Adhesive resin

Abstract

The present invention includes repeating units (a) derived from petroleum resin monomers; repeating units (b) derived from α-methylstyrene; and repeating units (c) derived from (meth)acrylic monomers. The tackifier resin in which hydrogen is added to at least a part of the unsaturated bonds contained in the repeating units (a) to (c) is excellent in compatibility with the base polymer, and the transparency and adhesive strength of the adhesive containing the same are improved.

Description

Technical Field

[0001] The present invention relates to an adhesion - imparting resin.

Background Art

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

[0003] For example, at an automobile manufacturing site, adhesives are used when fixing automobile interior members inside the automobile. Also, at manufacturing sites of electronic devices such as mobile phones and liquid crystal displays, adhesives are used for fixing cushioning materials provided inside electronic products to protect them from impact, fixing exterior members of electronic products, and fixing members constituting image display devices such as liquid crystal display devices, organic EL display devices, and PDPs.

[0004] From the perspective of reducing environmental load, the conversion from solvent - based adhesives to water - based adhesives has been progressing for the above - mentioned adhesives. Recently, among aqueous media, water - based acrylic adhesives in which acrylic polymers and the like are dispersed are preferably used.

[0005] In general, from the perspective of further improving adhesiveness such as adhesive strength and constant - load holding power, adhesion - imparting resins are often used in combination with the acrylic adhesives.

[0006] However, in the case of adhesion - imparting resins, when the compatibility with the acrylic polymers contained in the acrylic adhesives deteriorates, the adhesives become opaque, the photocuring reaction is not easily carried out, and the heat resistance also deteriorates.

[0007] Therefore, the need for an adhesion - imparting resin with excellent compatibility with acrylic polymers is increasing.

Summary of the Invention

Problems to be Solved by the Invention

[0008] The technical problem to be solved by the present invention is to provide an adhesion - imparting resin having excellent compatibility with a base polymer and a method for producing the same.

Means for Solving the Problem

[0009] One aspect of the present invention relates to an adhesion - imparting resin containing 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 - based monomer, wherein at least a part of the repeating units (a) to (c) is hydrogenated.

Effect of the Invention

[0010] The adhesion - imparting resin according to the present invention has improved compatibility with a base polymer and a reduced ultraviolet light absorption level.

[0011] Therefore, the adhesion - imparting resin according to the present invention has excellent compatibility with the base polymer, and the transparency and heat resistance of the adhesive containing the base polymer and the adhesion - imparting resin are improved.

[0012] Also, due to the reduction of the ultraviolet light absorption level, the irradiation amount of ultraviolet light reaching the photoinitiator increases, and the heat resistance of the adhesive is improved.

Brief Description of the Drawings

[0013]

Figure 1

Embodiments for Carrying Out the Invention

[0014] Hereinafter, many aspects and various specific examples of the present invention will be described more specifically.

[0015] The terms and words used in this specification and the claims are ordinary, but should not be construed as limited to their dictionary meanings. Based on the principle that the inventor can suitably define the concept of a term in order to best explain his or her invention, they must be construed as meanings and concepts that conform to the technical idea of the present invention.

[0016] The terms used in the present invention are merely used to explain specific embodiments and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In the present invention, terms such as "comprising" or "having" are used to specify the presence of features, numbers, steps, operations, components, parts, or combinations thereof described in the specification, and it should be understood that they do not preclude the possibility of the presence or addition of one or more other features, numbers, steps, operations, components, parts, or combinations thereof.

[0017] Specifically, one aspect of the present invention relates to a tackifying resin in which at least a part of the unsaturated bonds contained in the repeating unit (a) derived from a petroleum resin monomer, the repeating unit (b) derived from α-methylstyrene, and the repeating unit (c) derived from a (meth)acrylic monomer have been hydrogenated.

[0018] For example, hydrogen is added to at least a part of the unsaturated bonds contained in the repeating unit (a) to the repeating unit (c) by a hydrogenation reaction carried out in the presence of a hydrogenation catalyst.

[0019] The hydrogenation reaction means that hydrogen is added to the double or triple bond of a molecule having an unsaturated bond to saturate the valence. The hydrogenation reaction is divided into a complete hydrogenation reaction in which hydrogen is added to all unsaturated bonds in the molecule and a partial hydrogenation reaction in which hydrogen is partially added. The hydrogenation defined in the present invention means a state in which hydrogen is added to at least a part of the unsaturated bonds contained in the repeating unit (a) to the repeating unit (c) to saturate the valence.

[0020] According to one specific example, by adding hydrogen to at least a part of the unsaturated bonds contained in the repeating unit (a) to the repeating unit (c), the ultraviolet absorbance of the tackifier resin decreases. When the ultraviolet absorbance of the tackifier resin decreases, the amount of ultraviolet light reaching the photoinitiator contained in the adhesive containing the tackifier resin increases. Thereby, the heat resistance (SAFT) of the adhesive containing the tackifier resin is improved.

[0021] According to one specific example, the petroleum resin monomer can include a liquid C5 to C20 fraction, diolefin, or dicyclopentadiene that can be put into practical use.

[0022] According to another specific example, the petroleum resin monomer can include a C5 fraction, a C9 fraction, diolefin, or dicyclopentadiene.

[0023] For example, the C5 fraction includes 1-pentene, 2-methyl-2-butene, n-pentane, propadiene, cyclopentadiene, piperylene, isoprene, cyclopentene, etc.

[0024] For example, the C9 fraction includes styrene monomers, dicyclopentadiene, indene, trans-β-methylstyrene, methylindene, vinyltoluene, or benzene / toluene / xylene (BTX), etc.

[0025] For example, the diolefin includes propadiene, dicyclopentadiene, cyclopentene, and the like.

[0026] According to one specific example, the petroleum resin monomer can include a C9 fraction.

[0027] According to one specific example, the C9 fraction can include a styrene monomer.

[0028] For example, the styrene monomer is represented by the following Chemical Formula 1.

[0029] <Chemical Formula 1> JPEG2025522203000002.jpg40170

[0030] Among the Chemical Formula 1, a1 is an integer from 0 to 5, R1 is hydrogen, deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group or a nitro group; or deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, C6-C 20 an aryl group or a C1-C 20 alkyl group or a C1-C 20 alkoxy group; or deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, C1-C 20 alkyl group, a C1-C 20 alkoxy group or a C6-C 20 aryl group which is substituted or unsubstituted with any combination of these.

[0031] According to one specific example, R1 and R2 are independently of each other hydrogen, deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group or a nitro group; or deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, C6-C 20A methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group, tert-pentyl group, neopentyl group, isopentyl group, sec-pentyl group, 3-pentyl group, sec-isopentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, n-heptyl group, isoheptyl group, sec-heptyl group, tert-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, sec-nonyl group, tert-nonyl group, n-decyl group, isodecyl group, sec-decyl group, tert-decyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, isobutoxy group, tert-butoxy group, n-pentoxy group, tert-pentoxy group, neopentoxy group, isopentoxy group, sec-pentoxy group, 3-pentoxy group, sec-isopentoxy group, n-hexoxy group, isohexoxy group, sec-hexoxy group, tert-hexoxy group, n-heptoxy group, isoheptoxy group, sec-heptoxy group, tert-heptoxy group, n-octoxy group, isooctoxy group, sec-octoxy group, tert-octoxy group, n-nonoxy group, isononoxy group, sec-nonoxy group, tert-nonoxy group, n-desoxy group, isodesoxy group, sec-desoxy group or tert-desoxy group; or Deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, C1-C 20 Alkyl group, C6-C 20 A phenyl group, naphthyl group, anthracenyl group, phenanthrenyl group or pyrenyl group which is substituted or unsubstituted with an aryl group or any combination thereof.

[0032] According to one specific example, R1 and R2 are, independently of each other, hydrogen, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a tert-pentyl group, a neopentyl group, an isopentyl group, a sec-pentyl group, a 3-pentyl group, a sec-isopentyl group, an n-hexyl group, an isohexyl group, a sec-hexyl group or a tert-hexyl group.

[0033] a1 is an integer from 0 to 5.

[0034] According to one specific example, the styrenic monomer can contain styrene.

[0035] According to one specific example, the tackifier resin can contain a repeating unit (b) derived from α-methylstyrene.

[0036] According to one specific example, the tackifier resin can contain a repeating unit (b) derived from α-methylstyrene as a molecular weight regulating unit. For example, when the tackifier resin contains the repeating unit (b) derived from α-methylstyrene, the weight average molecular weight of the tackifier resin decreases. Thereby, the tackifier resin of the present application satisfies that the weight average molecular weight is 5,000 g / mol or less or 3,000 g / mol, and the compatibility and reactivity with the base polymer described later are improved. Thereby, the transparency and heat resistance of the pressure-sensitive adhesive containing the tackifier resin are further improved.

[0037] According to one specific example, hydrogen can be added to at least a part of the unsaturated bonds contained in the repeating unit (a) and the repeating unit (b). For example, hydrogen is added to a part of the aromatic rings which are the unsaturated bonds contained in the repeating unit (a) and the repeating unit (b).

[0038] For example, in the adhesion-imparting resin, hydrogen is added to at least a part of the unsaturated bonds contained in the repeating unit (a) and the repeating unit (b), and it contains a repeating unit represented by the following Chemical Formula 1-1.

[0039] <Chemical Formula 1-1> JPEG2025522203000003.jpg50170

[0040] Among the Chemical Formula 1-1, a11 is an integer from 0 to 5, R 11 and R 12 are, independently of each other, hydrogen, deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group or a nitro group; or deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, a C6-C 20 aryl group or a C1-C 20 alkyl group or a C1-C 20 alkoxy group which is substituted or unsubstituted with these or any combination thereof; or deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, a C1-C 20 alkyl group, a C1-C 20 alkoxy group or a C6-C 20 aryl group which is substituted or unsubstituted with these or any combination thereof.

[0041] According to one specific example, among the Chemical Formula 1-1, R 11 is hydrogen, and R 12 is also hydrogen or a methyl group.

[0042] According to one specific example, since the tackifying resin contains the repeating unit represented by the chemical formula 1-1, i) the tackifying resin can be polymerized using a hydrogenated petroleum resin monomer or hydrogenated α-methylstyrene, ii) after polymerizing a petroleum resin monomer and α-methylstyrene to form a polymer, a hydrogenation reaction can be carried out, or iii) after polymerizing a petroleum resin monomer, α-methylstyrene and a (meth)acrylic monomer to form a polymer, a hydrogenation reaction can be carried out.

[0043] For example, since the tackifying resin contains the repeating unit represented by the chemical formula 1-1, i) the tackifying resin can be polymerized using the monomer represented by the following formula (1-2), ii) after polymerizing a petroleum resin monomer and α-methylstyrene to form a polymer, a hydrogenation reaction can be carried out, or iii) after polymerizing a petroleum resin monomer, α-methylstyrene and a (meth)acrylic monomer to form a polymer, a hydrogenation reaction can be carried out.

[0044] <Chemical formula 1-2> JPEG2025522203000004.jpg45170

[0045] Among the chemical formula 1-2, a11 is an integer from 0 to 5, R 11 and R 12 are independently of each other hydrogen, deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group or a nitro group; or deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, a C6-C 20 aryl group or a C1-C 20 alkyl group or a C1-C 20 alkoxy group substituted or unsubstituted with these or any combination thereof; or deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, a C1-C 20 alkyl group, a C1-C 20 alkoxy group or a C6-C 20 aryl group substituted or unsubstituted with these or any combination thereof.

[0046] According to one specific example, among the chemical formulas 1-2, R 11 is hydrogen, and R 12 is also hydrogen or a methyl group.

[0047] According to one specific example, the (meth)acrylic monomer can be represented by the following chemical formula 2.

[0048] <Chemical formula 2> JPEG2025522203000005.jpg35170

[0049] Among the chemical formula 2, R2 and R3 are independently of each other hydrogen, deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group or a nitro group; or deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, C6-C 20 an aryl group or a C1-C 20 alkyl group or a C1-C 20 alkoxy group which is substituted or unsubstituted with these or any combination thereof; or deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, C1-C 20 alkyl group, a C1-C 20 alkoxy group or a C6-C 20 aryl group which is substituted or unsubstituted with these or any combination thereof.

[0050] According to one specific example, R3 and R4 are independently of each other hydrogen, deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group or a nitro group; or deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, C6-C 20A methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group, tert-pentyl group, neopentyl group, isopentyl group, sec-pentyl group, 3-pentyl group, sec-isopentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, n-heptyl group, isoheptyl group, sec-heptyl group, tert-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, sec-nonyl group, tert-nonyl group, n-decyl group, isodecyl group, sec-decyl group, tert-decyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, isobutoxy group, tert-butoxy group, n-pentoxy group, tert-pentoxy group, neopentoxy group, isopentoxy group, sec-pentoxy group, 3-pentoxy group, sec-isopentoxy group, n-hexoxy group, isohexoxy group, sec-hexoxy group, tert-hexoxy group, n-heptoxy group, isoheptoxy group, sec-heptoxy group, tert-heptoxy group, n-octoxy group, isooctoxy group, sec-octoxy group, tert-octoxy group, n-nonoxy group, isononoxy group, sec-nonoxy group, tert-nonoxy group, n-desoxy group, isodesoxy group, sec-desoxy group or tert-desoxy group; or substituted or unsubstituted with an aryl group or any combination thereof; deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, C1-C 20 alkyl group, C6-C 20 a phenyl group, naphthyl group, anthracenyl group, phenanthrenyl group or pyrenyl group substituted or unsubstituted with an aryl group or any combination thereof.

[0051] According to one specific example, R3 is also hydrogen, a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group or tert-butyl group.

[0052] According to another specific example, R3 is also hydrogen or a methyl group.

[0053] According to one specific example, R4 is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a tert-pentyl group, a neopentyl group, an isopentyl group, a sec-pentyl group, a 3-pentyl group, a sec-isopentyl group, an n-hexyl group, an isohexyl group, a sec-hexyl group or a tert-hexyl group.

[0054] According to another specific example, R4 is also a methyl group or an ethyl group.

[0055] According to one specific example, 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.

[0056] According to one specific example, the content of the repeating unit (a) derived from the petroleum resin monomer may be less than or the same as the content of the repeating unit (b) derived from the α-methylstyrene. For example, the content of the repeating unit (a) derived from the petroleum resin monomer is less than the content of the repeating unit (b) derived from the α-methylstyrene.

[0057] For example, when the content of the repeating unit (b) derived from α-methylstyrene as the molecular weight regulating unit is greater than the content of the repeating unit (a) derived from the petroleum resin monomer, the weight average molecular weight of the tackifying resin can be more easily adjusted to 3,000 g / mol or less.

[0058] According to a specific example, the content of the repeating unit (a) derived from the petroleum resin monomer is 10 to 50% by weight based on the total weight of the tackifying resin, the content of the repeating unit (b) derived from α-methylstyrene is 10 to 80% by weight based on the total weight of the tackifying resin, and the content of the repeating unit (c) derived from the (meth)acrylic monomer is 5 to 40% by weight based on the total weight of the tackifying resin.

[0059] For example, the content of the repeating unit (a) derived from the petroleum resin monomer is 10 to 50% by weight, 10 to 45% by weight, 15 to 45% by weight, 20 to 45% by weight, 20 to 40% by weight or 25 to 40% by weight based on the total weight of the tackifying resin.

[0060] For example, the content of the repeating unit (b) derived from α-methylstyrene is 10 to 80% by weight, 20 to 80% by weight, 30 to 80% by weight or 30 to 60% by weight based on the total weight of the tackifying resin.

[0061] For example, the content of the repeating unit (c) derived from the (meth)acrylic monomer is 5 to 40% by weight, 5 to 35% by weight or 10 to 35% by weight based on the total weight of the tackifying resin.

[0062] According to a specific example, the weight average molecular weight (Mw) of the tackifying resin can be 3,000 g / mol or less. For example, the weight average molecular weight (Mw) of the tackifying resin is 2,900 g / mol or less, 2,800 g / mol or less, 2,500 g / mol or less.

[0063] According to a specific example, the weight average molecular weight (Mw) of the tackifying resin may 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.

[0064] According to a specific example, the number average molecular weight (Mn) of the tackifying resin may be 1,000 g / mol or less.

[0065] For example, the number average molecular weight (Mn) of the tackifying resin is 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.

[0066] According to a specific example, the Z average molecular weight (Mz) of the tackifying resin may be 7,000 g / mol or less.

[0067] For example, the Z average molecular weight of the tackifying resin is 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.

[0068] According to one specific example, the dispersity (PDI) of the tackifying resin can be from 1 to 3. For example, the dispersity (PDI) of the tackifying resin is from 1.1 to 3, from 1.2 to 3, from 1.3 to 3, from 1 to 2, from 1.2 to 2, from 1.3 to 2, from 1 to 1.9, from 1.2 to 1.9 or from 1.31 to 1.9.

[0069] For example, when the average molecular weight value and the dispersity of the tackifying resin satisfy the above range, the compatibility with a base polymer, such as an acrylic polymer, is further improved.

[0070] According to one specific example, the softening point of the tackifying resin can be from 40 to 120 °C. For example, the softening point of the tackifying resin is from 45 to 120 °C, from 45 to 110 °C, from 45 to 100 °C, from 45 to 80 °C, from 50 to 120 °C, from 50 to 110 °C, from 50 to 100 °C, from 50 to 85 °C or from 50 to 80 °C.

[0071] According to one specific example, the viscosity of the tackifying resin at 160 °C can be from 20 cps to 200 cps. For example, the viscosity of the tackifying resin at 160 °C is from 20 cps to 150 cps, from 20 cps to 100 cps, from 20 cps to 80 cps, from 20 cps to 78 cps, from 30 cps to 150 cps, from 30 cps to 100 cps, from 30 cps to 80 cps, from 30 cps to 78 cps, from 35 cps to 150 cps, from 35 cps to 100 cps, from 35 cps to 80 cps or from 35 cps to 78 cps.

[0072] According to one specific example, the viscosity of the tackifying resin at 180 °C can be from 1 cps to 100 cps. For example, the viscosity of the tackifying resin at 180 °C is from 1 cps to 80 cps, from 1 cps to 60 cps, from 1 cps to 40 cps, from 1 cps to 34 cps, from 1 cps to 32 cps, from 10 cps to 80 cps, from 10 cps to 60 cps, from 10 cps to 40 cps, from 10 cps to 34 cps or from 10 cps to 32 cps.

[0073] According to one specific example, 1 The mol% of the repeating unit (b) derived from the (meth)acrylic monomer measured through 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% based on the total number of moles of the repeating units derived from the monomers contained in the tackifier resin.

[0074] For example, the mol% of the repeating unit (c) derived from the (meth)acrylic monomer 1 can be confirmed through peak analysis obtained by H-NMR measurement.

[0075] According to one specific example, the aromaticity of the tackifier resin before hydrogenation measured via NMR can be 1 to 90%.

[0076] For example, the aromaticity of the tackifier resin 1 can be confirmed through peak analysis obtained by H-NMR measurement.

[0077] According to one specific example, the UV absorbance (THF solvent, concentration 70 ppm) of the tackifier resin at wavelengths of 240 nm to 260 nm can be 0.1 or less. For example, the UV absorbance means the average absorbance value measured against ultraviolet light with wavelengths of 240 nm to 260 nm after dissolving the tackifier resin in a THF solvent so that the concentration becomes 70 ppm.

[0078] Still another aspect of the present invention can provide a method for producing a tackifier resin, which includes a petroleum resin monomer; α-methylstyrene; and a (meth)acrylic monomer, and has a UV absorbance (THF solvent, concentration 70 ppm) at wavelengths of 240 nm to 260 nm of 0.1 or less.

[0079] According to one specific example, a first monomer composition containing a petroleum resin monomer and α-methylstyrene can be prepared. After adding a polymerization catalyst to the first monomer composition, catalytic polymerization is carried out to produce a first polymer composition containing a first polymer. Next, after adding a hydrogenation catalyst to the first polymer composition, a hydrogenation reaction is carried out to add hydrogen to a part of the unsaturated bonds contained in the first polymer, thereby producing a partially hydrogenated first polymer composition. Next, a (meth)acrylic monomer is added to the first polymer composition to which hydrogen has been added to a part thereof, thereby preparing a second monomer composition. Next, the second monomer composition is thermally polymerized to carry out a deaeration reaction, thereby producing a tackifying resin.

[0080] According to another specific example, a first monomer composition containing a petroleum resin monomer and α-methylstyrene can be prepared. After adding a polymerization catalyst to the first monomer composition, catalytic polymerization is carried out to produce a first polymer composition containing a first polymer. Next, a (meth)acrylic monomer is added to the first polymer composition to prepare a second monomer composition. Next, the second monomer composition is thermally polymerized to produce a second polymer composition containing a second polymer. Next, after adding a hydrogenation catalyst to the second polymer composition, a hydrogenation reaction is carried out to add hydrogen to a part of the unsaturated bonds contained in the second polymer, and after carrying out a partial hydrogenation reaction, a deaeration reaction is carried out to produce a tackifying resin.

[0081] According to another specific example, a first monomer composition containing a petroleum resin monomer, α-methylstyrene, and a vinyl monomer can be prepared. After adding a polymerization catalyst to the first monomer composition, catalytic polymerization is carried out to produce a first polymer composition containing a first polymer. Next, a (meth)acrylic monomer is added to the first polymer composition to prepare a second monomer composition. Next, the second monomer composition is thermally polymerized to carry out a deaeration reaction, thereby producing a tackifying resin.

[0082] For example, the vinyl monomer includes the vinyl cycloalkane monomer. For example, the vinyl monomer includes a vinyl cyclopentane monomer, a vinyl cyclohexane monomer, or a combination thereof. For example, the vinyl monomer is represented by the following Chemical Formula 1-2.

[0083] For example, for the types, contents, and physical properties of the petroleum resin monomer, the (meth)acrylic monomer, and the α-methylstyrene, and the physical properties of the tackifier resin, refer to the foregoing description.

[0084] For example, among the monomer composition, the monomer means the remaining composition excluding the solvent among the components included in the monomer composition.

[0085] According to one specific example, the monomer composition may further include a solvent.

[0086] For example, the solvent includes xylene.

[0087] According to one specific example, the polymerization catalyst can include a Lewis acid, a halohydric acid, AlCl3, BF3, or any combination thereof. For example, the polymerization catalyst includes AlCl3, BF3, SnCl4, TiCl4, AgClO4, I2, or any combination thereof.

[0088] According to one specific example, the catalytic polymerization can be carried out at a temperature of 100°C or lower. For example, the catalytic polymerization is 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.

[0089] According to one specific example, the thermal polymerization can be carried out in a temperature range of 150 to 300°C. For example, the thermal polymerization is carried out in a temperature range of 200 to 300°C, 220 to 300°C, 230 to 300°C, 200 to 280°C, or 200 to 260°C.

[0090] For example, the degassing reaction is carried out at a temperature of 150°C to 300°C and a pressure of 1 mbar to 50 mbar for 1 minute to 20 minutes.

[0091] According to another specific example, the degassing reaction can be carried out at a temperature of 220°C to 280°C and a pressure of 5 mbar to 25 mbar for 5 minutes to 15 minutes or at a temperature of 240°C to 260°C and a pressure of 5 mbar to 15 mbar for 8 minutes to 12 minutes.

[0092] According to one specific example, the hydrogenation reaction can be carried out in the presence of a hydrogenation catalyst (hydrogenation catalyst). For example, the hydrogenation catalyst includes a palladium-based catalyst.

[0093] According to one specific example, the hydrogenation reaction can be carried out in the presence of a hydrogenation catalyst (hydrogenation catalyst) at a temperature of 100 to 300°C and a pressure of 20 to 100 bar for 1 to 3 hours.

[0094] According to one specific example, the above-mentioned tackifying resin can be applied to an adhesive. According to another specific example, the above-mentioned tackifying resin can be applied to an acrylic adhesive.

[0095] Still another aspect of the present invention provides an adhesive containing the above-mentioned tackifying resin. For example, the tackifying resin imparts adhesive strength to the adhesive.

[0096] According to one specific example, the adhesive can include the above-mentioned tackifying resin and a base polymer. For example, the adhesive is an acrylic adhesive containing the above-mentioned tackifying resin and an acrylic polymer. For example, the tackifying resin is excellent in compatibility with the base polymer, such as an acrylic polymer, and excellent in transparency and adhesion of the adhesive.

[0097] According to one specific example, the adhesive can be a photocurable adhesive.

[0098] For example, the adhesive further includes a crosslinking agent, a photoinitiator, etc. in addition to the tackifier and the base polymer.

[0099] According to one specific example, the photoinitiator 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, benzyldiphenyldisulfide, benzyldimethyl ketal, Irgacure series manufactured by Ciba Specialty Chemicals, anthraquinone, naphthoquinone, 3,3-dimethyl-4-methoxybenzophenone, benzophenone, pivalone ethyl ether, 1,1-dichloroacetophenone, p-t-butyldichloroacetophenone, dimer of hexaaryl imidazole, 2,2'-diethoxyacetophenone, 2,2'-diethoxy-2-phenylacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, phenylglyoxylic acid, α-hydroxyisobutylphenone, dibenzospiro, 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 photoinitiator is contained in the adhesive in an amount of 0.01 to 10% by weight or 0.02 to 5% by weight.

[0100] According to one specific example, the content of the tackifying resin in the adhesive may be 1% by weight or more based on the total weight of the adhesive.

[0101] According to another specific example, the content of the tackifying resin in the adhesive may be 1 to 30% by weight, 5 to 30% by weight, 10 to 30% by weight, 1 to 25% by weight, 5 to 25% by weight, or 10 to 25% by weight based on the total weight of the adhesive.

[0102] According to one specific example, the adhesive is transparent. In this case, light can uniformly penetrate the adhesive, and the photocuring reaction can proceed uniformly. As a result, the heat resistance of the adhesive is further improved.

[0103] According to one specific example, the adhesive can contain a base polymer, the tackifier resin, and a photoinitiator. In this case, the tackifier resin has a low absorbance to ultraviolet rays, the amount of ultraviolet rays reaching the photoinitiator increases, and the polymerization reaction by light irradiation is further promoted. Thereby, the adhesive strength and shear adhesive strength of the adhesive containing the tackifier resin are improved.

[0104] [Definition of Terms] In this specification, C1-C 20 The alkyl group means a linear or branched aliphatic hydrocarbon monovalent group having 1 to 20 carbon atoms. Specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group, tert-pentyl group, neopentyl group, isopentyl group, sec-pentyl group, 3-pentyl group, sec-isopentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, n-heptyl group, isoheptyl group, sec-heptyl group, tert-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, sec-nonyl group, tert-nonyl group, n-decyl group, isodecyl group, sec-decyl group, tert-decyl group, etc. are included. In this specification, C1-C 20 The alkylene group means a divalent group having the same structure as the C1-C 20 alkyl group.

[0105] In this specification, C1-C 20 The alkoxy group is -OA101 (where A101 is the C1-C 20It means a monovalent group having the chemical formula of (alkyl group), and specific examples thereof include a methoxy group, an ethoxy group, an isopropyloxy group, and the like.

[0106] In this specification, C6-C 20 An aryl group means a monovalent group having a carbocyclic aromatic system with 6 to 20 carbon atoms, and includes a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, or the like. The C6-C 20 When the aryl group contains two or more rings, the two or more rings may be linked to each other.

[0107] Hereinafter, the present invention will be described in more detail with reference to examples. It will be apparent to those skilled in the art that these examples are for further specifically explaining the present invention and that the scope of the present invention is not limited by these examples.

[0108] Example 1. Production of Adhesion-Giving Resin Styrene (SM) and α-methylstyrene (AMS) were injected into a 2,000 ml chemical reactor equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen injection device, according to the compounding amounts described in Table 1 below (SM: 280 g, AMS: 420 g), and xylene as a solvent was injected so that the weight ratio to the sum of the weights of styrene and α-methylstyrene (AMS) was 1:1, to prepare a first composition. After adding 0.1% by weight of the catalyst BF3 to the first monomer composition, it was polymerized at 30 °C for 120 minutes, and then 10 g of calcium hydroxide was added and neutralized to produce a first polymer composition.

[0109] Next, 280 g of a palladium catalyst (KOH-5, manufactured by NECC) was added to the first polymer composition, and a hydrogenation reaction was carried out for 90 minutes under the conditions of a hydrogen pressure of 80 bar and a reaction temperature of 270 °C to produce a hydrogenated resin composition.

[0110] Next, methyl acrylate (MA) was injected into 420 g of the hydrogenated resin composition according to the content shown in Table 1 (MA: 350 g), and xylene as a solvent was further injected so that the weight ratio to methyl acrylate (MA) became 1:1, to prepare a second composition. Next, the second composition was thermally polymerized at a temperature of 240 °C for 2 hours to produce a second polymer composition.

[0111] Next, the second polymer composition was subjected to a degassing reaction at a temperature of 250 °C and a pressure condition of 10 mbar for 10 minutes to produce a tackifier resin.

[0112] Examples 2 to 10 and Comparative Examples 1 to 3 A tackifier resin was produced in the same manner as in Example 1, except that styrene (SM), α-methylstyrene (AMS), methyl acrylate (MA), the first polymer composition, and the hydrogenation reaction target were changed as shown in Table 1 below.

[0113] When the hydrogenation target is the first polymer composition, the first polymer composition, which is a polymer of styrene and α-methylstyrene, is hydrogenated. When the hydrogenation target is the second polymer composition, after preparing a second polymer composition in which methyl acrylate (MA) is added to a polymer of styrene and α-methylstyrene, the prepared second polymer composition is hydrogenated.

[0114]

Table 1

[0115] Evaluation Example 1. Measurement of Molecular Weight Using gel permeation chromatography (GPC, product of Hewlett-Packard, model HP-1100), the weight average molecular weight (Mw), number average molecular weight (Mn), Z average molecular weight (Mz), and PDI (Polymer density index) of the tackifier resins produced in Examples 1 to 10 and Comparative Examples 1 to 3 were measured.

[0116] The weight-average molecular weight (Mw), number-average molecular weight (Mn), Z-average molecular weight (Mz), and PDI (Polymer density index) of the tackifying resin were measured as follows: Each of the tackifying resins produced in Examples 1 to 10 and Comparative Examples 1 to 3 was dissolved in tetrahydrofuran to a concentration of 4000 ppm. Then, 100 μl was injected into GPC. The mobile phase of GPC was tetrahydrofuran, which was flowed in at a flow rate of 1.0 mL / min and measured at 30°C. Three columns of Agilent PIgel (1,000 + 500 + 100 Å) were connected in series. As a detector, an RI detector (product of Hewlett Packard, HP-1047A) was used to measure at 30°C. The measurement results are shown in Table 2 below.

[0117] Evaluation Example 2. Measurement of Softening Point For each of the tackifying resins produced 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 circular mold, and then placed in a beaker containing glycerin. After placing a ball on the ring containing the resin, the temperature was increased by 2.5°C per minute, and the temperature (softening point) at which the resin melted and the ball dropped was measured and shown in Table 2 below.

[0118] Evaluation Example 3. Measurement of UV (240 to 262 nm) Absorbance Level After putting THF into the UV measurement cell and performing calibration, each of the tackifying resins produced in Examples 1 to 10 and Comparative Examples 1 to 3 was mixed with THF to produce a solution with a concentration of 70 ppm. Then, after putting it into the UV measurement cell and setting the mode of the UV measurement instrument to Absorption, the absorbance level at wavelengths from 200 to 350 nm was measured. The measurement results are shown in Figure 1 and Table 2 below, respectively.

[0119]

Table 2

[0120] Production of Acrylic Adhesive 15% by weight of the tackifier resin and 85% by weight of the acrylic polymer in Examples 1 to 10 and Comparative Examples 1 to 3 were mixed, and 1% by weight of a photoinitiator was further added to produce acrylic adhesives respectively.

[0121] Evaluation Example 5. Measurement of Adhesive Strength and Shear Adhesion

[0122] (1) Measurement of Adhesive Strength Measurement was carried out using a UTM device.

[0123] First, an acrylic adhesive containing the tackifier resin according to Examples 1 to 10 and Comparative Examples 1 to 3 was applied to a PET film to a thickness of 50 μm to produce a tape. Then, after irradiating 65 mJ of UV through an exposure device, the tape was attached to a SUS 304 steel plate. After attaching the part with the PET film to the UTM grip, measurement was carried out at a speed of 30 mm / min. At this time, the numerical value input into the UTM equipment means the adhesive strength (N / in). The measurement results are shown in Table 3 below.

[0124] (2) Measurement of Shear Adhesion (SAFT, Shear Adhesion Failure Test) The shear adhesion of the acrylic adhesives containing the tackifier resins according to Examples 1 to 10 and Comparative Examples 1 to 3 was evaluated by the ASTM D3654 method.

[0125] Test pieces of tape coated with 20 to 30 micrometers of the acrylic adhesive respectively were each cut into pieces about 2 inches × 6 inches. The cut test pieces were each pasted onto release paper, made into a size of 1 inch wide and 2 inches long, and then pasted onto a washed SUS304 steel plate (at this time, they were pasted so that the non - adhering test pieces were about 2 cm or more, and the parts necessary for measurement were crimped by reciprocating the roll once using a roll - down device manufactured by Cheminstruments). The test pieces that did not adhere to the SUS 304 steel plate were cut with scissors so that they were about 2 cm. The test pieces that did not adhere to the SUS 304 steel plate were sandwiched in a ring for measuring cohesion and adhered to the passing test pieces. Taking the horizontal ends of the SUS 304 steel plate to which the test pieces were adhered with the fixing adhesive tape as a reference, two pieces were pasted in front and behind in parallel respectively, and two were taken and fixed in parallel between the ring for measuring cohesion and the SUS 304 steel plate with a stapler. The test pieces were cut so that the test pieces were pasted onto the SUS 304 steel plate in a size of 1 inch wide and 1 inch high.

[0126] It was placed on the SUS steel plate stand in the shear test oven. A 1 - kg weight was suspended from the ring for measuring the holding power attached to the test piece. Then, the oven temperature was raised at a rate of 0.4 °C / min, and the temperature when the weight fell was recorded in Table 3 below.

[0127]

Table 3

[0128] As shown in Table 3 above, when comparing the adhesive strengths of acrylic adhesives each containing the tackifier resins according to Examples 1 to 10 and Comparative Examples 1 to 3, the acrylic adhesives containing the tackifier resins according to Examples 1 to 10 were excellent in compatibility with the acrylic polymer, had a low UV absorbance in the tackifier resin, and the amount of ultraviolet rays reaching the photoinitiator increased, promoting the photopolymerization reaction. As a result, the acrylic adhesives containing the tackifier resins according to Examples 1 to 10 had improved adhesive strength and shear adhesive strength compared to the acrylic adhesives containing the tackifier resins according to Comparative Examples 1 to 3.

[0129] The above-described Examples and Comparative Examples are examples for explaining the present invention, and the present invention is not limited thereto. Since those skilled in the art can implement the present invention in various modifications therefrom, the technical protection scope of the present invention will have to be determined by the appended claims.

Claims

1. A repeating unit (a) derived from a petroleum resin monomer, a repeating unit (b) derived from α-methylstyrene, and a repeating unit (c) derived from a (meth)acrylic monomer, and a tackifying resin in which hydrogen is added to at least a part of the unsaturated bonds contained in the repeating unit (a) to the repeating unit (c).

2. The tackifying resin according to claim 1, wherein hydrogen is added to at least a part of the unsaturated bonds contained in the repeating unit (a) and the repeating unit (b).

3. The tackifying resin according to claim 1, wherein the petroleum resin monomer contains a C9 fraction monomer.

4. The tackifying resin according to claim 3, wherein the C9 fraction monomer contains a styrene monomer represented by the following chemical formula 1: <Chemical formula 1> Among the above chemical formula 1, a1 is an integer of 0 to 5, R １ is hydrogen, deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group or a nitro group; or Deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, C ６ -C ２０ C substituted or unsubstituted with an aryl group or any combination thereof １ -C ２０ alkyl group or C １ -C ２０ alkoxy group; or Deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, C １ -C ２０ alkyl group, C １ -C ２０ substituted or unsubstituted C with an alkoxy group or any combination thereof ６ -C ２０ is an aryl group.

5. The tackifying resin according to claim 3, wherein the C9 oil fraction monomer contains styrene.

6. The tackifying resin according to claim 1, wherein the (meth)acrylic monomer is represented by the following chemical formula 2: <Chemical formula 2> Among the above chemical formula 2, R ２ and R ３ are, independently of one another, hydrogen, deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group or a nitro group; or Deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, C ６ -C ２０ A C substituted or unsubstituted with an aryl group or any combination thereof １ -C ２０ An alkyl group or C １ -C ２０ An alkoxy group; or Deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, C １ -C ２０ alkyl group, C １ -C ２０ substituted or unsubstituted C with an alkoxy group or any combination thereof ６ -C ２０ is an aryl group.

7. The tackifying resin according to claim 1, wherein the (meth)acrylic monomer contains 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 content of the repeating unit (a) derived from the petroleum resin monomer is 10 to 50% by weight based on the total weight of the tackifying resin, the content of the repeating unit (b) derived from α-methylstyrene is 10 to 80% by weight based on the total weight of the tackifying resin, and the content of the repeating unit (c) derived from the (meth)acrylic monomer is 5 to 40% by weight based on the total weight of the tackifying resin. The tackifying resin according to claim 1.

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

10. The number average molecular weight (Mn) of the tackifying resin is 2,000 g / mol or less, and the Z average molecular weight (Mz) of the tackifying resin is 7,000 g / mol or less. The PDI (Polymer Dispersion Index) of the tackifier resin is from 1 to 3, the tackifier resin according to claim 1.

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

12. The UV absorbance (THF solvent, concentration 70 ppm) of the tackifier resin at a wavelength of 240 nm to 260 nm is 0.1 or less, the tackifier resin according to claim 1.

13. A repeating unit (a) derived from a petroleum resin monomer, a repeating unit (b) derived from α-methylstyrene, and a repeating unit (c) derived from a (meth)acrylic monomer, and the UV absorbance (THF solvent, concentration 70 ppm) at a wavelength of 240 nm to 260 nm is 0.1 or less, the tackifier resin.

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