KR101808404B1 - Analytical Method and System for Monomer of Acrylate Adhesive - Google Patents
Analytical Method and System for Monomer of Acrylate Adhesive Download PDFInfo
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- KR101808404B1 KR101808404B1 KR1020160002651A KR20160002651A KR101808404B1 KR 101808404 B1 KR101808404 B1 KR 101808404B1 KR 1020160002651 A KR1020160002651 A KR 1020160002651A KR 20160002651 A KR20160002651 A KR 20160002651A KR 101808404 B1 KR101808404 B1 KR 101808404B1
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- eha
- sensitive adhesive
- acrylate
- pressure
- analysis
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- 239000000178 monomer Substances 0.000 title claims abstract description 128
- 238000004458 analytical method Methods 0.000 title claims abstract description 68
- 239000000853 adhesive Substances 0.000 title claims description 23
- 230000001070 adhesive effect Effects 0.000 title claims description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title abstract description 98
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims abstract description 130
- 238000000034 method Methods 0.000 claims abstract description 32
- 238000000045 pyrolysis gas chromatography Methods 0.000 claims abstract description 31
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 88
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 86
- 238000004445 quantitative analysis Methods 0.000 claims description 19
- 229920001577 copolymer Polymers 0.000 claims description 13
- 230000000379 polymerizing effect Effects 0.000 abstract description 7
- 239000000523 sample Substances 0.000 description 37
- 239000000203 mixture Substances 0.000 description 22
- 238000005481 NMR spectroscopy Methods 0.000 description 21
- 238000011088 calibration curve Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 17
- 238000000197 pyrolysis Methods 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 238000004008 high resolution magic-angle spinning Methods 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 239000002313 adhesive film Substances 0.000 description 7
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 230000001681 protective effect Effects 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 239000012790 adhesive layer Substances 0.000 description 5
- 238000005979 thermal decomposition reaction Methods 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000010835 comparative analysis Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000004949 mass spectrometry Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 238000000371 solid-state nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- 238000012565 NMR experiment Methods 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- KCAMXZBMXVIIQN-UHFFFAOYSA-N octan-3-yl 2-methylprop-2-enoate Chemical compound CCCCCC(CC)OC(=O)C(C)=C KCAMXZBMXVIIQN-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000000538 analytical sample Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000001880 high-resolution magic angle spinning nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229940030980 inova Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000013365 molecular weight analysis method Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- VFHDDANHQLKHJQ-UHFFFAOYSA-N prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C VFHDDANHQLKHJQ-UHFFFAOYSA-N 0.000 description 1
- 238000005143 pyrolysis gas chromatography mass spectroscopy Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
- G01N30/7206—Mass spectrometers interfaced to gas chromatograph
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/86—Signal analysis
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/44—Resins; Plastics; Rubber; Leather
- G01N33/442—Resins; Plastics
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/84—Preparation of the fraction to be distributed
- G01N2030/8405—Preparation of the fraction to be distributed using pyrolysis
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- General Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
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Abstract
The present invention provides a method for confirming the monomer content ratio of an acrylate-based pressure-sensitive adhesive polymerized with two or more kinds of acrylate monomers, comprising the steps of: (1) preparing a pressure-sensitive adhesive obtained by polymerizing the same acrylate monomers as the acrylate- (2) pyrolysis GC / MS analysis of the acrylate-based pressure-sensitive adhesive using the standard product prepared in the step (1); And (3) normalizing the analysis result of the step (2) to confirm the weight ratio of the two or more kinds of acrylate monomers. And a method for analyzing the amount of monomers of an acrylate-based pressure-sensitive adhesive.
Description
The present invention relates to a monomer quantitative analysis method and an analysis system of an acrylate-based pressure-sensitive adhesive.
Pressure-sensitive adhesive (PSA) is an important material used for attaching surfaces between various substrates through adhesion and cohesion properties. PSA is mainly characterized by its fast tack properties, its adhesion property with the surface of the substrate when adhered to the substrate surface, and its cohesion property between the PSA and the PSA. Due to these properties, PSA is widely used in electronic devices, optical materials, and automotive materials.
As a general analytical method for such a pressure sensitive adhesive, pyrolysis-pyrolysis-gas chromatography mass spectrometry (Py-GC / MS) including on-line derivatization was used to detect the composition of the acrylic monomer, the content of each monomer contained in the pressure-sensitive adhesive is analyzed by nuclear magnetic resonance (HR-MAS) analysis using HR-MAS (high resolution-magic angle spinning) NMR.
However, the HR-MAS solid-state NMR equipment used in this analysis method is not expensive and can not be universally used in production facilities such as factories or general laboratories. Therefore, it is necessary and necessary to find a method for analyzing and quantifying the composition of acrylic monomers in equipment that is less expensive than HR-MAS solid phase NMR and can be used universally.
As Py-GC / MS, Py-GC / MS can be considered as an equipment which can be used at lower cost and general use than HR-MAS solid phase NMR. However, Py-GC / The composition of the pyrolysates was analyzed and used only for the qualitative analysis such as analysis of the monomer component constituting the polymer.
Therefore, it is necessary to investigate analytical methods that can generally use the monomer content analysis of acrylate pressure-sensitive adhesive in a general laboratory by examining such Py-GC / MS quantitatively and obtaining information on pyrolysis efficiency.
The present invention can accurately analyze the content of monomers contained in an acrylate-based pressure sensitive adhesive using Py-GC / MS, which is inexpensive and universally usable without expensive equipment such as HR-MAS solid state NMR equipment And a method for quantitatively analyzing a monomer of an acrylate-based pressure-sensitive adhesive.
For the above purpose,
The present invention provides a method for confirming the monomer content ratio of an acrylate-based pressure-sensitive adhesive polymerized with two or more kinds of acrylate monomers, comprising the steps of: (1) preparing a pressure-sensitive adhesive obtained by polymerizing the same acrylate monomers as the acrylate- (2) pyrolysis GC / MS analysis of the acrylate-based pressure-sensitive adhesive using the standard product prepared in the step (1); And (3) normalizing the analysis result of the step (2) to confirm the weight ratio of the two or more kinds of acrylate monomers. And a method for quantitatively analyzing a monomer of an acrylate-based pressure-sensitive adhesive.
The present invention also provides a system for confirming a monomer content ratio of an acrylate-based pressure-sensitive adhesive polymerized with two or more acrylate monomers, comprising: (1) preparing a pressure-sensitive adhesive obtained by polymerizing the same acrylate monomers as the acrylate- module; (2) a module for pyrolytic C / MS analysis of the acrylate-based pressure-sensitive adhesive using the standard product prepared in the step (1); And (3) a module for standardizing the analysis results of step (2) to determine the weight ratio of the two or more kinds of acrylate monomers. Based on the weight of the acrylate-based pressure-sensitive adhesive.
The present invention also provides a computer readable recording medium on which a program for executing the above method is recorded.
According to the monomer quantitative analysis method of the acrylate-based pressure-sensitive adhesive of the present invention, the content of monomers contained in the acrylate-based pressure-sensitive adhesive can be analyzed using Py-GC / MS, which is an inexpensive and generally available equipment.
Further, according to the method for quantitative analysis of monomers of the acrylate-based pressure-sensitive adhesive of the present invention, one-point calibration using one standard product or calibration The amount of monomers contained in the acrylate adhesive can be accurately analyzed by a five-point calibration.
1 is a graph showing the EGA-MS experimental data of the acrylate-based pressure sensitive adhesive prepared in the synthesis example of the present invention.
2 is a view showing a decomposition mechanism of the acrylate-based pressure-sensitive adhesive of the present invention by thermal decomposition.
3 is a graph showing the calibration curves of ethylhexyl acrylate (EHA) and butyl acrylate (BA) monomer standard solutions according to the pyrolyzer temperatures of the acrylate-based pressure sensitive adhesive of Comparative Example 1 of the present invention Graph.
4 is a graph showing a pyrogram of an acrylate pressure-sensitive adhesive according to a pyrolyzer temperature of an acrylate-based pressure-sensitive adhesive of Comparative Example 1 of the present invention.
5 is a graph showing a calibration curve obtained using an acrylate-based pressure-sensitive adhesive of Comparative Example 2 of the present invention.
6 is a graph typically showing 1H HR-MAS solid phase NMR spectrum using an acrylate pressure-sensitive adhesive of Comparative Example 2 of the present invention.
7 is a graph showing the results of weight ratio analysis of EHA and BA monomers of an acrylate-based pressure-sensitive adhesive of Comparative Example 2 of the present invention.
8 is a schematic diagram showing the difference in the thermal decomposition rate of the pressure-sensitive adhesive according to the EHA and BA content ratios of the present invention.
9 is a graph showing the results of weight ratio analysis of EHA and BA monomers of the acrylate-based pressure-sensitive adhesive of Example 1 of the present invention.
10 is a graph showing a calibration curve obtained using the acrylate-based pressure-sensitive adhesive of Example 2 of the present invention.
11 is a graph showing the results of analysis of weight ratios of EHA and BA monomers of the acrylate-based pressure-sensitive adhesive of Example 2 of the present invention.
Hereinafter, the present invention will be described in detail. The following detailed description is merely an example of the present invention, and therefore, the present invention is not limited thereto.
In the present invention, pyrolysis GC / MS analysis is carried out using a standard product which is known to contain two or more kinds of acrylate monomers contained in an acrylate-based pressure-sensitive adhesive, and the results of the analysis are standardized so that the weight ratio of the two or more acrylate monomers Monomer (I) / acrylate monomer (II)) in a quantitative manner.
In recent years, pressure sensitive adhesive (PSA) has been studied as an important material for attaching the surface between various substrates through adhesive force and bonding force characteristic. Particularly, PSA is widely used for electronic devices, optical materials, and automobile materials because it has a high interface adhesion ability, a capability of not sticking away from the substrate surface when the PSA is adhered to the surface of the substrate, and a cohesive ability that does not fall between the PSA .
Therefore, there is a need for a technique for analyzing the quantitative content of monomers constituting the pressure-sensitive adhesive. However, in the prior art, it is not necessary to prepare a separate calibration curve using an inexpensive and generally available apparatus, There has been a lack of a technique capable of accurately analyzing the content of monomers contained in the acrylate-based pressure-sensitive adhesive by one-point calibration or five-point calibration using an acrylate-based pressure-sensitive adhesive.
Accordingly, the inventors of the present invention discovered that the above problems can be solved by analyzing a pressure-sensitive adhesive obtained by polymerizing acrylate monomers of the same type as the acrylate-based pressure-sensitive adhesive to be analyzed as a standard product by Py-GC / MS.
For this purpose, the present invention relates to a method for confirming the monomer content ratio of an acrylate-based pressure-sensitive adhesive polymerized with two or more kinds of acrylate monomers, comprising the steps of: (1) preparing a pressure sensitive adhesive obtained by polymerizing the same acrylate monomers as the acrylate- ; (2) pyrolysis GC / MS analysis of the acrylate-based pressure-sensitive adhesive using the standard product prepared in the step (1); And (3) standardizing the analysis results of the step (2) to determine the weight ratio of the two or more kinds of acrylate monomers.
The present invention relates to a monomer quantitative analysis method of an acrylate-based pressure-sensitive adhesive for confirming a monomer content ratio of an acrylate-based pressure-sensitive adhesive polymerized with two or more acrylate monomers.
The pressure-sensitive adhesive used in the present invention is an acrylate-based pressure-sensitive adhesive obtained by polymerizing an acrylate-based pressure-sensitive adhesive, specifically, two or more acrylate monomers, and may be a copolymer containing two or more acrylate diacrylates as monomers.
The two or more acrylate monomers may be selected from the group consisting of ethylhexyl acrylate (EHA), butyl acrylate (BA), methyl acrylate (MA), ethyl acrylate (EA), ethyl (2) selected from the group consisting of ethylhexyl methacrylate (EHMA), butyl methacrylate (BMA), methyl methacrylate (MMA) and ethyl methacrylate (EHA) and butyl acrylate (BA) can be preferably used.
First, the monomer quantitative analysis method of the acrylate-based pressure-sensitive adhesive of the present invention comprises the steps of (1) preparing a pressure-sensitive adhesive on which the same acrylate monomers as the acrylate-based pressure-sensitive adhesive are polymerized.
The pyrolysis mechanism of the acrylate resin can be classified into depolymerization, chain cleavage, and elimination as shown in FIG. 2 below. In the case of acrylate resin, the component reduced by the depolymerization And the composition of the polymer resin can be analyzed.
At this time, depending on the ratio of the two or more kinds of acrylate monomers contained in the acrylate-based pressure sensitive adhesive to be analyzed, the thermal decomposition rate of the depolymerization of the thermal decomposition mechanism of the acrylate copolymer constituting the acrylate-based pressure sensitive adhesive varies. The method for quantitative determination of monomers of the acrylate-based pressure sensitive adhesive of the present invention is based on this point and is characterized in that a pressure sensitive adhesive known to have the same monomer as the two or more acrylate monomers constituting the acrylate- The exact monomer content ratio can be obtained by GC / MS analysis.
In this case, the standard product to be prepared in the step (1) may be the same as or different from the acrylate-based pressure-sensitive adhesive of the comparative analysis object in the ratio of two or more kinds of acrylate monomers. When the ratio of two or more kinds of acrylate monomers in the standard product is the same as that of the acrylate-based adhesive in the comparative analysis, it can be standardized by one-point calibration in the step (3) described later. Further, when the ratio of the two or more kinds of acrylate monomers in the standard product is different from that of the acrylate-based adhesive in the comparative analysis, standardization can be performed by a five-point calibration method in the step (3) described below.
For example, as a method for using a pressure-sensitive adhesive having the same ratio of an acrylate-based pressure-sensitive adhesive and two or more acrylate monomers as a standard product as described above, the protective film of the pressure-sensitive adhesive film using the acrylate- After that, the adhesive layer may be taken and analyzed.
Next, the monomer quantitative analysis method of the acrylate-based pressure-sensitive adhesive of the present invention includes (2) pyrolysis GC / MS analysis of the acrylate-based pressure sensitive adhesive using the standard prepared in the step (1).
The analyzer used in the Py-GC / MS analysis in the monomer quantitative analysis method of the acrylate pressure-sensitive adhesive of the present invention is not particularly limited as long as it is an analyzer used for gas chromatography and mass spectrometry, (PY-2010iD, Frontier Laboratories) and columns (Ultra ALLOY + -5 ((5% -10%)) columns, preferably GC / MS (Agilent 7890A GC system, 5975C inert XL mass selective detector, Agilent Technologies Korea) Phenyl) -methylpolysiloxane) metal column (0.25 mm ID x 30 m L., film coated with 0.25 um thick film, Frontier Laboratories).
In the monomer quantitative analysis method of the acrylate-based pressure-sensitive adhesive of the present invention, pyrolysis GC / MS analysis in the step (2) can be pyrolyzed at a pyrolysis temperature of 500 to 700 ° C, more preferably 550 to 650 ° C Pyrolysis temperature conditions.
The method for quantitative analysis of monomers of the acrylate-based pressure sensitive adhesive of the present invention includes the step of (3) standardizing the analysis result of the step (2) to confirm the weight ratio of the two or more kinds of acrylate monomers.
In the monomer quantitative analysis method of the acrylate-based pressure-sensitive adhesive of the present invention, the method of standardizing the analysis result of the step (2) is not particularly limited as long as the weight ratio of the two or more kinds of acrylate monomers can be confirmed, The analysis results of step (2) may be calibrated at one-point or five-point to analyze the content of the two or more acrylate monomers, The weight ratio of two or more kinds of acrylate monomers can be confirmed.
Specifically, in step (3), when the ratio of two or more kinds of acrylate monomers in the standard product to be prepared is the same as that of the acrylate-based adhesive to be analyzed, standardization can be performed by one-point calibration, If you do not know the monomer ratio, you can standardize it with a five-point calibration.
As described above, the monomer quantitative analysis method of the acrylate-based pressure-sensitive adhesive of the present invention can be applied to a one-point calibration using one standard product without preparing a separate calibration curve, or a five-point calibration using a calibration curve it is possible to accurately analyze the content of monomers contained in the acrylate-based pressure-sensitive adhesive by a five-point calibration.
delete
The present invention provides a computer-readable recording medium on which a program for executing the analysis method is recorded.
The present invention also provides a system for confirming a monomer content ratio of an acrylate-based pressure-sensitive adhesive polymerized with two or more acrylate monomers, comprising: (1) preparing a pressure-sensitive adhesive obtained by polymerizing the same acrylate monomers as the acrylate- module; (2) a module for performing pyrolysis GC / MS analysis of the acrylate-based pressure-sensitive adhesive using the standard product prepared in the step (1); And (3) a module for standardizing the analysis result of the step (2) to determine the weight ratio of the two or more kinds of acrylate monomers.
In the monomer quantitative analysis system of the acrylate-based pressure-sensitive adhesive, description of the overlapping structure with the monomer quantitative analysis method of the acrylate-based pressure-sensitive adhesive is the same.
Also, in the present invention, the term module refers to a unit for processing a specific function or operation, which can be realized by hardware, software, or a combination of hardware and software.
Hereinafter, the present invention will be described in more detail with reference to examples. However, the embodiments of the present invention described below are illustrative only and the scope of the present invention is not limited to these embodiments. The scope of the present invention is indicated in the claims, and moreover, includes all changes within the meaning and range of equivalency of the claims.
Example
Acrylate series Manufacture of Adhesive
[Synthesis Example]
Ethylhexyl acrylate (EHA) and butyl acrylate (BA) were added in a weight ratio as shown in Table 1 below using ethyl acetate as a solvent, 500 ppm of AIBN (2,2'-azo-bis-diisobutyronitrile) was added as a reagent and the mixture was polymerized at 65 ° C for 5 hours. After the polymerization was completed, the viscosity was maintained at 1000 to 2000 cP by adding an additional ethyl acetate solvent to control viscosity suitable for the coating. The prepared adhesive solution was coated on the surface of the PET film with a thickness of 25 μm using a bar coater and dried in an oven at 120 ° C. for 5 minutes to remove the solvent and unreacted monomers. After drying, a releasing film (PET) having different peeling force was laminated on the coated surface to produce a pressure-sensitive adhesive film having a releasing film on both sides.
In this experiment, as shown in the following Table 1, five different types of ethylhexyl acrylate and butyl acrylate used in the production of the pressure sensitive adhesive were used.
(weight%)
BA: butyl acrylate
EHA: Ethylhexyl acrylate
[Example 1]
In order to use a pressure sensitive adhesive having the composition ratio of the same monomers as those of the five kinds of pressure sensitive adhesives prepared in Synthesis Example as a standard product, the protective film of the five kinds of pressure sensitive adhesive films prepared in Synthesis Example 1 was removed and the pressure sensitive adhesive layer was taken, micro-balance, transferred to a sample cup and analyzed by Py-GC / MS. Thereafter, the adhesive film of the five kinds of pressure sensitive adhesives prepared in Synthesis Example 1 was removed in the same manner, and the pressure sensitive adhesive layer was measured with a micrometer balance of about 1 mg each, transferred to a sample cup, and subjected to Py-GC / MS analysis , The contents of EHA and BA monomers were analyzed and standardized by a one-point calibration to obtain a weight ratio.
[Example 2]
In order to use a pressure sensitive adhesive having a different composition ratio as a standard product, the protective film of the five types of pressure sensitive adhesive films prepared in Synthesis Example 1 was removed and the pressure sensitive adhesive layer was taken. Respectively. Thereafter, the adhesive layer of each of the five pressure sensitive adhesives prepared in Synthesis Example 1 was removed in the same manner, and about 1 mg of the pressure sensitive adhesive layer was measured with a minute balance and transferred to a sample cup. Py-GC / MS analysis Respectively. In the case of analyzing the pressure sensitive adhesives having different composition ratios by a standard product, the five-point calibration curve shows the composition ratio (NMR analysis data) of the EHA or BA monomers on the x axis and the area ratio ((area of EHA or BA ) / (Total area of EHA and BA)), and the area ratio obtained from the sample was substituted into the calibration curve, and the content of EHA and BA monomer was analyzed and standardized to obtain a weight ratio.
[Comparative Example 1]
EHA and BA monomers were used to make a standard product calibration curve and a standard product solution was prepared to quantify the monomer produced from the pyrolysis product of the pressure-sensitive adhesive. EHA and BA were transferred to a 50-mL volumetric flask at a dose of 1500 mg, 2500 mg, 3500 mg and 6000 mg, respectively, and the weight was accurately measured up to 0.1 mg and filled up to the mark with acetonitrile. Each standard solution was injected into a Py-GC / MS using a liquid sampler at 1 μL to obtain a chromatogram. After removal of the protective film, the adhesive layer was transferred to a sample cup and measured by Py-GC / MS. The area counts of the detected EHA and BA were substituted into the calibration curve, and the content of each monomer was determined and standardized to obtain a weight ratio.
[Comparative Example 2]
A sample C (EHA50 BA50) pressure-sensitive adhesive was used in the above synthetic examples in order to prepare a standard product calibration curve of EHA and BA by using a monomer produced by pyrolysis from the pressure-sensitive adhesive polymer. After transferring 150 mg, 250 mg, 400 mg and 600 mg each to a 40 mL vial, weigh accurately to 0.1 mg, add 5 mL of ethyl acetate, and shake for 2 hours to completely dissolve the adhesive. The standard solution was transferred to a sample cup with 10 μL using a 50 μL syringe, and the ethyl acetate was dried and analyzed by Py-GC / MS. After removal of the protective film, the adhesive layer was transferred to a sample cup and measured by Py-GC / MS. The EHA and BA contents obtained by substituting in the calibration curve were standardized to obtain a weight ratio.
Experimental Example
Analysis condition
(One) Py - GC / MS analysis
An Agilent 7890A GC system equipped with a 5975C inert XLz mass selective detector from Agilent Technologies, Inc. (Agilent Technologies, USA) was used for the analysis and a pyrolyzer was used with a PY-2010iD from Frontier Laboratories Inc. (Fukushima, Japan). After the GC oven temperature was maintained at 50 ° C for 5 minutes at the set pyrolyzer temperature (500 ° C, 600 ° C, 700 ° C), the temperature was raised to 320 ° C at 20 ° C per minute and left for 5 minutes to obtain a chromatogram (total operating time: 23.5 min).
Column: Ultra ALLOY + -5 ((5% -phenyl) -methylpolysiloxane) metal column (0.25 mm ID × 30 mm L., film coated with 0.25 μm thickness, Frontier Laboratories, Japan)
Carrier gas: He
Column flow rate: 1 mL / min
Split ratio of injector: 1/50
MSD scan mode: 20-600m / z.
(2) Gel Permeation Chromatography (GPC) analysis
The GPC analysis was carried out by removing the protective film from each of the adhesive films, completely dissolving the adhesive layer in tetrahydrofuran (THF) at a concentration of 1 mg / mL, and filtering it with a 0.45 μm membrane filter as an analytical sample . Each sample solution was injected into GPC to obtain a chromatogram and a calibration curve of a cubic equation was obtained using polystyrene standards of 3900000, 723000, 316500, 70950, 31400, 8450, 3940, and 485 Da, Relative molecular weight and molecular weight distribution were calculated by substituting the retention time of the sample solution. GPC was analyzed using Agilent 1200 HPLC with a refractive index (RI) detector. Two Polymer Lab mixed B columns were connected and THF was analyzed with a solvent at a flow rate of 1.0 mL / min. The amount of sample used for GPC analysis was 100 μL and the analysis time was 25 minutes.
(3) Nuclear Magnetic Resonance (NMR) analysis
1H HR-MAS NMR experiments were performed using Agilent's
EHA and BA -OCH 2 - proton peaks: 4.25-3.66 ppm
Aliphatic proton peaks of EHA and BA: 2.52-0.52 ppm
In order to calculate the molar ratio between BA and EHA through 1 H HR MAS NMR spectrum, if the number of moles of EHA is A and the number of moles of BA is B, the area value of -OCH 2 - proton peaks in NMR spectrum is 2A + 2B, The area value of the peak is 18A + 10B. The relative molar ratios of A and B, ie, EHA and BA, were calculated by solving these equations in a simultaneous equations. The molar number of BA was divided by the number of moles of EHA to show the calculated molar ratio based on EHA 1.00 mole. The molar ratio calculated from the above was multiplied by the molecular weight (EHA (mw 184), BA (mw 128)) of each structure, and the weight was determined.
(4) Evolved Gas Analysis-Mass Spectrometry (EGA-MS) analysis
(PY-2020iD double-shot pyrolyzer, manufactured by Mitsubishi Rayon Co., Ltd.) with an ALLOY-DTM deactivated metal column (0.15 mm ID x 2.5 m L. with a coated film thickness of 0.01 μm, Frontier Laboratories, Fukushima, Japan) Frontier Laboratories) and an Agilent 7890A GC system (Agilent Technologies Korea, Seoul, South Korea) equipped with a 5975C inert XL mass selective detector (MSD). The sample of the adhesive was transferred into a sample cup at 400 and the pyrogram was obtained by raising the temperature of the pyrolyzer from 100 째 C to 20 째 C per minute up to 600 째 C (total operation time: 25 minutes). The remaining EGA-MS analysis conditions are as follows.
Carrier gas: He
Column flow rate: 1 mL / min
Split ratio of injector: 1/50
Temperature of injector oven and interface of GC / MS: 300 ° C
Interface temperature of pyrolyzer: 320 ℃
MSD scan mode: 20-600m / z.
Analysis
1. Evolved Gas Analysis-Mass Spectrometry (EGA-MS) analysis
EGA-MS analysis was performed to compare the pyrolysis patterns of the five acrylate-based pressure-sensitive adhesives prepared in the above Synthesis Examples according to the temperature rise temperature
The results of analyzing the thermal decomposition pattern of the pressure-sensitive adhesive while raising the temperature from 100 ° C to 600 ° C at a rate of 20 ° C per minute are shown in FIG. Pyrolysis began to take place at 260 ° C, peaking at 390 ° C, and pyrolysis at 550 ° C being complete. The pyrolysis efficiency of the pressure - sensitive adhesive at 500 ℃, 600 ℃ and 700 ℃ was examined based on the pyrogram and pyrolysis temperature was selected for monomer quantitative analysis.
2. Comparative Example Analysis for 1
EHA and BA monomers were used as standards and the pyrolysis temperature was changed to 500 ° C., 600 ° C. and 700 ° C., a calibration curve was formed. As a result, a good linearity was obtained as shown in FIG. 3, and a least square regression factor At least 0.991.
FIG. 4 shows the result of analyzing sample C (EHA50 BA50) while changing the temperature of the pyrolyzer to 500 ° C, 600 ° C and 700 ° C. In FIG. 4, A shows the result of pyrolyzer chromatogram of a monomer standard at 600 ° C, and B, C and D show the results of fatigue of sample C (EHA50 BA50) at 500 ° C, 600 ° C and 700 ° C, Gram results.
As the temperature increased, the amount of oligomers detected was relatively small due to the large amount of pyrolysis. At 700 ℃, depolymerization of EHA and BA depolymerized much, and the amount of monomer detected was considerably reduced. EHA and BA were detected with similar sensitivity at 500 ℃ and 600 ℃, and 600 ℃, which is a small fraction of oligomers detected by pyrolysis, was found to be the optimum condition for pyrolysis.
As a result of analyzing the monomer content ratio of sample C (EHA50 BA50) with EHA and BA monomers as standard products, it was found that the accuracy was lacking as compared with NMR data as shown in Table 2 below, and the depolymerized EHA and BA Was less than 2%.
(° C)
(RSD%)
(30.4)
(34.3)
(19.0)
(34.0)
(34.6)
(15.7)
3. Comparative Example Analysis for 2
The results of the analysis using EHA and BA monomers as standard products in Comparative Example 1 were inconsistent with the NMR results, and as in Comparative Example 2, samples EHA50 BA50 adhesive films were used as reference materials and depolymerized EHA and BA And a calibration curve was prepared according to the weight. Then, the content calculated from the pressure-sensitive adhesive sample was standardized, and the weight ratio was calculated to calculate the weight ratio of the monomers of the pressure-sensitive adhesive films having different composition ratios.
The pyrolysis temperature of the pyrolyzer was set at 600 ° C. As a result of preparing a calibration curve using Sample C (EHA50 BA50) as a standard product, it showed good linearity as shown in Fig. 5 and had a least square regression factor of at least 0.998 or more.
The results of the analysis of Comparative Example 2 are shown in Table 3 below. Sample C (EHA50 BA50) was BA: EHA = 50.8: 49.2 similar to NMR (BA: EHA = 51.1: 48.9) That is, when the BA content was 30%, it was analyzed as 32.8%, and when the BA content was 10%, the deviation increased to 17.6%. 33.6% for 30% of EHA, and 17.6% for 10% of EHA. During the analysis, the inter-sample precision was reproducible by RSD% of 0.8 to 7.1% in three measurements (Table 3).
In addition, molecular weight analysis by GPC analysis showed that the BA increased as the BA content was increased, but the reactivity of BA was somewhat better than that of EHA, resulting in an increase in the polymer chain. The results of NMR analysis were similar to those used for polymerization, and the reactivity of BA was relatively higher than that of EHA by about 1%. The results of a representative 1 H HR-MAS solid phase NMR spectrum are shown in FIG.
(RSD%)
(7.1)
(1.5)
(6.6)
(3.2)
(0.8)
(0.9)
(1.1)
(2.2)
(1.3)
(6.1)
(4.49)
(4.82)
(4.61)
(4.24)
(3.68)
7 is a graph showing the results of weight ratio analysis of the monomers of the five adhesive films prepared in Synthesis Example using the sample C (EHA50 BA50) adhesive film shown in Table 3 as a standard. The NMR results were in agreement with the feed ratio, while the Py-GC / MS analysis (Comparative Example 2) yielded results in which a small amount of monomers were analyzed in large amounts.
Therefore, it was found that the samples having the same BA / EHA content as the standard samples exhibited similar values to the NMR results, whereas those with different content ratios showed an increase in the deviation.
As shown in FIG. 8, when the same thermal energy is applied to the polymer, the depolymerization ratio of the polymer having the same composition ratio is on average, but when the composition ratio is different from that of the monomer, It is considered that the proportion to be detected by depolymerization will be relatively high, and the monomer having a high composition ratio is likely to be decomposed into oligomers.
4. Example Analysis for 1
It was judged that an accurate monomer content ratio would be obtained by using a pressure sensitive adhesive having the same composition ratio as a standard product, and a pressure sensitive adhesive having the same composition ratio was used as a standard product, and the monomer content of the five pressure sensitive adhesive films The ratio was analyzed.
The temperature of the pyrolyzer was set at 600 ° C, and 1 mg of the pressure-sensitive adhesive was used as a solid sample. The pressure-sensitive adhesive sample was also quantified as a one-point calibration using 1 mg of the solid sample. . The results of the analysis are shown in Table 4.
(RSD%)
(3.0)
(0.4)
(8.9)
(3.9)
(0.9)
(1.0)
(1.0)
(2.5)
(0.5)
(4.6)
(4.49)
(4.82)
(4.61)
(4.24)
(3.68)
As shown in Table 4, the weight ratio of the five kinds of monomers was found to be in good agreement with the results of NMR analysis. As a result of measuring 3 times per sample, the RSD% was 0.5 to 8.9%, which was reproducible.
In addition, the weight ratio of the monomers of the five types of pressure-sensitive adhesive films was analyzed using the pressure-sensitive adhesive films having the same composition ratios shown in Table 4 as a standard, and the results are shown in Fig. 9 in comparison with Comparative Example 2.
As a result, compared with Comparative Example 2 (DELTA), the results corresponding to NMR and feed ratio were obtained. Therefore, it can be seen that the analysis of the weight ratio of the monomer component of the acrylate pressure-sensitive adhesive can obtain a good analysis result by one-point calibration using Py-GC / MS analysis using an adhesive film having the same composition ratio as a standard product there was.
5. Example Analysis for 2
A calibration curve was prepared by using a pressure sensitive adhesive having different composition ratios such as Sample A (EHA90 BA10) to E (EHA10 BA90) as a standard, and is shown in Fig. As a result, it was confirmed that the linearity is very good.
Thus, the monomer content ratios of the five adhesive films were analyzed using a pressure sensitive adhesive having a different composition ratio as a standard product. The temperature of the pyrolyzer was set at 600 ° C, and 1 mg of the pressure-sensitive adhesive standard was used as a solid sample. The pressure-sensitive adhesive sample was also quantitated by a five-point calibration using 1 mg of the solid sample, .
The results of the analysis are shown in Table 5 below.
(RSD%)
(2.4)
(0.4)
(8.6)
(3.7)
(1.0)
(1.0)
(1.3)
(3.1)
(0.9)
(11.5)
(4.49)
(4.82)
(4.61)
(4.24)
(3.68)
As shown in Table 5, the weight ratios of the monomers of the five kinds of samples are similar to those of the NMR analysis, but in terms of accuracy, the sample B (BA30 EHA70) to the sample D (BA70 EHA30) (BA30 EHA70) to sample D (BA70 EHA30), the RSD% was 1.0 to 8.6%, which was reproducible.
The results of the analysis of the weight ratios of the monomers of the five types of pressure-sensitive adhesive films using the pressure-sensitive adhesives having different composition ratios shown in Table 5 as a standard are compared with those of Comparative Examples 2 and 1, Respectively.
In the case of Example 1 (X) and Example 2 (*), unlike Comparative Example 2 (DELTA), results corresponding to NMR data and feed ratio were obtained. Therefore, in the case of the sample B (BA30 EHA70) to the sample D (BA70 EHA30), the analysis of the weight ratio of the monomer component of the acrylate pressure-sensitive adhesive can be carried out by Py-GC / MS using a pressure sensitive adhesive having a different composition ratio as a standard product. Results were obtained.
Claims (17)
(1) preparing an EHA50 BA50 pressure sensitive adhesive as a standard product;
(2) pyrolysis GC / MS analysis of the copolymer adhesive of EHA and BA at a temperature of 550 to 650 ° C using the standard product prepared in the step (1); And
(3) a step of calibrating the analysis result of the step (2) by one-point and then normalizing to confirm the weight ratio of the monomers of EHA and BA. Method for Quantitative Analysis of Monomer of Adhesive.
(1) preparing EHA10 BA90 pressure-sensitive adhesive, EHA30 BA70 pressure-sensitive adhesive, EHA50 BA50 pressure-sensitive adhesive, EHA70 BA30 pressure-sensitive adhesive and EHA90 BA10 pressure-sensitive adhesive as standard products;
(2) pyrolysis GC / MS analysis of the copolymer adhesive of EHA and BA at a temperature of 550 to 650 ° C using the standard product prepared in the step (1); And
(3) a step of calibrating the analytical result of the step (2) by five-point and then standardizing to confirm the weight ratio of the monomers of EHA and BA to the monomer of the copolymeric pressure- Quantitative analysis method.
(1) module for preparing EHA50 BA50 pressure-sensitive adhesive as a standard product;
(2) a module for performing pyrolysis GC / MS analysis of the copolymer adhesive of EHA and BA at a temperature of 550 to 650 ° C using the standard product prepared in the step (1); And
(3) a module for checking the results of the analysis of step (2) by one-point and then standardizing the EHA and BA monomers to determine the weight ratio of the monomers of EHA and BA. Quantitative analysis system.
(1) a module for preparing EHA10 BA90 adhesive, EHA30 BA70 adhesive, EHA50 BA50 adhesive, EHA70 BA30 adhesive and EHA90 BA10 adhesive as standard products;
(2) a module for performing pyrolysis GC / MS analysis of the copolymer adhesive of EHA and BA at a temperature of 550 to 650 ° C using the standard product prepared in the step (1); And
(3) a module for confirming the weight ratio of monomers of EHA and BA by calibrating the analysis result of the step (2) by five-point and then standardizing the monomers of the copolymers of EHA and BA Quantitative analysis system.
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