Tackifying resin

Abstract

The present disclosure provides a tackifying resin comprising: a repeating unit (a) from a petroleum resin-based monomer; a repeating unit (b) derived from alpha-methylstyrene; and a repeating unit (c) derived from a (meth) acrylic monomer, in which at least some of the unsaturated bonds contained in the repeating units (a) to (c) are hydrogenated. The tackifier resin has excellent compatibility with a base polymer, and thus can improve transparency and adhesive strength of an adhesive including the tackifier resin.

Description

Technical Field

[0001] The present disclosure relates to a tackifying resin. Background Art

[0002] Adhesives are used as materials for fixing members in various fields including automobiles, electronic and electrical products, and construction materials.

[0003] For example, at automobile manufacturing sites, adhesives are used to secure automotive interior components to the interior of the vehicle. Furthermore, at the manufacturing sites of electronic devices such as mobile phones and liquid crystal displays, adhesives are used to secure cushioning materials installed inside electronic products to protect them from impact, to secure external components of electronic products, and to secure components that make up image display devices such as liquid crystal displays, organic electroluminescent (EL) displays, and plasma display panels (PDPs).

[0004] Adhesives have been transitioning from solvent-based adhesives to water-based adhesives in order to reduce environmental impact. In recent years, there has been a growing trend toward water-based acrylic adhesives comprising acrylic polymers dispersed in an aqueous medium.

[0005] Acrylic adhesives are often used as a mixture with a tackifying resin to further enhance adhesive properties such as bond strength and constant weight holding power.

[0006] However, when used with such a tackifying resin, compatibility with an acrylic polymer contained in an acrylic adhesive may be deteriorated, which may make the adhesive opaque and thus less likely to undergo a photocuring reaction, and heat resistance may also be deteriorated.

[0007] Therefore, the demand for tackifying resins having excellent compatibility with acrylic polymers has been increasing. Summary of the Invention

[0008] Technical issues

[0009] In order to solve the above problems, the present disclosure provides a tackifying resin having excellent compatibility with a base polymer and a method for preparing the tackifying resin.

[0010] Technical Solution

[0011] One aspect of the present disclosure relates to a tackifying resin comprising: repeating units (a) derived from a petroleum resin-based monomer; repeating units (b) derived from α-methylstyrene; and repeating units (c) derived from a (meth)acrylic acid monomer, wherein at least a portion of the repeating units (a) to (c) are hydrogenated.

[0012] Beneficial effects

[0013] Tackifying resins according to the present disclosure may have improved compatibility with base polymers and may have reduced levels of ultraviolet absorption.

[0014] Therefore, the tackifying resin according to the present disclosure may have excellent compatibility with the base polymer, and thus, an adhesive including the base polymer and the tackifying resin may have improved transparency and heat resistance.

[0015] Furthermore, as the ultraviolet absorption level decreases, the amount of ultraviolet rays reaching the photopolymerization initiator increases, and thus, the heat resistance of the adhesive can be improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 : is a graph showing the measurement results of the ultraviolet absorbance of tackifying resins according to Examples and Comparative Examples. DETAILED DESCRIPTION

[0017] Hereinafter, further aspects and various embodiments of the present disclosure will be described in more detail.

[0018] The terms or words used in this specification should not be limited to the conventional meanings or the meanings in the dictionary, and should be understood as the meanings and concepts that are consistent with the technical concept of the present disclosure based on the concept that the inventor can appropriately define the terms in order to interpret the present disclosure in the best way.

[0019] The terms used in this specification are only used to describe the purpose of specific embodiments and are not intended to limit the present disclosure. As used in this specification, unless the context clearly indicates otherwise, the singular form is also intended to include the plural form. In the present disclosure, it should be understood that terms such as "including" or "having" are intended to specify the features, numbers, steps, operations, components, parts or combinations thereof described in the specification, but do not preclude the possibility of existing or adding one or more other features, numbers, steps, operations, components, parts or combinations thereof.

[0020] Specifically, one aspect of the present disclosure relates to a tackifying resin comprising: repeating units (a) derived from a petroleum resin-based monomer; repeating units (b) derived from α-methylstyrene; and repeating units (c) derived from a (meth)acrylic acid monomer, wherein at least a portion of the unsaturated bonds contained in the repeating units (a) to (c) are hydrogenated.

[0021] For example, at least a portion of the unsaturated bonds contained in the repeating units (a) to (c) may be hydrogenated by a hydrogenation reaction performed in the presence of a hydrogenation catalyst.

[0022] A hydrogenation reaction refers to the addition of hydrogen to double or triple bonds of a molecule having unsaturated bonds to saturate the valences. Hydrogenation reactions can be divided into complete hydrogenation, in which hydrogen is added to all unsaturated bonds in a molecule, and partial hydrogenation, in which hydrogen is added to a portion of the unsaturated bonds in a molecule. The hydrogenation defined in the present disclosure may refer to a state in which at least a portion of the unsaturated bonds contained in repeating units (a) to (c) are hydrogenated to saturate the valences.

[0023] According to one embodiment, at least a portion of the unsaturated bonds contained in repeating units (a) to (c) may be hydrogenated to reduce the UV absorbance of the tackifying resin. When the UV absorbance of the tackifying resin decreases, the adhesive containing the tackifying resin may have an increased amount of UV rays reaching the photopolymerization initiator contained in the adhesive. Therefore, the heat resistance (shear adhesion failure test (SAFT)) of the adhesive containing the tackifying resin may be improved.

[0024] According to one embodiment, the petroleum resin-based monomer may include a commercially available liquid C5-C20 fraction, diene, or dicyclopentadiene.

[0025] According to another embodiment, the petroleum resin-based monomer may include a C5 fraction, a C9 fraction, a diene, or dicyclopentadiene.

[0026] For example, the C5 fraction may include 1-pentene, 2-methyl-2-butene-n-pentane, propadiene, cyclopentadiene, piperylene, isoprene, cyclopentene, and the like.

[0027] For example, the C9 fraction may include styrenic monomers, dicyclopentadiene, indene, trans-β-methylstyrene, methylindene, vinyltoluene, or benzene / toluene / xylene (BTX), among others.

[0028] For example, the diene may include propadiene, dicyclopentadiene, cyclopentene, and the like.

[0029] According to one embodiment, the petroleum resin-based monomer may include a C9 fraction.

[0030] According to one embodiment, the C9 fraction may include styrenic monomers.

[0031] For example, a styrene-based monomer can be represented by Formula 1:

[0032] <Formula 1>

[0033]

[0034] In formula 1,

[0035] a1 is an integer from 0 to 5,

[0036] R1 is: hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxy, cyano or nitro;

[0037] C1-C 20 Alkyl or C1-C 20 Alkoxy, each unsubstituted or substituted with deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, C6-C 20 aryl or any combination thereof; or

[0038] C6-C 20 Aryl, which is unsubstituted or substituted by deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, C1-C 20 Alkyl, C1-C 20 alkoxy or any combination thereof.

[0039] According to one embodiment, R1 and R2 are each independently: hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxyl, cyano or nitro;

[0040] methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, tert-pentyl, neopentyl, isopentyl, sec-pentyl, 3-pentyl, sec-isopentyl, n-hexyl, isohexyl, sec-hexyl, tert-hexyl, n-heptyl, isoheptyl, sec-heptyl, tert-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, sec-nonyl, tert-nonyl, n-decyl, isodecyl, sec-decyl, tert-decyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert- butoxy, n-pentoxy, tert-pentoxy, neopentoxy, isopentoxy, sec-pentoxy, 3-pentoxy, sec-isopentoxy, n-hexyloxy, isohexyloxy, sec-hexyloxy, tert-hexyloxy, n-heptyloxy, isoheptyloxy, sec-heptyloxy, tert-heptyloxy, n-octyloxy, isooctyloxy, sec-octyloxy, tert-octyloxy, n-nonyloxy, isononyloxy, sec-nonyloxy, tert-nonyloxy, n-decyloxy, isodecyloxy, sec-decyloxy or tert-decyloxy, each unsubstituted or substituted by deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, C6-C 20 aryl or any combination thereof; or

[0041] Phenyl, naphthyl, anthracenyl, phenanthrenyl or pyrenyl, each unsubstituted or substituted by deuterium, -F, -Cl, -Br, -I, hydroxyl, cyano, C1-C 20 Alkyl, C6-C 20 aryl or any combination thereof.

[0042] According to one embodiment, R1 and R2 can each independently be hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, tert-pentyl, neopentyl, isopentyl, sec-pentyl, 3-pentyl, sec-isopentyl, n-hexyl, isohexyl, sec-hexyl or tert-hexyl.

[0043] a1 can be an integer from 0 to 5.

[0044] According to one embodiment, the styrenic monomer may include styrene.

[0045] According to one embodiment, the tackifying resin may comprise repeating units (b) derived from α-methylstyrene.

[0046] According to one embodiment, the tackifying resin may include repeating units (b) from alpha-methylstyrene as a unit for regulating molecular weight. For example, when the tackifying resin includes repeating units (b) from alpha-methylstyrene, the weight average molecular weight of the tackifying resin may be reduced. Therefore, the tackifying resin of the present disclosure may meet a weight average molecular weight of less than 5,000 g / mol or 3,000 g / mol, thereby improving compatibility and reactivity with the base polymer described below. Therefore, the transparency and heat resistance of the adhesive comprising the tackifying resin may be further improved.

[0047] According to one embodiment, at least a portion of the unsaturated bonds contained in repeating units (a) and (b) may be hydrogenated. For example, a portion of the aromatic rings contained in repeating units (a) and (b) as unsaturated bonds may be hydrogenated.

[0048] For example, in the tackifying resin, at least a portion of the unsaturated bonds contained in the repeating units (a) and (b) may be hydrogenated, so that the tackifying resin may include a repeating unit represented by Formula 1-1:

[0049] <Formula 1-1>

[0050]

[0051] Among them, in formula 1-1,

[0052] a11 is an integer from 0 to 5,

[0053] R 11 and R 12 are each independently: hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxy, cyano or nitro;

[0054] C1-C 20 Alkyl or C1-C 20 Alkoxy, each unsubstituted or substituted with deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, C6-C20 aryl or any combination thereof; or

[0055] C6-C 20 Aryl, which is unsubstituted or substituted by deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, C1-C 20 Alkyl, C1-C 20 alkoxy or any combination thereof.

[0056] According to one embodiment, in Formula 1-1, R 11 It can be hydrogen, R 12 It may be hydrogen or methyl.

[0057] According to one embodiment, the tackifying resin may include a repeating unit represented by Formula 1-1 by: i) polymerizing the tackifying resin using a hydrogenated petroleum resin monomer or hydrogenated α-methylstyrene; ii) polymerizing the petroleum resin monomer and α-methylstyrene to form a polymer, and then performing a hydrogenation reaction; or iii) polymerizing the petroleum resin monomer, α-methylstyrene, and a (meth)acrylic acid monomer to form a polymer, and then performing a hydrogenation reaction.

[0058] For example, the tackifying resin may include the repeating unit represented by Formula 1-1 by: i) polymerizing the tackifying resin using a monomer represented by Formula 1-2; ii) polymerizing a petroleum resin-based monomer and α-methylstyrene to form a polymer, followed by a hydrogenation reaction; or iii) polymerizing a petroleum resin-based monomer, α-methylstyrene, and a (meth)acrylic acid monomer to form a polymer, followed by a hydrogenation reaction:

[0059] <Formula 1-2>

[0060]

[0061] Among them, in formula 1-2,

[0062] a11 is an integer from 0 to 5,

[0063] R 11 and R 12 are each independently: hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxy, cyano or nitro;

[0064] C1-C 20 Alkyl or C1-C 20 Alkoxy, each unsubstituted or substituted with deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, C6-C 20 aryl or any combination thereof; or

[0065] C6-C 20Aryl, which is unsubstituted or substituted by deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, C1-C 20 Alkyl, C1-C 20 alkoxy or any combination thereof.

[0066] According to one embodiment, in Formula 1-2, R 11 It can be hydrogen, R 12 It may be hydrogen or methyl.

[0067] According to one embodiment, the (meth)acrylic acid monomer may be represented by Formula 2:

[0068] <Formula 2>

[0069]

[0070] In formula 2,

[0071] R2 and R3 are each independently: hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxyl, cyano or nitro;

[0072] C1-C 20 Alkyl or C1-C 20 Alkoxy, each unsubstituted or substituted with deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, C6-C 20 aryl or any combination thereof; or

[0073] C6-C 20 Aryl, which is unsubstituted or substituted by deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, C1-C 20 Alkyl, C1-C 20 alkoxy or any combination thereof.

[0074] According to one embodiment, R3 and R4 are each independently: hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxyl, cyano or nitro;

[0075] methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, tert-pentyl, neopentyl, isopentyl, sec-pentyl, 3-pentyl, sec-isopentyl, n-hexyl, isohexyl, sec-hexyl, tert-hexyl, n-heptyl, isoheptyl, sec-heptyl, tert-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, sec-nonyl, tert-nonyl, n-decyl, isodecyl, sec-decyl, tert-decyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert- butoxy, n-pentoxy, tert-pentoxy, neopentoxy, isopentoxy, sec-pentoxy, 3-pentoxy, sec-isopentoxy, n-hexyloxy, isohexyloxy, sec-hexyloxy, tert-hexyloxy, n-heptyloxy, isoheptyloxy, sec-heptyloxy, tert-heptyloxy, n-octyloxy, isooctyloxy, sec-octyloxy, tert-octyloxy, n-nonyloxy, isononyloxy, sec-nonyloxy, tert-nonyloxy, n-decyloxy, isodecyloxy, sec-decyloxy or tert-decyloxy, each unsubstituted or substituted by deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, C6-C 20 aryl or any combination thereof; or

[0076] Phenyl, naphthyl, anthracenyl, phenanthrenyl or pyrenyl, each unsubstituted or substituted by deuterium, -F, -Cl, -Br, -I, hydroxyl, cyano, C1-C 20 Alkyl, C6-C 20 aryl or any combination thereof.

[0077] According to one embodiment, R3 may be hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.

[0078] According to another embodiment, R3 may be hydrogen or methyl.

[0079] According to one embodiment, R4 can be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, tert-pentyl, neopentyl, isopentyl, sec-pentyl, 3-pentyl, sec-isopentyl, n-hexyl, isohexyl, sec-hexyl or tert-hexyl.

[0080] According to another embodiment, R4 may be methyl or ethyl.

[0081] According to one embodiment, the (meth)acrylic monomer may include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl acrylate, or any combination thereof.

[0082] According to one embodiment, the amount of the repeating unit (a) derived from the petroleum resin monomer may be less than or equal to the amount of the repeating unit (b) derived from α-methylstyrene. For example, the amount of the repeating unit (a) derived from the petroleum resin monomer may be less than the amount of the repeating unit (b) derived from α-methylstyrene.

[0083] For example, when the amount of the repeating unit (b) derived from α-methylstyrene as the unit for adjusting the molecular weight is greater than the amount of the repeating unit (a) derived from the petroleum resin-based monomer, the weight average molecular weight of the tackifier resin can be more easily adjusted to 3,000 g / mol or less.

[0084] According to one embodiment, the amount of the repeating unit (a) derived from the petroleum resin-based monomer may be 10 to 50 wt % based on the total weight of the tackifying resin, the amount of the repeating unit (b) derived from α-methylstyrene may be 10 to 80 wt % based on the total weight of the tackifying resin, and the amount of the repeating unit (c) derived from the (meth)acrylic acid monomer may be 5 to 40 wt % based on the total weight of the tackifying resin.

[0085] For example, the amount of the repeating unit (a) derived from the petroleum resin-based monomer may be 10 to 50 wt%, 10 to 45 wt%, 15 to 45 wt%, 20 to 45 wt%, 20 to 40 wt%, or 25 to 40 wt%, based on the total weight of the tackifying resin.

[0086] For example, the amount of the repeating units (b) derived from α-methylstyrene may be 10 to 80 wt%, 20 to 80 wt%, 30 to 80 wt%, or 30 to 60 wt%, based on the total weight of the tackifying resin.

[0087] For example, the amount of the repeating unit (c) derived from the (meth)acrylic acid monomer may be 5 to 40 wt%, 5 to 35 wt%, or 10 to 35 wt%, based on the total weight of the tackifying resin.

[0088] According to one embodiment, the weight average molecular weight (Mw) of the tackifying resin may be 3,000 g / mol or less. For example, the Mw of the tackifying resin may be 2,900 g / mol or less, 2,800 g / mol or less, or 2,500 g / mol or less.

[0089] According to one embodiment, the Mw of the tackifying resin can be 200 to 3,000 g / mol, 400 to 3,000 g / mol, 500 to 3,000 g / mol, 600 to 3,000 g / mol, 200 to 2,500 g / mol, 400 to 2,500 g / mol, 500 to 2,500 g / mol, 600 to 2,500 g / mol, 200 to 2,450 g / mol, 400 to 2,450 g / mol, 500 to 2,450 g / mol, or 600 to 2,450 g / mol.

[0090] According to one embodiment, the number average molecular weight (Mn) of the tackifying resin may be 1,000 g / mol or less.

[0091] For example, the tackifying resin can have an Mn of 850 g / mol or less, 800 g / mol or less, 200 to 1,000 g / mol, 400 to 1,000 g / mol, 600 to 1,000 g / mol, 200 to 850 g / mol, 400 to 850 g / mol, 600 to 850 g / mol, 200 to 800 g / mol, 400 to 800 g / mol, 600 to 800 g / mol, or 720 to 800 g / mol.

[0092] According to one embodiment, the Z-average molecular weight (Mz) of the tackifying resin may be 7,000 g / mol or less.

[0093] For example, the Mz of the tackifying resin can be 100 to 7,000 g / mol, 100 to 6,900 g / mol, 500 to 7,000 g / mol, 1,000 to 7,000 g / mol, 1,000 to 5,000 g / mol, or 1,000 to 2,500 g / mol.

[0094] According to one embodiment, the polymer dispersion index (PDI) of the tackifying resin may be 1 to 3. For example, the PDI of the tackifying resin may be 1.1 to 3, 1.2 to 3, 1.3 to 3, 1 to 2, 1.2 to 2, 1.3 to 2, 1 to 1.9, 1.2 to 1.9, or 1.3 to 1.9.

[0095] For example, when the Mw and PDI of the tackifying resin satisfy the above ranges, the compatibility with the base polymer, for example, an acrylic polymer, can be further improved.

[0096] According to one embodiment, the softening point of the tackifying resin may be 40 to 120° C. For example, the softening point of the tackifying resin may be 45 to 120° C., 45 to 110° C., 45 to 100° C., 45 to 80° C., 50 to 120° C., 50 to 110° C., 50 to 100° C., 50 to 85° C., or 50 to 80° C.

[0097] According to one embodiment, the viscosity of the tackifying resin at 160° C. may be 20 cps to 200 cps. For example, the viscosity of the tackifying resin at 160° C. may be 20 cps to 150 cps, 20 cps to 100 cps, 20 cps to 80 cps, 20 cps to 78 cps, 30 cps to 150 cps, 30 cps to 100 cps, 30 cps to 80 cps, 30 cps to 78 cps, 35 cps to 150 cps, 35 cps to 100 cps, 35 cps to 80 cps, or 35 cps to 78 cps.

[0098] According to one embodiment, the viscosity of the tackifying resin at 180° C. may be 1 cps to 100 cps. For example, the viscosity of the tackifying resin at 180° C. may be 1 cps to 80 cps, 1 cps to 60 cps, 1 cps to 40 cps, 1 cps to 34 cps, 1 cps to 32 cps, 10 cps to 80 cps, 10 cps to 60 cps, 10 cps to 40 cps, 10 cps to 34 cps, or 10 cps to 32 cps.

[0099] According to one embodiment, based on the total number of moles of repeating units from monomers contained in the tackifying resin, 1 The mol% of the repeating unit (c) derived from the (meth)acrylic acid monomer measured by H-NMR may be 1 to 80 mol%, 1 to 70 mol%, 1 to 60 mol%, 5 to 50 mol%, or 10 to 50 mol%.

[0100] For example, the mole % of the repeating units (c) derived from the (meth)acrylic acid monomer can be determined by analyzing 1 The peaks were confirmed by H-NMR measurement.

[0101] According to one embodiment, the aromaticity of the tackifying resin before hydrogenation may be 1 to 90% as measured by NMR.

[0102] For example, by analyzing 1 The aromaticity of the tackifying resin can be confirmed by measuring the obtained peaks by H-NMR.

[0103] According to one embodiment, the ultraviolet absorbance of the tackifying resin at a wavelength of 240 nm to 260 nm (THF solvent, concentration of 70 ppm) may be 0.1 or less. For example, the ultraviolet absorbance may refer to the average absorbance value measured for ultraviolet rays with a wavelength of 240 nm to 260 nm after dissolving the tackifying resin in THF solvent to a concentration of 70 ppm.

[0104] Another aspect of the present disclosure may provide a method for preparing a tackifying resin, the tackifying resin comprising: a petroleum resin-based monomer; α-methylstyrene; and a (meth)acrylic acid monomer, and having an ultraviolet absorbance at a wavelength of 240 nm to 260 nm (THF solvent, concentration of 70 ppm) of 0.1 or less.

[0105] According to one embodiment, the first monomer composition comprising a petroleum resin monomer and alpha-methylstyrene can be prepared. A polymerization catalyst can be added to the first monomer composition, and then catalytic polymerization can be carried out to prepare the first polymer composition comprising the first polymer. Subsequently, a hydrogenation catalyst can be added to the first polymer composition, and then a hydrogenation reaction can be carried out to hydrogenate a part of the unsaturated bonds contained in the first polymer, thereby preparing the partially hydrogenated first polymer composition. Subsequently, a (meth) acrylic acid monomer can be added to the partially hydrogenated first polymer composition, to prepare the second monomer composition. Subsequently, thermal polymerization and exhaust reaction can be carried out to the second monomer composition, to prepare tackifying resin.

[0106] According to another embodiment, a first monomer composition comprising a petroleum resin monomer and alpha-methylstyrene can be prepared. A polymerization catalyst can be added to the first monomer composition, and then catalytic polymerization can be carried out to prepare the first polymer composition comprising the first polymer. Subsequently, a (meth) acrylic acid monomer can be added to the first polymer composition to prepare a second monomer composition. Subsequently, the second monomer composition can be thermally polymerized to prepare a second polymer composition comprising the second polymer. Subsequently, a hydrogenation catalyst can be added to the second polymer composition, a hydrogenation reaction can be carried out, a partial hydrogenation reaction can be carried out to hydrogenate a portion of the unsaturated bonds contained in the second polymer, and then, an exhaust reaction can be carried out to prepare a tackifying resin.

[0107] According to another embodiment, a first monomer composition comprising a petroleum resin monomer, α-methylstyrene and a vinyl monomer can be prepared. A polymerization catalyst can be added to the first monomer composition, and then catalytic polymerization can be performed to prepare a first polymer composition comprising a first polymer. Subsequently, a (meth) acrylic acid monomer can be added to the first polymer composition to prepare a second monomer composition. Subsequently, the second monomer composition can be subjected to thermal polymerization and exhaust reaction to prepare a tackifying resin.

[0108] For example, the vinyl monomer may include a vinyl cycloalkane monomer. For example, the vinyl monomer may include a vinyl cyclopentane monomer, a vinyl cyclohexane monomer, or any combination thereof. For example, the vinyl monomer may be represented by Formula 1-2.

[0109] For example, the types, amounts and properties of the petroleum resin monomers, (meth)acrylic acid monomers and α-methylstyrene, and the properties of the tackifying resin can be referred to the above description.

[0110] For example, the monomer in the monomer composition may refer to the remaining components except for the solvent contained in the monomer composition.

[0111] According to one embodiment, the monomer composition may further include a solvent.

[0112] For example, the solvent may include xylene.

[0113] According to one embodiment, the polymerization catalyst may include a Lewis acid, a halogenated hydrogen acid, AlCl 3 , BF 3 , or any combination thereof. For example, the polymerization catalyst may include AlCl 3 , BF 3 , SnCl 4 , TiCl 4 , AgClO 4 , I 2 , or any combination thereof.

[0114] According to one embodiment, the catalytic polymerization may be carried out at a temperature below 100° C. For example, the catalytic polymerization may be carried out in a temperature range of -50 to 100° C., -30 to 100° C., -10 to 100° C., -50 to 80° C., -30 to 80° C., or -10 to 80° C.

[0115] According to one embodiment, the thermal polymerization may be performed at a temperature ranging from 150 to 300° C. For example, the thermal polymerization may be performed at a temperature of 200 to 300° C., 220 to 300° C., 230 to 300° C., 200 to 280° C., or 200 to 260° C.

[0116] For example, the exhaust reaction may be performed at a temperature of 150° C. to 300° C. and a pressure of 1 mbar to 50 mbar for 1 minute to 20 minutes.

[0117] According to another embodiment, the exhaust reaction may be performed at a temperature of 220 to 280° C. and a pressure of 5 to 25 mbar for 5 to 15 minutes, or at a temperature of 240 to 260° C. and a pressure of 5 to 15 mbar for 8 to 12 minutes.

[0118] According to one embodiment, the hydrogenation reaction may be carried out in the presence of a hydrogenation catalyst (hydrogenation catalyst). For example, the hydrogenation catalyst may include a palladium-based catalyst.

[0119] According to one embodiment, the hydrogenation reaction may be performed at a temperature of 100 to 300° C. and a pressure of 20 to 100 bar in the presence of a hydrogenation catalyst (hydrogenation catalyst) for 1 to 3 hours.

[0120] According to one embodiment, the tackifying resin can be applied to an adhesive. According to another embodiment, the tackifying resin can be applied to an acrylic adhesive.

[0121] Another aspect of the present disclosure may provide an adhesive comprising the above-mentioned tackifying resin. For example, the tackifying resin may impart adhesive strength to the adhesive.

[0122] According to one embodiment, an adhesive may include: a tackifying resin; and a base polymer. For example, the adhesive may be an acrylic adhesive including a tackifying resin; and an acrylic polymer. For example, the tackifying resin may have excellent compatibility with the base polymer, such as the acrylic polymer, and thus, the adhesive may have excellent transparency and adhesive strength.

[0123] According to one embodiment, the adhesive may be a photocurable tackifying resin.

[0124] For example, the adhesive may further contain a cross-linking agent and a photopolymerization initiator in addition to the tackifying resin and the base polymer.

[0125] According to one embodiment, the photopolymerization initiator may be one or more selected from the group consisting of benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, benzyl diphenyl disulfide, benzyl dimethyl ketal, and the like. Chemicals, Inc.'s Irgacure series, anthraquinone, naphthoquinone, 3,3-dimethyl-4-methoxybenzophenone, benzophenone, neopentyl ketone ethyl ether, 1,1-dichloroacetophenone, p-tert-butyldichloroacetophenone, dimers of hexaaryl-imidazoles, 2,2′-diethoxyacetophenone, 2,2′-diethoxy-2-phenylacetophenone, 2,2′-dichloro-4-phenoxyacetophenone, phenylglyoxylate, α-hydroxyisobutylbenzophenone, dibenzospan, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-propanone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, tribromophenyl sulfone, triarylphosphine oxide, and tribromomethylphenyl sulfone. For example, the photopolymerization initiator may be included in the adhesive in an amount of 0.01 to 10 wt % or 0.02 to 5 wt %.

[0126] According to one embodiment, the amount of the tackifying resin in the adhesive may be 1 wt % or more based on the total weight of the adhesive.

[0127] According to another embodiment, the amount of tackifying resin in the adhesive can be 1 to 30 wt%, 5 to 30 wt%, 10 to 30 wt%, 1 to 25 wt%, 5 to 25 wt%, or 10 to 25 wt%, based on the total weight of the adhesive.

[0128] According to one embodiment, the adhesive may be transparent. In this case, the adhesive allows light to penetrate uniformly, thereby allowing the photocuring reaction to proceed uniformly. Therefore, the heat resistance of the adhesive may be further improved.

[0129] According to one embodiment, the adhesive may include a base polymer, a tackifying resin, and a photopolymerization initiator. In this case, the tackifying resin may have a low absorbance to ultraviolet light, so that the amount of ultraviolet light reaching the photopolymerization initiator increases, thereby further promoting the polymerization reaction under light irradiation. Therefore, the adhesive strength and shear bond strength of the adhesive including the tackifying resin can be improved.

[0130] [Definition of terms]

[0131] In this manual, C1-C 20 Alkyl refers to a linear or branched aliphatic hydrocarbon monovalent group having 1 to 20 carbon atoms, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, tert-pentyl, neopentyl, isopentyl, sec-pentyl, 3-pentyl, sec-isopentyl, n-hexyl, isohexyl, sec-hexyl, tert-hexyl, n-heptyl, isoheptyl, sec-heptyl, tert-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, sec-nonyl, tert-nonyl, n-decyl, isodecyl, sec-decyl, tert-decyl, and the like. In this specification, C1-C 20 Alkylene refers to a group having C1-C 20 Alkyl is a divalent group of the same structure.

[0132] In this manual, C1-C 20 Alkoxy refers to a group having the formula -OA 101 A monovalent group (wherein A 101 It is C1-C 20 Specific examples thereof include methoxy, ethoxy, isopropoxy and the like.

[0133] In this manual, C6-C 20 Aryl refers to a monovalent group of a carbocyclic aromatic system having 6 to 20 carbon atoms, including phenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, etc. 20When the aryl group includes two or more rings, the two or more rings may be linked to each other.

[0134] Hereinafter, the present disclosure will be described in more detail by way of examples. These examples are for illustrative purposes only, so as to describe the present disclosure in more detail, and it will be apparent to those skilled in the art that these examples should not be construed as limiting the scope of the present disclosure.

[0135] Example 1. Preparation of tackifying resin

[0136] A 2,000 ml chemical reactor equipped with a stirrer, reflux condenser, thermometer, and nitrogen injection device was charged with styrene (SM) and α-methylstyrene (AMS) in the amounts described in Table 1 below (SM: 280 g, AMS: 420 g). Xylene was also added as a solvent so that the weight ratio relative to the combined weight of SM and AMS was 1:1, thereby preparing a first composition. 0.1 wt% of BF3 as a catalyst was added to the first composition, and polymerization was carried out at 30°C for 120 minutes. The mixture was then neutralized by adding 10 g of calcium hydroxide to prepare a first polymer composition.

[0137] Subsequently, 280 g of a palladium catalyst (KOH-5, NECC, Inc.) was added to the first polymer composition, and then a hydrogenation reaction was performed under conditions of a hydrogen pressure of 80 bar and a reaction temperature of 270° C. for 90 minutes to prepare a hydrogenated resin composition.

[0138] Subsequently, methyl acrylate (MA) was injected into 420 g of the hydrogenated resin composition according to the amount described in Table 1 below (MA: 180 g), and xylene was additionally injected as a solvent so that its weight ratio relative to MA was 1:1, thereby preparing a second composition. Subsequently, the second composition was thermally polymerized at a temperature of 240° C. for 2 hours to prepare a second polymer composition.

[0139] Subsequently, the second polymer composition was subjected to a degassing reaction at a temperature of 250° C. and a pressure of 10 mbar for 10 minutes to prepare a tackifying resin.

[0140] Examples 2 to 10 and Comparative Examples 1 to 3

[0141] A tackifying resin was prepared in the same manner as in Example 1, except that SM, AMS, MA, first polymer composition, and target to be hydrogenated were changed as shown in Table 1 below.

[0142] When the target to be hydrogenated is the first polymer composition, hydrogenating the first polymer composition which is a polymer of SM and AMS,

[0143] When the target to be hydrogenated is a second polymer composition, MA is added to a polymer of SM and AMS to prepare the second polymer composition, and then, the second polymer composition is hydrogenated.

[0144] [Table 1]

[0145]

[0146]

[0147] Evaluation Example 1. Molecular weight measurement

[0148] The weight average molecular weight (Mw), number average molecular weight (Mn), Z average molecular weight (Mz), and polymer dispersion index (PDI) of the tackifying resins prepared in Examples 1 to 10 and Comparative Examples 1 to 3 were measured using gel permeation chromatography (GPC, a product of Hewlett Packard, model name HP-1100).

[0149] To measure Mw, Mn, Mz, and PDI, each tackifying resin prepared in Examples 1 to 10 and Comparative Examples 1 to 3 was dissolved in tetrahydrofuran to a concentration of 4,000 ppm, and 100 μl of each dissolved resin was injected into a GPC column. Here, tetrahydrofuran was used as the mobile phase of GPC and flowed at a flow rate of 1.0 mL / min at 30°C. As the chromatographic column, three Plgel columns manufactured by Agilent Technologies, Inc. were used. They were connected in series. As a detector, an RI detector (product of Hewlett Packard, HP-1047A) was used, and the measurement was performed at 30° C. The measurement results are shown in Table 2 below.

[0150] Evaluation Example 2. Softening Point Measurement

[0151] For each of the tackifying resins prepared in Examples 1 to 10 and Comparative Examples 1 to 3, the softening point was measured using the ring and ball softening method (ASTM E28). The resin was melted and poured into a ring mold, which was then placed in a beaker containing glycerin. A ball was placed on the ring containing the resin, and the temperature was then increased by 2.5°C per minute. The temperature (softening point) at which the resin melted and the ball fell was measured and recorded in Table 2 below.

[0152] Evaluation Example 3. Measurement of ultraviolet (240 to 262 nm) absorbance level

[0153] THF was placed in an ultraviolet measuring cell and calibrated. Then, each tackifying resin prepared in Examples 1 to 10 and Comparative Examples 1 to 3 was mixed with THF to prepare a solution with a concentration of 70 ppm. Subsequently, the solution was placed in an ultraviolet measuring cell, the mode of the ultraviolet measuring device was set to absorption, and then, the absorbance level at a wavelength of 200 to 350 nm was measured. The measurement results are shown below. Figure 1 and Table 2.

[0154] [Table 2]

[0155]

[0156] Preparation of acrylic adhesive

[0157] 15 wt % of each tackifying resin of Examples 1 to 10 and Comparative Examples 1 to 3 was mixed with 85 wt % of an acrylic polymer, and 1 wt % of a photopolymerization initiator was additionally added thereto to prepare an acrylic adhesive.

[0158] Evaluation Example 5. Adhesion Strength and Shear Adhesion Measurement

[0159] (1) Adhesion strength measurement

[0160] The measurements were performed using a universal testing machine (UTM).

[0161] First, each acrylic adhesive prepared from the tackifying resins of Examples 1 to 10 and Comparative Examples 1 to 3 was coated on a PET film at a thickness of 50 microns to prepare an adhesive tape. Subsequently, the adhesive tape was irradiated with ultraviolet light by an exposure device, and then the resulting adhesive tape was adhered to a SUS-304 steel plate. The portion adhered to the PET film was mounted on a UTM fixture, and the adhesive strength was measured at a speed of 30 mm / min. At this time, the numerical value displayed on the UTM device represents the adhesive strength (N / mm). The measurement results are shown in Table 3 below.

[0162] (2) Shear adhesion measurement (SAFT, shear adhesion failure test)

[0163] The shear adhesion of the acrylic adhesives including the tackifying resins according to Examples 1 to 10 and Comparative Examples 1 to 3 was evaluated according to the ASTM D3654 method.

[0164] The sample tapes on which each acrylic adhesive was coated with a thickness of 20 to 30 microns were cut into pieces of 2 inches by 6 inches. Each cut sample was adhered to a release paper, cut into pieces measuring 1 inch by 2 inches (width by length), and then adhered to a washed SUS 304 steel plate (at this time, the length of the non-adhered sample was at least 2 cm, and pressing was performed by moving the roller back and forth once on the portion required for measurement using a roll-down device from Cheminstruments, Inc.). The sample not adhered to the SUS 304 steel plate was cut into a size of about 2 in length using scissors. The sample not adhered to the SUS 304 steel plate was placed on a ring for measuring cohesion and adhered to the passed sample. Two unattached specimens were attached to each of the front and rear sides of the SUS304 steel plate parallel to the horizontal end of the specimen using fixed transparent tape. Then, they were fixed in a parallel position between the ring for measuring cohesion and the SUS304 steel plate using a stapler. The remaining specimens were cut so that the specimens were attached to the SUS304 steel plate in a size of 1 inch × 1 inch (width × length).

[0165] A SUS304 steel plate was hung on a SUS steel plate holder in a shear test furnace. A 1 kg weight was hung on a ring attached to the specimen for measuring holding force. The furnace temperature was then raised at a rate of 0.4°C per minute, and the temperature at which the weight was lowered is shown in Table 3 below.

[0166] [Table 3]

[0167]

[0168]

[0169] As shown in Table 3, when the adhesive strengths of the acrylic adhesives containing the tackifying resins of Examples 1 to 10 and Comparative Examples 1 to 3 were compared,

[0170] The acrylic adhesives containing the tackifying resins of Examples 1 to 10 exhibited excellent compatibility with acrylic polymers. Furthermore, the tackifying resins had low UV absorbance, thereby increasing the amount of UV light reaching the photopolymerization initiator and promoting the photopolymerization reaction. Consequently, the acrylic adhesives containing the tackifying resins of Examples 1 to 10 exhibited improved adhesive strength and shear adhesive strength compared to the acrylic adhesives containing the tackifying resins of Comparative Examples 1 to 3.

[0171] The above embodiments and comparative examples have been described as examples to describe the present disclosure, and therefore, the present disclosure is not limited thereto. It will be apparent to those skilled in the art that various modifications can be made to this specification to implement the present disclosure, and therefore, the technical protection scope of the present disclosure should be defined by the appended claims.

Claims

1. A tackifying resin comprising: Repeating units (a) derived from petroleum resin monomers; Repeating units (b) derived from α-methylstyrene; and Repeating units (c) derived from (meth)acrylic acid monomers, in, At least a portion of the unsaturated bonds contained in the repeating units (a) to (c) are hydrogenated.

2. The tackifying resin according to claim 1, in, At least a portion of the unsaturated bonds contained in the repeating units (a) and (b) are hydrogenated.

3. The tackifying resin according to claim 1, in, The petroleum resin monomers include C9 fraction monomers.

4. The tackifying resin according to claim 3, in, The C9 fraction-based monomers include styrene-based monomers represented by Formula 1: <Formula 1> Among them, in formula 1, a1 is an integer from 0 to 5, R1 is: hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxyl, cyano or nitro; C1-C 20 Alkyl or C1-C 20 Alkoxy, each unsubstituted or substituted with deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, C6-C 20 aryl or any combination thereof; or C6-C 20 Aryl, which is unsubstituted or substituted with deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, C1-C 20 Alkyl, C1-C 20 alkoxy or any combination thereof.

5. The tackifying resin according to claim 3, in, The C9 fraction-type monomers include styrene.

6. The tackifying resin according to claim 1, in, The (meth)acrylic acid monomer is represented by Formula 2: <Formula 2> Among them, in formula 2, R2 and R3 are each independently: hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxyl, cyano or nitro; C1-C 20 Alkyl or C1-C 20 Alkoxy, each unsubstituted or substituted with deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, C6-C 20 aryl or any combination thereof; or C6-C 20 Aryl, which is unsubstituted or substituted with deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, C1-C 20 Alkyl, C1-C 20 alkoxy or any combination thereof.

7. The tackifying resin according to claim 1, in, The (meth)acrylic acid monomer includes acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl acrylate or any combination thereof.

8. The tackifying resin according to claim 1, in, The amount of the repeating unit (a) derived from a petroleum resin monomer is 10 wt % to 50 wt % based on the total weight of the tackifying resin. The amount of the repeating unit (b) derived from α-methylstyrene is 10 wt % to 80 wt % based on the total weight of the tackifying resin, The amount of the repeating unit (c) derived from a (meth)acrylic acid monomer is 5 to 40 wt % based on the total weight of the tackifying resin.

9. The tackifying resin according to claim 1, in, The weight average molecular weight (Mw) of the tackifying resin is 2,000 g / mol or less.

10. The tackifying resin according to claim 1, in, The number average molecular weight (Mn) of the tackifying resin is 2,000 g / mol or less, The Z average molecular weight (Mz) of the tackifying resin is 7,000 g / mol or less, The polymer dispersion index (PDI) of the tackifying resin is 1 to 3.

11. The tackifying resin according to claim 1, in, The softening point of the tackifying resin is 40°C to 120°C.

12. The tackifying resin according to claim 1, in, The tackifier resin has an ultraviolet absorbance of 0.1 or less at a wavelength of 240 nm to 260 nm in a THF solvent at a concentration of 70 ppm.

13. A tackifying resin comprising: Repeating units (a) derived from petroleum resin monomers; Repeating units (b) derived from α-methylstyrene; and Repeating units (c) derived from (meth)acrylic acid monomers, in, In a THF solvent with a concentration of 70 ppm, the ultraviolet absorbance at a wavelength of 240 nm to 260 nm is 0.1 or less.

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