Adhesive-imparting resin and method for producing the same

Abstract

The present invention relates to an adhesion - imparting resin containing a repeating unit (a) derived from a petroleum resin - based monomer, a repeating unit (b) derived from a (meth)acrylic monomer, and a repeating unit (c) derived from α - methylstyrene as a molecular weight - regulating unit, having a weight - average molecular weight of 2,000 g / mol or less, and a method for producing the same. The adhesion - imparting resin is excellent in compatibility with a base polymer, and can improve the transparency and adhesive strength of an adhesive containing the same.

Description

Technical Field

[0001] The present invention relates to an adhesion-imparting resin and a method for producing the same.

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 a manufacturing site for electronic devices such as mobile phones and liquid crystal displays, adhesives are used for fixing cushioning materials provided inside the electronic products to protect them from impact, fixing exterior members of the electronic products, and fixing members constituting image display devices such as liquid crystal display devices, organic EL display devices, and PDPs.

[0004] As for the adhesives, from the viewpoint of reducing the environmental load, the conversion from solvent-based adhesives to water-based adhesives is progressing. Recently, among water-based media, water-based acrylic adhesives in which acrylic polymers and the like are dispersed are preferably used.

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

[0006] However, in the case of the adhesion-imparting resin, when the compatibility with the acrylic polymer contained in the acrylic adhesive deteriorates, the adhesive becomes opaque, the photocuring reaction is not easily carried out, and the heat resistance also deteriorates.

[0007] Therefore, the need for an adhesion-imparting resin having 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 an acrylic polymer and a method for producing the same.

Means for Solving the Problems

[0009] One aspect of the present invention relates to an adhesion - imparting resin containing a repeating unit (a) derived from a petroleum resin - based monomer, a repeating unit (b) derived from a (meth) acrylic - based monomer, and a repeating unit (c) derived from α - methylstyrene as a molecular weight - regulating unit, and having a weight - average molecular weight of 2,000 g / mol or less.

Effects of the Invention

[0010] The adhesion - imparting resin according to the present invention can have improved compatibility in relation to an acrylic polymer.

[0011] Further, the adhesion - imparting resin according to the present invention is excellent in compatibility with the acrylic polymer, and the transparency and heat resistance of an acrylic adhesive containing the acrylic polymer and the adhesion - imparting resin can be improved.

Modes for Carrying Out the Invention

[0012] Hereinafter, many aspects and various embodiments of the present invention will be described more specifically.

[0013] Terms and words used in this specification and the claims should not be construed as being limited to their ordinary or dictionary meanings. Based on the principle that the inventor can preferably define the concept of a term in order to explain his invention in the best way, they must be construed as meanings and concepts that conform to the technical idea of the present invention.

[0014] The terms used in the present invention are merely used to describe specific embodiments and are not intended to limit the present invention. Singular expressions include plural expressions unless clearly stated otherwise in the context. In the present invention, terms such as "including" 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 the presence or addition possibility of one or more other features, numbers, steps, operations, components, parts, or combinations thereof, etc. is not precluded in advance.

[0015] Specifically, one aspect of the present invention relates to an adhesion - imparting resin containing a repeating unit (a) derived from a petroleum resin - based monomer, a repeating unit (b) derived from a (meth)acrylic - based monomer, and a repeating unit (c) derived from α - methylstyrene as a molecular weight - regulating unit, and having a weight - average molecular weight of 2,000 g / mol or less.

[0016] For example, the adhesion - imparting resin contains a repeating unit (c) derived from α - methylstyrene, and the weight - average molecular weight decreases. Thereby, the adhesion - imparting resin of the present application satisfies the above - mentioned range of the weight - average molecular weight, and the compatibility and reactivity with an acrylic - based polymer described later are improved. Thereby, the transparency and heat resistance of the adhesive containing the adhesion - imparting resin are further improved.

[0017] According to one embodiment, the petroleum resin - based monomer can include a liquid C5 to C20 fraction, diolefin, or dicyclopentadiene that can be put into practical use.

[0018] According to another embodiment, the petroleum resin - based monomer can include a C5 fraction, a C9 fraction, diolefin, or dicyclopentadiene.

[0019] For example, the C5 fraction includes 1 - pentene, 2 - methyl - 2 - butene, n - pentane, propadiene, cyclopentadiene, piperylene, isoprene, cyclopentene, etc.

[0020] For example, the C9 fraction contains styrene monomers, dicyclopentadiene, indene, trans-β-methylstyrene, methylindene, vinyltoluene, or benzene / toluene / xylene (BTX), etc.

[0021] For example, the diolefin contains propadiene, dicyclopentadiene, cyclopentene, etc.

[0022] According to one embodiment, the petroleum resin monomer can contain a C9 fraction.

[0023] According to one embodiment, the C9 fraction can contain styrene monomers.

[0024] For example, the styrene monomer is represented by the following Chemical Formula 1.

[0025] <Chemical Formula 1> JPEG2025522594000001.jpg6844

[0026] 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, 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.

[0027] According to one embodiment, 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 20 an aryl group or a 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, a 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, an n-desyloxy (n-decyloxy) group, isodesyloxy (isodecyloxy) group, sec-desyloxy (sec-decyloxy) group or tert-desyloxy (tert-decyloxy) group; or, deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, C1-C 20 an alkyl group, C6-C 20It is 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.

[0028] According to one embodiment, R1 and R2 are, independently of each other, hydrogen, 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 or tert-hexyl group.

[0029] a1 is an integer from 0 to 5.

[0030] According to one embodiment, the styrene monomer can contain styrene.

[0031] According to one embodiment, the (meth)acrylic monomer can be represented by the following Chemical Formula 2.

[0032] <Chemical Formula 2> JPEG2025522594000002.jpg5064

[0033] Among the above Chemical Formula 2, R2 and R3 are, independently of each other, hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group or nitro group; or deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, C6-C 20 an aryl group or a C1-C 20 alkyl group or C1-C 20 alkoxy group which is substituted or unsubstituted with any combination thereof; or deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, C1-C 20 alkyl group, C1-C 20 alkoxy group or a C6-C 20It is an aryl group.

[0034] According to one embodiment, 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, a C6-C 20 aryl group or a 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, a 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 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 C6-C 20It is 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.

[0035] According to one embodiment, R3 can be 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 or a tert-butyl group.

[0036] According to another embodiment, R3 can be hydrogen or a methyl group.

[0037] According to one embodiment, R4 can be 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.

[0038] According to another embodiment, R4 can be a methyl group or an ethyl group.

[0039] According to one embodiment, the (meth)acrylic monomer can include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate or any combination thereof.

[0040] According to one embodiment, the adhesion-imparting resin can include a repeating unit (c) derived from α-methylstyrene as a molecular weight regulating unit.

[0041] According to one embodiment, the content of the repeating unit (a) derived from the petroleum resin monomer is less than or the same as the content of the repeating unit (c) derived from α-methylstyrene as the molecular weight regulating unit.

[0042] For example, when the content of the repeating unit (c) derived from α-methylstyrene as the molecular weight adjusting unit is less than the content of the repeating unit (a) derived from the petroleum resin monomer, the weight average molecular weight of the adhesion-imparting resin can be more easily adjusted to 2,000 g / mol or less.

[0043] According to one embodiment, the ratio of the content of the repeating unit (c) derived from α-methylstyrene to the content of the repeating unit (a) derived from the petroleum resin monomer as the molecular weight adjusting unit can be 0.1 to 10 or less.

[0044] For example, the ratio of the content of the repeating unit (c) derived from α-methylstyrene to the content of the repeating unit (a) derived from the petroleum resin monomer as the molecular weight adjusting unit can be 0.1 to 8, 0.1 to 6, 0.1 to 5, 0.1 to 4, 0.2 to 8, 0.2 to 6, 0.2 to 5, 0.2 to 4, 0.25 to 8, 0.25 to 6, 0.25 to 5, 0.25 to 4, 0.5 to 8, 0.5 to 6, 0.5 to 5, 0.5 to 4, more than 1 and 2.5 or less, more than 1 and 2 or less, more than 1 and 1.8 or less, more than 1 and 1.6 or less, 1.2 to 3, 1.2 to 2.5, 1.2 to 2, 1.4 to 2, 1.2 to 1.8, or 1.4 to 1.6.

[0045] According to one embodiment, the content of the repeating unit (a) derived from the petroleum resin monomer is 5 to 40% by weight based on the total weight of the adhesion-imparting resin, the content of the repeating unit (b) derived from the (meth)acrylic monomer is 5 to 80% by weight based on the total weight of the adhesion-imparting resin, and the content of the repeating unit (c) derived from α-methylstyrene is 10 to 60% by weight based on the total weight of the adhesion-imparting resin.

[0046] For example, the content of the repeating unit (a) derived from the petroleum resin monomer is 10 to 40% by weight, 10 to 38% by weight, 10 to 30% by weight, or 15 to 30% by weight based on the total weight of the adhesion-imparting resin.

[0047] For example, the content of the repeating unit (b) derived from a (meth)acrylic monomer is 5 to 80% by weight, 15 to 80% by weight, 20 to 80% by weight, or 30 to 70% by weight based on the total weight of the adhesion-imparting resin.

[0048] For example, the content of the repeating unit (c) derived from α-methylstyrene is 15 to 60% by weight, 10 to 55% by weight, 10 to 50% by weight, 10 to 45% by weight, 10 to 40% by weight, or 15 to 40% by weight based on the total weight of the adhesion-imparting resin.

[0049] According to one embodiment, the weight average molecular weight (Mw) of the adhesion-imparting resin can be 2,000 g / mol or less.

[0050] For example, the weight average molecular weight (Mw) of the adhesion-imparting resin is 1,900 g / mol or less, 1,800 g / mol or less, or 1,500 g / mol or less.

[0051] According to one embodiment, the weight average molecular weight (Mw) of the adhesion-imparting resin can be 600 to 2,000 g / mol, 700 to 2,000 g / mol, 850 to 2,000 g / mol, 950 to 2,000 g / mol, 600 to 1,500 g / mol, 700 to 1,500 g / mol, 850 to 1,500 g / mol, 950 to 1,500 g / mol, 600 to 1,450 g / mol, 700 to 1,450 g / mol, 850 to 1,450 g / mol, or 950 to 1,450 g / mol.

[0052] According to one embodiment, the number average molecular weight (Mn) of the adhesion-imparting resin can be 1,000 g / mol or less.

[0053] For example, the number average molecular weight (Mn) of the adhesion-imparting 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.

[0054] According to one embodiment, the Z average molecular weight (Mz) of the adhesion-imparting resin can be 7,000 g / mol or less.

[0055] For example, the Z average molecular weight of the adhesion-imparting 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, 1,190 to 7,000 g / mol, or 1,230 to 7,000 g / mol.

[0056] According to one embodiment, the dispersity (PDI) of the adhesion-imparting resin can be 1 to 3. For example, the dispersity (PDI) of the adhesion-imparting resin is 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, 1.3 to 1.9, or 1.31 to 1.9.

[0057] For example, when the average molecular weight value and the dispersity of the adhesion-imparting resin satisfy the above ranges, the compatibility with the acrylic polymer is further improved.

[0058] According to one embodiment, the softening point of the adhesion-imparting resin can be 40 to 120 °C. For example, the softening point of the adhesion-imparting resin is 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 80 °C, 60 to 120 °C, 60 to 110 °C, 60 to 100 °C, or 60 to 80 °C.

[0059] According to one embodiment, the viscosity of the adhesion-imparting resin at 160°C can be 20 cps to 200 cps. For example, the viscosity of the adhesion-imparting resin at 160°C can 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.

[0060] According to one embodiment, the viscosity of the adhesion-imparting resin at 180°C can be 1 cps to 100 cps. For example, the viscosity of the adhesion-imparting resin at 180°C can 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.

[0061] According to one embodiment, the mol% of the repeating unit (b) derived from the (meth)acrylic monomer measured through 1H-NMR can be 1 to 80 mol%, 1 to 76 mol%, 1 to 75 mol%, 5 to 80 mol%, 10 to 80 mol%, 20 to 80 mol%, 21 to 80 mol%, 20 to 76 mol%, 20 to 75 mol%, 21 to 76 mol%, or 21 to 75 mol% based on the total number of moles of the repeating units derived from the monomers contained in the adhesion-imparting resin.

[0062] For example, the mol% of the repeating unit (b) derived from the (meth)acrylic monomer can be confirmed through peak analysis obtained by 1H-NMR measurement. The mol% of the repeating unit (b) derived from the (meth)acrylic monomer is calculated by integrating the peak value in the range of 4 to 3.3 ppm after normalizing the integrated value in the range of 8 to 6 ppm, which is the aromatic detection section, to 5 and then calculating the -OCH3 integrated value.

[0063] Next, the mol% of the repeating unit (b) derived from the (meth)acrylic monomer is calculated as the ratio of the -OCH3 integrated value to the peak integrated value in the entire range of 9 to 0 ppm.

[0064] According to one embodiment, the aromaticity of the adhesion-imparting resin measured via NMR can be 20 to 99 mol%.

[0065] For example, the aromaticity of the adhesion-imparting resin measured via NMR can be 20 to 97 mol%, 20 to 95 mol%, 20 to 90 mol%, or 20 to 89 mol%.

[0066] For example, the aromaticity of the adhesion-imparting resin is calculated from the value obtained by subtracting the mol% of the repeating unit (b) derived from the (meth)acrylic monomer from 100 mol%.

[0067] Still another aspect of the present invention provides a manufacturing method for producing an adhesion-imparting resin from a petroleum resin monomer and a monomer composition containing a (meth)acrylic monomer and α-methylstyrene.

[0068] For example, a first monomer composition containing a petroleum resin monomer and α-methylstyrene is prepared. After adding a catalyst described later to the first monomer composition, catalytic polymerization can be carried out to produce a first polymer composition. Next, a (meth)acrylic monomer is added to the first polymer composition to prepare a second monomer composition. Then, the second monomer composition is thermally polymerized to perform a degassing reaction to produce an adhesion-imparting resin.

[0069] For example, with respect to the types 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.

[0070] According to one embodiment, the content of the petroleum resin monomer in the monomer composition with respect to the total weight of the monomers is 5 to 40% by weight, the content of the (meth)acrylic monomer is 5 to 80% by weight, and the content of α-methylstyrene can be 10 to 60% by weight, based on the total weight of the monomer composition.

[0071] For example, the content of the petroleum resin monomer can be 10 to 40% by weight, 10 to 38% by weight, 10 to 30% by weight, or 15 to 30% by weight with respect to the total weight of the monomers in the monomer composition.

[0072] For example, the content of the (meth)acrylic monomer can be 5 to 80% by weight, 15 to 80% by weight, 20 to 80% by weight, or 30 to 70% by weight with respect to the total weight of the monomers in the monomer composition.

[0073] For example, the content of α-methylstyrene can be 15 to 60% by weight, 10 to 55% by weight, 10 to 50% by weight, 10 to 45% by weight, 10 to 40% by weight, or 15 to 40% by weight with respect to the total weight of the monomers contained in the monomer composition.

[0074] For example, the monomers in the monomer composition mean the remaining components excluding the solvent among the components contained in the monomer composition.

[0075] According to one embodiment, the monomer composition may further contain a solvent.

[0076] For example, the solvent includes xylene.

[0077] According to one embodiment, the production of the adhesion - imparting resin includes a step of catalytically polymerizing the first monomer composition containing the petroleum resin - based monomer and the α - methylstyrene to produce a primary polymerization composition, and a step of adding a (meth)acrylic - based monomer to the primary polymerization composition to prepare a second monomer composition and thermally polymerizing the second monomer composition to produce a secondary polymerization composition. A degassing reaction can be performed on the secondary polymerization composition to produce the adhesion - imparting resin.

[0078] According to one embodiment, the catalytic polymerization is carried out in the presence of a catalyst, and the catalyst can include a Lewis acid, a halohydric acid, AlCl3, BF3, or any combination thereof. For example, the catalyst includes AlCl3, BF3, SnCl4, TiCl4, AgClO4, I2, or any combination thereof.

[0079] According to one embodiment, the catalytic polymerization can be carried out at a temperature of 100°C or lower. For example, the catalytic polymerization can 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.

[0080] According to one embodiment, the thermal polymerization can be carried out in a temperature range of 150 to 300°C. For example, the thermal polymerization can be 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.

[0081] For example, the degassing reaction can be carried out at a temperature of 150°C to 300°C, a pressure of 1 mbar to 50 mbar for 1 minute to 20 minutes.

[0082] According to another embodiment, the degassing reaction can be carried out at a temperature of 220°C to 280°C, a pressure of 5 mbar to 25 mbar for 5 minutes to 15 minutes or at a temperature of 240°C to 260°C, a pressure of 5 mbar to 15 mbar for 8 minutes to 12 minutes.

[0083] According to one embodiment, the above-described adhesion-imparting resin can be applied to an adhesive. According to another embodiment, the above-described adhesion-imparting resin can be applied to an acrylic adhesive.

[0084] Still another aspect of the present invention provides an adhesive containing the above-described adhesion-imparting resin. For example, the adhesion-imparting resin imparts an adhesive force to the adhesive.

[0085] According to one embodiment, the adhesive can be an acrylic adhesive containing the adhesion-imparting resin and an acrylic polymer. For example, the adhesion-imparting resin is excellent in compatibility with the acrylic polymer and excellent in transparency of the acrylic adhesive. For example, by containing epoxy, the adhesion-imparting resin is excellent in reactivity with the acrylic polymer and excellent in heat resistance of the acrylic adhesive.

[0086] According to one embodiment, the acrylic adhesive can be a photocurable acrylic adhesive.

[0087] For example, the acrylic adhesive further contains a crosslinking agent, a polymerization initiation catalyst, a curing accelerator, etc. in addition to the adhesion-imparting agent and the acrylic polymer.

[0088] According to one embodiment, the content of the adhesion-imparting resin in the acrylic adhesive can be 1% by weight or more based on the total weight of the acrylic adhesive.

[0089] According to another embodiment, the content of the adhesion-imparting resin in the acrylic adhesive can 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 acrylic adhesive.

[0090] According to an embodiment, the acrylic adhesive is transparent. In this case, light can uniformly penetrate the acrylic adhesive, and the photocuring reaction can proceed uniformly. As a result, the heat resistance of the acrylic adhesive is further improved.

[0091] [Definition of Terms] In this specification, C1-C 20 The alkyl group means a monovalent group of a linear or branched aliphatic hydrocarbon having 1 to 20 carbon atoms, and 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.

[0092] In this specification, C1-C 20 The alkoxy group is -OA 101 (where A 101 is the C1-C 20 alkyl group) and means a monovalent group having the chemical formula thereof, and specific examples thereof include methoxy group, ethoxy group, isopropyloxy group, etc. are included.

[0093] In this specification, C6-C 20An 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, etc. The C6-C 20 When the aryl group contains two or more rings, the two or more rings may be linked to each other.

[0094] 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.

[0095] <Example 1. Production of Adhesion - imparting Resin> Styrene (SM) and α - methylstyrene (AMS) for molecular weight adjustment were injected into a 1,000 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: 140 g, AMS: 210 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, thereby preparing a first monomer 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 to produce a first polymer composition.

[0096] Next, methyl acrylate (MA) was injected into the first polymer composition according to the content described in Table 1 (MA: 350 g), and xylene as a solvent was further injected so that the weight ratio to methyl acrylate (MA) was 1:1, thereby preparing a second monomer composition. Then, the second monomer composition was thermally polymerized at a temperature of 240 °C for 2 hours to produce a second polymer composition.

[0097] Next, the second polymerization composition was subjected to a degassing reaction at a temperature of 250 °C and a pressure of 10 mbar for 10 minutes to produce an adhesion - imparting resin.

[0098] <Examples 2 to 11 and Comparative Examples 1 to 3> An adhesive-imparting resin was produced in the same manner as in Example 1, except that the weight of the monomer, the weight of the molecular weight regulating unit, and the weight of the solvent were changed as shown in Table 1 below.

[0099]

Table 1

[0100] <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 adhesive-imparting resins produced in Examples 1 to 7 and Comparative Examples 1 to 2 were measured.

[0101] The measurement of the weight average molecular weight (Mw), number average molecular weight (Mn), Z average molecular weight (Mz), and PDI (Polymer density index) of the adhesive-imparting resin was carried out by dissolving each of the adhesive-imparting resins produced in Examples 1 to 7 and Comparative Examples 1 to 2 in tetrahydrofuran to a concentration of 4000 ppm, and then injecting 100 μl into the GPC. The mobile phase of the GPC was tetrahydrofuran, which was flowed in at a flow rate of 1.0 mL / min and carried out at 30°C. Three columns of Agilent PIgel (1,000 + 500 + 100 Å) were connected in series. As the detector, an RI detector (product of Hewlett Packard, HP-1047A) was used for measurement at 30°C. The measurement results are shown in Table 2 below.

[0102] <Evaluation Example 2. Measurement of MA Mol% and Aromatic Mol%> For each of the adhesive-imparting resins produced in Examples 1 to 11 and Comparative Examples 1 to 3, 1 The 1H-NMR spectrum was measured from 0.0 to 9.0 ppm.

[0103] First, the integrated value of the range from 8 to 6 ppm, which is the aromatic detection range, was normalized to 5, and then the peak value in the range from 4 to 3.3 ppm was integrated to calculate the -OCH3 integrated value. Next, the MA mol% was calculated from the -OCH3 integrated value with respect to the peak integrated value for the entire range from 0.0 to 9.0 ppm.

[0104] Also, the aromatic mol% was calculated as the value obtained by subtracting the MA mol% from 100 mol%.

[0105] <Evaluation Example 3. Measurement of Softening Point, Viscosity (cps, 160 °C), and Viscosity (cps, 180 °C)> <Measurement of Softening Point> For each of the tackifier resins produced in Examples 1 to 11 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, placed in a beaker containing glycerin, and then a ball was placed 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 fell was measured and recorded in Table 2 below.

[0106] <Measurement of Viscosity> A viscometer manufactured by Brookfield was used. Using spindle No. 27, 10.5 g samples of the tackifier resins produced in Examples 1 to 11 and Comparative Examples 1 to 3 were respectively introduced into the chamber. After stabilizing at 160 °C for 30 minutes, the RPM value of the stirring shaft was adjusted, and the viscosity value when the torque had a value of 50% was recorded in Table 2 below respectively.

[0107] Also, after stabilizing at 180 °C for 30 minutes, the RPM value of the stirring shaft was adjusted, and the viscosity value when the torque had a 50% value was recorded in Table 2 below respectively.

[0108]

Table 2

[0109] <Manufacture of Acrylic Adhesive> 15% by weight of the adhesion - imparting resin of Examples 1 to 9 and Comparative Examples 1 to 3 was mixed with 85% by weight of an acrylic polymer to produce acrylic adhesives respectively.

[0110] <Evaluation Example 4. Evaluation of Transparency and Adhesive Strength (65 mJ Condition and 100 mJ Condition)> <Evaluation of Transparency> An aluminum container with a depth of 1 cm was prepared, on the inner bottom of which characters were described such that they could be confirmed by an observer looking down from above the container. Specific characters (e.g., English letters A, B, or C) were described on the inner bottom of the aluminum container so that the observer could confirm them. Then, the adhesion - imparting resins of Examples 1 to 9 and Comparative Examples 1 to 3 were each filled into their respective aluminum containers.

[0111] Then, the aluminum containers filled with the adhesion - imparting resins were observed from above to below, and it was evaluated whether the characters described on the inner bottom of the aluminum containers could be confirmed. Taking Comparative Example 1 as a reference (denoted as O), if it was easier to confirm the characters, it was evaluated as ◎, if the confirmation was less easy, it was evaluated as △, and if the confirmation was impossible, it was evaluated as X. The evaluation results were described in Table 3 below.

[0112] <Evaluation of Adhesive Strength> It was measured using a UTM machine (Universal testing machine). First, the acrylic adhesives produced from the adhesion - imparting resins of Examples 1 to 9 and Comparative Examples 1 to 3 were each coated on a PET film to a thickness of 50 μm to produce tapes.

[0113] After UV irradiation by an exposure device, it was attached to a SUS - 304 steel plate. After the part where the PET film was attached was mounted on a UTM grip (a gripping tool of the universal testing machine), it was measured at a speed of 30 mm / min. At this time, the numerical value input into the UTM equipment means the adhesive strength (N / in).

[0114]

Table 3

[0115] As shown in Table 3 above, when the transparency and adhesive strength of the acrylic adhesives each containing the adhesion-imparting resin according to Examples 1 to 11 and Comparative Examples 1 to 3 are compared respectively, The acrylic adhesives containing the adhesion-imparting resin according to Examples 1 to 11 are excellent in compatibility with the acrylic polymer, and the transparency and adhesive strength are simultaneously improved compared to the acrylic adhesives containing the adhesion-imparting resin according to Comparative Examples 1 to 3.

[0116] The above-described Examples and Comparative Examples are illustrative for explaining the present invention, and the present invention is not limited thereto. Those skilled in the art can implement the present invention in more various modifications, and thus the technical protection scope of the present invention will have to be determined by the appended claims.

Claims

1. Repeating unit (a) derived from a petroleum resin monomer; Repeating unit (b) derived from a (meth)acrylic monomer; and As a molecular weight regulating unit, it contains a repeating unit (c) derived from α-methylstyrene, An adhesion-imparting resin having a weight average molecular weight of 2,000 g / mol or less.

2. The adhesion-imparting resin according to claim 1, wherein the petroleum resin monomer contains a C9 fraction monomer.

3. The adhesion-imparting resin according to claim 2, wherein the C9 fraction monomer contains a styrene monomer represented by the following chemical formula 1: <Chemical formula 1> In the chemical formula 1, a1 is an integer from 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, a hydroxyl group, a cyano group, C １ -C ２０ An alkyl group, C １ -C ２０ Substituted with an alkoxy group or any combination thereof, or unsubstituted C ６ -C ２０ Is an aryl group.

4. The adhesion-imparting resin according to claim 2, wherein the C9 fraction monomer contains a styrene monomer.

5. The adhesion-imparting resin according to claim 1, wherein the (meth)acrylic monomer is represented by the following chemical formula 2: <Chemical formula 2> Among the 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 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 with an alkoxy group or any combination thereof, or unsubstituted C ６ -C ２０ is an aryl group.

6. The adhesion-imparting 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.

7. The adhesion-imparting resin according to claim 1, wherein the ratio of the content of the repeating unit (c) derived from α-methylstyrene to the content of the repeating unit (a) derived from the petroleum resin monomer is from 0.1 to 10.

8. The adhesion-imparting resin according to claim 1, wherein the ratio of the content of the repeating unit (c) derived from α-methylstyrene to the content of the repeating unit (a) derived from the petroleum resin monomer is from 0.5 to 4.

9. The content of the repeating unit (a) derived from the petroleum resin monomer is 5 to 40% by weight based on the total weight of the adhesion-imparting resin, The content of the repeating unit (b) derived from the (meth)acrylic monomer is 5 to 80% by weight based on the total weight of the adhesion-imparting resin, The content of the repeating unit (c) derived from α-methylstyrene is 10 to 60% by weight based on the total weight of the adhesion-imparting resin.

10. The weight average molecular weight (Mw) of the adhesion-imparting resin is 700 to 1,500 g / mol, and the adhesion-imparting resin according to claim 1.

11. The number average molecular weight (Mn) of the adhesion-imparting resin is 1,000 g / mol or less, The Z average molecular weight (Mz) of the adhesion-imparting resin is 7,000 g / mol or less, The PDI (Polymer Dispersity Index) of the adhesion-imparting resin is 1 to 3, and the adhesion-imparting resin according to claim 1.

12. The softening point of the adhesion-imparting resin is 40 to 120 °C, and the adhesion-imparting resin according to claim 1.

13. The viscosity (cps) of the adhesion-imparting resin at 160 °C is 20 to 200 cps, The viscosity (cps) at 180 °C is 1 to 100 cps, and the adhesion-imparting resin according to claim 1.

14. The molar% of the repeating unit (b) derived from the (meth)acrylic monomer, measured via NMR of the adhesion-imparting resin, is 1 to 70 mol%, The aromaticity (%) measured via NMR of the adhesion-imparting resin is 30 to 99%, and the adhesion-imparting resin according to claim 1.

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