KR101332634B1 - Mold release composition for uv curing and method of synthetic thereof - Google Patents
Mold release composition for uv curing and method of synthetic thereof Download PDFInfo
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- KR101332634B1 KR101332634B1 KR1020110043508A KR20110043508A KR101332634B1 KR 101332634 B1 KR101332634 B1 KR 101332634B1 KR 1020110043508 A KR1020110043508 A KR 1020110043508A KR 20110043508 A KR20110043508 A KR 20110043508A KR 101332634 B1 KR101332634 B1 KR 101332634B1
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- 239000000203 mixture Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 34
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 12
- 238000000016 photochemical curing Methods 0.000 claims abstract description 6
- 239000000376 reactant Substances 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000000126 substance Substances 0.000 claims description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000012952 cationic photoinitiator Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 238000009472 formulation Methods 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229920001187 thermosetting polymer Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 abstract description 22
- 229920005989 resin Polymers 0.000 abstract description 22
- 239000003795 chemical substances by application Substances 0.000 abstract description 14
- 238000001723 curing Methods 0.000 abstract description 7
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical group C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 abstract description 6
- 238000001029 thermal curing Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 description 10
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 9
- 239000004926 polymethyl methacrylate Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- DEZRYPDIMOWBDS-UHFFFAOYSA-N dcm dichloromethane Chemical compound ClCCl.ClCCl DEZRYPDIMOWBDS-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
- C08K5/357—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
- C08F220/365—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate containing further carboxylic moieties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
- C08F220/603—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen and containing oxygen in addition to the carbonamido oxygen and nitrogen
Abstract
본 발명은 이형제조성물 및 이를 합성하는 방법에 관한 것으로서, 하기 화학식 1(벤조옥사진) 그룹을 포함하여 이루어지는 것을 특징으로 한다.
[화학식 1]
본 발명에 의하면, 벤조옥사진 그룹이 포함된 모노머들을 이형제로 사용하고, 이를 경화성수지에 첨가함으로써, 경화후에 표면에너지를 현저히 낮출 수 있으며, 표면에너지를 제어함으로써, 몰드와의 이형력을 현저히 향상시킬 수 있는 장점이 있고, 광경화 및 열경화 모두 가능할 뿐만 아니라, 용이하게 경화되어, 경화성수지의 패턴형성성능에 영향을 미치지 않는 장점이 있다.The present invention relates to a release composition and a method for synthesizing the same, characterized in that it comprises a group of the following formula (1).
[Formula 1]
According to the present invention, by using a monomer containing a benzoxazine group as a release agent, by adding it to the curable resin, it is possible to significantly lower the surface energy after curing, and to significantly improve the release force with the mold by controlling the surface energy There is an advantage that can be, and both photocuring and thermal curing is possible, as well as easily cured, there is an advantage that does not affect the pattern forming performance of the curable resin.
Description
본 발명은 이형제조성물 및 이를 합성하는 방법에 관한 것으로, 더욱 상세하게는 종래와 달리, 벤조옥사진(Benzoxazine)그룹을 갖는 모노머를 포함하는 이형제조성물을 제조하고, 이를 경화성수지에 첨가하여, 경화 후에 표면에너지를 현저히 낮춤으로써, 몰드와의 이형력을 현저히 향상시킨 이형제조성물 및 이를 합성하는 방법에 관한 것이다.
The present invention relates to a release composition and a method for synthesizing the same, and more particularly, to prepare a release composition comprising a monomer having a benzoxazine group, unlike the prior art, and added to the curable resin, after curing By lowering the surface energy significantly, the present invention relates to a release composition that significantly improves the release force with the mold and a method of synthesizing the same.
최근 몰드를 이용한 패턴형성공정에 있어서, 패턴의 크기는 나노스케일로 점점 작아지는 추세이다. In the recent pattern formation process using a mold, the size of the pattern is becoming smaller and smaller on the nanoscale.
이에, 몰드와 경화성수지 사이의 넓은 접촉영역때문에, 패턴전사후에 몰드제거과정에서, 패턴이 손상되거나 몰드가 패턴간에 완전히 제거되지 못 하는 문제가 발생하고 있다.Thus, due to the large contact area between the mold and the curable resin, there is a problem that the pattern is damaged during the mold removal process after the pattern transfer or the mold is not completely removed between the patterns.
이러한 문제는 몰드와 수지간에 서로 다른 물성을 가지기 때문으로, 경화전후에 경화성수지의 밀도차이와 경화성수지의 표면에너지로 인해 발생한다. This problem is due to the different physical properties between the mold and the resin, it occurs due to the density difference of the curable resin and the surface energy of the curable resin before and after curing.
따라서, 나노 패턴형성공정에서, 경화성수지의 표면에너지를 낮추고, 몰드와 경화성수지와의 이형력을 증가시킬 수 있는 이형제의 개발이 요구되고 있다.Therefore, in the nano-pattern forming process, development of a release agent capable of lowering the surface energy of the curable resin and increasing the release force between the mold and the curable resin is required.
본 발명은 상기 문제점을 해결하기 위한 것으로서, 벤조옥사진 그룹이 포함된 모노머들을 이형제로 사용하고, 이를 경화성수지에 첨가함으로써, 경화후에 표면에너지를 현저히 낮출 수 있는 이형제조성물을 제공하는 것을 목적으로 한다.An object of the present invention is to provide a release composition that can significantly lower the surface energy after curing by using a monomer containing a benzoxazine group as a release agent, and adding it to the curable resin. .
또한, 표면에너지를 제어함으로써, 몰드와의 이형력을 현저히 향상시킨 이형제조성물을 제공하는 것을 목적으로 한다.In addition, an object of the present invention is to provide a release composition that significantly improves the release force with the mold by controlling the surface energy.
또한, 광경화 및 열경화 모두 가능할 뿐만 아니라, 용이하게 경화되어, 경화성수지의 패턴형성성능에 영향을 미치지 않는 이형제조성물을 제공하는 것을 목적으로 한다.It is also an object of the present invention to provide a release composition that is not only capable of photocuring and thermal curing but also easily cured and does not affect the pattern forming performance of the curable resin.
뿐만 아니라, 간단하면서도 경제적인 공정으로 다양한 모노머를 합성함으로써, 이형제원료로 사용하기 위한 이형제조성물을 합성하는 방법을 제공하는 것을 목적으로 한다.
In addition, it is an object to provide a method for synthesizing a release preparation for use as a release agent raw material by synthesizing various monomers in a simple and economic process.
상기와 같은 목적을 달성하기 위한 본 발명에 따른 이형제조성물은, 하기 화학식 1(벤조옥사진) 그룹을 포함하여 이루어지는 것을 특징으로 한다.The release preparation according to the present invention for achieving the above object is characterized by comprising the following formula (1).
[화학식 1][Formula 1]
또한, 상기 이형제조성물은 하기 화학식 2, 화학식 3 또는 화학식 4 모노머 중 적어도 하나를 포함하여 이루어지는 것을 특징으로 한다. 하기 화학식의 R1는 수소기 혹은 메틸기 중에서 선택되며, R2, R3, R4는 탄소수 2 내지 20을 가지는 지방족 알칸 중에서 선택된다.In addition, the release composition is characterized in that it comprises at least one of the following formula (2), (3) or (4) monomers. R1 of the following formula is selected from hydrogen or methyl group, R2, R3, R4 is selected from aliphatic alkanes having 2 to 20 carbon atoms.
[화학식 2](2)
[화학식 3](3)
[화학식 4][Formula 4]
또한, 상기 이형제조성물은 광(photo) 또는 열(thermal)에 의해 경화되는 것을 특징으로 하며, 상기 광경화는 양이온 광개시제에 의하며, 상기 열경화는 100℃ 내지 300℃에서 이루어지는 것을 특징으로 한다.In addition, the release composition is characterized in that the curing by light (photo) or thermal (thermal), the photocuring is by a cationic photoinitiator, the thermal curing is characterized in that at 100 ℃ to 300 ℃.
또한, 상기 이형제조성물은, 경화되면, 표면에너지가 감소하는 것을 특징으로 한다.
In addition, the release composition is characterized in that when the cured, the surface energy is reduced.
다음으로, 본 발명에 따른 이형제조성물을 합성하는 방법은, 하기 화학식 5에 하기 화학식 6을 첨가하여 반응물을 제조하는 반응물 제조단계; 상기 반응물에 1,4-다이옥산을 환류방식으로 공급함으로써, 반응시키는 반응단계;를 포함하여 이루어지며, 상기 반응단계를 통해 하기 화학식 7이 형성되는 것을 특징으로 한다.Next, a method of synthesizing a release composition according to the present invention comprises the steps of preparing a reactant by adding the following formula (6) to formula (5); 1,4-dioxane is supplied to the reactants in a reflux manner, the reaction step of reacting, including, and characterized in that the following formula (7) is formed through the reaction step.
[화학식 5][Chemical Formula 5]
[화학식 6][Chemical Formula 6]
[화학식 7][Formula 7]
상기 화학식 6 내지 7에서, R은 수소기 또는 메틸기 중에서 선택된다.In Chemical Formulas 6 to 7, R is selected from a hydrogen group or a methyl group.
상기 반응단계에서, 반응시간은 40시간 내지 90시간인 것을 특징으로 한다.In the reaction step, the reaction time is characterized in that 40 to 90 hours.
또한, 상기 화학식 7에 하기 화학식 8 또는 하기 화학식 9를 첨가하여 제 2반응물을 제조하는 제 2반응물 제조단계; 상기 제 2반응물에 트리에틸아민(triethylamine)과 디클로로메탄(Dichloromethane)을 첨가함으로써, 반응시키는 제 2반응단계;를 더 포함하여 이루어지는 것을 특징으로 한다.In addition, a second reactant manufacturing step of preparing a second reactant by adding the following formula (8) or formula (9) to the formula (7); Characterized in that it further comprises; a second reaction step of reacting by adding triethylamine and dichloromethane (dichloromethane) to the second reactant.
[화학식 8][Formula 8]
[화학식 9][Chemical Formula 9]
상기 화학식 8에서, R1은 수소기 또는 메틸기 중에서 선택된다.In Formula 8, R 1 is selected from a hydrogen group or a methyl group.
또한, 상기 화학식 7에 하기 화학식 10을 첨가하여 제 3반응물을 제조하는 제 3반응물 제조단계; 상기 제 3반응물에 디부틸틴 디라우레이트(dibutyltin dilaurate)를 첨가함으로써, 반응시키는 제 3반응단계;를 더 포함하여 이루어지는 것을 특징으로 한다.In addition, the third reactant manufacturing step of preparing a third reactant by adding the following formula 10 to the formula (7); Characterized in that it further comprises; a third reaction step of reacting by adding dibutyltin dilaurate (dibutyltin dilaurate) to the third reactant.
[화학식 10][Formula 10]
상기 화학식 10에서, R1은 수소기 또는 메틸기 중에서 선택된다.
In Formula 10, R 1 is selected from a hydrogen group or a methyl group.
본 발명의 이형제조성물 및 이를 합성하는 방법에 따르면, 벤조옥사진 그룹이 포함된 모노머들을 이형제로 사용하고, 이를 경화성수지에 첨가함으로써, 경화후에 표면에너지를 현저히 낮출 수 있는 장점이 있다.According to the release composition of the present invention and a method for synthesizing the same, by using monomers containing a benzoxazine group as a release agent and adding it to the curable resin, there is an advantage of significantly lowering surface energy after curing.
또한, 표면에너지를 제어함으로써, 몰드와의 이형력을 현저히 향상시킬 수 있는 장점이 있다.In addition, by controlling the surface energy, there is an advantage that can significantly improve the release force with the mold.
또한, 본 발명의 이형제는 광경화 및 열경화 모두 가능할 뿐만 아니라, 용이하게 경화되어, 경화성수지의 패턴형성성능에 영향을 미치지 않는 장점이 있다.In addition, the release agent of the present invention is not only capable of photocuring and thermal curing, but also easily cured, there is an advantage that does not affect the pattern forming performance of the curable resin.
뿐만 아니라, 간단하면서도 경제적인 공정으로 다양한 모노머를 합성함으로써, 본 발명의 이형제원료를 제조할 수 있는 장점이 있다.In addition, by synthesizing a variety of monomers in a simple and economic process, there is an advantage that can be prepared the release agent raw material of the present invention.
도 1은 본 발명에 따른 이형제조성물을 합성하는 방법을 순차적으로 나타낸 순서도
도 2는 본 발명의 이형제조성물을 합성하는 방법 제 1실시예를 나타낸 반응식
도 3은 본 발명의 이형제조성물을 합성하는 방법 제 2실시예를 나타낸 반응식
도 4는 비교예의 표면접촉각 측정과정을 촬영한 사진
도 5는 본 발명의 실시예 1 내지 3의 표면접촉각 측정과정을 촬영한 사진
도 6은 본 발명의 실시예 4 내지 6의 표면접촉각 측정과정을 촬영한 사진1 is a flow chart sequentially showing a method for synthesizing a release composition according to the present invention
Figure 2 is a reaction scheme showing a first embodiment of a method for synthesizing the release composition of the present invention
Figure 3 is a reaction scheme showing a second embodiment of the method for synthesizing the release composition of the present invention
Figure 4 is a photograph taken the surface contact angle measurement process of the comparative example
Figure 5 is a photograph taken the surface contact angle measurement process of Examples 1 to 3 of the present invention
Figure 6 is a photograph of the surface contact angle measurement process of Examples 4 to 6 of the present invention
이하, 본 발명에 의한 이형제조성물 및 이를 합성하는 방법에 대하여 본 발명의 바람직한 하나의 실시형태를 첨부된 도면을 참조하여 상세히 설명한다. 본 발명은 하기의 실시예에 의하여 보다 더 잘 이해될 수 있으며, 하기의 실시예는 본 발명의 예시목적을 위한 것이고, 첨부된 특허청구범위에 의하여 한정되는 보호범위를 제한하고자 하는 것은 아니다.Hereinafter, a release preparation according to the present invention and a method for synthesizing the same will be described in detail with reference to the accompanying drawings. The present invention may be better understood by the following examples, which are for the purpose of illustrating the present invention and are not intended to limit the scope of protection defined by the appended claims.
이하에서 설명되는 본 발명에서는, 합성된 이형제조성물을 이용하여, 범용고분자인 폴리메틸메타크릴레이트와 혼용함으로써, 이형제로서 필요한 표면에너지 제어에 대한 효과를 접촉각 측정을 통해 규명하고자 한다. In the present invention described below, by using a synthesized release composition, by mixing with a polymethyl methacrylate, which is a general-purpose polymer, the effect on the surface energy control required as a release agent through the contact angle measurement.
먼저, 본 발명에 따른 이형제조성물은, 하기 화학식 1(벤조옥사진) 그룹을 포함하여 이루어진다. 이는 본 발명자가 다양한 실험과 연구를 통해, 하기 화학식 1(벤조옥사진)그룹을 갖는 화합물을 경화성수지에 첨가하는 경우에, 경화성수지의 표면에너지가 현저히 저하됨을 밝혀냄으로써, 이를 이형제로 활용한 것이다.First, the release composition according to the present invention comprises the following general formula (1). The inventors have found that the surface energy of the curable resin is significantly lowered when the compound having the following Chemical Formula 1 (benzoxazine) group is added to the curable resin through various experiments and researches, and thus used as a release agent. .
여기서, 경화성수지는 어떠한 방식이든 경화되는 수지이면 무방하며, 열 또는 UV 중 적어도 하나에 의해 경화되는 수지이면 더 바람직하다.The curable resin may be any resin that is cured in any manner, and more preferably a resin that is cured by at least one of heat or UV.
[화학식 1][Formula 1]
이렇게 상기 화학식 1(벤조옥사진)그룹을 포함하는 화합물이면 이형제로서 역할을 수행할 수 있으나, 표면에너지를 더 낮춤으로써, 이형력을 극대화시키기 위해서는, 하기 화학식 2, 화학식 3 또는 화학식 4 모노머 중 적어도 하나를 포함하는 것이 바람직하다. 더욱 바람직하게는 하기 화학식 3 모노머를 단독으로 사용하는 것이 가장 효과적이다.As such, if the compound containing Formula 1 (benzoxazine) group may serve as a release agent, by lowering the surface energy further, in order to maximize the release force, at least one of the following Formula 2, Formula 3 or Formula 4 monomers: It is preferable to include one. More preferably, the following Chemical Formula 3 monomers are used alone.
이는 수차례의 합성 및 실험을 통해, 경화성수지의 표면에너지를 최대한 낮춰줌으로써, 실제 패턴형성공정에서 몰드와의 이형력을 극대화시킬 수 있는 화합물이다.
It is a compound that can maximize the release force with the mold in the actual pattern forming process by lowering the surface energy of the curable resin as much as possible through several synthesis and experiments.
[화학식 2](2)
[화학식 3](3)
[화학식 4][Formula 4]
상기 화학식 2 내지 화학식 4에서, R1은 수소기 또는 메틸기 중에서 선택되며, R2, R3 및 R4는 탄소수 2 내지 20을 가지는 지방족 알칸 중에서 선택된다.In Formulas 2 to 4, R 1 is selected from a hydrogen group or a methyl group, and R 2 , R 3 and R 4 are selected from aliphatic alkanes having 2 to 20 carbon atoms.
본 발명의 이형제조성물은 광(photo) 또는 열(thermal)에 의해 경화될 수 있다. 종래와 달리, 본 발명의 이형제조성물은 광과 열 둘 중 어느 것에 의하더라도 용이하게 경화되며, 경화 후에 표면에너지가 감소하게 된다.The release formulations of the present invention can be cured by photo or thermal. Unlike the prior art, the release composition of the present invention is easily cured by either light or heat, and the surface energy decreases after curing.
또한, 상기 광경화는 양이온 광개시제에 의하는 것이 바람직하며, 상기 열경화는 100℃ 내지 300℃에서 이루어지는 것이 바람직하고, 더욱 바람직하게는 150℃ 내지 250℃, 가장 바람직하게는 200℃인 것이 효과적이다. 100℃미만인 경우에는 반응이 일어나지 못 하거나 반응이 일어나더라도 충분히 경화되지 못 해 표면에너지 감소효과가 미미한 문제가 있으며, 300℃를 초과하는 경우에는 경화성수지 자체가 변질될 수 있는 문제가 있다.In addition, the photocuring is preferably by a cationic photoinitiator, the thermosetting is preferably made at 100 ℃ to 300 ℃, more preferably 150 ℃ to 250 ℃, most preferably 200 ℃ effective. . If the temperature is less than 100 ° C., the reaction may not occur or may not be sufficiently cured even if the reaction occurs, resulting in a slight surface energy reduction effect. If the temperature exceeds 300 ° C., the curable resin itself may be deteriorated.
또한, 본 발명의 이형제조성물은, 경화되면, 화학구조가 변경됨으로써, 표면에너지가 감소하는 것을 특징으로 한다. 따라서, 광 또는 열경화가 필요하며, 이는 패턴형성공정에서 몰드제거를 위해 필수적이므로, 몰드를 이용한 패턴형성과정에 최적화된 이형제로 사용될 수 있다.
In addition, the release composition of the present invention is characterized in that when the cured, the chemical structure is changed, thereby reducing the surface energy. Therefore, light or heat curing is required, and since it is essential for mold removal in the pattern forming process, it can be used as a mold release agent optimized for the pattern forming process using a mold.
다음으로, 본 발명의 이형제조성물을 합성하는 방법은, 도 1에 나타난 바와 같이, 반응물 제조단계(S10), 반응단계(S20)를 포함하여 이루어진다. Next, the method for synthesizing the release composition of the present invention, as shown in Figure 1, comprises a reactant preparation step (S10), the reaction step (S20).
이는 제 1실시예로써, 먼저, 반응물 제조단계(S10)는 하기 화학식 5에 하기 화학식 6을 첨가하여 반응물을 제조하는 단계이다. 이는 반응물을 제조하는 과정으로, 반응단계(S20)과 동시에 일어날 수도 있다.This is a first embodiment, first, the reactant preparation step (S10) is a step of preparing a reactant by adding the following formula (6) to the following formula (5). This is a process for preparing a reactant, and may occur simultaneously with the reaction step (S20).
다음으로, 반응단계(S20)는 상기 반응물에 1,4-다이옥산을 환류방식으로 공급함으로써, 반응시키는 단계이다. 이는 환류방식으로 서서히 반응을 일으킴으로써, 순도높은 반응결과물, 하기 화학식 7을 형성하기 위한 과정이다. Next, the reaction step (S20) is a step of reacting by supplying 1,4-dioxane to the reactants in a reflux manner. This is a process for forming a reaction product having a high purity, the following formula 7 by causing a reaction in a reflux mode.
상기 반응물 제조단계(S10)와 반응단계(S20)는 도 2에 나타난 바와 같다.The reactant manufacturing step (S10) and the reaction step (S20) are as shown in FIG.
[화학식 5][Chemical Formula 5]
[화학식 6][Chemical Formula 6]
[화학식 7][Formula 7]
상기 반응단계(S20)에서, 반응시간은 40시간 내지 90시간이 바람직하며, 더욱 바람직하게는 60시간 내지 80시간, 가장 바람직하게는 72시간인 것이 효과적이다. 40시간미만인 경우에는 반응결과물인 화학식 7이 형성되기 어려운 문제가 있으며, 90시간을 초과하는 경우에는 경제성이 저하될 뿐만 아니라, 오히려 화학식 7의 결함이 발생될 수 있는 문제가 있다.In the reaction step (S20), the reaction time is preferably 40 hours to 90 hours, more preferably 60 hours to 80 hours, most preferably 72 hours is effective. If it is less than 40 hours, there is a problem that the reaction product of Formula 7 is difficult to be formed, and if it exceeds 90 hours, not only economic efficiency is deteriorated, but there is a problem that a defect of Formula 7 may occur.
상기 화학식 7 또한 모노머로써, 이형제조성물로 사용될 수 있으나, 이하의 공정을 더 거침으로써, 상기 본 발명의 이형제조성물에서 사용된 보다 효율적인 모노머를 제조할 수 있다.Formula 7 may also be used as a release composition as a monomer, but by going through the following process, a more efficient monomer used in the release composition of the present invention may be prepared.
다음으로, 제 2실시예로써, 상기 반응단계(S20)이후에, 제 2반응물 제조단계(S30)는 상기 화학식 7에 하기 화학식 8 또는 하기 화학식 9를 첨가하여 제 2반응물을 제조하는 과정이고, 제 2반응단계(S31)는 상기 제 2반응물에 트리에탄올아민(tri-ethanolamine)와 디클로로메탄(Dichloromethane)을 첨가함으로써, 반응시키는 과정을 더 포함할 수 있다. Next, as a second embodiment, after the reaction step (S20), the second reactant manufacturing step (S30) is a process for preparing a second reactant by adding the following formula (8) or formula (9) to the formula (7), The second reaction step (S31) may further include a step of reacting by adding triethanolamine and dichloromethane to the second reactant.
제 2반응물 제조단계(S30)와 제 2반응단계(S40)는 도 3에 나타난 바와 같다.The second reactant manufacturing step (S30) and the second reaction step (S40) are as shown in FIG.
[화학식 8][Formula 8]
[화학식 9][Chemical Formula 9]
다음으로, 제 3실시예로써, 상기 반응단계(S20)이후에, 제 3반응물 제조단계(S31)는 상기 화학식 7에 하기 화학식 10을 첨가하여 제 3반응물을 제조하는 과정이고, 제 3반응단계(S41)는 상기 제 3반응물에 디부틸틴 디라우레이트(dibutyltin dilaurate)를 첨가함으로써, 반응시키는 과정이다.Next, as a third embodiment, after the reaction step (S20), the third reactant manufacturing step (S31) is a process for preparing a third reactant by adding the following formula 10 to the formula (7), the third reaction step (S41) is a process of reacting by adding dibutyltin dilaurate to the third reactant.
제 3반응물 제조단계(S31) 및 제 3반응단계(S41)는 도 3에 나타난 바와 같다.The third reactant manufacturing step (S31) and the third reaction step (S41) are as shown in FIG.
[화학식 10][Formula 10]
상기 본 발명에 제조된 이형제조성물의 표면에너지 감소효과에 대한 실험결과는 다음과 같다. Experimental results for the surface energy reduction effect of the release preparation prepared in the present invention are as follows.
먼저, 비교예는 범용고분자인 PMMA를 이용하여, 표면접촉각을 측정하였다.First, the comparative example measured the surface contact angle using PMMA which is a general purpose polymer.
다음으로, 실시예 1 내지 3은, 이하의 본 발명의 이형제조성물들을 각각 200℃에서 30초간 열경화시킨 후 표면접촉각을 측정하였다. 실시예 1은 본 발명의 화학식 2(R1=H, R2=C6H12), 실시예 2는 본 발명의 화학식 3(R3=C6H12), 실시예 3은 본 발명의 화학식 4(R1=CH3, R2=C6H12)를 이용하였다.Next, in Examples 1 to 3, the release compositions of the present invention were thermally cured at 200 ° C. for 30 seconds, respectively, and then measured surface contact angles. Example 1 is Formula 2 (R 1 = H, R 2 = C 6 H 12 ) of the present invention, Example 2 is Formula 3 (R 3 = C 6 H 12 ), and Example 3 of the present invention Formula 4 (R 1 = CH 3 , R 2 = C 6 H 12 ) was used.
이에 대한 결과는 이하 <표 1>, 도 5에 나타난 바와 같다.
The results are as shown in Table 1 and FIG. 5.
상기 <표 1> 및 도 5에 나타난 바와 같이, 본 발명의 범위에 속하는 이형제를 사용한 실시예 1 내지 3이, 종래 패턴형성공정에 사용되던 경화성수지인 비교예보다 표면접촉각이 50%이상 월등히 커졌음을 알 수 있으며, 이는 그만큼 본 발명의 이형제들이 몰드용 범용고분자인 PMMA보다 표면에너지가 현저히 낮다는 것을 의미한다.
As shown in Table 1 and Figure 5, Examples 1 to 3 using a release agent belonging to the scope of the present invention is significantly greater than the surface contact angle 50% or more than the comparative example of the curable resin used in the conventional pattern forming process As can be seen, this means that the release agents of the present invention have a significantly lower surface energy than PMMA, a general purpose polymer for mold.
다음으로, 상기 본 발명의 이형제조성물을 PMMA에 소량(PMMA 100중량%에 대하여, 1중량%) 첨가하여, 이를 몰드에 적용하여, 200℃에서 30초간 열경화시킨 후, 표면접촉각을 측정하였다. Next, the release composition of the present invention was added to PMMA in a small amount (1% by weight based on 100% by weight of PMMA), applied to a mold, and thermally cured at 200 ° C for 30 seconds, and then the surface contact angle was measured.
실시예 4는 상기 실시예 1의 화학식 2를 PMMA에 1중량% 첨가한 것이고, 실시예 5는 상기 실시예 2의 화학식 3을 PMMA에 1중량% 첨가한 것이며, 실시예 6은 화학식 4를 PMMA에 1중량% 첨가한 것이다. Example 4 is 1% by weight of Formula 2 of Example 1 added to PMMA, Example 5 is 1% by weight of
이에 대한 결과는 이하 <표 2>, 도 6에 나타난 바와 같다.
The results are as shown in Table 2 and FIG. 6 below.
상기 <표 2> 및 도 6에 나타난 바와 같이, 본 발명의 이형제조성물을 사용한 실시예 4 내지 6이, 종래 패턴형성공정에 사용되던 경화성수지인 비교예보다 표면접촉각이 50%이상 월등히 커졌음을 알 수 있으며, 이는 그만큼 본 발명의 이형제들이 몰드용 범용고분자인 PMMA보다 표면에너지가 현저히 낮다는 것을 의미한다. As shown in Table 2 and Figure 6, Examples 4 to 6 using the release composition of the present invention is significantly larger than the surface contact angle 50% or more than the comparative example of the curable resin used in the conventional pattern forming process As can be seen, this means that the release agents of the present invention have a significantly lower surface energy than PMMA, a general purpose polymer for mold.
또한, 본 발명에서도 화학식 3을 사용한 실시예 2의 표면에너지가 가장 낮아, 이형력이 가장 뛰어남을 알 수 있었다.In addition, in the present invention, the surface energy of Example 2 using the formula (3) was the lowest, it was found that the best release force.
즉, 종래에 비해, 본 발명의 이형제가 이형력이 현저히 향상되었음을 상기 실험을 통해 확인할 수 있었다.
That is, compared to the prior art, the release agent of the present invention was confirmed that the release force is significantly improved through the experiment.
이상에서 본 발명의 바람직한 실시예를 설명하였으나, 본 발명은 다양한 변화와 변경 및 균등물을 사용할 수 있다. 본 발명은 상기 실시예를 적절히 변형하여 동일하게 응용할 수 있음이 명확하다. 따라서 상기 기재 내용은 하기 특허청구범위의 한계에 의해 정해지는 본 발명의 범위를 한정하는 것이 아니다.While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. It is clear that the present invention can be suitably modified and applied in the same manner. Therefore, the above description does not limit the scope of the present invention, which is defined by the limitations of the following claims.
Claims (9)
[화학식 2]
[화학식 3]
[화학식 4]
(상기 화학식 2 내지 화학식 4에서, R1은 수소기 또는 메틸기 중에서 선택되며, R2, R3 및 R4는 탄소수 2 내지 20을 가지는 지방족 알칸 중에서 선택된다)
Release formulation characterized in that it comprises at least one of the following formula (2), (3) or (4) monomers
(2)
(3)
[Chemical Formula 4]
(In Formula 2 to Formula 4, R 1 is selected from hydrogen or methyl group, R 2 , R 3 and R 4 is selected from aliphatic alkanes having 2 to 20 carbon atoms)
상기 이형제조성물은 광(photo) 또는 열(thermal)에 의해 경화되는 것을 특징으로 하는 이형제조성물
The method of claim 2,
The release composition is a release composition, characterized in that the cured by light (photo) or thermal (thermal)
상기 광경화는 양이온 광개시제에 의하며, 상기 열경화는 100℃ 내지 300℃에서 이루어지는 것을 특징으로 하는 이형제조성물
The method of claim 3, wherein
The photocuring is by a cationic photoinitiator, the thermosetting is a release composition, characterized in that at 100 ℃ to 300 ℃
상기 이형제조성물은, 경화되면, 표면에너지가 감소하는 것을 특징으로 하는 이형제조성물
The method of claim 2,
The release composition, when cured, release composition, characterized in that the surface energy is reduced
상기 반응물에 1,4-다이옥산을 환류방식으로 공급함으로써, 반응시키는 반응단계;를 포함하여 이루어지며,
상기 반응단계를 통해 하기 화학식 7이 형성되고,
[화학식 5]
[화학식 6]
[화학식 7]
(상기 화학식 6 내지 7에서, R은 수소기 또는 메틸기 중에서 선택된다)
상기 화학식 7에 하기 화학식 8 또는 하기 화학식 9를 첨가하여 제 2반응물을 제조하는 제 2반응물 제조단계;
상기 제 2반응물에 트리에틸아민(triethylamine)과 디클로로메탄(Dichloromethane)을 첨가함으로써, 반응시키는 제 2반응단계;를 더 포함하거나,
상기 화학식 7에 하기 화학식 10을 첨가하여 제 3반응물을 제조하는 제 3반응물 제조단계;
상기 제 3반응물에 디부틸틴 디라우레이트(dibutyltin dilaurate)를 첨가함으로써, 반응시키는 제 3반응단계;를 더 포함하여 이루어지는 것을 특징으로 하는 이형제조성물을 합성하는 방법
[화학식 8]
[화학식 9]
[화학식 10]
(상기 화학식 8에서, R1은 수소기 또는 메틸기 중에서 선택되고, 상기 화학식 10에서, R1은 수소기 또는 메틸기 중에서 선택된다)
Reactant preparation step of preparing a reactant by adding the following formula (6) to the formula (5);
It comprises a; reaction step of reacting by supplying 1,4-dioxane to the reactants in a reflux manner,
Formula 7 is formed through the reaction step,
[Chemical Formula 5]
[Chemical Formula 6]
(7)
(In Formulas 6 to 7, wherein R is selected from a hydrogen group or a methyl group)
Preparing a second reactant by adding the following Formula 8 or the following Formula 9 to Formula 7;
A second reaction step of reacting by adding triethylamine and dichloromethane to the second reactant;
A third reactant preparing step of preparing a third reactant by adding the following Formula 10 to Formula 7;
Method for synthesizing a release composition, characterized in that further comprising; a third reaction step of reacting by adding dibutyltin dilaurate (dibutyltin dilaurate) to the third reactant
[Chemical Formula 8]
[Chemical Formula 9]
[Formula 10]
(In Chemical Formula 8, R 1 is selected from a hydrogen group or a methyl group, and in Formula 10, R 1 is selected from a hydrogen group or a methyl group)
상기 반응단계에서, 반응시간은 40시간 내지 90시간인 것을 특징으로 하는 이형제조성물을 합성하는 방법
The method according to claim 6,
In the reaction step, the reaction time is a method for synthesizing a release composition, characterized in that 40 hours to 90 hours.
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