzene, 1,2,4-trimethoxybenzene, 1,3,5-trimethoxybenzene, etc. These trialkoxybenzenes or their derivatives may be used alone or in combination of two or more. Among these, 1,2,3-trimethoxybenzene is preferred because it has less steric hindrance and readily interacts with the adherend.

[0036] In the above constituent unit (A-4) and the above constituent unit (A-4'), R 5 Each of these represents a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a polar functional group, an aliphatic hydrocarbon group having a polar functional group, or an aromatic hydrocarbon group having a polar functional group. The above aliphatic hydrocarbon group is not particularly limited and includes, for example, linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms. The above aromatic hydrocarbon group is not particularly limited and includes, for example, substituted or unsubstituted aryl groups having 1 to 20 carbon atoms. The above polar functional groups are not particularly limited and include, for example, carboxyl groups, carbonyl groups, alkoxy groups, hydroxyl groups, nitrile groups, nitro groups, and the like. The aliphatic hydrocarbon group having the above polar functional group is not particularly limited, and for example, a group in which one or more hydrogens in the above aliphatic hydrocarbon group are substituted with the above polar functional group can be used. The aromatic hydrocarbon group having the above polar functional group is also not particularly limited, and for example, a group in which one or more hydrogens in the above aromatic hydrocarbon group are substituted with the above polar functional group can be used. Furthermore, in the compound of the present invention, multiple R components are contained in one structural unit (A-4). 5 These may be the same or different. Also, multiple Rs contained in different constituent units (A-4) 5 These may be the same or different. Similarly, multiple Rs contained within a single constituent unit (A-4') 5 These may be the same or different. Also, multiple Rs contained in different constituent units (A-4') 5 They may be the same or they may be different.

[0037] In the above constituent unit (A-4) and the above constituent unit (A-4'), R 6 and R 7 Each of these represents either a hydrogen atom or an aliphatic hydrocarbon group. The above aliphatic hydrocarbon group is not particularly limited and includes, for example, linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms. In the compound of the present invention, multiple R groups are contained in one structural unit (A-4). 6 and R 7 These may be the same or different. Also, multiple Rs contained in different constituent units (A-4) 6 and R 7 These may be the same or different. Similarly, multiple Rs contained within a single constituent unit (A-4') 6 and R 7 These may be the same or different. Also, multiple Rs contained in different constituent units (A-4') 6 and R 7 They may be the same or they may be different.

[0038] In the above constituent units (A-4) and (A-4'), k is an integer between 1 and 4, and k' is an integer between 1 and 5, but from the viewpoint of ease of obtaining raw materials, it is preferable that k and k' be 1, 2, or 3. It is more preferable that k and k' be 1, as this can further increase the adhesive strength of the adhesive composition, and in particular, it can further increase the adhesive strength even to adherends with low polarity.

[0039] More specifically, the above-mentioned constituent units (A-4) and (A-4') include, for example, constituent units derived from aminobenzene or its derivatives (when k is 1). The above-mentioned aminobenzene or its derivatives are not particularly limited and include, for example, aniline, methylaniline, ethylaniline, dimethylaniline, diethylaniline, etc. These aminobenzenes or their derivatives may be used alone or in combination of two or more.

[0040] The above-mentioned component (A) may consist solely of petroleum-derived materials, but it is preferable that it also contains bio-derived materials. The depletion of petroleum resources and the emission of carbon dioxide from the combustion of petroleum-derived products are serious concerns. Therefore, attempts are being made to conserve petroleum resources by using bio-derived materials instead of petroleum-derived materials. It is preferable from the standpoint of conserving petroleum resources if the above-mentioned component (A) contains bio-derived materials. Furthermore, if the above-mentioned component (A) contains bio-derived materials, since bio-derived materials are originally produced by absorbing carbon dioxide from the atmosphere, it is thought that burning them will not increase the total amount of carbon dioxide in the atmosphere, which is also preferable from the standpoint of reducing carbon dioxide emissions. Examples of monomers constituting the above-mentioned constituent unit (A), which includes bio-derived materials, include resorcinol, dihydroxyphenylethylamine hydrochloride, dihydroxyhydrocinnamic acid, dihydroxyphenylalanine, dihydroxybenzaldehyde, dihydroxybenzyl alcohol, pyrogallol, 1,2,4-trihydroxybenzene, phloroglucinol, 6-hydroxy-L-dopa, gallic acid, methyl gallate, butyl gallate, isobutyl gallate, isoamyl gallate, hexadecyl gallate, stearyl gallate, trihydroxyacetophenone, trihydroxybenzaldehyde, trihydroxybenzamide, trihydroxynitrobenzene, and the like.

[0041] The content of the above-mentioned constituent unit (A) in the compound of the present invention is not particularly limited, but a preferred lower limit is 1 mol%, and a preferred upper limit is 60 mol%. If the content of the above-mentioned constituent unit (A) is 1 mol% or more, the adhesive strength of the adhesive composition can be further increased by incorporating the compound into the adhesive composition, and in particular, the adhesive strength can be further increased even for adherends with low polarity. If the content of the above-mentioned constituent unit (A) is 60 mol% or less, the compound can have the desirable physical properties required when used as a tackifying resin. A more preferred lower limit for the content of the above-mentioned constituent unit (A) is 5 mol%, a more preferred upper limit is 50 mol%, an even more preferred lower limit is 10 mol%, and an even more preferred upper limit is 30 mol%.

[0042] The compound of the present invention has a constituent unit (B) derived from at least one monomer (b) selected from the group consisting of terpene monomers, vinyl monomers, and conjugated diene monomers. That is, in addition to the above constituent unit (A), the compound of the present invention further has a constituent unit (B) derived from at least one monomer (b) selected from the group consisting of terpene monomers, vinyl monomers, and conjugated diene monomers. By having the above constituent unit (B), the compound can have suitable physical properties required when used as a tackifying resin. In particular, since incorporating the compound into the adhesive composition can further enhance the adhesive strength of the adhesive composition, constituent units derived from terpene monomers or vinyl monomers are preferred, and it is also preferable to use a combination of constituent units derived from terpene monomers and constituent units derived from vinyl monomers. Furthermore, from the viewpoint of improving the compatibility between the compound and the base polymer, especially between the compound and the styrene elastomer, constituent units derived from terpene monomers or conjugated diene monomers are preferred. Since these constituent units have an aliphatic hydrocarbon group with an unsaturated double bond, the presence of these constituent units in the compound improves the compatibility between the compound and the base polymer, especially between the compound and the styrene elastomer, and suppresses a decrease in the adhesive strength of the adhesive composition due to deterioration of compatibility.

[0043] The above terpene monomers are not particularly limited, and examples include α-pinene, β-pinene, limonene, dipentene, δ-3-carene, dimethyloctatriene, allocimene, myrcene, ocimene, linalool, and cosmene. Among these, α-pinene, β-pinene, or limonene are preferred because incorporating the compound into the adhesive composition can further enhance the adhesive strength of the adhesive composition. The vinyl monomers mentioned above are not particularly limited, but from the viewpoint of improving the compatibility between the compound and the base polymer, and especially the compatibility between the compound and the acrylic polymer, vinyl monomers that do not have a structure containing two or more aromatic rings in one molecule (for example, naphthalene structure, anthracene structure, biphenyl structure, anthraquinone structure, benzophenone structure, etc.) are preferred. Examples of vinyl monomers that do not have a structure containing two or more aromatic rings in one molecule include ethylene, propylene, butylene, hexene, vinyl acetate, vinyl chloride, styrene, α-methylstyrene, coumarone, indene, vinyltoluene, divinylbenzene, divinyltoluene, and 2-phenyl-2-butene. Among these, styrene is preferred because incorporating the compound into the adhesive composition can further increase the adhesive strength of the adhesive composition. The above-mentioned conjugated diene monomers are not particularly limited and include, for example, butadiene, isoprene, piperylene, and cyclopentadiene. Among these, isoprene is preferred because incorporating the compound into the adhesive composition can further enhance the adhesive strength of the adhesive composition. These monomers (b) may be used individually or in combination of two or more.

[0044] The above constituent unit (B) may consist solely of petroleum-derived materials, but it is preferable that it includes bio-derived materials. The depletion of petroleum resources and the emission of carbon dioxide from the combustion of petroleum-derived products are serious concerns. Therefore, attempts are being made to conserve petroleum resources by using bio-derived materials instead of petroleum-derived materials. It is preferable from the standpoint of conserving petroleum resources if the above constituent unit (B) includes bio-derived materials. Furthermore, if the above constituent unit (B) includes bio-derived materials, since bio-derived materials are originally produced by absorbing carbon dioxide from the atmosphere, it is thought that burning them will not increase the total amount of carbon dioxide in the atmosphere, which is also preferable from the standpoint of reducing carbon dioxide emissions. Examples of monomers (b) that constitute the above-mentioned constituent unit (B) containing bio-derived materials include terpene monomers, ethylene, propylene, hexene, butadiene, isoprene, and the like.

[0045] The content of the above-mentioned constituent unit (B) in the compound of the present invention is not particularly limited, but a preferred lower limit is 40 mol%, and a preferred upper limit is 99 mol%. If the content of the above-mentioned constituent unit (B) is 40 mol% or more, the compound can have the desirable physical properties required when used as a tackifying resin. If the content of the above-mentioned constituent unit (B) is 99 mol% or less, the content of the above-mentioned constituent unit (A) can be sufficiently secured, so by incorporating the compound into an adhesive composition, the adhesive strength of the adhesive composition can be further increased, and in particular, the adhesive strength can be further increased even for adherends with low polarity. A more preferred lower limit for the content of the above-mentioned constituent unit (B) is 50 mol%, and a more preferred upper limit is 90 mol%.

[0046] The compounds of the present invention are not particularly limited as long as they are compounds having the above-mentioned structural unit (A) and the above-mentioned structural unit (B), but it is preferable that they are copolymers having a structure represented by the following formula. Copolymers having such a structure are obtained by a cationic polymerization method as described later, and can further increase the adhesive strength of adhesive compositions, and in particular can further increase the adhesive strength even to low-polarity adherends.

[0047] [ka]

[0048] In the formula, A represents a constituent unit (A), B represents a constituent unit (B), and s and t each represent an integer greater than or equal to 1. * represents a connection.

[0049] The compounds of the present invention are not particularly limited as long as they are compounds having the above-mentioned structural unit (A) and structural unit (B), but are preferably copolymers having the above-mentioned structural unit (A) and structural unit (B), and may further have other structural units. In the case of copolymers, the above-mentioned structural unit (A) and structural unit (B) may be copolymerized randomly, or they may be copolymerized in a regular or periodic manner, for example, when each forms a block segment and the block segments are bonded to each other.

[0050] The compounds of the present invention preferably have an aliphatic hydrocarbon group having an unsaturated double bond. The compounds of the present invention may have the aliphatic hydrocarbon group having the unsaturated double bond in the above-mentioned structural unit (A) or structural unit (B), or in other structural units. In particular, from the viewpoint of ease of synthesis and improving the compatibility between the compound and the base polymer, especially between the compound and the styrene elastomer, it is preferable to have the aliphatic hydrocarbon group having the unsaturated double bond in the above-mentioned structural unit (B) or other structural units. The above-mentioned structural unit (B) or other structural units having the aliphatic hydrocarbon group having the unsaturated double bond are not particularly limited, but structural unit (B) derived from at least one monomer (b) selected from the group consisting of terpene monomers and conjugated diene monomers is preferred. That is, the compounds of the present invention preferably have the aliphatic hydrocarbon group having the unsaturated double bond in structural unit (B) derived from at least one monomer (b) selected from the group consisting of terpene monomers and conjugated diene monomers. In particular, it is preferable that the compound be contained in the structural units derived from terpene monomers, as incorporating the compound into the adhesive composition can further enhance the adhesive strength of the adhesive composition.

[0051] Other constituent units mentioned above include, for example, constituent units derived from other phenolic monomers not included in constituent unit (A), and constituent units derived from maleic anhydride. The other phenolic monomers mentioned above are not particularly limited and include, for example, phenol, cresol, xylenol, propylphenol, norylphenol, methoxyphenol, bromophenol, bisphenol A, bisphenol F, bisphenol S, dihydroxynaphthalene, and the like. These other phenolic monomers may be used individually or in combination of two or more.

[0052] The molecular weight of the compound of the present invention is not particularly limited, but a preferred lower limit of 400 and a preferred upper limit of 10,000 is the weight-average molecular weight (Mw). If the weight-average molecular weight (Mw) is within the above range, the compound can have the desirable physical properties required when used as a tackifying resin. A more preferred lower limit of 500 and a more preferred upper limit of 5000 is the weight-average molecular weight (Mw), a still more preferred lower limit of 700 and a still more preferred upper limit of 3000 is the weight-average molecular weight (Mw). To adjust the weight-average molecular weight (Mw) to the above range, for example, the composition of the compound, polymerization method, polymerization conditions, etc., can be adjusted.

[0053] The weight-average molecular weight (Mw) and the molecular weight distribution (Mw / Mn), as described later, can be measured by the following method. The compound solution is filtered through a filter (material: polytetrafluoroethylene, pore diameter: 0.2 μm). The resulting filtrate is supplied to a gel permeation chromatograph (e.g., Waters 2690 Separations Model), and GPC measurement is performed under conditions of sample flow rate of 1 ml / min and column temperature of 40°C to measure the polystyrene-equivalent molecular weight of the compound and determine the weight-average molecular weight (Mw) and molecular weight distribution (Mw / Mn). For example, a GPC KF-802.5L (Showa Denko Corporation) is used as the column, and a differential refractometer is used as the detector.

[0054] The Young's modulus of the compound of the present invention is not particularly limited, but a preferred lower limit of the Young's modulus at 25°C is 10 MPa. If the Young's modulus at 25°C is 10 MPa or higher, the compound can have appropriate hardness and possess suitable physical properties required when used as a tackifying resin rather than an adhesive. A more preferred lower limit of the Young's modulus at 25°C is 50 MPa, and an even more preferred lower limit is 70 MPa. The upper limit of Young's modulus at 25°C is not particularly limited, but from the viewpoint of preventing the adhesive composition containing the compound from becoming too hard and reducing the adhesive strength, a preferred upper limit is 10,000 MPa, and a more preferred upper limit is 5,000 MPa. To adjust the Young's modulus at 25°C to the above range, for example, one can adjust the molecular weight of the compound, the composition and content of the constituent units (A) and (B) in the compound, etc. The Young's modulus at 25°C can be measured by performing a tensile test using a tensile testing apparatus (e.g., ORIENTEC's Tensilon) under the conditions of a tensile speed of 200 mm / min, a grip distance of 15 mm, and a temperature of 25°C. The sample for this test can be prepared, for example, by filling a mold measuring 10 × 50 mm with the compound and melting it at a temperature 100°C higher than the glass transition temperature to produce a 1 mm thick test specimen.

[0055] The glass transition temperature of the compound of the present invention is not particularly limited, but a preferred lower limit is 0°C and a preferred upper limit is 200°C. If the glass transition temperature is within the above range, the compound can be easily adjusted to have a Young's modulus within that range and can have the desirable physical properties required when used as a tackifying resin. A more preferred lower limit for the glass transition temperature is 10°C and a more preferred upper limit is 150°C. The glass transition temperature can be measured using a differential scanning calorimeter (e.g., Hitachi High-Tech Science Corporation, SII Exstar 6000 / DSC 6220) under a nitrogen atmosphere at a heating rate of 10°C / min, and the value obtained in the first run can be used.

[0056] The iodine value of the compound of the present invention is not particularly limited, but a preferred lower limit is 2 g / 100 g and a preferred upper limit is 180 g / 100 g. If the above iodine value is 2 g / 100 g or more, it is possible to suppress the decrease in adhesive strength of the adhesive composition due to deterioration of the compatibility between the compound and the base polymer, in particular, between the compound and the styrene-based elastomer. If the above iodine value is 180 g / 100 g or less, by incorporating the above iodine value into the adhesive composition, the adhesive strength of the adhesive composition can be further increased, and in particular, the adhesive strength can be further increased even for adherends with low polarity. A more preferred lower limit for the above iodine value is 70 g / 100 g and a more preferred upper limit is 170 g / 100 g. The iodine value is an indicator of the amount of unsaturated double bonds (C=C bond amount), and refers to the value measured in accordance with the method described in "JIS K 0070:1992".

[0057] The content of bio-derived carbon (carbon atoms) in the compound of the present invention is not particularly limited, but it is preferable that the content of bio-derived carbon (carbon atoms) is 10% or more. A bio-derived carbon content of 10% or more is an indicator that a product is "bio-based." A bio-derived carbon content of 10% or more is preferable from the viewpoint of conserving petroleum resources and reducing carbon dioxide emissions. A more preferable lower limit for the bio-derived carbon content is 30%, an even more preferable lower limit is 60%, an even more preferable lower limit is 70%, and an even more preferable lower limit is 90%. There is no particular upper limit to the bio-derived carbon content, and it may be 100%. Furthermore, while carbon derived from biological sources contains a certain percentage of the radioactive isotope C-14, carbon derived from petroleum contains almost no C-14. Therefore, the carbon content of the above-mentioned biological sources can be calculated by measuring the concentration of C-14 contained in the compound. Specifically, this can be measured in accordance with ASTM D6866-20, a standard widely used in the bioplastics industry.

[0058] The compounds of the present invention also include hydrogenated compounds of the compounds described above. A hydrogenated compound is a compound in which the carbon-carbon double bond present in the compounds described above has been saturated by hydrogenation. Even such hydrogenated compounds can be suitably used as tackifying resins to be incorporated into adhesive compositions, and can increase the adhesive strength of the adhesive composition, and in particular can increase the adhesive strength even to adherends with low polarity.

[0059] The method for producing the compound of the present invention is not particularly limited, but for example, the following method is preferred. That is, a method for producing a compound having a constituent unit (A) derived from monomer (a) having a solvation free energy Δμ with polytetrafluoroethylene of -30 kcal / mol or less, and a constituent unit (B) derived from at least one monomer (b) selected from the group consisting of terpene monomers, vinyl monomers and conjugated diene monomers, wherein monomer (a) and monomer (b) are copolymerized. Such a method for producing a compound is also one of the present inventions.

[0060] The above monomer (a) is not particularly limited as long as its solvation free energy Δμ with polytetrafluoroethylene is -30 kcal / mol or less, but it is preferably at least one selected from the group consisting of monomer (a-1), monomer (a-2), monomer (a-3), and monomer (a-4) represented by the following formula.

[0061] [ka]

[0062] In the formula, R 1 Each of the following represents a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a polar functional group, an aliphatic hydrocarbon group having a polar functional group, or an aromatic hydrocarbon group having a polar functional group, and n'' represents an integer between 2 and 5. The above n'' is preferably 2 or 3, and more preferably 3.

[0063] [ka]

[0064] [ka]

[0065] [ka]

[0066] In the formula, R 2 , R 3 and R 5 Each of the following represents a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a polar functional group, an aliphatic hydrocarbon group having a polar functional group, or an aromatic hydrocarbon group having a polar functional group. 4 R represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an aliphatic hydrocarbon group with a polar functional group, or an aromatic hydrocarbon group with a polar functional group, respectively. 6 and R 7 Each represents either a hydrogen atom or an aliphatic hydrocarbon group. m'' represents an integer between 1 and 5. l'' represents an integer between 2 and 5. k'' represents an integer between 1 and 5.

[0067] In the method for producing the compound of the present invention, it is preferable to copolymerize the above monomer (a) and the above monomer (b) by cationic polymerization. By using cationic polymerization, monomer (a) and monomer (b) can be copolymerized without prior chemical modification to protect the functional groups of monomer (a), such as phenolic hydroxyl groups, carboxyl groups, alkoxy groups, and amino groups, and subsequent deprotection is also unnecessary. Therefore, monomer (a) and monomer (b) can be copolymerized in a simpler one-step reaction process, leading to a reduction in impurities and an improvement in yield.

[0068] A preferred method for copolymerizing monomer (a) and monomer (b) by cationic polymerization is to react monomer (a) and monomer (b) in the presence of a Lewis acid. This method is thought to generate cations of monomer (b), leading to cationic polymerization between monomers (b) and a Fridel-Crafts alkylation reaction between monomer (a) and monomer (b). Repeated reactions of this nature allow for the production of a copolymer having constituent units (A) derived from monomer (a) and constituent units (B) derived from monomer (b). The Lewis acid mentioned above is not particularly limited, and conventionally known Lewis acids can be used, such as aluminum chloride (AlCl3), diethylaluminum chloride (Et2AlCl2), tin(IV) chloride (SnCl4), titanium(IV) chloride (TiCl4), boron trichloride (BCl3), and boron trifluoride ether complex (BF3·EtO). Among these, aluminum chloride (AlCl3) is preferred because it yields a higher yield.

[0069] More specifically, for example, if pyrogallol is used as monomer (a) and α-pinene is used as monomer (b), and these are reacted in the presence of aluminum chloride (AlCl3), which is a Lewis acid, the reaction shown in the following scheme is expected to proceed. Specifically, a cation of monomer (b), α-pinene, is generated, and cationic polymerization of α-pinenes proceeds (upper part of the scheme below), while a Fridel-Crafts alkylation reaction proceeds between monomer (a), pyrogallol, and monomer (b), α-pinene (middle part of the scheme below). By repeatedly performing such reactions, a copolymer having structural units derived from pyrogallol and structural units derived from α-pinene can be obtained (lower part of the scheme below). Such a copolymer will have structural units derived from pyrogallol in the main chain skeleton or at the ends of the main chain skeleton.

[0070] [ka]

[0071] In the formula, s and t each represent an integer greater than or equal to 1. * represents a concatenation.

[0072] The compounds of the present invention can be suitably used as tackifying resins to be incorporated into adhesive compositions. An adhesive composition containing a base polymer and the compound (T1) of the present invention is also one of the present inventions. The content of compound (T1) of the present invention in the adhesive composition of the present invention is not particularly limited, but even a small amount compared to conventional tackifying resins can increase the adhesive strength of the adhesive composition, with a preferred lower limit of 1 part by weight and a preferred upper limit of 35 parts by weight per 100 parts by weight of the base polymer. If the content of compound (T1) of the present invention is 1 part by weight or more, the adhesive strength of the adhesive composition can be further increased, and in particular, the adhesive strength can be further increased even for adherends with low polarity. If the content of compound (T1) of the present invention is 35 parts by weight or less, it is possible to suppress the adhesive composition from becoming too hard and reducing the adhesive strength. A more preferred lower limit for the content of compound (T1) of the present invention is 3 parts by weight, a more preferred upper limit is 30 parts by weight, an even more preferred lower limit is 5 parts by weight, and an even more preferred upper limit is 20 parts by weight.

[0073] The adhesive composition of the present invention may further contain at least one tackifying resin (T2) selected from the group consisting of rosin ester resins, terpene resins, and petroleum resins. Among these, rosin ester resins or terpene resins are preferred because they can further increase the adhesive strength of the adhesive composition.

[0074] The above-mentioned tackifying resin (T2) has a preferred lower limit of 70°C and a preferred upper limit of 170°C for its softening temperature. If the softening temperature is 70°C or higher, it is possible to suppress the adhesive composition from becoming too soft and reducing the adhesive strength. If the softening temperature is 170°C or lower, the wettability of the interface of the adhesive layer formed from the adhesive composition is improved, and it is possible to suppress interfacial delamination. A more preferred lower limit for the softening temperature is 120°C. The softening temperature is the softening temperature measured according to the JIS K2207 ring-and-ball method.

[0075] The tackifying resin (T2) described above has a preferred lower limit of 25 and a preferred upper limit of 150 for its hydroxyl value. Having the hydroxyl value within this range improves the wettability of the interface of the adhesive layer formed from the adhesive composition, thereby suppressing interfacial delamination. A more preferred lower limit for the hydroxyl value is 30, and a more preferred upper limit is 130. The hydroxyl value can be measured according to JIS K1557 (phthalic anhydride method).

[0076] The content of the tackifying resin (T2) is not particularly limited, but a preferred lower limit is 10 parts by weight and a preferred upper limit is 100 parts by weight per 100 parts by weight of the base polymer. If the content of the tackifying resin (T2) is 10 parts by weight or more, the adhesive strength of the adhesive composition can be further increased. If the content of the tackifying resin (T2) is 100 parts by weight or less, it is possible to suppress the adhesive composition from becoming too hard and reducing the adhesive strength. A more preferred lower limit for the content of the tackifying resin (T2) is 15 parts by weight, a more preferred upper limit is 60 parts by weight, an even more preferred upper limit is 50 parts by weight, and an even more preferred upper limit is 40 parts by weight.

[0077] The above-mentioned base polymer is not particularly limited and examples include acrylic polymers, rubber polymers, urethane polymers, and silicone polymers. Among these, acrylic polymers are preferred because they are relatively stable against light, heat, and moisture. Rubber polymers are also preferred because they have low adherend selectivity, can adhere to various adherends, and are less likely to peel off from adherends even when immersed in alkaline chemical solutions. Among the above-mentioned rubber polymers, styrene elastomers, which are block copolymers having blocks derived from styrene monomers and blocks derived from conjugated diene monomers, or hydrogenated versions thereof, are more preferred.

[0078] The above acrylic polymer preferably has a constituent unit derived from at least one selected from the group consisting of alkyl (meth)acrylate esters with 1 to 12 C1 of the alkyl group and alkyl (meth)acrylate esters with 13 to 18 C1 of the alkyl group, from the viewpoint of improving initial tack and thus improving ease of bonding at low temperatures. Examples of alkyl (meth)acrylate esters having 1 to 12 carbon atoms in the alkyl group include 2-ethylhexyl (meth)acrylate, butyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. Examples of alkyl (meth)acrylate esters having 13 to 18 carbon atoms in the alkyl group include tridecyl methacrylate and stearyl (meth)acrylate. In particular, it is preferable to use 2-ethylhexyl (meth)acrylate or butyl (meth)acrylate because the above acrylic polymer can exhibit high adhesive strength. The content of constituent units in the above-mentioned acrylic polymer that are derived from at least one selected from the group consisting of alkyl (meth)acrylate esters with 1 to 12 C1 of the alkyl group and alkyl (meth)acrylate esters with 13 to 18 C1 of the alkyl group is not particularly limited. The preferred lower limit of the above content is 10% by weight, the preferred upper limit is 100% by weight, the more preferred lower limit is 30% by weight, the more preferred upper limit is 95% by weight, the still preferred lower limit is 50% by weight, and the still preferred upper limit is 90% by weight. By keeping the above content within this range, the above-mentioned acrylic polymer can exhibit high adhesive strength.

[0079] The above acrylic polymer preferably has constituent units derived from monomers having crosslinkable functional groups. Because the above-mentioned acrylic polymer has structural units derived from monomers having the above-mentioned crosslinkable functional groups, when a crosslinking agent is added, a crosslinked structure of the acrylic polymer is formed in the adhesive layer formed from the adhesive composition. This increases the gel fraction and bulk strength of the adhesive layer, thereby improving the adhesive strength. The above-mentioned crosslinkable functional groups are not particularly limited and include, for example, amino groups, carboxyl groups, carbonyl groups, hydroxyl groups, epoxy groups, isocyanate groups, etc.

[0080] Examples of monomers having the above-mentioned crosslinkable functional group include hydroxyalkyl (meth)acrylate, glycerin dimethacrylate, glycidyl (meth)acrylate, 2-methacryloyloxyethyl isocyanate, (meth)acrylic acid, itaconic acid, maleic anhydride, crotonic acid, maleic acid, fumaric acid, etc. More specifically, examples of the above-mentioned hydroxyalkyl (meth)acrylate include 2-hydroxyethyl (meth)acrylate, etc. These monomers having the above-mentioned crosslinkable functional group may be used alone or in combination of two or more. In particular, from the viewpoint of increasing the gel fraction and bulk strength of the adhesive layer formed from the adhesive composition, monomers having a hydroxyl group such as hydroxyalkyl (meth)acrylate and glycerin dimethacrylate, or monomers having a carboxyl group such as (meth)acrylic acid are preferred.

[0081] The content of constituent units derived from the monomer having the crosslinkable functional group in the above acrylic polymer is not particularly limited, but a preferred lower limit is 0.01% by weight and a preferred upper limit is 20% by weight. By keeping the content of constituent units derived from the monomer having the crosslinkable functional group within this range, the gel fraction and bulk strength of the adhesive layer formed from the adhesive composition are increased, and the adhesive strength is improved. A more preferred lower limit for the content of constituent units derived from the monomer having the crosslinkable functional group is 0.05% by weight and a more preferred upper limit is 5% by weight.

[0082] The above acrylic polymer may optionally include structural units derived from other copolymerizable polymerizable monomers other than the alkyl (meth)acrylate esters described above and the monomers having the above crosslinkable functional groups.

[0083] To obtain the above-mentioned acrylic polymer, a mixture of monomers as described above can be subjected to a radical reaction in the presence of a polymerization initiator. Conventional known methods can be used to perform the radical reaction of the above-mentioned monomer mixture, i.e., polymerization methods, such as solution polymerization (boiling point polymerization or constant temperature polymerization), emulsion polymerization, suspension polymerization, and bulk polymerization.

[0084] The weight-average molecular weight (Mw) of the above acrylic polymer is not particularly limited, but a preferred lower limit is 200,000 and a preferred upper limit is 2,000,000. If the weight-average molecular weight (Mw) is 200,000 or more, the bulk strength of the adhesive layer formed from the adhesive composition increases, improving the adhesive strength. If the weight-average molecular weight (Mw) is 2,000,000 or less, the wettability of the interface of the adhesive layer formed from the adhesive composition improves, suppressing interfacial delamination. A more preferred lower limit for the weight-average molecular weight (Mw) is 400,000 and a more preferred upper limit is 1,500,000.

[0085] The ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) of the above acrylic polymer (molecular weight distribution, Mw / Mn) is not particularly limited, but a preferred lower limit is 1.05 and a preferred upper limit is 5.0. When Mw / Mn is 5.0 or less, the proportion of low-molecular-weight components is suppressed, the bulk strength of the adhesive layer formed from the adhesive composition increases, and the adhesive strength improves. A more preferred upper limit for Mw / Mn is 4.5, an even more preferred upper limit is 4, and an even more preferred upper limit is 3.5. To adjust the weight-average molecular weight (Mw) and molecular weight distribution (Mw / Mn) within the above range, for example, the composition, polymerization method, polymerization conditions, etc., of the acrylic polymer can be adjusted.

[0086] The above-mentioned styrene-based elastomer may be a block copolymer having rubber elasticity at room temperature and comprising a hard segment portion and a soft segment portion. The block derived from the styrene-based monomer constitutes the hard segment portion, and the block derived from the conjugated diene monomer constitutes the soft segment portion.

[0087] The above styrene monomers are not particularly limited and include, for example, styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene, vinylethylbenzene, divinylbenzene, trivinylbenzene, divinylnaphthalene, t-butoxystyrene, vinylbenzyldimethylamine, (4-vinylbenzyl)dimethylaminoethyl ether, N,N-dimethylaminoethylstyrene, N,N-dimethylaminomethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-t-butylstyrene, 3-t-butylstyrene, 4-t-butylstyrene, vinylxylene, vinylnaphthalene, vinylpyridine, diphenylethylene, and tertiary amino group-containing diphenylethylene. The above tertiary amino group-containing diphenylethylene is not particularly limited and includes, for example, 1-(4-N,N-dimethylaminophenyl)-1-phenylethylene. These styrene monomers may be used individually or in combination of two or more.

[0088] The above-mentioned conjugated diene monomers are not particularly limited and include, for example, isoprene, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 2-phenyl-1,3-butadiene, 3-methyl-1,3-pentadiene, and 2-chloro-1,3-butadiene. These conjugated diene monomers may be used individually or in combination of two or more.

[0089] Examples of the styrene-based elastomers mentioned above include styrene-isoprene-styrene (SIS) block copolymer, styrene-butadiene-styrene (SBS) block copolymer, and styrene-chloroprene-styrene block copolymer. Among these, SIS block copolymer and SBS block copolymer are preferred, and SIS block copolymer is more preferred, because they tend to exhibit high adhesive strength and are less likely to peel off the adherend even when immersed in an alkaline chemical solution. These styrene-based elastomers may be used individually or in combination of two or more.

[0090] The styrene-based elastomer may contain, in addition to a triblock copolymer of a block derived from the styrene-based monomer and a block derived from the conjugated diene monomer, a diblock copolymer of a block derived from the styrene-based monomer and a block derived from the conjugated diene monomer. The content of the diblock copolymer in the styrene-based elastomer (hereinafter also referred to as the "diblock ratio") is not particularly limited, but a preferred lower limit is 50% by weight, and a more preferred lower limit is 70% by weight. If the diblock ratio is within the above range, the adhesion of the adhesive composition to the adherend will be improved, and the adhesive strength will be enhanced. The upper limit of the diblock ratio is not particularly limited, but from the viewpoint of maintaining the cohesive force of the adhesive composition, a preferred upper limit is 90% by weight. The diblock ratio can be calculated from the peak area ratio of each copolymer measured by gel permeation chromatography (GPC).

[0091] The amount of blocks derived from the styrene monomer in the above-mentioned styrene-based elastomer (hereinafter also referred to as "styrene content") is not particularly limited, but a preferred upper limit is 20% by weight, and a more preferred upper limit is 16% by weight. If the styrene content is within the above range, the adhesive composition will not become too hard, the adhesion to the adherend will be improved, and the adhesive strength will be enhanced. The lower limit of the styrene content is not particularly limited, but from the viewpoint of maintaining the cohesive force of the adhesive composition, a preferred lower limit is 8% by weight. The styrene content is, 1 It can be calculated from the peak area ratio of each block measured by 1H-NMR.

[0092] The weight-average molecular weight of the styrene-based elastomer is not particularly limited, but a preferred lower limit is 50,000 and a preferred upper limit is 600,000. If the weight-average molecular weight is 50,000 or more, the bulk strength of the adhesive layer formed from the adhesive composition increases, improving the adhesive strength. If the weight-average molecular weight is 600,000 or less, it is possible to prevent the compatibility between the styrene-based elastomer and other components from decreasing too much. A more preferred lower limit for the weight-average molecular weight is 100,000 and a more preferred upper limit is 500,000.

[0093] In the present invention, if the base polymer is the acrylic polymer, the adhesive composition preferably contains a crosslinking agent. By adjusting the type and amount of the crosslinking agent, it becomes easier to adjust the gel fraction of the adhesive layer formed from the adhesive composition. The crosslinking agent is not particularly limited and examples include isocyanate-based crosslinking agents, aziridine-based crosslinking agents, epoxy-based crosslinking agents, and metal chelate-type crosslinking agents. Among these, isocyanate-based crosslinking agents are preferred. The preferred lower limit of the crosslinking agent content is 0.01 parts by weight, the preferred upper limit is 10 parts by weight, the more preferred lower limit is 0.1 parts by weight, and the more preferred upper limit is 5 parts by weight, relative to 100 parts by weight of the acrylic polymer.

[0094] The adhesive composition of the present invention may contain a silane coupling agent for the purpose of improving adhesive strength. The silane coupling agent is not particularly limited and includes, for example, epoxy silanes, acrylic silanes, methacrylic silanes, amino silanes, isocyanate silanes, and the like.

[0095] The adhesive composition of the present invention may contain a coloring agent for the purpose of providing light-shielding properties. The coloring agent is not particularly limited and examples include carbon black, aniline black, titanium dioxide, etc. Among these, carbon black is preferred because it is relatively inexpensive and chemically stable.

[0096] The adhesive composition of the present invention may optionally contain conventionally known fine particles and additives such as inorganic fine particles, conductive fine particles, antioxidants, foaming agents, organic fillers, and inorganic fillers.

[0097] An adhesive tape having an adhesive layer containing the adhesive composition of the present invention is also one of the present inventions. When the base polymer is the acrylic polymer, the gel fraction of the adhesive layer is not particularly limited, but a preferred lower limit is 10% by weight and a preferred upper limit is 70% by weight. If the gel fraction is 10% by weight or more, the bulk strength of the adhesive layer increases and the adhesive strength improves. If the gel fraction is 70% by weight or less, the wettability of the interface of the adhesive layer improves and interfacial delamination can be suppressed. A more preferred lower limit for the gel fraction is 15% by weight, a more preferred upper limit is 60% by weight, an even more preferred lower limit is 20% by weight, and an even more preferred upper limit is 50% by weight. The gel fraction of the adhesive layer can be adjusted within the above range by, for example, adjusting the composition and weight-average molecular weight of the acrylic polymer, or by adjusting the type and amount of the crosslinking agent.

[0098] The gel fraction of the adhesive layer can be measured by the following method. A test specimen is prepared by cutting adhesive tape into a flat rectangular shape measuring 50 mm x 100 mm. The test specimen is immersed in ethyl acetate at 23°C for 24 hours, then removed from the ethyl acetate and dried at 110°C for 1 hour. The weight of the dried test specimen is measured, and the gel fraction is calculated using the following formula (1). Note that the test specimen does not have a release film laminated on it to protect the adhesive layer. Gel fraction (weight %) = 100 × (W2 - W0) / (W1 - W0) (1) (W0: Weight of the substrate, W1: Weight of the test specimen before immersion, W2: Weight of the test specimen after immersion and drying)

[0099] When the base polymer is the acrylic polymer, the preferred lower limit of the shear storage modulus (hereinafter simply referred to as "shear storage modulus") at 25°C, measured at a measurement frequency of 10 Hz using a dynamic viscoelasticity measuring device for the adhesive layer, is 1.0 × 10⁻⁶. 4 Pa, the preferred upper limit is 5.0 × 10 5 It is Pa. If the shear storage modulus of the adhesive layer is within the above range, the adhesive strength of the adhesive layer will be further improved. The shear storage modulus of the adhesive layer is 3.0 × 10⁻⁶. 4 It is more preferable that it be Pa or higher, 5.0 × 10 4 It is even more preferable that it be Pa or higher, 4.0 × 10 5 It is more preferable that it be less than or equal to Pa, 3.5 × 10 5 It is even more preferable that the shear storage modulus is Pa or less. The shear storage modulus of the adhesive layer can be adjusted by the type and polymerization ratio of the monomers constituting the base polymer, the molecular weight of the base polymer, the gel fraction of the adhesive layer, the presence or absence of the tackifying resin (T2), the type and content of the compound (T1) of the present invention and the tackifying resin (T2), etc.

[0100] The shear storage modulus of the adhesive layer can be measured by the following method. First, a measurement sample consisting only of the adhesive layer is prepared. Using a dynamic viscoelasticity measuring device such as a viscoelastic spectrometer (e.g., DVA-200, manufactured by IT Measurement Control Co., Ltd., or an equivalent), the storage modulus at 25°C is measured when the dynamic viscoelastic spectrum from -50°C to 200°C is measured under the conditions of a low-speed heating shear deformation mode of 5°C / min and a measurement frequency of 10Hz.

[0101] When the base polymer is the acrylic polymer, it is preferable that the adhesive layer has a peak in the loss tangent (tanδ, hereinafter simply referred to as "loss tangent") measured at a measurement frequency of 10 Hz using a dynamic viscoelasticity measuring device between -20°C and 20°C. The loss tangent of the adhesive layer having a peak within the above range makes it easier to achieve both adhesive strength and holding power in the adhesive layer. It is more preferable that the loss tangent has a peak at 15°C or below, and even more preferable that it has a peak at 12°C or below. It is more preferable that the loss tangent has a peak at -15°C or above, and even more preferable that it has a peak at -10°C or above. The loss tangent of the adhesive layer can be obtained by measuring the dynamic viscoelastic spectrum from -100°C to 200°C using a viscoelastic spectrometer (e.g., DVA-200, manufactured by IT Measurement & Control Co., Ltd., or an equivalent) under the conditions of a low-speed heating shear deformation mode at 5°C / min and a measurement frequency of 10Hz.

[0102] The thickness of the adhesive layer is not particularly limited, but a preferred lower limit is 20 μm, a preferred upper limit is 100 μm, a more preferred lower limit is 25 μm, and a more preferred upper limit is 80 μm. If the thickness of the adhesive layer is within this range, the adhesive layer can have sufficient adhesive strength. The thickness of the adhesive layer can be measured using a dial thickness gauge (for example, the "ABS Digimatic Indicator" manufactured by Mitutoyo).

[0103] The adhesive tape of the present invention may have a base material. In this case, the adhesive layer may be laminated on one side of the base material, or on both sides of the base material. The above-mentioned substrate is not particularly limited and includes, for example, a resin film. The above-mentioned resin film is not particularly limited and includes, for example, a polyolefin resin film such as polyethylene film or polypropylene film, a polyester resin film such as polyethylene terephthalate (PET) film, an ethylene-vinyl acetate copolymer film, a polyvinyl chloride resin film, or a polyurethane resin film. In addition, as the above-mentioned substrate, polyolefin foam sheets such as polyethylene foam sheets or polypropylene foam sheets, and polyurethane foam sheets can also be mentioned. Among these, PET film is preferred. The thickness of the above-mentioned substrate is not particularly limited, but a preferred lower limit is 5 μm, a preferred upper limit is 30 μm, a more preferred lower limit is 8 μm, and a more preferred upper limit is 20 μm.

[0104] The adhesive tape of the present invention may optionally have other layers besides the adhesive layer and the substrate described above.

[0105] The method for manufacturing the adhesive tape of the present invention is not particularly limited. For example, when the adhesive layer is laminated on both sides of the substrate, the following method can be used. First, a solvent is added to the base polymer, the compound of the present invention (T1), the tackifying resin (T2), the crosslinking agent, etc., to prepare a solution of adhesive composition A. This solution of adhesive composition A is applied to the surface of the substrate, and the solvent in the solution is completely dried and removed to form an adhesive layer A. Next, a release film is placed on top of the formed adhesive layer A with its release treated surface facing the adhesive layer A. Next, a separate release film is prepared, and a solution of adhesive composition B is applied to the release surface of this release film. By completely drying and removing the solvent in the solution, a laminated film is produced in which adhesive layer B is formed on the surface of the release film. The obtained laminated film is then placed on the back surface of a substrate on which adhesive layer A is formed, with adhesive layer B facing the back surface of the substrate, to create a laminate. The laminate is then pressed with a rubber roller or the like. This makes it possible to obtain a double-sided adhesive tape having adhesive layers on both sides of the substrate, and on which the surface of the adhesive layer is covered with a release film.

[0106] Alternatively, two sets of laminated films may be prepared in the same manner, and these laminated films may be placed on each of the two sides of a substrate with the adhesive layer of the laminated film facing the substrate to create a laminate, which can then be pressed with a rubber roller or the like. This makes it possible to obtain a double-sided adhesive tape having adhesive layers on both sides of the substrate, with the surface of the adhesive layer covered with a release film.

[0107] The applications of the adhesive composition and adhesive tape of the present invention are not particularly limited, but because they have high adhesive strength, and especially high adhesive strength even to low-polarity substrates (for example, substrates made of polyolefin resin or fluororesin that are difficult to adhere to), they can be used, for example, for fixing electronic equipment components or automotive components. More specifically, they can be used, for example, for fixing components in televisions, monitors, portable electronic devices, automotive electronic devices, etc. The shape of the adhesive tape of the present invention in these applications is not particularly limited and examples include square, rectangular, frame-shaped, circular, oval, donut-shaped, etc. [Effects of the Invention]

[0108] According to the present invention, it is possible to increase the adhesive strength of an adhesive composition, and in particular, to provide a compound that can increase the adhesive strength even to adherends with low polarity. Furthermore, according to the present invention, it is possible to provide a method for producing the compound, an adhesive composition containing the compound, and an adhesive tape having an adhesive layer containing the adhesive composition. [Modes for carrying out the invention]

[0109] The embodiments of the present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0110] (Synthesis Example 1) (Preparation of acrylic polymers) 100 parts by weight of ethyl acetate was placed in a reactor equipped with a thermometer, stirrer, and condenser, and after purging with nitrogen, the reactor was heated and reflux was started. 30 minutes after the ethyl acetate boiled, 0.08 parts by weight of azobisisobutyronitrile was added as a polymerization initiator. The monomer mixture shown in Table 1 was then added dropwise and evenly over 1 hour and 30 minutes to allow the reaction to proceed. 30 minutes after the end of the dropwise addition, 0.1 parts by weight of azobisisobutyronitrile was added, and the polymerization reaction was continued for a further 5 hours. By adding ethyl acetate to the reactor and cooling while diluting, a solution of acrylic polymer with a solid content of 25% by weight was obtained. The obtained acrylic polymer solution was filtered through a filter (material: polytetrafluoroethylene, pore diameter: 0.2 μm). The resulting filtrate was supplied to a gel permeation chromatograph (Waters, 2690 Separations Model), and GPC measurements were performed under conditions of a sample flow rate of 1 ml / min and a column temperature of 40°C to measure the polystyrene-equivalent molecular weight of the acrylic polymer, and to determine the weight-average molecular weight (Mw) and molecular weight distribution (Mw / Mn). A GPC KF-806L column (Showa Denko Corporation) was used, and a differential refractometer was used as the detector.

[0111] (Synthesis Example 2) (Preparation of acrylic polymers) An acrylic polymer was obtained in the same manner as in Synthesis Example 1, except that the amount of ethyl acetate added was changed to 50 parts by weight.

[0112] (Synthesis Example 3) (Preparation of acrylic polymers) An acrylic polymer was obtained in the same manner as in Synthesis Example 1, except that the monomer mixture was modified as shown in Table 1.

[0113] [Table 1]

[0114] (Synthesis example A) (Preparation of compound (T1)) Fifty parts by weight of toluene were added to a reactor equipped with a thermometer, stirrer, and condenser. After purging with nitrogen, the reactor was heated and reflux was initiated. After 30 minutes, 2 parts by weight of aluminum chloride (AlCl3) were added while maintaining the toluene at 75°C. To this, a solution of 22.3 parts by weight of monomer (a) and 27.7 parts by weight of monomer (b) (molar ratio as shown in Table 2) dissolved in 50 parts by weight of toluene was gradually added dropwise over 1 hour and 30 minutes to allow the reaction to proceed. After polymerization for 4 hours, the hydrochloric acid generated from aluminum chloride (AlCl3) was neutralized by cooling while adding 0.1 parts by weight of pyridine to the reactor. The precipitate formed by neutralization was filtered, and after liquid-liquid extraction of the obtained filtrate, the toluene was evaporated to obtain the solid compound (T1). For monomer (a), the solvation free energy Δμ with polytetrafluoroethylene was calculated using molecular dynamics. Regarding the obtained compound (T1) l ¹H-NMR measurements were performed to confirm that compound (T1) is a copolymer having a constituent unit (A) derived from monomer (a) pyrocatechol and a constituent unit (B) derived from monomer (b) α-pinene. The obtained compound (T1) was dissolved in tetrahydrofuran, and the resulting solution was filtered through a filter (material: polytetrafluoroethylene, pore diameter: 0.2 μm). The obtained filtrate was supplied to a gel permeation chromatograph (Waters, 2690 Separations Model), and GPC measurements were performed under conditions of a sample flow rate of 1 ml / min and a column temperature of 40°C to measure the polystyrene-equivalent molecular weight of compound (T1) and determine the weight-average molecular weight (Mw). A GPC KF-802.5L column (Showa Denko Corporation) was used, and a differential refractometer was used as the detector.

[0115] The obtained compound (T1) was measured using a differential scanning calorimeter (Hitachi High-Tech Science Corporation, SII Exstar 6000 / DSC 6220) under a nitrogen atmosphere and a heating rate of 10°C / min. The glass transition temperature was determined using the value obtained in the first run.

[0116] The obtained compound (T1) was filled into a mold measuring 10 × 50 mm and melted at a temperature 100°C higher than the glass transition temperature to produce a 1 mm thick specimen. This specimen was subjected to a tensile test using a tensile testing apparatus (ORIENTEC, Tensilon) under the conditions of a tensile speed of 200 mm / min, a grip distance of 15 mm, and a temperature of 25°C, and the Young's modulus at 25°C was measured.

[0117] 0.250 g of the obtained compound (T1) was weighed and diluted with 50 mL of cyclohexane. Next, 10.0 mL of Wies' reagent (Wako Pure Chemical Industries, Ltd., 0.1 mol / L iodine chloride-acetic acid solution) was added and shaken well, and the reaction was allowed to proceed for 30 minutes. 10 mL of 15 wt% potassium iodide aqueous solution was then added, followed by 30 mL of water, and the mixture was stirred. Furthermore, 0.1 N sodium thiosulfate aqueous solution (Wako Pure Chemical Industries, Ltd.) was gradually added dropwise until the solution turned pale yellow, at which point 3 drops of starch solution (10 g / L) were added. Then, 0.1 N sodium thiosulfate aqueous solution (Wako Pure Chemical Industries, Ltd.) was gradually added dropwise until the blue color of the solution disappeared (dropping volume Y mL). Next, the blank dropping volume (dropping volume Z mL) was determined in the same manner, except that the sample (compound (T1)) was not added. The iodine value of compound (T1) was measured using the following formula. Iodine value (g / 100g) = (ZY) × 1.269 / 0.250

[0118] The bio-derived carbon content of the obtained compound (T1) was measured according to ASTM D6866-20.

[0119] (Synthesis examples B-M and O) (Preparation of compound (T1)) Compound (T1) was obtained in the same manner as in synthesis example A, except that monomers (a) and (b) were changed as shown in Table 2.

[0120] (Synthesis example N) (Preparation of compound (T1)) Fifty parts by weight of toluene were added to a reactor equipped with a thermometer, stirrer, and condenser, and after purging with nitrogen, the reactor was heated and reflux was started. After 30 minutes, while maintaining the toluene at 75°C, two parts by weight of aluminum chloride (AlCl3) were added. To this, a solution of 50 parts by weight of monomers (a) and (b) (molar ratio as shown in Table 2) dissolved in 50 parts by weight of toluene was gradually added dropwise over 1 hour and 30 minutes to allow the reaction to proceed. After polymerization for 4 hours, the hydrochloric acid generated from aluminum chloride (AlCl3) was neutralized by cooling while adding 0.1 parts by weight of pyridine to the reactor. The precipitate formed by neutralization was filtered, and after liquid-liquid extraction of the obtained filtrate, the toluene was evaporated to obtain a solid compound (T1). Regarding the obtained compound (T1) l ¹H-NMR measurements confirmed that compound (T1) is a copolymer having a constituent unit (A-2') derived from monomer (a) 4-vinylbenzoic acid and a constituent unit (B) derived from monomer (b) α-pinene.

[0121] [Table 2]

[0122] (Example 1) (1) Manufacturing of adhesive tape 30 parts by weight of compound (T1) (Synthesis Example A) were added to 100 parts by weight of the solid content of an acrylic polymer (Synthesis Example 1). Furthermore, 30 parts by weight of ethyl acetate (manufactured by Fuji Chemical Co., Ltd.) and 2.5 parts by weight of an isocyanate crosslinking agent (manufactured by Nippon Polyurethane Co., Ltd., trade name "Coronate L45") were added, and the mixture was stirred to obtain a solution of the adhesive composition. A 150 μm thick release film was prepared, and a solution of the adhesive composition was applied to the release-treated surface of this release film. By drying it at 100°C for 5 minutes, a 50 μm thick adhesive layer was formed. This adhesive layer was bonded to the surface of a 50 μm thick corona-treated PET film, which served as the substrate. Next, the same adhesive layer was bonded to the opposite surface of the substrate in the same manner. The film was then cured by heating at 40°C for 48 hours. As a result, an adhesive tape was obtained in which adhesive layers were laminated on both sides of the substrate, and the surface of the adhesive layer was covered with a release film.

[0123] (2) Measurement of gel fraction Test specimens were prepared by cutting adhesive tape into flat rectangular shapes measuring 50 mm x 100 mm. The test specimens were immersed in ethyl acetate at 23°C for 24 hours, then removed from the ethyl acetate and dried at 110°C for 1 hour. The weight of the dried test specimens was measured, and the gel fraction was calculated using the following formula (1). Note that no release film to protect the adhesive layer was laminated onto the test specimens. Gel fraction (weight %) = 100 × (W2 - W0) / (W1 - W0) (1) (W0: Weight of the substrate, W1: Weight of the test specimen before immersion, W2: Weight of the test specimen after immersion and drying)

[0124] (3) Measurement of shear storage modulus A measurement sample consisting only of the adhesive layer was prepared. The storage modulus at 25°C was measured from the obtained measurement sample when the dynamic viscoelastic spectrum was measured from -50°C to 200°C using a viscoelastic spectrometer (IT Measurement Control Co., Ltd., DVA-200) under the conditions of a low-speed heating shear deformation mode of 5°C / min and a measurement frequency of 10Hz.

[0125] (4) Measurement of the peak temperature of the loss tangent (tanδ) A measurement sample consisting only of the adhesive layer was prepared. Using a viscoelastic spectrometer (IT Measurement Control Co., Ltd., DVA-200), the dynamic viscoelastic spectrum was measured from -100°C to 200°C under the conditions of a low-speed heating shear deformation mode of 5°C / min and a measurement frequency of 10Hz. The peak temperature of the loss tangent (tanδ) was obtained from the resulting dynamic viscoelastic spectrum.

[0126] (Examples 2-25, Comparative Examples 1-2) An adhesive tape was obtained in the same manner as in Example 1, except that the types and amounts of the acrylic polymer, compound (T1), tackifying resin (T2), and crosslinking agent were changed as shown in Table 3. The tackifying resin (T2) and crosslinking agent used are shown below. For the tackifying resin (T2), the value of the smallest solvation free energy Δμ between the monomer constituting the tackifying resin (T2) and polytetrafluoroethylene is indicated.

[0127] Rosin ester resin (manufactured by Arakawa Chemical Industries, Ltd., product name "Pine Crystal KE359", Δμ = -5 kcal / mol) Terpene phenol resin (manufactured by Yasuhara Chemical Co., Ltd., product name "YS Polystar G150", Δμ = -25 kcal / mol) Isocyanate-based crosslinking agent (manufactured by Nippon Polyurethane Co., Ltd., product name "Coronate L45") Epoxy crosslinking agent (manufactured by Mitsubishi Gas Chemical Company, product name "Tetrad E5XM")

[0128] (Example 26) 30 parts by weight of compound (T1) (Synthesis Example A) was added to 100 parts by weight of solids of a styrene-based elastomer (SIS block copolymer, manufactured by Zeon Corporation, Quintac 3520, styrene content: 15% by weight, diblock ratio: 78% by weight). Furthermore, 30 parts by weight of toluene (manufactured by Fuji Chemical Co., Ltd.) was added and the mixture was stirred to obtain a solution of the adhesive composition. A 150 μm thick release film was prepared, and a solution of the adhesive composition was applied to the release-treated surface of this release film. By drying it at 100°C for 5 minutes, a 50 μm thick adhesive layer was formed. This adhesive layer was bonded to the surface of a 50 μm thick corona-treated PET film, which served as the substrate. Next, the same adhesive layer was bonded to the opposite surface of the substrate in the same manner. The film was then cured by heating at 40°C for 48 hours. As a result, an adhesive tape was obtained in which adhesive layers were laminated on both sides of the substrate, and the surface of the adhesive layer was covered with a release film.

[0129] (Examples 27-57, Comparative Examples 3-4) Adhesive tapes were obtained in the same manner as in Example 26, except that the types and amounts of the styrene elastomer, compound (T1), and tackifying resin (T2) were changed as shown in Tables 4 and 5. The styrene elastomer and tackifying resin (T2) used are shown below. For the tackifying resin (T2), the value of the smallest solvation free energy Δμ between the monomer constituting the tackifying resin (T2) and polytetrafluoroethylene is indicated.

[0130] Styrene-based elastomer (SIS block copolymer, manufactured by Zeon Corporation, Quintac 3520, styrene content: 15% by weight, diblock ratio: 78% by weight) Styrene-based elastomer (SIS block copolymer, manufactured by Zeon Corporation, Quintac 3433N, styrene content: 16% by weight, diblock ratio: 56% by weight) Styrene-based elastomer (SIS block copolymer, manufactured by Zeon Corporation, Quintac 3421, styrene content: 14% by weight, diblock ratio: 26% by weight) Styrene-based elastomer (SIS block copolymer, manufactured by Zeon Corporation, Quintac 3450, styrene content: 19% by weight, diblock ratio: 30% by weight) Styrene-based elastomer (SIS block copolymer, manufactured by Zeon Corporation, Quintac 3280, styrene content: 25% by weight, diblock ratio: 17% by weight) Styrene-based elastomer (SBS block copolymer, manufactured by Kraton Polymers Japan, Kraton DX410, styrene content: 18% by weight, diblock ratio: 60% by weight) Terpene resin (manufactured by Yasuhara Chemical Co., Ltd., product name "YS Resin PX1150", Δμ = -5 kcal / mol)

[0131] <Rating> The adhesive tapes obtained in the examples and comparative examples were evaluated using the following method. The results are shown in Tables 3 to 5.

[0132] (1) 180° peel test Test specimens were obtained by cutting adhesive tape to a width of 25 mm. The adhesive layer of the obtained test specimens was placed on a stainless steel (SUS304) plate (manufactured by Nippon Test Panel Co., Ltd.), a polypropylene (PP) plate (manufactured by Nippon Test Panel Co., Ltd.), or a polytetrafluoroethylene (PTFE) plate (manufactured by Nippon Test Panel Co., Ltd.). Next, a 2 kg rubber roller was passed back and forth over the test specimen at a speed of 300 mm / min to bond the test specimen to the stainless steel (SUS304) plate, polypropylene (PP) plate, or polytetrafluoroethylene (PTFE) plate. After that, the specimens were left to stand at 23°C for 1 hour to prepare test samples. The test samples after standing were subjected to a tensile test in the 180° direction at a peeling speed of 300 mm / min in accordance with JIS Z0237, and the peeling force was measured.

[0133] SUS 180° Peel Test ◎: Peeling force of 20 N / inch or more ○: Peeling force of 15 N / inch or more, less than 20 N / inch △: Peeling force of 10 N / inch or more, and less than 15 N / inch ×: Peeling force less than 10 N / inch

[0134] 180° Peel Test against PP ◎: Peeling force of 15 N / inch or more ○: Peeling force of 10 N / inch or more, less than 15 N / inch △: Peeling force of 5 N / inch or more, and less than 10 N / inch ×: Peeling force less than 5N / inch

[0135] PTFE 180° Peel Test ◎: Peeling force of 5N / inch or more ○: Peeling force of 3 N / inch or more, less than 5 N / inch △: Peeling force of 1 N / inch or more, and less than 3 N / inch ×: Peeling force less than 1 N / inch

[0136] (2) Alkali resistance test A test specimen was prepared by cutting adhesive tape to 25 mm x 75 mm, peeling off the release film from one side, and attaching it to a 23 μm thick polyethylene terephthalate (PET) film for backing. Under 23°C conditions, the release film covering the other adhesive side of the test specimen was peeled off, and the test specimen was pressed onto the surface of a stainless steel (SUS304) plate using a 2 kg roller for one pass-through to obtain a test sample before chemical immersion. Sodium hydroxide was diluted with deionized water to prepare an alkaline chemical solution with a pH of 12. The test sample before chemical immersion was immersed in the alkaline chemical solution for one day under 60°C conditions. After that, the test sample was removed from the alkaline chemical solution, washed with deionized water, and dried at 23°C for one hour to obtain a test sample after chemical immersion. The presence or absence of peeling of the adhesive tape from the stainless steel plate was observed for the obtained test samples before and after chemical immersion. ○: The adhesive tape did not peel off. △: There was only slight peeling at the end of the adhesive tape. ×: The entire surface has peeled off.

[0137] [Table 3]

[0138] [Table 4]

[0139] [Table 5] [Industrial applicability]

[0140] According to the present invention, it is possible to increase the adhesive strength of an adhesive composition, and in particular, to provide a compound that can increase the adhesive strength even to adherends with low polarity. Furthermore, according to the present invention, it is possible to provide a method for producing the compound, an adhesive composition containing the compound, and an adhesive tape having an adhesive layer containing the adhesive composition.

Claims

1. A constituent unit (A) derived from monomer (a) whose solvation free energy Δμ with polytetrafluoroethylene is -30 kcal / mol or less, It comprises a constituent unit (B) derived from at least one monomer (b) selected from the group consisting of terpene monomers, vinyl monomers, and conjugated diene monomers. A compound characterized by the following features.

2. The compound according to claim 1, characterized in that its Young's modulus at 25°C is 10 MPa or more.

3. Furthermore, the compound according to claim 1 or 2 is characterized by having an aliphatic hydrocarbon group having an unsaturated double bond.

4. The compound according to claim 1, 2, or 3, characterized in that the content of the constituent unit (A) is 1 mol% or more and 60 mol% or less.

5. The compound according to claim 1, 2, 3, or 4, characterized in that its weight-average molecular weight is 400 or more and 10,000 or less.

6. The compound according to claim 1, 2, 3, 4, or 5, characterized in that its glass transition temperature is 0°C or higher and 200°C or lower.

7. The compound according to claim 1, 2, 3, 4, 5, or 6, characterized in that the content of bio-derived carbon in the carbon of the compound is 10% or more.

8. The compound according to claim 1, 2, 3, 4, 5, 6, or 7, characterized in that the constituent unit (A) is at least one selected from the group consisting of constituent units (A-1) and (A-1') represented by the following formula. 【Chemistry 1】 In the formula, R １ Each of the following represents a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a polar functional group, an aliphatic hydrocarbon group having a polar functional group, or an aromatic hydrocarbon group having a polar functional group, where n is an integer between 2 and 4, and n' is an integer between 2 and 5.

9. The compound according to claim 8, characterized in that n and n' are 2 in the constituent unit (A-1) and the constituent unit (A-1').

10. The compound according to claim 8, characterized in that n and n' are 3 in the constituent unit (A-1) and the constituent unit (A-1').

11. The compound according to claim 1, 2, 3, 4, 5, 6, or 7, characterized in that the constituent unit (A) is at least one selected from the group consisting of constituent units (A-2), (A-2'), (A-3), (A-3'), (A-4), and (A-4') represented by the following formula. 【Chemistry 2】 【Transformation 3】 【Chemistry 4】 In the formula, R ２ , R ３ and R ５ Each of the following represents a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a polar functional group, an aliphatic hydrocarbon group having a polar functional group, or an aromatic hydrocarbon group having a polar functional group. ４ R represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an aliphatic hydrocarbon group having a polar functional group, or an aromatic hydrocarbon group having a polar functional group, respectively. ６ and R ７ Each represents either a hydrogen atom or an aliphatic hydrocarbon group. m represents an integer between 1 and 4, and m' represents an integer between 1 and 5. l represents an integer between 2 and 4, and l' represents an integer between 2 and 5. k represents an integer between 1 and 4, and k' represents an integer between 1 and 5.

12. The compound according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11, characterized in having the aforementioned structural unit (A) in or at the end of the main chain skeleton.

13. A method for producing a compound having a constituent unit (A) derived from a monomer (a) whose solvation free energy Δμ with polytetrafluoroethylene is -30 kcal / mol or less, and a constituent unit (B) derived from at least one monomer (b) selected from the group consisting of terpene monomers, vinyl monomers and conjugated diene monomers, The monomer (a) and the monomer (b) are copolymerized. A method for producing compounds characterized by the above.

14. The method for producing the compound according to claim 13, characterized in that the monomer (a) is at least one selected from the group consisting of monomer (a-1), monomer (a-2), monomer (a-3), and monomer (a-4) represented by the following formula. 【Transformation 5】 In the formula, R １ Each of the following represents a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a polar functional group, an aliphatic hydrocarbon group having a polar functional group, or an aromatic hydrocarbon group having a polar functional group, and n' ' represents an integer between 2 and 5. 【Transformation 6】 【Transformation 7】 【Transformation 8】 In the formula, R ２ , R ３ and R ５ each represent a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a polar functional group, an aliphatic hydrocarbon group having a polar functional group, or an aromatic hydrocarbon group having a polar functional group. R ４ each represent an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an aliphatic hydrocarbon group having a polar functional group, or an aromatic hydrocarbon group having a polar functional group. R ６ and R ７ each represent a hydrogen atom or an aliphatic hydrocarbon group. m'' represents an integer of 1 or more and 5 or less. l'' represents an integer of 2 or more and 5 or less. k'' represents an integer of 1 or more and 5 or less.

15. A method for producing the compound according to claim 13 or 14, characterized in that monomer (a) and monomer (b) are copolymerized by cationic polymerization.

16. An adhesive composition characterized by containing a base polymer and a compound (T1) according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12.

17. The adhesive composition according to claim 16, characterized in that the content of the compound (T1) according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 is 1 part by weight or more and 35 parts by weight or less per 100 parts by weight of the base polymer.

18. Furthermore, the adhesive composition according to claim 16 or 17 is characterized by containing at least one tackifying resin (T2) selected from the group consisting of rosin ester resins, terpene resins, and petroleum resins.

19. The adhesive composition according to claim 18, characterized in that the content of the tackifying resin (T2) is 10 parts by weight or more and 100 parts by weight or less per 100 parts by weight of the base polymer.

20. The adhesive composition according to claim 16, 17, 18, or 19, characterized in that the base polymer is an acrylic polymer.

21. The adhesive composition according to claim 20, characterized in that the acrylic polymer has constituent units derived from monomers having crosslinkable functional groups.

22. The adhesive composition according to claim 21, characterized in that the acrylic polymer contains 0.01% by weight or more and 20% by weight or less of constituent units derived from the monomer having the crosslinkable functional group.

23. The adhesive composition according to claim 20, 21, or 22, characterized in that the acrylic polymer has a weight-average molecular weight of 200,000 or more and 2,000,000 or less.

24. The adhesive composition according to claim 16, 17, 18, or 19, characterized in that the base polymer is a styrene elastomer which is a block copolymer having a block derived from a styrene monomer and a block derived from a conjugated diene monomer or a hydrogenated product thereof.

25. The adhesive composition according to claim 24, characterized in that the styrene-based elastomer is a styrene-isoprene-styrene (SIS) block copolymer or a styrene-butadiene-styrene (SBS) block copolymer.

26. The adhesive composition according to claim 24 or 25, characterized in that the styrene-based elastomer has a diblock ratio of 50% by weight or more.

27. The adhesive composition according to claim 24, 25, or 26, characterized in that the styrene-based elastomer has a styrene content of 20% by weight or less.

28. An adhesive tape characterized by having an adhesive layer containing the adhesive composition according to claim 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, or 27.

29. The adhesive layer contains the adhesive composition according to claim 20, 21, 22, or 23, wherein the shear storage modulus of the adhesive layer at 25°C, measured at a measurement frequency of 10 Hz using a dynamic viscoelasticity measuring device, is 1.0 × 10⁻⁶. ４ Pa or more, 5.0×10 ５ The adhesive tape according to claim 28, characterized in that it is Pa or less.

30. The adhesive tape according to claim 29, characterized in that the adhesive layer has a peak in the loss loss tangent, measured using a dynamic viscoelasticity measuring device at a measurement frequency of 10 Hz, between -20°C and 20°C.

31. The adhesive tape according to claim 28, 29, or 30, characterized in that it is used for fixing electronic equipment components or in-vehicle components.

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