Adhesion-imparting 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] This invention relates to a tackifying resin. [Background technology]

[0002] Adhesives are used as fastening materials in a wide range of fields, including automobiles, electronic products, and building materials.

[0003] For example, in automobile manufacturing, adhesives are used to secure interior components to the inside of a vehicle. Also, in the manufacturing of electronic devices such as mobile phones and liquid crystal displays, adhesives are used to secure cushioning materials placed inside electronic products to protect them from impact, to secure exterior components of electronic products, and to secure components that make up image display devices such as liquid crystal displays, organic EL displays, and PDPs.

[0004] Regarding the aforementioned adhesives, there is a shift from solvent-based adhesives to water-based adhesives from the perspective of reducing environmental impact, and recently, among water-based media, water-based acrylic adhesives in which acrylic polymers are dispersed are preferred.

[0005] In general, acrylic adhesives are often used in combination with tackifying resins to further improve their adhesive properties, such as bonding strength and constant load holding capacity.

[0006] However, in the case of tackifying resins, if the compatibility with the acrylic polymer contained in the acrylic adhesive deteriorates, the adhesive becomes opaque, the photocuring reaction does not proceed easily, and the heat resistance also deteriorates.

[0007] Therefore, the need for tackifying resins with excellent compatibility with acrylic polymers is increasing. [Overview of the Initiative] [Problems that the invention aims to solve]

[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 petroleum resin - based monomers, repeating units (b) derived from α - methylstyrene, and repeating units (c) derived from (meth) acrylic monomers, 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 an 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 a photoinitiator increases, and the heat resistance of the adhesive is improved.

Brief Description of the Drawings

[0013] [Figure 1] It is a graph of the results of measuring the UV absorbance of the adhesion - imparting resin according to the examples and comparative examples.

Modes 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 should not be interpreted in a manner limited to their ordinary but dictionary definitions, but rather in a manner consistent with the technical idea of ​​the present invention, based on the principle that inventors may suitably define the concepts of terms in order to best describe their invention.

[0016] The terms used in this invention are used solely to describe specific embodiments and are not intended to limit the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this invention, terms such as “includes” or “having” are used to specify the existence of features, numbers, stages, operations, components, parts, or combinations thereof described in the specification, and should not be understood to preemptively exclude the possibility of the existence or addition of one or more other features, numbers, stages, operations, components, parts, or combinations thereof.

[0017] Specifically, one aspect of the present invention relates to a tackifying resin comprising repeating units (a) derived from a petroleum resin monomer; repeating units (b) derived from α-methylstyrene; and repeating units (c) derived from a (meth)acrylic monomer, wherein hydrogen is added to at least some of the unsaturated bonds contained in the repeating units (a) to (c).

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

[0019] The hydrogenation reaction described above means that hydrogen is added to the double or triple bonds of a molecule having unsaturated bonds to saturate its valence. The hydrogenation reaction can be 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 added to only some of the bonds. In this invention, hydrogenation means that hydrogen is added to at least some of the unsaturated bonds contained in the repeating unit (a) to the repeating unit (c), resulting in a state in which the valence is saturated.

[0020] In one specific example, the addition of hydrogen to at least some of the unsaturated bonds contained in the repeating units (a) to (c) reduces the ultraviolet absorbance of the tackifying resin. When the ultraviolet absorbance of the tackifying resin decreases, the amount of ultraviolet light reaching the photopolymerization initiator contained in the adhesive containing the tackifying resin increases. This improves the heat resistance (SAFT) of the adhesive containing the tackifying resin.

[0021] In one specific example, the petroleum resin monomer may contain a liquid C5 to C20 fraction, diolefin, or dicyclopentadiene that is suitable for practical use.

[0022] According to other specific examples, the petroleum resin monomer may contain a C5 fraction, a C9 fraction, a diolefin, or dicyclopentadiene.

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

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

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

[0026] In one specific example, the petroleum resin monomer may contain a C9 fraction.

[0027] In one specific example, the C9 fraction may contain styrene monomers.

[0028] For example, the styrene monomer is represented by the following chemical formula 1.

[0029] <Chemical formula 1> JPEG0007852094000001.jpg40170

[0030] Of the above chemical formula 1, a1 is an integer between 0 and 5. R1 is 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 C1-C substituted or unsubstituted with aryl groups or any combination thereof 20 Alkyl or C1-C 20 Alkoxy group; or Deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, C1-C 20 Alkyl alkyl group, C1-C 20 C6-C substituted or unsubstituted with an alkoxy group or any combination thereof 20 It is an aryl group.

[0031] In one specific example, R1 and R2 are independently 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, 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] In one specific example, R1 and R2 are independently 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 between 0 and 5.

[0034] In one specific example, the styrene monomer may contain styrene.

[0035] In one specific example, the tackifying resin may contain repeating units (b) derived from α-methylstyrene.

[0036] In one specific example, the tackifying resin may contain repeating units (b) derived from α-methylstyrene as molecular weight adjustment units. For example, when the tackifying resin contains repeating units (b) derived from α-methylstyrene, the weight-average molecular weight of the tackifying resin decreases. As a result, the tackifying resin of the present application satisfies a weight-average molecular weight of 5,000 g / mol or less or 3,000 g / mol, improving compatibility and reactivity with the base polymer described later. This further improves the transparency and heat resistance of the adhesive containing the tackifying resin.

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

[0038] For example, the tackifying resin contains repeating units represented by the following chemical formula 1-1, in which hydrogen is added to at least some of the unsaturated bonds contained in the repeating units (a) and (b).

[0039] <Chemical formula 1-1> JPEG0007852094000002.jpg50170

[0040] Of the above chemical formulas 1-1, a11 is an integer between 0 and 5. R 11 and R 12 These 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 C1-C substituted or unsubstituted with aryl groups or any combination thereof 20 Alkyl or C1-C 20 Alkoxy group; or Deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, C1-C 20 Alkyl alkyl group, C1-C 20 C6-C substituted or unsubstituted with an alkoxy group or any combination thereof 20 It is an aryl group.

[0041] For example, in the chemical formula 1-1, R 11 is hydrogen, R 12 It can also be a hydrogen or a methyl group.

[0042] In one specific example, since the tackifying resin contains repeating units represented by the chemical formula 1-1, the tackifying resin can be polymerized by i) using a hydrogenated petroleum resin monomer or hydrogenated α-methylstyrene, ii) forming a polymer by polymerizing a petroleum resin monomer and α-methylstyrene, and then undergoing a hydrogenation reaction, or iii) forming a polymer by polymerizing a petroleum resin monomer, α-methylstyrene, and (meth)acrylic monomer, and then undergoing a hydrogenation reaction.

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

[0044] <Chemical formula 1-2> JPEG0007852094000003.jpg45170

[0045] Of the above chemical formulas 1 and 2, a11 is an integer between 0 and 5. R 11 and R 12 These 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 C1-C substituted or unsubstituted with aryl groups or any combination thereof 20 Alkyl or C1-C 20 Alkoxy group; or Deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, C1-C 20 Alkyl alkyl group, C1-C 20 C6-C substituted or unsubstituted with an alkoxy group or any combination thereof 20 It is an aryl group.

[0046] In one specific example, of the chemical formulas 1-2, R 11 is hydrogen, R 12 It can also be a hydrogen or a methyl group.

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

[0048] <Chemical formula 2> JPEG0007852094000004.jpg35170

[0049] Of the chemical formula 2 mentioned above, R2 and R3 are independently 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, C6-C 20 C1-C substituted or unsubstituted with aryl groups or any combination thereof 20 Alkyl or C1-C 20 Alkoxy group; or Deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, C1-C 20 Alkyl alkyl group, C1-C 20 C6-C substituted or unsubstituted with an alkoxy group or any combination thereof 20 It is an aryl group.

[0050] In one specific example, R3 and R4 are independently 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, C6-C 20Methyl 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 alkyl group, C6-C 20 These are phenyl, naphthyl, anthracenyl, phenantrenyl, or pyrenyl groups, substituted or unsubstituted with an aryl group or any combination thereof.

[0051] In one specific example, 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.

[0052] According to other specific examples, R3 can be either a hydrogen atom or a methyl group.

[0053] In one specific example, R4 can be 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, or tert-hexyl group.

[0054] According to other specific examples, R4 can be either a methyl group or an ethyl group.

[0055] In 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] In one specific example, the content of repeating units (a) derived from petroleum resin monomers may be less than or equal to the content of repeating units (b) derived from α-methylstyrene. For example, the content of repeating units (a) derived from petroleum resin monomers is less than the content of repeating units (b) derived from α-methylstyrene.

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

[0058] In one specific example, the content of repeating units (a) derived from petroleum resin monomers is 10 to 50% by weight relative to the total weight of the tackifying resin, the content of repeating units (b) derived from α-methylstyrene is 10 to 80% by weight relative to the total weight of the tackifying resin, and the content of repeating units (c) derived from (meth)acrylic monomers is 5 to 40% by weight relative to the total weight of the tackifying resin.

[0059] For example, the content of repeating units (a) derived from petroleum resin monomers 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 relative to the total weight of the tackifying resin.

[0060] For example, the content of repeating units (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 relative to the total weight of the tackifying resin.

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

[0062] In one specific example, the weight-average molecular weight (Mw) of the tackifying resin may be 3,000 g / mol or less. For example, the weight-average molecular weight (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.

[0063] In one 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] In one 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] In one 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] In one specific example, the degree of dispersion (PDI) of the tackifying resin can be 1 to 3. For example, the degree of dispersion (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 1.31 to 1.9.

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

[0070] In one specific example, 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.

[0071] In one specific example, 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.

[0072] In one specific example, 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.

[0073] To give one specific example, 1 The mol% of repeating units (b) derived from the (meth)acrylic monomer, as 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%, based on the total number of moles of repeating units derived from the monomer contained in the tackifying resin.

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

[0075] In one specific example, the aromaticity of the tackifying resin before hydrogenation, as measured by NMR, can be between 1% and 90%.

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

[0077] In one specific example, the UV absorbance of the tackifying resin at wavelengths of 240 nm to 260 nm (in THF solvent, at a concentration of 70 ppm) may be 0.1 or less. For example, the UV absorbance refers to the average absorbance value measured in response to ultraviolet light at wavelengths of 240 nm to 260 nm after dissolving the tackifying resin in THF solvent to a concentration of 70 ppm.

[0078] A further aspect of the present invention is the ability to provide a method for producing a tackifying resin comprising a petroleum resin monomer; α-methylstyrene; and a (meth)acrylic monomer, wherein the UV absorbance at a wavelength of 240 nm to 260 nm (THF solvent, concentration 70 ppm) is 0.1 or less.

[0079] In 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 some of the unsaturated bonds contained in the first polymer to produce a partially hydrogenated first polymer composition. Next, a (meth)acrylic monomer is added to the partially hydrogenated first polymer composition to prepare a second monomer composition. Next, the second monomer composition is thermally polymerized and a degassing reaction is carried out to produce a tackifying resin.

[0080] According to other specific examples, 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 perform a partial hydrogenation reaction in which hydrogen is added to some of the unsaturated bonds contained in the second polymer, and then a degassing reaction is carried out to produce a tackifying resin.

[0081] In other specific examples, 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 the first polymer. 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 and a degassing reaction is carried out to produce a tackifying resin.

[0082] For example, the vinyl monomer includes the vinylcycloalkane monomer. For example, the vinyl monomer includes vinylcyclopentane monomer, vinylcyclohexane monomer, or a combination thereof. For example, the vinyl monomer is represented by the following chemical formulas 1-2.

[0083] For example, the type, content and physical properties of the petroleum resin monomer, the (meth)acrylic monomer, and the α-methylstyrene, as well as the physical properties of the tackifying resin, should be referenced from the above description.

[0084] For example, in the monomer composition, the monomer refers to the remaining components of the monomer composition, excluding the solvent.

[0085] In one specific example, the monomer composition may further contain a solvent.

[0086] For example, the solvent includes xylene.

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

[0088] In one specific example, the catalytic polymerization may be carried out at a temperature of 100°C or lower. 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.

[0089] In one specific example, the thermal polymerization may be carried out in a temperature range of 150 to 300°C. For example, the thermal polymerization may 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.

[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 to 20 minutes.

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

[0092] In one specific example, the hydrogenation reaction can be carried out in the presence of a hydrogenation catalyst. For example, the hydrogenation catalyst may include a palazine-based catalyst.

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

[0094] In one specific example, the aforementioned tackifying resin can be applied to adhesives. In another specific example, the aforementioned tackifying resin can be applied to acrylic adhesives.

[0095] Another aspect of the present invention is to provide an adhesive comprising the aforementioned tackifying resin. For example, the tackifying resin imparts tackiness to the adhesive.

[0096] In one specific example, the adhesive may include the tackifying resin and the base polymer. For example, the adhesive is an acrylic adhesive comprising the tackifying resin and an acrylic polymer. For example, the tackifying resin has excellent compatibility with the base polymer, such as an acrylic polymer, and provides excellent transparency and adhesive strength to the adhesive.

[0097] In one specific example, the adhesive may be a photocurable adhesive.

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

[0099] In one specific example, the photopolymerization initiator is benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, benzyl diphenyl disulfide, benzyl dimethyl ketal, Ciba Specialty Chemicals It may be one or more selected from the group consisting of the Irgacure series manufactured by Chemicals, anthraquinone, naphthoquinone, 3,3-dimethyl-4-methoxybenzophenone, benzophenone, pivalon ethyl ether, 1,1-dichloroacetophenone, pt-butyldichloroacetophenone, hexaarylimidazole dyma, 2,2'-diethoxyacetophenone, 2,2'-diethoxy-2-phenylacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, phenylglyoxylic acid, α-hydroxyisobutylphenone, dibenzospan, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-propanone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, tribromophenylsulfone, triarylphosphine oxide, and tribromomethylphenylsulfone. For example, the photopolymerization initiator is included in the adhesive in an amount of 0.01 to 10% by weight or 0.02 to 5% by weight.

[0100] In 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 other specific examples, 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] In one specific example, the adhesive is transparent. In this case, light is uniformly transmitted through the adhesive, allowing the photocuring reaction to proceed uniformly. This further improves the heat resistance and other properties of the adhesive.

[0103] In one specific example, the adhesive may include a base polymer, a tackifying resin, and a photopolymerization initiator. In this case, the tackifying resin has a low absorbance to ultraviolet light, increasing the amount of ultraviolet light reaching the photopolymerization initiator, and further promoting the polymerization reaction by light irradiation. This improves the adhesive strength and shear strength of the adhesive containing the tackifying resin.

[0104] [Definition of Terms] In this specification, C1-C 20 Alkyl groups refer to monovalent aliphatic hydrocarbon groups with 1 to 20 carbon atoms, either linear or branched. Specific examples 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, and tert-decyl groups. In this specification, C1-C 20 The alkylene group is the C1-C 20 This refers to a divalent group that has the same structure as an alkyl group.

[0105] In this specification, C1-C 20 The alkoxy group is -OA101 (where A101 is the C1-C 20This refers to a monovalent group having the chemical formula alkyl group, and specific examples include the methoxy group, ethoxy group, and isopropyloxy group.

[0106] In this specification, C6-C 20 The aryl group refers to a monovalent group having a carbon-cyclic aromatic system with 6 to 20 carbon atoms, and includes phenyl, naphthyl, anthracenyl, phenantrenyl, or pyrenyl groups. 20 If the aryl group contains two or more rings, these two or more rings can be linked to each other.

[0107] The present invention will be described in more detail below with reference to examples. These examples are provided to illustrate the present invention in more detail, and it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples.

[0108] Example 1. Production of tackifying resin A 2,000 ml chemical reactor equipped with a stirrer, reflux condenser, thermometer, and nitrogen injection device was injected with styrene (SM) and α-methylstyrene (AMS) in the amounts shown in Table 1 below (SM: 280 g, AMS: 420 g). Xylene, the solvent, was then injected in a weight ratio of 1:1 to the sum of the weights of styrene and α-methylstyrene (AMS) to prepare the first composition. After adding 0.1% by weight of catalyst BF3 to the first monomer composition, polymerization was carried out at 30°C for 120 minutes, and then 10 g of calcium hydroxide was added to neutralize the mixture to produce the first polymer composition.

[0109] Next, 280 g of 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 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 (MA:350 g) shown in Table 1, and xylene, the solvent, was further injected in a weight ratio of 1:1 with methyl acrylate (MA) to prepare the second composition. Then, the second composition was thermally polymerized at a temperature of 240°C for 2 hours to produce the second polymer composition.

[0111] 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 a tackifying resin.

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

[0113] When the target for hydrogenation is the first polymer composition, the first polymer composition, which is a polymer of styrene and α-methylstyrene, is hydrogenated. When the target for hydrogenation is a second polymer composition, a second polymer composition is prepared by adding methyl acrylate (MA) to a polymer of styrene and α-methylstyrene, and then the prepared second polymer composition is hydrogenated.

[0114] [Table 1]

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

[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 resins were measured by dissolving each of the tackifying resins produced in Examples 1 to 10 and Comparative Examples 1 to 3 in tetrahydrofuran to a concentration of 4000 ppm, then injecting 100 μl of each solution into a GPC. The GPC mobile phase was tetrahydrofuran, flowed at a rate of 1.0 mL / min, and measured at 30°C. Three Agilent PIgel columns (1,000 + 500 + 100 Å) were connected in series. An RI detector (Hewlett-Packard HP-1047A) was used as the detector and measured at 30°C. The measurement results are shown in Table 2 below.

[0117] Evaluation Example 2: Measurement of Softening Point The softening point of each tackifying resin produced in Examples 1 to 10 and Comparative Examples 1 to 3 was measured using the ring and ball softening method (ASTME28). The resin was melted and poured into an annular mold, which was then placed in a beaker containing glycerin. A ball was then placed on the ring containing the resin, and the temperature was increased by 2.5°C per minute. The temperature at which the resin melted and the ball fell (softening point) was measured and recorded in Table 2 below.

[0118] Evaluation Example 3. Measurement of UV (240 to 262 nm) absorbance level After placing THF into a UV measurement cell and performing calibration, solutions with a concentration of 70 ppm were prepared by blending the tackifying resins produced in Examples 1 to 10 and Comparative Examples 1 to 3 with THF, respectively. Next, after placing these solutions into the UV measurement cell, the UV measurement device was set to absorption mode, and the absorbance levels at wavelengths of 200 to 350 nm were measured. The measurement results are shown in Figure 1 and Table 2 below, respectively.

[0119] [Table 2]

[0120] Manufacturing of acrylic adhesives Each of the following acrylic adhesives was prepared by mixing 15% by weight of the tackifying resin from Examples 1 to 10 and Comparative Examples 1 to 3 with 85% by weight of the acrylic polymer, and then adding 1% by weight of the photopolymerization initiator.

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

[0122] (1) Measurement of adhesive strength Measurements were taken using UTM equipment.

[0123] First, an acrylic adhesive containing the tackifying resin described in 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. Next, after irradiating with 65 mJ of UV light via an exposure device, the tape was attached to a SUS 304 steel plate. After attaching the portion with the PET film to a UTM grip, measurements were taken at a speed of 30 mm / min. At this time, the value input to the UTM equipment represents 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 tackifying resins according to Examples 1 to 10 and Comparative Examples 1 to 3 was evaluated by the ASTM D3654 method.

[0125] Each test piece tape, coated with 20 to 30 micrometers of the aforementioned acrylic adhesive, was cut to approximately 2 inches x 6 inches. Each cut test piece was attached to release paper to create a 1-inch wide by 2-inch long piece, which was then attached to a cleaned SUS304 steel plate (at this time, the non-adhering portion was attached to be at least 2 cm, and the portion necessary for measurement was pressed by passing the roll back and forth once using a roll-down machine manufactured by Cheminstruments). The non-adhering portion of the test piece was cut with scissors so that approximately 2 cm remained attached to the SUS304 steel plate. The non-adhering test piece was placed in a cohesion measurement ring and adhered to the test piece passing through it. Using the lateral edge of the SUS304 steel plate to which the test piece was attached with fixing adhesive tape as a reference, two pieces were attached parallel to each other on the front and back sides, and two pieces were secured parallel to each other between the cohesion measurement ring and the SUS304 steel plate using a stapler. The test specimen was cut so that it could be attached to a SUS 304 steel plate with dimensions of 1 inch wide and 1 inch high.

[0126] The specimen was placed on a stainless steel plate stand inside a shear test oven. A 1 kg weight was suspended from a holding power measuring ring attached to the specimen. The oven temperature was then increased to 0.4 °C / min, and the temperature at which the weight fell was recorded in Table 3 below.

[0127] [Table 3]

[0128] As shown in Table 3 above, when comparing the adhesive strength of acrylic adhesives containing the tackifying resins of Examples 1 to 10 and Comparative Examples 1 to 3, the acrylic adhesives containing the tackifying resins of Examples 1 to 10 exhibited excellent compatibility with the acrylic polymer, and the low UV absorption rate contained in the tackifying resin increased the amount of ultraviolet light reaching the photopolymerization initiator, thereby promoting the photopolymerization reaction. As a result, the acrylic adhesives containing the tackifying resins of Examples 1 to 10 showed improved adhesive strength and shear adhesion compared to the acrylic adhesives containing the tackifying resins of Comparative Examples 1 to 3.

[0129] The examples and comparative examples described above are illustrative for illustrating the present invention, and the present invention is not limited thereto. Those skilled in the art can implement the present invention in a variety of ways; therefore, the scope of technical protection of the present invention must be defined by the appended claims.

Claims

1. Repeating units (a) derived from petroleum resin monomers, Repeating unit (b) derived from α-methylstyrene, A tackifying resin comprising a repeating unit (c) derived from a (meth)acrylic monomer, At least some of the unsaturated bonds contained in the repeating unit (a) to the repeating unit (c) are to which hydrogen is added. The content of repeating units (a) derived from petroleum resin monomers is 10 to 50% by weight relative to the total weight of the tackifying resin. The content of repeating units (b) derived from α-methylstyrene is 10 to 80% by weight relative to the total weight of the tackifying resin. The content of repeating units (c) derived from (meth)acrylic monomers is 5 to 40% by weight relative to the total weight of the tackifying resin. The weight-average molecular weight (Mw) of the tackifying resin is 2,000 g / mol or less. Petroleum resin monomers are given by the following chemical formula 1: <Chemical formula 1> Of the above chemical formula 1, a1 is an integer between 0 and 5. R1 is hydrogen or a C1-C20 alkyl group; Includes styrene monomers as indicated, Adhesion-enhancing resin.

2. The tackifying resin according to claim 1, wherein hydrogen is added to at least some 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 comprises styrene.

4. The (meth)acrylic monomer is the tackifying resin according to claim 1, represented by the following chemical formula 2: <Chemical formula 2> Of the chemical formula 2 mentioned above, R ２ and R ３ These 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, C ６ -C ２０ C substituted or unsubstituted with an aryl group or any combination thereof １ -C ２０ Alkyl 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 1, wherein the (meth)acrylic monomer comprises 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.

6. 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 tackifying resin according to claim 1, wherein the PDI (Polymer Dispersity Index) of the tackifying resin is 1 to 3.

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

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

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