Resin composition

Abstract

To provide a resin composition having high stability against a solvent comprising an alcohol.SOLUTION: There is provided a resin composition comprising the following components (a) to (c), wherein the resin composition has a peak area ratio A / B×100 of 60% or more and a peak area ratio A / C×100 of 45% or more in the infrared spectral measurement, where A is a peak area derived from a hydroxyl group, B is a peak area derived from a methylene group and C is a peak area derived from a carbonyl group: component (a) is a chlorinated polyolefin resin having a chlorine content of 10 to 50 wt.%; component (b) is an epoxy-based compound; and component (c) is an antioxidant.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a resin composition. [Background technology]

[0002] Thermoplastic resins, taking advantage of their property of being deformed by heat, are used in various forms of products by molding them into fixed shapes such as spheres, cylinders, boxes, etc., as well as flat shapes such as sheets and films. However, since thermoplastic resins are basically transparent, relatively soft, and easily scratched, their surfaces are printed or painted for the purpose of protection or improving their appearance.

[0003] Thermoplastic resins are classified into polar and non-polar resins. Among non-polar resins, polyolefin resins such as polypropylene and polyethylene have been widely adopted in recent years because they are inexpensive and have many excellent properties such as moldability, chemical resistance, water resistance, electrical properties, and safety.

[0004] However, unlike polar resins such as acrylic resins and polyester resins, polyolefin resins are non-polar and crystalline, and therefore have the problem that inks, paints, adhesives, etc. do not adhere easily to them.

[0005] As a method for improving the above-mentioned problems related to adhesion, a method has been proposed in which polyolefin resin is contained in ink, paint, adhesive, etc. Since chlorinated polyolefin resin has low solubility in solvents other than aromatic ones, it has been common to use it by dissolving it in an aromatic solvent such as toluene.

[0006] In recent years, from the viewpoint of environmental issues, there has been a demand for chlorinated polyolefin resin compositions using solvents that do not contain aromatic solvents such as toluene at painting and printing sites. In response to this demand, it has been proposed to subject chlorinated polyolefin resins to an oxidation treatment in order to increase the polarity of the resin and improve its solubility in alcohol-based solvents (see Patent Document 1). [Prior art documents] [Patent documents]

[0007] [Patent Document 1] International Publication No. 2014 / 057608 Summary of the Invention [Problem to be solved by the invention]

[0008] As environmental awareness grows year by year, there is a demand for chlorinated polyolefin resins that are stably soluble in larger amounts of alcohol-based solvents. However, the oxidation-treated chlorinated polyolefin resins disclosed in Patent Document 1 have insufficient stability in solvent compositions containing alcohol-based solvents, and further improvements are required.

[0009] Therefore, an object of the present invention is to provide a chlorinated polyolefin resin composition which has better solubility in alcohol-based solvents than conventional chlorinated polyolefin resin compositions. [Means for solving the problem]

[0010] The present invention provides the following [1] to [4]. [1] A resin composition comprising the following components (a) to (c), wherein the resin composition has a peak area ratio A / B×100 of 60% or more and a peak area ratio A / C×100 of 45% or more in infrared spectroscopy measurement: (where A is the peak area derived from the hydroxyl group, B is the peak area derived from the methylene group, and C is the peak area derived from the carbonyl group.) Component (a): chlorinated polyolefin resin having a chlorine content of 10 to 50% by weight Component (b): Epoxy compound Ingredient (c): Antioxidant [2] The resin composition according to [1], wherein the weight average molecular weight of component (a) is 1,000 to 50,000. [3] The resin composition according to [1], wherein component (c) contains a phenol-based antioxidant. [4] A paint, binder, adhesive, or ink comprising the resin composition according to [1]. Effect of the Invention

[0011] According to the present invention, it is possible to provide a chlorinated polyolefin resin composition which has good adhesion to polyolefin resins and is more soluble in alcohol-based solvents than conventional compositions. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] <Resin composition> The resin composition of the present invention comprises component (a): a chlorinated polyolefin resin having a chlorine content of 10 to 50% by weight, component (b): an epoxy compound, and component (c): an antioxidant, and in infrared spectroscopy measurement, the peak area ratio A / B×100 is 60% or more, and the peak area ratio A / C×100 is 45% or more.

[0013] A is the peak area due to hydroxyl groups, usually at a wavelength of 3265 cm -1 ~3616cm -1 B is the peak area derived from the methylene group, usually at a wavelength of 1400 cm -1 ~1500cm -1 C is the peak area derived from the carbonyl group, usually at a wavelength of 1657 cm -1 ~1845cm -1 is the peak area.

[0014] The peak area ratio A / B×100 is 60% or more, preferably 70% or more, and more preferably 80% or more. The upper limit of the peak area ratio A / B×100 is not limited, but is usually 110% or less.

[0015] The peak area ratio C / B×100 is from 100 to 180%, and preferably from 120 to 150%.

[0016] The peak area ratio A / C×100 is 45% or more, and preferably 50% or more. The upper limit of the peak area ratio A / C×100 is not limited, but may be 100% or more.

[0017] When A / B×100 and A / C×100 of the resin composition are within the above ranges, the resin composition has sufficient solubility in a solvent composition containing an alcohol-based solvent.

[0018] The reason why the resin composition of the present invention exhibits excellent effects is presumed to be as follows. Since the resin composition satisfies the above ranges of A / B×100, C / B×100, and A / C×100, more hydrogen bonds are formed between the alcohol-based solvent and the resin composition, thereby improving the affinity between the alcohol-based solvent and the resin composition. Therefore, the resin composition of the present invention has good solubility in a solvent composition containing a polar solvent such as alcohol.

[0019] The infrared spectrum and peak area of ​​the resin composition of the present invention can be measured for a resin composition containing at least a chlorinated polyolefin resin, an epoxy stabilizer, and an antioxidant. That is, the infrared spectrum and peak area of ​​the resin composition of the present invention include the infrared spectrum and peak area of ​​not only the chlorinated polyolefin resin but also the epoxy stabilizer and the antioxidant.

[0020] The method for producing the resin composition of the present invention is not particularly limited, but it can be produced by mixing a chlorinated polyolefin resin solution, an epoxy compound, and an antioxidant.

[0021] <Component (a): Chlorinated polyolefin resin> The chlorine content of the chlorinated polyolefin resin of the present invention is preferably 10 to 50% by weight, more preferably 20 to 40% by weight, and even more preferably 30 to 40% by weight. When the chlorine content is 10% by weight or more, sufficient solubility can be exhibited in a composition containing an alcohol-based solvent. On the other hand, when the chlorine content is 50% by weight or less, good adhesion to a polyolefin-based substrate can be maintained. The chlorine content is a value measured in accordance with JIS-K7229. Examples of alcohol-based solvents include ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, and cyclohexanol.

[0022] The polyolefin resin used as a raw material for the chlorinated polyolefin resin of the present invention is not particularly limited, but examples thereof include crystalline polypropylene, amorphous polypropylene, ethylene-propylene copolymer, ethylene-propylene-α-olefin copolymer, and propylene-α-olefin copolymer.

[0023] Ethylene-propylene-α-olefin copolymer and propylene-α-olefin copolymer are resins obtained by copolymerizing ethylene-propylene and propylene as main components with α-olefin, respectively. There is no particular limitation on the form of the copolymer, and examples thereof include block copolymers and random copolymers. Examples of the α-olefin component include ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and 4-methyl-1-pentene. When a propylene-α-olefin copolymer is used as a raw material, the content of the propylene component is preferably 50 mol% or more in terms of adhesion to polyolefin resins.

[0024] The polyolefin resin used as the raw material for the chlorinated polyolefin resin of the present invention may be one type alone or a combination of two or more types. The melting point of the polyolefin resin is preferably 100 to 180°C, more preferably 120 to 170°C.

[0025] The weight average molecular weight of the chlorinated polyolefin resin of the present invention is preferably 3,000 to 200,000, more preferably 5,000 to 100,000, and more preferably 5,000 to 50,000. By having a weight average molecular weight of 3,000 or more, the cohesive force of the resin and the adhesion to the substrate can be kept good. By having a weight average molecular weight of 200,000 or less, the compatibility with other resins can be kept good. The weight average molecular weight of the chlorinated polyolefin resin of the present invention is a value measured by gel permeation chromatography (GPC) using polystyrene resin as the standard.

[0026] The chlorinated polyolefin resin of the present invention may be an acid-modified chlorinated polyolefin resin into which an α,β-unsaturated carboxylic acid and / or a derivative thereof is introduced. Examples of the α,β-unsaturated carboxylic acid and its derivative include maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, mesaconic acid, itaconic acid, itaconic anhydride, aconitic acid, aconitic anhydride, himic anhydride, (meth)acrylic acid, and (meth)acrylic acid ester. The amount of the α,β-unsaturated carboxylic acid and / or its derivative introduced is not particularly limited, but is preferably 0 to 20% by weight, more preferably 0 to 10% by weight, based on 100% by weight of the chlorinated polyolefin resin.

[0027] The method for producing the chlorinated polyolefin resin of the present invention is not particularly limited, but the following production method can be exemplified.

[0028] The first example is as follows. First, polyolefin resin is dispersed or dissolved in a medium such as water, carbon tetrachloride, or chloroform. Then, at least one gas selected from air, oxygen, and ozone is blown in during or before or after a normal chlorination reaction at a temperature range of 50 to 120°C under pressure or normal pressure in the presence of a catalyst or under irradiation of ultraviolet light. This makes it possible to obtain a chlorinated polyolefin resin having a hydroxyl group and a carbonyl group introduced therein. If the reaction temperature during blowing in the gas (e.g., oxygen) is set high, the molecular weight reduction (degradation) due to the scission of the polymer chain progresses quickly. Therefore, in the case of blowing in the gas for the purpose of degradation, it is preferable that the reaction temperature is high. On the other hand, by setting the reaction temperature low, the peak area ratio A / C×100 tends to increase.

[0029] The second example is as follows. First, a polyolefin resin having hydroxyl and carbonyl groups introduced therein by thermal degradation and ultraviolet irradiation in air is dispersed or dissolved in a medium such as water, carbon tetrachloride, or chloroform. Then, gaseous chlorine is blown in at a temperature range of 50 to 120°C under pressure or normal pressure in the presence of a catalyst or under ultraviolet irradiation. This allows a chlorinated polyolefin resin having hydroxyl and carbonyl groups introduced therein to be obtained.

[0030] Moreover, a chlorinated polyolefin resin having hydroxyl groups and carbonyl groups introduced therein can also be obtained by combining the above two methods.

[0031] The amount of hydroxyl groups and carbonyl groups introduced into the chlorinated polyolefin resin can be controlled by appropriately adjusting conditions such as reaction temperature and reaction time.

[0032] <Component (b): Epoxy stabilizer> A stabilizer is usually added to the chlorinated polyolefin resin. An epoxy compound is preferable as the stabilizer. Examples of the epoxy compound include compounds having an epoxy equivalent of about 100 to 500 and having one or more epoxy groups per molecule. Examples of the epoxy compound include the following compounds: epoxidized vegetable oils (epoxidized soybean oil, epoxidized linseed oil, etc.) obtained by epoxidizing vegetable oils having natural unsaturated groups with peracids such as peracetic acid; epoxidized fatty acid esters obtained by epoxidizing unsaturated fatty acids such as oleic acid, tall oil fatty acid, and soybean oil fatty acid; epoxidized alicyclic compounds such as epoxidized tetrahydrophthalate; epoxidized glycidyl ether, ethylene glycol glycidyl ether, propylene glycol glycidyl ether, and glycidyl ether obtained by condensing bisphenol A or polyhydric alcohol with epichlorohydrin. Polyethers such as cholesteryl glycidyl ether, neopentyl glycol diglycidyl ether, glycerol polyglycidyl ether, and sorbitol polyglycidyl ether; and monoepoxy compounds such as ethers such as butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, sec-butylphenyl glycidyl ether, tert-butylphenyl glycidyl ether, and phenol polyethylene oxide glycidyl ether. Examples of the stabilizer include stabilizers used as stabilizers for polyvinyl chloride resins. Examples of the stabilizer include metal soaps such as calcium stearate and lead stearate, organometallic compounds such as dibutyltin dilaurate and dibutyl maleate, and hydrotalcite compounds. Among the above, preferred are neopentyl glycol diglycidyl ether and glycerol polyglycidyl ether.

[0033] The stabilizer may be used alone or in combination of two or more kinds. When a stabilizer is added, the amount of the stabilizer added is preferably 1 to 20% by weight (solid content equivalent) relative to the chlorinated polyolefin resin, and more preferably 10 to 20% by weight.

[0034] <Component (c): Antioxidant> The chlorinated polyolefin resin in the present invention preferably contains an antioxidant. Examples of the antioxidant include phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants, and phenol-based antioxidants are preferred.

[0035] Examples of phenol-based antioxidants include 2-methyl-4,6-bis[(octylthio)methyl]-phenol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,6-di-tert-butyl-p-cresol, 2,4-bis-(α,α-dimethylbenzyl)phenol, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and the like. propionate, thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide], 2,4-dimethyl-6-(1-methylpentadecyl)phenol, diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate, 3, 3',3'',5,5',5''-Hexa-tert-butyl-α,α',α''-(mesitylene-2,4,6-triyl)tri-p-cresol, Ethylene bis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], Hexamethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-tert-butyl- 4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazine-2-ylamino)phenol, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenylacrylate, 2,4-di-tert-butylphenol. Among these, 2-methyl-4,6-bis[(octylthio)methyl]-phenol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octyl 3-[4-hydroxy-3,5-bis(propan-2-yl)phenyl]propanoate are more preferred.

[0036] Examples of phosphorus-based antioxidants include monophosphite compounds (e.g., triphenyl phosphite, trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, tris(nonylphenyl)phosphite) and diphosphite compounds (e.g., distearyl pentaerythritol diphosphite, tetra(tridecyl)-1,1,3-tris(2-methyl-5-tert-butyl-4-hydroxyphenyl)butane diphosphite). Among these, triphenyl phosphite is preferred, and tris(2,4-tert-butylphenyl)phosphite is more preferred.

[0037] Examples of sulfur-based antioxidants include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, pentaerythritol-tetrakis-(β-lauryl-thio-propionate), and 3,9-bis(2-dodecylthioethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane.

[0038] The antioxidant may be used alone or in combination of two or more kinds. When an antioxidant is added, the amount of the antioxidant added is preferably 0.01 to 5% by weight (solid content equivalent) relative to the chlorinated polyolefin resin, and more preferably 0.05 to 1% by weight.

[0039] The resin composition of the present invention is useful as a component of an ink composition. The ink composition is preferably an ink composition for gravure printing or an ink composition for flexographic printing. The content of the chlorinated polyolefin resin in the ink composition for offset printing or the ink composition for flexographic printing is preferably 1 to 30% by weight. In view of the object of the present invention, it is preferable that the ink composition further contains an alcohol-based solvent. When the ink composition contains an alcohol-based solvent, the content of the alcohol-based solvent is usually about 1 to 30% by weight of the total solvent in the ink composition, but by using the chlorinated polyolefin resin of the present invention, it is possible to contain up to about 50% by weight. In addition to the chlorinated polyolefin resin and the alcohol-based solvent, the ink composition may contain components that are usually contained in ink compositions as necessary.

[0040] The gravure printing ink composition of the present invention can be printed on various substrates by gravure printing. The flexographic printing ink composition of the present invention can be printed on various substrates by flexographic printing. Examples of substrates include paper and resin films. The gravure printing method and the flexographic printing method can be performed according to the respective information. EXAMPLES

[0041] The present invention will be described in detail below with reference to examples. The following examples are provided to better explain the present invention, but are not intended to limit the present invention. The methods for measuring physical properties are as described below unless otherwise specified.

[0042] [Weight average molecular weight (Mw)] The resins produced in the Production Examples were measured by GPC under the following conditions. Equipment: HLC-8320GPC (Tosoh Corporation) Column: TSK-gel G-6000H×L, G-5000H×L, G-4000H×L, G-3000H×L, G-2000H×L (manufactured by Tosoh Corporation) Eluent: Tetrahydrofuran Flow rate: 1mL / min Temperature: Pump oven, column oven 40℃ Injection volume: 100μL Standard material: Polystyrene EasiCal PS-1 (Agilent Technology, Inc.)

[0043] [Chlorine content (%)] The measurements were carried out according to JIS-K7229:1995.

[0044] [Solution stability test] 15 g of the resin composition (solid matter) obtained in the examples and comparative examples was dissolved in 15 g of ethyl acetate to prepare a 50 wt% ethyl acetate solution, and 30 g of this solution was taken in a 100 mL glass sample bottle. 11 g of isopropyl alcohol (IPA) was added to this, and after thorough stirring, the solution was left to stand for more than 1 hour to confirm the state of the solution. Thereafter, 2 g of isopropyl alcohol was added at a time, and the state of the solution was similarly confirmed and evaluated. All of the above operations were carried out in a room maintained at 25°C.

[0045] <Example 1> 5.0 kg of crystalline polypropylene (melting point: 125°C) produced using a metallocene catalyst as a polymerization catalyst was placed in a glass-lined reaction vessel, 33 L (liters, the same applies below) of chloroform was added, and the mixture was thoroughly dissolved at a temperature of 97°C under a pressure of 0.25 MPa. Then, 5.0 g of t-butylperoxy-2-ethylhexanoate was added, and a chlorination reaction was carried out while controlling the pressure inside the vessel at 0.2 MPa, to obtain a reaction liquid with a chlorine content of 33% by weight. During the chlorination reaction, oxygen was blown in. The reaction liquid obtained here was coated on a KBr plate, dried, and measured at 400 cm using an infrared spectrophotometer (FT-IR-4100, JASCO Corporation). -1 ~4000cm -1 The infrared absorption spectrum of the compound was measured and analyzed using the attached software (Spectro Manager, JASCO Corporation). As a result, the 3265 cm -1 ~3616cm -1 The area enclosed by the spectral curve and the baseline is A, and the 1400 cm -1The area enclosed by the spectrum curve at 1500 cm-1 and the baseline is B, and the area at 1657 cm-1 originating from the carbonyl group is C. -1 ~1845cm -1 When the area surrounded by the spectrum curve and the baseline is C, A / B×100 was 43% and C / B×100 was 69%. Next, an epoxy compound was added to the obtained reaction solution as a stabilizer at 15% by weight relative to the resin, and Irganox 1520L was added as an antioxidant at 0.1% by weight relative to the resin. Chloroform was removed using a vented twin-screw extruder equipped with a vent port for distilling off the reaction solvent under reduced pressure, and the chlorinated polyolefin resin was extruded in the form of strands and cooled with water. The mixture was then pelletized using a water-cooled pelletizer to obtain a solid chlorinated polyolefin resin. The chlorine content of the obtained chlorinated polyolefin resin was 34%. The weight average molecular weight (Mw) of the obtained chlorinated polyolefin resin calculated by the standard polystyrene conversion method using gel permeation chromatography (GPC; HLC8320GPC, manufactured by Tosoh Corporation) was 10,000.

[0046] <Example 2> The same procedure as in Example 1 was repeated except that, as antioxidants, Irganox 1010 was used in place of Irganox 1520L at 0.1% by weight based on the resin, and Adeka STAB PEP-36A was used at 0.1% by weight based on the resin.

[0047] <Example 3> The same procedure as in Example 1 was repeated, except that Irganox 1135 was used as the antioxidant in place of Irganox 1520L, at 0.1% by weight based on the resin.

[0048] <Comparative Example 1> The same procedure as in Example 1 was carried out except that no antioxidant was added.

[0049] Table 1 shows the compounding compositions and test results of the examples and comparative examples.

[0050] [Table 1]

[0051] From the results in Table 1, it can be seen that Examples 1 to 3 have better solution stability than Comparative Example 1, which does not use an antioxidant. Since the solution stability in alcohol-containing solvents is better as A / B is larger, it is presumed that the addition of an antioxidant prevents a decrease in the area ratio of B / A due to the thermal history of the twin-screw extruder. Among them, Example 1, which uses Irganox 1520L as the antioxidant, has extremely good solution stability compared to Examples 2 and 3, and the stability continues even after one day. From the above results, it can be seen that the resin composition of the present invention exhibits high solution stability in alcohol-containing solvents.

Claims

1. A resin composition comprising the following components (a) to (c), wherein the resin composition has a characteristic that, when measured by infrared spectroscopy, The peak area ratio A / B×100 is 60% or more, The peak area ratio A / C×100 is 45% or more. Resin composition. (wherein A is the peak area derived from a hydroxyl group, B is the peak area derived from a methylene group, C is the peak area due to the carbonyl group. Component (a): A chlorinated polyolefin resin having a chlorine content of 10 to 50% by weight. Component (b): Epoxy compound Component (c): Antioxidant

2. The resin composition according to claim 1, wherein the weight average molecular weight of component (a) is 1,000 to 50,000.

3. The resin composition of claim 1 , wherein component (c) comprises a phenolic antioxidant.

4. A paint, a binder, an adhesive, or an ink, comprising the resin composition according to claim 1.

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