KR100831081B1 - Adhesive resin for expansion sheet using mutually reactive copolymers and expansion sheet using their adhesive - Google Patents
Adhesive resin for expansion sheet using mutually reactive copolymers and expansion sheet using their adhesive Download PDFInfo
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- KR100831081B1 KR100831081B1 KR1020070018119A KR20070018119A KR100831081B1 KR 100831081 B1 KR100831081 B1 KR 100831081B1 KR 1020070018119 A KR1020070018119 A KR 1020070018119A KR 20070018119 A KR20070018119 A KR 20070018119A KR 100831081 B1 KR100831081 B1 KR 100831081B1
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- methacrylate
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- 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
- C09J135/00—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 a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J135/06—Copolymers with vinyl aromatic monomers
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- 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
- C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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- 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
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
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Abstract
Description
도 1은 본 발명에 따른 발포시트의 단면도,1 is a cross-sectional view of the foam sheet according to the present invention,
도 2는 상호반응성 중합체들의 가교반응기구를 화학식으로 표시한 도면이다.FIG. 2 is a diagram showing a crosslinking mechanism of interreactive polymers in chemical formula. FIG.
* 도면의 주요부분에 대한 부호 설명 * Explanation of symbols on the main parts of the drawings
1 : 기재 1: description
2 : 표면처리 층 2: surface treatment layer
3 : 상호 반응성 공중합체들이 혼합된 발포 점착층 3: foam adhesive layer mixed with mutually reactive copolymers
4 : 이형필름4: release film
본 발명은 상호 반응성 공중합체들을 이용하여 상온에서 가교가 진행되지 않고 장기간 안정한 발포시트용 점착수지 및 이를 이용하여 접착 강도가 우수함과 동시에 높은 온도에서 피착체로부터 간단하게 박리할 수 있는 발포시트(가열 박리형 점착 시트)에 관한 것이다. The present invention is an adhesive resin for a foam sheet that is stable for a long time without cross-linking at room temperature using mutually reactive copolymers and a foam sheet that can be easily peeled from the adherend at a high temperature while using excellent adhesive strength (heating Release type adhesive sheet).
피착체에 점착한 발포시트는 가열처리에 의하고 피착체로부터 간단하게 박리할 수 있도록 하기 위하여, 열팽창성 마이크로스피어를 함유한다. 점착층을 가열하면 열팽창성 마이크로스피어가 발포 및 팽창하여 점착층을 뚫고 나와 피착체와의 접착 면적을 감소시키고 박리하는 것이다. The foam sheet adhered to the adherend contains thermally expandable microspheres in order to be easily peeled off from the adherend by heat treatment. When the pressure-sensitive adhesive layer is heated, the thermally expandable microspheres foam and expand to penetrate the pressure-sensitive adhesive layer to reduce the adhesion area with the adherend and peel off.
종래, 발포 시트 가공품에 사용된 점착수지는 일반적으로 가교관능기로서 수산기를 가지는 단량체와 아크릴 단량체의 공중합체 수지로 이소시아네이트 가교제를 사용하고 있다. 그러나 최근 전자 제품에 적용되는 발포시트는 150℃ 이상의 고온에서 발포되는 것이 요구되고 있으나, 고온에서 발포되는 발포시트용 마이크로스피어는 150℃에서 발포가 시작되어 고온용으로 사용하는 것이 한계로 되어 있다. 이러한 한계는 응집력이나 지지력이 큰 점착수지가 마이크로스피어의 팽창을 억제해 주어야 해결할 수 있으며 또 다른 방법으로는 점착수지를 구성하는 비닐단량체의 화학적 설계에 의하여 조절할 수 있으나 그리 용이하지 않다. Conventionally, the adhesive resin used for the foam sheet processed product generally uses an isocyanate crosslinking agent as a copolymer resin of the monomer and acrylic monomer which have a hydroxyl group as a crosslinking functional group. However, in recent years, the foam sheet applied to electronic products is required to be foamed at a high temperature of 150 ℃ or more, the microspheres for foam sheet foamed at a high temperature is limited to use for high temperature since the foam is started at 150 ℃. These limitations can be solved by cohesive or supportive adhesive resins that suppress the expansion of microspheres. Another method can be controlled by chemical design of the vinyl monomer constituting the adhesive resin, but it is not so easy.
따라서 점착성, 응집력, 내열성, 유연성 그리고 탄성 등을 고려하여 가교방법을 변화시키는 것이 좋은 방법이다. Therefore, it is good to change the crosslinking method in consideration of adhesiveness, cohesion, heat resistance, flexibility and elasticity.
특히 기존의 발포시트용 점착수지의 경우에 발포시트용 점착수지 생산 단계에서 마이크로스피어의 완전한 혼합 및 분산을 위하여 많은 시간이 요구되는데 이러한 과정에서 첨가된 가교제가 서서히 가교반응이 진행되어 점도가 높아지거나 겔화가 진행되어 코팅 공정에 큰 결함을 주게 된다. 특히 마이크로스피어의 팽창을 억제해 주기위해 가교도를 높일수록 더 심각한 문제가 발생하게 된다. Especially in the case of the conventional adhesive resin for foam sheet, a lot of time is required for the complete mixing and dispersion of microspheres in the production of adhesive resin for foam sheet. In this process, the crosslinking agent is gradually crosslinked to increase viscosity. Gelation proceeds and causes a large defect in the coating process. In particular, as the degree of crosslinking is increased to suppress the expansion of the microspheres, more serious problems occur.
또한, 종래의 가열 박리형 발포시트에 이용되는 점착수지는 가교관능기가 포함된 아크릴계 수지로서 가교제를 혼합한 후 마이크로스피어의 혼합 및 분산 그리고 코팅 시 가교가 진행되어 점도가 변하며 따라서 코팅을 일정하게 하는데 문제점이 있다. 특히 이러한 현상은 가교도를 높이기 위하여 가교 관능기의 비율이 클 경우 역시 더욱 큰 문제가 된다. In addition, the adhesive resin used in the conventional heat-peelable foam sheet is an acrylic resin containing a crosslinking functional group, and after mixing the crosslinking agent, crosslinking occurs during mixing and dispersion of the microspheres and coating, and thus the viscosity changes and thus the coating is uniform. There is a problem. In particular, this phenomenon is also a problem when the ratio of the cross-linking functional group is large in order to increase the degree of crosslinking.
상기의 단점은 해결하기 위하여, 본 발명에서 수득한 점착수지를 사용하여 얻어진 발포시트는 고온조건이나 고온 반복 조건에서 수행되는 FPCB의 공정 중 FPCB의 탈부착, 반도체 웨이퍼의 그라인딩, 반도체 칩, 칩 콘덴서, 칩 바리스터 및 인덕터 등의 제조 공정에서 부품의 전극인쇄, 고정, 절단, 열에 의한 탈·부착 등 분야에서 이용될 수 있다.In order to solve the above disadvantages, the foam sheet obtained by using the adhesive resin obtained in the present invention is detached and attached to the FPCB during the process of the FPCB performed under high temperature conditions or high temperature repeat conditions, grinding of the semiconductor wafer, semiconductor chips, chip capacitors, In the manufacturing process of chip varistors and inductors, it can be used in the fields such as electrode printing, fixing, cutting, detachment and attachment of heat.
본 출원인은 상기의 단점을 개선하기 위하여 마이크로스피어를 포함하는 점착수지를 상호 반응성 공중합체들을 혼합하여 사용하면 가사시간을 충분하게 늘일 수 있고, 혼합한 후에도 2내지 3일을 방치하여도 점도 변화가 거의 없다는 사실을 발견하고 본 발명을 완성하였다. In order to improve the above disadvantages, the present applicant can use a mixture of mutually reactive copolymers containing microspheres to sufficiently increase the pot life, and even after mixing for 2 to 3 days, the viscosity changes. The present invention has been completed by finding the fact that there is little.
즉, 두 관능기, 즉 카르복시기와 옥사졸린기의 반응에 의하여 아마이드-에스터의 화학적 가교결합 생성과 동시에 수소결합과 같은 물리적 가교결합을 부여할 수 있음을 알게되었고, 또한 가교도를 높여서 가교 밀도가 치밀하고 응집력이 강하기 때문에 마이크로스피어가 점착층을 발포 또는 팽창시키기 위하여 더 높은 온도 가 요구되게 되어 고온에서 발포가 일어나도록 하는 효과를 가짐을 또한 알게되었다. That is, it was found that by the reaction of two functional groups, that is, a carboxyl group and an oxazoline group, it is possible to impart chemical crosslinking of the amide-ester and to impart physical crosslinking such as hydrogen bonding. It has also been found that because of the high cohesive force, the microspheres require higher temperatures to foam or expand the adhesive layer and have the effect of causing foaming at high temperatures.
따라서 이러한 가열 발포형 점착시트는 일반적인 조건에서 마이크로스피어가 팽창할 수 있는 발포온도보다 더 높은 온도에서 점착층에 함유시켰던 마이크로스피어를 발포시켜 접착력을 저하시키고 피착체로부터 용이하게 박리할 수 있으며, 특히 150℃ 이상의 고온이나 고온에서 여러 차례 반복되는 작업, 즉 일정한 온도에서 가열한 상태에서 작업을 한 후 냉각하고 다시 가열 작업 등의 반복을 할 때, 발포시트는 발포온도가 계속적으로 낮아지므로 고온에서 발포되는 발포시트가 요구되는데, 이러한 목적에 본 발명의 점착제를 제공할 수 있음을 알게 되었다.Therefore, such a heat-foamable pressure-sensitive adhesive sheet can lower the adhesive strength and easily peel off from the adherend by foaming the microspheres contained in the pressure-sensitive adhesive layer at a temperature higher than the foaming temperature at which the microspheres can expand under normal conditions. When the work is repeated several times at a temperature higher than 150 ° C. or at a high temperature, that is, after cooling in a state of heating at a constant temperature and then cooling and heating again, the foam sheet is continuously foamed at a high temperature since the foaming temperature is continuously lowered. There is a need for a foam sheet, which has been found to provide the pressure-sensitive adhesive of the present invention for this purpose.
본 발명에서 카르복시기와 옥사졸린기를 관능기로 가지는 상호 반응성 공중합체들을 혼합하여 얻은 점착수지는 상온에서 고도로 안정화되는데 100℃ 이상에서 반응하여 에스터-아마이드 결합이 생성되어 가교가 이루어지므로 마이크로스피어가 팽창할 때 점착제의 응집력 및 탄성이 증가하여 마이크로스피어의 발포온도가 더욱 높아지며, 따라서 초기 점착 강도가 우수한 동시에 기재와 지지력 유지가 우수하고 높은 온도에서 가열 처리하여야 만, 접착력이 저하 내지 상실이 가능하므로 고온가열 박리형 점착 시트를 제공할 수 있다. In the present invention, the adhesive resin obtained by mixing the mutual reactive copolymers having a carboxyl group and an oxazoline group as a functional group is highly stabilized at room temperature, and is reacted at 100 ° C. or higher to form an ester-amide bond and crosslink, thereby expanding the microspheres. The cohesive force and elasticity of the pressure-sensitive adhesive increases, so that the foaming temperature of the microsphere is higher. Therefore, the initial adhesive strength is excellent and the base and the holding force are excellent. A mold adhesive sheet can be provided.
상기의 효과를 가지는 본 발명은 상호반응성 카르복시기를 가지는 제1공중합체와 옥사졸린기를 가지는 제2공중합체 2가지 액이 혼합되는 점착제이지만, 상온에서 가교반응이 일어나지 않아 안정성이 뛰어나서 상온에서는 장기보관이 가능하며 100℃ 부근에서 가교가 진행되기 때문에 효과적인 고밀도 점착층을 가지는 발포시 트의 제조에 용이하다. The present invention having the above effect is a pressure-sensitive adhesive in which two liquids of the first copolymer having an interreactive carboxyl group and the second copolymer having an oxazoline group are mixed, but the crosslinking reaction does not occur at room temperature, and thus the long-term storage at room temperature is excellent. It is possible to facilitate the production of foam sheet having an effective high-density adhesive layer because crosslinking proceeds in the vicinity of 100 ℃.
또한 본 발명은 상호 반응성기인 카르복시기와 옥사졸린을 각각 가지는 아크릴 공중합체들을 혼합하여 얻어진 점착제와 이것에 마이크로스피어를 분산하여 제조한 발포시트용 코팅 수지를 사용하여 150℃ 이상의 높은 온도에서 발포가 될 수 있는 발포시트를 제조할 수 있다. In addition, the present invention can be foamed at a high temperature of 150 ℃ or more using a pressure-sensitive adhesive obtained by mixing acrylic copolymers each having a carboxyl group and an oxazoline, which are mutually reactive groups, and a coating resin prepared by dispersing microspheres therein. Foam sheet can be prepared.
본 발명은 상호 반응성 공중합체를 이용한 발포시트용 점착수지 및 이를 이용한 발포시트에 관한 것으로서, 상기의 점착수지는 열팽창성 마이크로스피어를 포함하는 상호반응성 공중합체들을 혼합하여 제조되는 것을 특징으로 하며, 이렇게 제조되는 점착수지를 기재의 한면 또는 양면에 도포하여 점착층을 형성하고 이 점착층이 가열에 의하여 발포 또는 팽창하는 발포시트(가열 박리형 점착시트)를 제조하는 것을 특징으로 한다.The present invention relates to an adhesive resin for a foam sheet using a mutual reactive copolymer and a foam sheet using the same, characterized in that the adhesive resin is prepared by mixing interreactive copolymers including thermally expandable microspheres, The pressure-sensitive adhesive resin is coated on one or both sides of the substrate to form a pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer is characterized in that a foam sheet (heat-peelable pressure-sensitive adhesive sheet) is produced by foaming or expanding by heating.
이하, 본 발명에 의한 점착수지 및 이를 이용하는 발포시트에 관하여 상술하도록 한다.Hereinafter, the adhesive resin and the foam sheet using the same according to the present invention will be described in detail.
본 발명에 의한 점착수지는 열팽창성 마이크로스피어 및 상호 반응성 공중합체들을 포함하는 것을 특징으로 한다.The adhesive resin according to the present invention is characterized by including thermally expandable microspheres and mutually reactive copolymers.
상기의 열팽창성 마이크로스피어는, 이소부탄, 프로판, 펜탄과 같이 용이하게 가스화하고 열팽창성을 나타내는 물질이고, 그 껍질은 염화비닐리덴, 아크릴로니트릴, 메틸메타크릴레이트 등의 공중합체로서 열 융해성 물질이나 열팽창할 수 있는 물질로 이루어져있으며, 껍질의 성분 및 두께에 따라 100내지 170℃의 여러 온도 조건에서 팽창되는 것이 판매되고 있다. 그러나 이 온도는 최대 발포점의 온도이고, 발포 시작온도는 이보다 20 내지 50℃가 낮아진다.The thermally expandable microspheres are substances which easily gasify and exhibit thermal expansion like isobutane, propane and pentane, and their shells are thermally soluble as copolymers such as vinylidene chloride, acrylonitrile and methyl methacrylate. It is composed of a material or a thermally expandable material, and depending on the composition and thickness of the shell, it is sold to expand under various temperature conditions of 100 to 170 ° C. However, this temperature is the maximum foaming point temperature, the foaming start temperature is 20 to 50 ℃ lower than this.
상기의 마이크로스피어는 평균 입경이 10 내지 25 ㎛인 것이 점착수지에 분산이 유리하고, 가열 처리에 의한 점착층의 변형이 크고 점착력의 저하가 뚜렷하다. 또한 건조된 발포 점착층은 열팽창성 마이크로스피어의 최대입경보다도 두꺼운 층으로 형성한 것이 점착층의 표면을 평활화하고 가열 처리 전에 있어서 안정된 접착력을 달성하는 것이 바람직하다. Dispersion is advantageous in the adhesive resin that the microspheres have an average particle diameter of 10 to 25 µm, the deformation of the adhesive layer by heat treatment is large, and the drop in adhesive strength is obvious. In addition, it is preferable that the dried foamed adhesive layer is formed of a layer thicker than the maximum particle diameter of the thermally expandable microspheres to smooth the surface of the adhesive layer and achieve stable adhesion before heat treatment.
가열처리에 의한 점착층의 접착력 저하 현상을 바람직하게 이용하기 위해서는 열팽창성 마이크로스피어는 10배 이상의 체적 팽창율로 발포한 후 파열되지 않는 것이 좋다. 열팽창성 마이크로스피어의 배합량은, 점착층의 팽창율이나 접착력의 저하성 등에 따르고 적절하게 결정할 수 있지만, 일반적으로 점착층을 형성하는 점착수지 100 중량부당 5 내지 20 중량부가 바람직하다.In order to preferably use the phenomenon of lowering the adhesive strength of the pressure-sensitive adhesive layer by heat treatment, the thermally expandable microspheres are preferably not broken after foaming at a volume expansion rate of 10 times or more. Although the compounding quantity of a thermally expansible microsphere can be suitably determined according to expansion ratio of an adhesion layer, the fall of adhesive force, etc., 5-20 weight part is generally preferable per 100 weight part of adhesive resin which forms an adhesion layer.
한편, 마이크로스피어를 분산시키는 상호 반응성 공중합체는 비닐단량체, 공단량체 그리고 카르복시기를 포함하는 단량체를 공중합시킨 제1공중합체와 비닐단량체, 공단량체 그리고 옥사졸린기를 포함하는 단량체를 공중합시킨 제2공중합체를 혼합한 수지이다. On the other hand, the cross-reactive copolymer for dispersing the microsphere is a second copolymer copolymerized with a copolymer of a monomer comprising a vinyl monomer, a comonomer and a carboxyl group and a monomer including a vinyl monomer, a comonomer and an oxazoline group. It is resin which mixed.
상기 제1공중합체 및 제2공중합체를 이루는 비닐단량체 및 비닐 공단량체는 필요에 의해 적절히 선택하여 사용가능한 것으로 제한하지 않지만, 발포시트의 점착성, 응집력, 내열성, 유연성 등을 부여할 목적으로 사용되는 것으로서, 메틸아크 릴레이트, 메틸메타크릴레이트, 에틸아크릴에이트, 에틸메타크릴레이트, 프로필아크릴레이트, 프로필메타크릴레이트, 부틸아크릴레이트, 부틸메타크릴레이트, 헥실아크릴레이트, 헥실메타크릴레이트, 옥틸아크릴레이트, 2-에틸헥실아크릴레이트 등의 알킬기 함유 비닐단량체; 히드록시에틸아크릴에이트, 히드록시에틸메타크릴레이트, 히드록시프로필아크릴레이트, 히드록시프로필메타크릴레이트, 히드록시부틸아크릴레이트, 히드록시부틸메타크릴레이트, 히드록시헥실아크릴레이트, 히드록시헥실메타크릴레이트 등의 히드록실기 함유 비닐단량체; N,N-디메틸 아크릴아미드, N,N-디메틸 메타크릴아미드 등의 N-치환 아미드계 비닐단량체; 메톡시에틸아크릴레이트, 메톡시에틸메타크릴레이트, 에톡시에틸아크릴레이트, 에톡시에틸메타크릴레이트 등의 알콕시알킬아크릴레이트 비닐단량체; 비닐아세테이트, 비닐프로피오네이트, N-비닐피롤리돈, 메틸비닐피롤리돈, 비닐피리딘, 비닐피페리돈, 비닐피리미딘, 비닐피페라진, 비닐피라진, 비닐피롤, 비닐이미다졸, 비닐옥사졸, 비닐몰폴린, N-비닐카르복사아미드, 스틸렌, α-메틸스틸렌, N-비닐카프로락탐 등의 비닐단량체; 아크릴로니트릴, 메타크릴로니트릴 등의 시아노아크릴레이트 비닐단량체; 글리시딜아크릴레이트, 글리시딜메타크릴레이트 등의 에폭시기 함유 아크릴 단량체; 폴리에틸렌글리콜아크릴레이트, 폴리에틸렌글리콜메타크릴레이트, 폴리프로필렌글리콜아크릴레이트, 폴리프로필렌글리콜메타크릴레이트, 메톡시에틸렌글리콜아크릴레이트, 메톡시폴리에틸렌글리콜메타크릴레이트, 메톡시폴리프로필렌글리콜아크릴레이트, 메톡시폴리프로필렌글리콜메타크릴레이트 등의 글리콜계 아크릴에스테르단량체; 테트라히드로퍼프릴아크릴레이트, 테트라히드로퍼프릴메타크릴레이트, 2-메 톡시에틸 아크릴레이트 등의 아크릴산 에스테르단량체; 이소프렌, 부타디엔, 이소부틸렌, 비닐에테르 등의 단량체; 또는 이들 중 2이상의 혼합물로 이루어지는 그룹 중에서 선택된 것이 될 수 있다.The vinyl monomers and vinyl comonomers constituting the first copolymer and the second copolymer are not limited to those which can be appropriately selected and used as necessary, but are used for the purpose of imparting adhesiveness, cohesion, heat resistance, flexibility, etc. of the foam sheet. As such, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, hexyl acrylate, hexyl methacrylate, octyl acryl Alkyl group-containing vinyl monomers such as acrylate and 2-ethylhexyl acrylate; Hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxyhexyl acrylate, hydroxyhexyl methacrylate Hydroxyl group-containing vinyl monomers such as late; N-substituted amide vinyl monomers such as N, N-dimethyl acrylamide and N, N-dimethyl methacrylamide; Alkoxyalkyl acrylate vinyl monomers such as methoxyethyl acrylate, methoxyethyl methacrylate, ethoxyethyl acrylate, and ethoxy ethyl methacrylate; Vinyl acetate, vinyl propionate, N-vinylpyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole, vinylimidazole, vinyloxazole Vinyl monomers such as vinylmorpholine, N-vinylcarboxamide, styrene, α-methylstyrene, and N-vinylcaprolactam; Cyanoacrylate vinyl monomers such as acrylonitrile and methacrylonitrile; Epoxy group-containing acrylic monomers such as glycidyl acrylate and glycidyl methacrylate; Polyethylene glycol acrylate, polyethylene glycol methacrylate, polypropylene glycol acrylate, polypropylene glycol methacrylate, methoxy ethylene glycol acrylate, methoxy polyethylene glycol methacrylate, methoxy polypropylene glycol acrylate, methoxy poly Glycol-based acrylic ester monomers such as propylene glycol methacrylate; Acrylic acid ester monomers such as tetrahydroperpril acrylate, tetrahydroperryl methacrylate and 2-methoxyethyl acrylate; Monomers such as isoprene, butadiene, isobutylene and vinyl ether; Or a group consisting of two or more of these mixtures.
상기 카르복실기를 함유하는 제1공중합체 및 옥사졸린기를 함유하는 제2공중합체를 구성하는 비닐단량체 및 공단량체는 전체 점착수지의 80내지 95중량%의 양으로 도입되는 것이 바람직하다. 상기 비닐 및 공단량체가 80중량% 미만으로 포함되는 경우, 가교관능기의 함량이 많아져서 고도의 가교도를 가지게 되므로 점착력이 크게 상실되고 취성이 생기게 된다. 또한 극성이 큰 관능기를 가지는 단량체와 공중합 시 극성 및 반응성 비의 차이로 중합속도나 공중합체 구성비의 조절이 어려워진다. 상기 비닐 공단량체는 2가지 종류이상 혼합하여 사용할 수 있으며, 일반적인 비닐 공단량체로서 함량조절에 의해 수득되는 점착수지의 특성을 다소 증가시킬 수 있다. The vinyl monomer and comonomer constituting the first copolymer containing the carboxyl group and the second copolymer containing the oxazoline group are preferably introduced in an amount of 80 to 95% by weight of the total adhesive resin. When the vinyl and the comonomer is included in less than 80% by weight, the content of the crosslinking functional group is increased to have a high degree of crosslinking, so that the adhesive force is largely lost and brittleness is generated. In addition, it is difficult to control the polymerization rate or the copolymer composition ratio due to the difference in polarity and reactivity ratio when copolymerizing with a monomer having a large polar functional group. The vinyl comonomer may be used in a mixture of two or more kinds, and may slightly increase the properties of the adhesive resin obtained by controlling the content as a general vinyl comonomer.
카르복시기를 포함하는 제1공중합체는 용액 중합에 의하여 제조하고, 가교성을 부여할 목적으로, 예를 들면 아크릴산이나 메타크릴산, 카르복시에틸 아크릴레이트나 카르복시 펜틸 아크릴레이트, 이타콘산이나 말레산, 후말산, 크로톤산과 같은 카르복실기 함유 단량체; 무수 말레산이나 무수이타콘산과 같은 산무수물 단량체;와 같은 관능성 단량체 등이 2종 또는 3종 이상을 공중합한 것 등이다. The first copolymer containing a carboxyl group is prepared by solution polymerization and for the purpose of imparting crosslinking properties, for example, acrylic acid or methacrylic acid, carboxyethyl acrylate or carboxy pentyl acrylate, itaconic acid or maleic acid, Carboxyl group-containing monomers such as malic acid and crotonic acid; Functional monomers, such as an acid anhydride monomer like maleic anhydride and an itaconic acid anhydride; These are what copolymerized 2 or 3 types or more.
상기 공중합체를 구성하는 가교 관능기로서 카르복시기를 포함하는 비닐단량체는 상기 공중합체의 전체 단량체에 대하여 5 내지 20중량%의 양으로 도입되는 것이 좋으며, 바람직하게는 5 내지 10중량%의 양으로 도입될 수 있다. 상기 카르복시 기를 포함하는 비닐단량체가 5중량% 미만으로 포함되는 경우, 가교도가 부족하여 막의 유연성이 커지거나 응집력이 저하되어 마이크로스피어의 팽창을 억제할 수 없다.The vinyl monomer containing a carboxyl group as a crosslinking functional group constituting the copolymer is preferably introduced in an amount of 5 to 20% by weight based on the total monomers of the copolymer, preferably in an amount of 5 to 10% by weight. Can be. When the vinyl monomer including the carboxyl group is included in less than 5% by weight, the degree of crosslinking is insufficient, thereby increasing the flexibility of the membrane or decreasing the cohesive force, thereby preventing the expansion of microspheres.
옥사졸린기를 포함하는 제2공중합체는 용액 중합에 의하여 제조하고, 가교성을 부여할 목적으로 사용되며, 옥사졸린기를 포함하는 비닐 단량체로는 2-비닐-2-옥사졸린, 2-비닐-4-비닐-2-옥사졸린, 2-비닐-5-비닐-2-옥사졸린, 2-이소프로페닐-2-옥사졸린, 2-이소프로페닐-5-에틸-2-옥사졸린, 2-이소프로페닐-5-메틸-2-옥사졸린, 2-(비닐벤질옥시-1-메틸에틸)-2-옥사졸린, 2-(2-히드록시-1-메틸에틸)아크릴레이트, 2-(2-히드록시-1-메틸에틸)메타크릴레이트 또는 이들 중 2이상의 혼합물로 이루어지는 그룹 중에서 선택된 것이 사용될 수 있다.The second copolymer containing an oxazoline group is prepared by solution polymerization and used for the purpose of imparting crosslinkability. Examples of the vinyl monomer containing an oxazoline group include 2-vinyl-2-oxazoline and 2-vinyl-4. -Vinyl-2-oxazoline, 2-vinyl-5-vinyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, 2-iso Propenyl-5-methyl-2-oxazoline, 2- (vinylbenzyloxy-1-methylethyl) -2-oxazoline, 2- (2-hydroxy-1-methylethyl) acrylate, 2- (2 -Hydroxy-1-methylethyl) methacrylate or a group selected from the group consisting of two or more thereof can be used.
상기 공중합체를 구성하는 옥사졸린기를 포함하는 비닐단량체는 상기 공중합체의 전체 단량체에 대하여 5 내지 20중량%의 양으로 도입되는 것이 좋으며, 바람직하게는 10내지 5중량%의 양으로 도입될 수 있다. 상기 옥사졸린기를 포함하는 비닐단량체가 5중량% 미만으로 포함되는 경우 가교도가 부족하여 막의 유연성이 커지거나 응집력이 저하되어 마이크로스피어의 팽창을 억제할 수 없다.The vinyl monomer including the oxazoline group constituting the copolymer is preferably introduced in an amount of 5 to 20% by weight based on the total monomers of the copolymer, and may be introduced in an amount of 10 to 5% by weight. . When the vinyl monomer including the oxazoline group is included in less than 5% by weight, the degree of crosslinking is insufficient, thereby increasing the flexibility of the membrane or decreasing the cohesive force, thereby preventing the expansion of the microspheres.
본 발명의 상호반응성 공중합체 혼합물을 이용한 발포시트용 점착수지는 1차 단계에서 카르복시기를 함유하는 제1공중합체를 합성하고, 2차 단계에서 옥사졸린기를 함유하는 제2공중합체를 합성하며 3차 단계에서 상기 제1공중합체와 제2공중합체를 혼합한 점착수지에 마이크로스피어를 분산시켜 제조한다. 이러한 점착 수지로 이루어진 점착 수지는 상온에서 장기 보관하여도 경시변화가 없는 안정한 코팅 액인 동시에 발포온도를 20내지 30℃까지 이상 높일 수 있다. Adhesive resin for foam sheet using the interreactive copolymer mixture of the present invention synthesizes a first copolymer containing a carboxyl group in the first step, and a second copolymer containing an oxazoline group in the second step In the step is prepared by dispersing the microspheres in the adhesive resin mixed with the first copolymer and the second copolymer. The pressure-sensitive adhesive resin made of such a pressure-sensitive adhesive resin is a stable coating liquid with no change over time even after long-term storage at room temperature and at the same time can increase the foaming temperature to 20 to 30 ℃ or more.
또한, 본 발명의 발포시트는 상기와 같이 제조되는 점착수지를 기재의 한 면 또는 양 면에 도포하여 점착층을 형성한 후에 이형필름을 도포하여 제조되며, 기재와 점착층의 사이에 양호한 부착력을 위해 표면처리하는 단계를 더 포함 하는 것을 특징으로 한다. 본 발명에 따른 발포시트의 일실시예의 단면도를 도 1에 나타내었으며, 기재(1), 표면처리층(2), 상호반응성 공중합체들을 혼합한 발포 점착층(3), 이형필름(4)으로 구성된다. In addition, the foam sheet of the present invention is produced by applying a release film after applying the adhesive resin prepared as described above to one or both sides of the substrate to form an adhesive layer, and has a good adhesion between the substrate and the adhesive layer It characterized in that it further comprises the step of surface treatment. A cross-sectional view of an embodiment of the foam sheet according to the present invention is shown in Figure 1, the
이하 본 발명의 내용을 실시예에 의해 보다 상세하게 설명하기로 한다. 다만 이들 실시예는 본 발명의 내용을 이해하기 위해 제시되는 것일 뿐 본 발명의 권리범위가 이들 실시예에 한정되어지는 것으로 해석되어서는 안 된다.Hereinafter, the content of the present invention will be described in more detail with reference to Examples. However, these examples are only presented to understand the content of the present invention and should not be construed that the scope of the present invention is limited to these embodiments.
[제조예 1][Production Example 1]
제 1단계; 제 1공중합체의 제조First step; Preparation of the First Copolymer
교반기, 콘덴서, 적가깔대기, 온도계, 재킷(JACKET)이 갖추어진 2L의 유리 반응기에 단량체로서 에틸아크릴레이트(45g), 공단량체인 n-부틸아크릴레이트(45g) 그리고 아크릴산(10g)을 혼합하고, 여기에 개시제 α,α'-아조비스이소부티로니트릴(0.01g)을 에틸아세테이트(100g)과 톨루엔(20g)을 넣고 70℃에서 라디칼 중합반응을 진행하였다. 약 30분 후 에틸아크릴레이트(135g), 공단량체인 n-부틸아크릴레이트(135g) 그리고 아크릴산(30g)을 혼합하고, 여기에 개시제 α,α'-아조비스이소부티로니트릴(0.5g)을 에틸아세테이트(100g)와 톨루엔(40g)을 적하 깔대기를 이용하여 약 90분간 적하를 진행하였다. 적하시 온도를 일정하게 조절하고 반응이 끝난 후 미반응 단량체가 남지 않도록 라디칼 개시제(1g)를 에틸아세테이트(50g)와 에탄올(50g)에 용해하여 60분간 적하하고, 추가로 3시간 더 반응시킨 후 제 1공중합체를 제조하였다.Ethyl acrylate (45 g), comonomer n-butyl acrylate (45 g) and acrylic acid (10 g) are mixed in a 2 L glass reactor equipped with a stirrer, a condenser, a dropping funnel, a thermometer and a jacket. The initiator α, α'-azobisisobutyronitrile (0.01 g) was added to ethyl acetate (100 g) and toluene (20 g), and the radical polymerization reaction was carried out at 70 ° C. After about 30 minutes, ethyl acrylate (135 g), comonomer n-butyl acrylate (135 g), and acrylic acid (30 g) were mixed, and the initiator α, α'-azobisisobutyronitrile (0.5 g) was added thereto. Ethyl acetate (100 g) and toluene (40 g) were added dropwise using a dropping funnel for about 90 minutes. After adjusting the temperature constantly at the time of dropping and dissolving the radical monomer (1 g) in ethyl acetate (50 g) and ethanol (50 g) to prevent unreacted monomer after the reaction was completed, the mixture was added dropwise for 60 minutes and further reacted for 3 hours. The first copolymer was prepared.
제 2단계; 제 2공중합체의 제조Second step; Preparation of Second Copolymer
교반기, 콘덴서, 적가깔대기, 온도계, 재킷(JACKET)이 갖추어진 2L의 유리 반응기에 단량체로서 에틸아크릴레이트(45g), 공단량체인 n-부틸아크릴레이트(45g) 그리고 2-이소프로필-2-옥사졸린(10g)을 혼합하였다. 여기에 개시제 α,α'-아조비스이소부티로니트릴(0.01g)을 에틸아세테이트(100g)과 톨루엔(20g)을 넣고 70℃에서 카르복시기를 포함하는 공중합체 중합과 같은 방법으로 진행하였다. 라디칼 중합반응을 진행하였다. 약 30분 후 에틸아크릴레이트(135g), 공단량체인 n-부틸아크릴레이트(135g) 그리고 아크릴산(30g)을 혼합하고, 여기에 개시제 α,α'-아조비스이소부티로니트릴(0.5g)을 에틸아세테이트(100g)와 톨루엔(40g)을 적하 깔대기를 이용하여 약 90분간 적하를 진행하였다. 적하시 온도를 일정하게 조절하고 반응이 끝난 후 미반응 단량체가 남지 않도록 라디칼 개시제(1g)를 에틸아세테이트(50g)와 에탄올(50g)에 용해하여 60분간 추가로 3시간 더 반응시킨 후, 제 2공중합체를 제조하였다.Ethyl acrylate (45 g) as a monomer, comonomer n-butyl acrylate (45 g) and 2-isopropyl-2-oxa in a 2 L glass reactor equipped with a stirrer, condenser, dropping funnel, thermometer, and jacket Sleepy (10 g) was mixed. An initiator α, α'-azobisisobutyronitrile (0.01 g) was added to ethyl acetate (100 g) and toluene (20 g), and the polymerization was carried out in the same manner as in the polymerization of a copolymer including a carboxyl group at 70 ° C. A radical polymerization reaction was performed. After about 30 minutes, ethyl acrylate (135 g), comonomer n-butyl acrylate (135 g), and acrylic acid (30 g) were mixed, and the initiator α, α'-azobisisobutyronitrile (0.5 g) was added thereto. Ethyl acetate (100 g) and toluene (40 g) were added dropwise using a dropping funnel for about 90 minutes. After adjusting the temperature constantly at the time of dropping, dissolving the radical initiator (1 g) in ethyl acetate (50 g) and ethanol (50 g) so as not to leave unreacted monomer after the reaction was completed, and further reacted for another 3 minutes, and then the second Copolymers were prepared.
제 3단계; 점착수지의 제조Third step; Preparation of Adhesive Resin
상기 제 1단계 및 2단계에서 제조되어진 두 공중합체 수지를 무게비로 1:1로 혼합하였다. 이 혼합된 수지(100g)에 마이크로스피어 F-50D(상품명, 마쯔모도사 제조, 100내지 105℃ 발포 시작)(10g)를 투입하고 분산시켜 점착수지를 제조하였다.The two copolymer resins prepared in the first and second steps were mixed at a weight ratio of 1: 1. A microsphere F-50D (trade name, manufactured by Matsudodo Co., Ltd., 100-105 ° C. foaming start) (10 g) was added to the mixed resin (100 g) and dispersed to prepare an adhesive resin.
[제조예 2][Production Example 2]
실시예 1의 제 1단계에서 사용된 단량체들의 중량비를 에틸아크릴레이트/n-부틸아크릴레이트/아크릴산= 4.5/4.5/1.5으로 사용한 것을 제외하고는 제조예 1과 같은 방법으로 점착수지를 제조하였다.A pressure-sensitive adhesive resin was prepared in the same manner as in Preparation Example 1, except that the weight ratio of the monomers used in the first step of Example 1 was used as ethyl acrylate / n-butyl acrylate / acrylic acid = 4.5 / 4.5 / 1.5.
[제조예 3][Production Example 3]
실시예 1의 제 1단계에서 사용된 단량체들의 중량비를 에틸아크릴레이트/n-부틸아크릴레이트/아크릴산= 4.5/4.5/0.6으로 사용한 것을 제외하고는 제조예 1과 같은 방법으로 점착수지를 제조하였다.A pressure-sensitive adhesive resin was manufactured in the same manner as in Preparation Example 1, except that the weight ratio of the monomers used in the first step of Example 1 was used as ethyl acrylate / n-butyl acrylate / acrylic acid = 4.5 / 4.5 / 0.6.
[제조예 4][Production Example 4]
실시예 1의 제 3단계에서 마이크로스피어 F-50D대신에 마이크로스피어 F-80GSD(상품명, 마쯔모도사 제조, 110내지 115℃ 발포 시작)를 사용한 것을 제외하고는 제조예 1과 같은 방법으로 점착수지를 제조하였다.Adhesive resin in the same manner as in Preparation Example 1 except that the microsphere F-80GSD (trade name, manufactured by Matsudodo, 110-115 ° C. foaming) was used instead of the microsphere F-50D in the third step of Example 1. Was prepared.
[제조예 5] Production Example 5
실시예 1의 제 3단계에서 마이크로스피어 F-50D대신에 마이크로스피어F-80VSD(상품명, 마쯔모도사 제조, 150내지 160℃ 발포 시작)를 사용한 것을 제외하고는 제조예 1과 같은 방법으로 점착수지를 제조하였다.Adhesive resin in the same manner as in Preparation Example 1, except that Microsphere F-80VSD (trade name, manufactured by Matsudodo, 150-160 ° C. foaming) was used instead of Microsphere F-50D in the third step of Example 1. Was prepared.
[실시예 1~5] [Examples 1-5]
제조예 1 내지 5에 의해 제조되는 점착수지를 각각 PET필름(50 ㎛)에 도포한 후 37 ㎛의 발포 점착층을 형성시켰으며 36㎛의 이형지를 부착하여 발포시트를 제조하였다. 이렇게 제조된 발포시트는 7일간 에이징을 시켜 최종 테스트에 사용하였 다. Each of the adhesive resins prepared in Preparation Examples 1 to 5 was coated on a PET film (50 μm), and then a foamed adhesive layer of 37 μm was formed, and a foam sheet was prepared by attaching a release paper of 36 μm. The foam sheet thus prepared was aged for 7 days and used for the final test.
[비교제조예 1][Comparative Production Example 1]
교반기, 콘덴서, 적가깔대기, 온도계, 재킷(JACKET)이 갖추어진 2L의 유리 반응기에 n-부틸아크릴레이트(48.5g), 에틸아크릴레이트(48.5g), 아크릴산(2g), 하이드록시프로필아크릴레이트(1.0g) 그리고 α,α'-아조비스이소부티로니트릴 (0.01g)을 에틸아세테이트(160g), 톨루엔(270g)에 용해하여 적하 깔때기(dropping funnel)에 넣고, 질소로 치환한 후 흐름이 계속되는 상태에서 80℃에서 적하하며 8시간 라디칼 중합을 진행하였으며 반응 말기에 과량의 라디칼 개시제를 투입하여 미반응 단량체가 남지 않도록 한 후, 마이크로스피어 F-50D(상표명, 마쯔모도사 제조, 100내지 105℃발포 시작) (10g)를 투입하고 분산시켜, 점착수지를 제조하였다.In a 2 L glass reactor equipped with a stirrer, condenser, dropping funnel, thermometer, and jacket, n-butyl acrylate (48.5 g), ethyl acrylate (48.5 g), acrylic acid (2 g), and hydroxypropyl acrylate ( 1.0 g) and α, α'-azobisisobutyronitrile (0.01 g) is dissolved in ethyl acetate (160 g) and toluene (270 g), placed in a dropping funnel, replaced with nitrogen, and the flow continues. After radical polymerization was carried out at 80 ° C. for 8 hours and an excessive amount of radical initiator was added at the end of the reaction so that unreacted monomers were not left. Then, microsphere F-50D (trade name, manufactured by Matsudodo, 100-105 ° C.) was used. (Starting foaming) (10g) was added and dispersed to prepare an adhesive resin.
[비교제조예 2][Comparative Production Example 2]
비교제조예 1에서 가교 관능기를 가지는 하이드록시프로필아크릴레이트(2.0g)의 양을 증가하여 사용한 것을 제외하고는 비교예 1과 같은 방법으로 점착수지를 제조하였다. A pressure-sensitive adhesive resin was prepared in the same manner as in Comparative Example 1 except that the amount of hydroxypropyl acrylate (2.0 g) having a crosslinking functional group was increased in Comparative Preparation Example 1.
[비교제조예 3][Comparative Production Example 3]
비교제조예 1에서 마이크로스피어 F-80GSD(상표명, 마쯔모도사 제조, 110내지 115℃ 발포 시작)를 투입한 것을 제외하고는 비교예 1과 같은 방법으로 점착수지를 제조하였다.Except that the microsphere F-80GSD (trade name, manufactured by Matsudodo, 110-115 ℃ foaming) in Comparative Preparation Example 1 was prepared in the same manner as in Comparative Example 1.
[비교제조예 4][Comparative Production Example 4]
비교제조예 1에서 마이크로스피어 F-80VSD(상표명, 마쯔모도사 제조, 150내 지 160℃ 발포시작)를 투입한 것을 제외하고는 비교예 1과 같은 방법으로 점착수지를 제조하였다.In Comparative Preparation Example 1 except that the microsphere F-80VSD (trade name, manufactured by Matsudodo, 150 to 160 ℃ foaming) was added to prepare a pressure-sensitive adhesive resin in the same manner as in Comparative Example 1.
[비교예 1~4][Comparative Examples 1-4]
상기 1 내지 4에 의해 제조되는 점착수지를 각각 이소시아네이트 가교제 AK-75(상표명, 애경화학)를 점착수지의 수산기 관능기의 2배의 양을 첨가하여 교반하여 점착수지를 제조하고, 이를 PET필름(50 ㎛)에 도포한 후, 37 ㎛의 발포 점착층을 형성시켰으며 36㎛의 이형지를 부착하여 발포시트를 제조하였다. 이렇게 제조된 발포시트는 7일간 에이징을 시켜 최종 테스트에 사용하였다.Adhesion resins prepared by the above 1 to 4, respectively, by adding 2 times the amount of an isocyanate crosslinking agent AK-75 (trade name, Aekyung Chemical) to the hydroxyl group functional groups of the adhesive resin to prepare the adhesive resin, PET film (50 After applying to the (μm), a foamed pressure-sensitive adhesive layer of 37 ㎛ was formed and a release sheet of 36 ㎛ was attached to prepare a foam sheet. The foam sheet thus prepared was aged for 7 days and used for the final test.
제조예 1 내지 5, 비교제조예 1 내지 4를 정리하여 표 1에 나타내었고, 상기 제조예, 비교제조예와 실시예 및 비교예에 따라 제조되는 점착수지 및 발포시트의 물리적인 성질을 다음과 같은 테스트 방법을 사용하여 측정하였고, 그 결과를 표 2 및 3에 기록하였다.Preparation Examples 1 to 5, Comparative Preparation Examples 1 to 4 are summarized in Table 1, and the physical properties of the adhesive resin and foam sheet prepared according to the Preparation Examples, Comparative Preparation Examples and Comparative Examples as follows. Measurements were made using the same test method and the results are reported in Tables 2 and 3.
1. 점착수지의 점도변화 측정 1. Measurement of viscosity change of adhesive resin
얻어진 점착수지를 일정한 온도에서 용매의 증발을 방지시키고 용기에 넣고 부룩필드 점도계(Brookfield, DV-II+)를 사용하여 시간이 지나간 후 점도를 측정하여 평가하였다.The obtained adhesive resin was prevented from evaporation of the solvent at a constant temperature, placed in a container, and evaluated by measuring the viscosity after time using a Brookfield viscometer (Brookfield, DV-II +).
2. 발포 온도 2. Foaming temperature
발포 온도는 Perkin-Elmer DSC 7을 이용하였으며 10℃/분의 속도로 얻었다. 발포온도는 마이크로스피어가 혼합된 점착수지를 PET필름에 형성시켜 에이징 후 가 교가 완전히 진행된 후 필름에서 시료를 채취하여 측정하였다. 얻어진 발포시트를 온도가 조절된 핫플레이트에 10mm 두께의 스테인레스 판을 얹어 온도가 평형이 된 후 발포 시트를 사이에 넣어 발포 온도를 측정하여 기기로 측정한 온도와 비교하였다. Foaming temperature was obtained using Perkin-Elmer DSC 7 and obtained at a rate of 10 ° C./min. Foaming temperature was measured by taking a sample from the film after the cross-linking process was completed by aging the adhesive resin mixed with the microsphere on the PET film. The obtained foam sheet was placed on a temperature-controlled hot plate and a 10 mm-thick stainless plate was equilibrated, and then the foam sheet was sandwiched between the foam sheets, and the foam temperature was measured.
3. 점착력 시험3. Adhesion test
이소프로판올로 완전히 세척된 시험판에 실시예 및 비교예로 얻은 폭 20mm, 길이 150mm의 가열 박리형 점착시트 시료를 두께 2mm, 폭 50mm, 길이 200mm의 시험편(SUS 304)에 점착면을 아래로 해서, 2kg의 자동식 압착 고무롤러장치로 30cm/min 속도로 왕복 1회 압착 시켜 접착하고 상온에서 30분간 방치하여, "KSA 1107 : 2004"에 의거해 180도 껍질 접착력(박리속도 300 mm/분, 23℃)을 측정한 방법으로 측정하였다. 3매의 시험편에서 측정한 점착력의 평균치를 구하였다. 2 kg of a 20 mm wide and 150 mm long heat-peelable pressure-sensitive adhesive sheet sample obtained in Examples and Comparative Examples on a test plate thoroughly washed with isopropanol was placed on a test piece (SUS 304) having a thickness of 2 mm, a width of 50 mm and a length of 200 mm. Automatic squeezed rubber roller device at 30cm / min squeezed once and bonded and left for 30 minutes at room temperature. 180 degree peel adhesion according to "KSA 1107: 2004" (peel rate 300 mm / min, 23 ℃) Was measured by the measuring method. The average value of the adhesive force measured by three test pieces was calculated | required.
상기와 같이, 본 발명에 의한 점착수지는 점도변화가 거의 발생되지 않았으며, 종래 기술에서 마이크로스피어를 동일한 제품을 사용한 경우보다 20 내지 30℃ 정도 더 높은 온도에서 발포가 될 수 있는 발포시트를 제조할 수 있다.As described above, the pressure-sensitive adhesive resin according to the present invention almost did not occur in the viscosity change, and manufactured a foam sheet that can be foamed at a temperature of about 20 to 30 ℃ higher than when using the same product in the microsphere in the prior art can do.
이상에서 상세히 설명한 바와 같이, 본 발명에 의한 카르복시 관능기를 가지는 제1공중합체와 옥사졸린을 포함하는 제2공중합체를 혼합한 상호 반응성 공중합체 혼합물을 사용한 점착용액으로 안정성이 뛰어난 발포 시트용 점착수지를 제조할 수 있다. As described in detail above, the adhesive resin for foam sheet having excellent stability as a pressure-sensitive adhesive solution using a mixture mixture of a first copolymer having a carboxyl functional group and a second copolymer containing oxazoline according to the present invention. Can be prepared.
또한 가교제의 반응성이 큰 다른 수지액의 경우 2액형으로 점착수지로 사용 직전에 혼합하여 사용하는 불편함이 있는데 이것은 시간이 지나감에 따라서 점착수지의 관능기와 가교제의 반응으로 인하여 점도가 커지거나 겔화가 진행되어 기재에 도포가 불가능하거나 균일한 도포가 불가능하게 된다. 따라서 코팅이 되더라도 두께가 달라져 생산되는 발포시트의 특성의 편차가 심하게 나타나게 된다. 그러나 카르복시기와 옥사졸린 반응기를 각각 포함한 상호반응성 공중합체 혼합물은 상온에서 전혀 반응하지 않으므로 이를 이용한 점착 수지는 상온에서 점착수지의 특성 편차가 작아 안정한 값을 얻을 수 있는 장점을 보여 주었다. In addition, in the case of other resin liquids having a high reactivity of the crosslinking agent, it is inconvenient to use them as a two-part type adhesive resin just before use. This is due to the reaction of the functional group of the adhesive resin with the crosslinking agent and gelation as time passes. Proceeds so that application to the substrate is impossible or uniform application is impossible. Therefore, even if the coating is different in thickness, the variation of the properties of the foam sheet produced will appear severely. However, since the reactive copolymer mixture including the carboxyl group and the oxazoline reactor, respectively, does not react at all at room temperature, the adhesive resin using the same has a small variation in the properties of the adhesive resin at room temperature, thereby showing a stable value.
또한 공중합체 가교제를 사용함으로서 수지끼리의 가교밀도가 크고, 수소결합과 같은 물리적 결합도 생성되어 응집력 및 유지력이 강하여 마이크로스피어의 팽창을 억제시켜서 발포 온도를 20내지 30℃까지 더 높일 수 있다. In addition, by using a copolymer crosslinking agent, the crosslinking density of the resins is high, and physical bonds such as hydrogen bonds are generated, and cohesive force and retention force are strong, thereby suppressing the expansion of the microspheres, thereby further increasing the foaming temperature to 20 to 30 ° C.
이상에서 기술한 바와 같이, 본 발명은 마이크로스피어를 함유하는 점착수지 를 형성함으로써 점착수지의 발포온도를 20내지 30℃ 더 높이고 코팅성, 점착력, 유지력, 응집력 등이 우수하고 다양한 기능성이 있는 발포시트용 코팅수지를 얻을 수 있어 전자·전기 재료분야 등에 있어서의 적용되는 고온 발포시트의 제조에 유용하다.As described above, the present invention forms a pressure-sensitive resin containing microspheres to increase the foaming temperature of the adhesive resin 20 to 30 ℃ more excellent foamability, excellent adhesion, adhesion, holding force, cohesion, etc. Coating resin can be obtained, which is useful for the production of high-temperature foam sheets applied in the field of electronic and electrical materials.
또한, 본 발명에 따라 제조되는 발포시트는 적절한 물품 등으로 된 피착체를 영구적으로 접착해 두는 용도에 이용하는 것도 가능하지만, 바람직한 용도 는 피착체를 소정 기간 접착하고 목적을 달성 후, 그 접착 상태를 제거하는 것이 바람직한 용도이다. 상기의 용도로서는 여러 가지가 있으며 그 예로서, 높은 온도에서 2가지 이상의 물품, 예를 들면 고분자로 된 물품과 금속, 섬유 또는 종이 등으로 된 각종의 전기, 전자 장치의 조립이나 절단, 연마 또는 FPCB 등의 회로 공정의 캐리어 테이프, 가고정제 또는 금속판이나 플라스틱 판, 유리 판 등의 오염 손상방지를 목적으로 한 표면 보호제나 마스킹제 등의 용도등에 사용할 수 있는 발포시트를 제공하는 것이다.In addition, the foam sheet produced according to the present invention can also be used for permanently adhering an adherend made of a suitable article or the like, but a preferred use is that after adhering the adherend for a predetermined time and achieving the object, Removal is the preferred use. There are various applications of the above. Examples thereof include assembling or cutting, grinding, or FPCB of two or more articles at high temperature, for example, articles made of a polymer and various electrical and electronic devices made of metal, fiber, or paper. The present invention provides a foamed sheet which can be used for a carrier tape, a temporary fixer, or a surface protecting agent or a masking agent for the purpose of preventing contamination damage of a metal plate, a plastic plate, a glass plate, or the like in a circuit process such as the above.
Claims (11)
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| Application Number | Priority Date | Filing Date | Title |
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| KR1020070018119A KR100831081B1 (en) | 2007-02-22 | 2007-02-22 | Adhesive resin for expansion sheet using mutually reactive copolymers and expansion sheet using their adhesive |
| JP2009550805A JP5235904B2 (en) | 2007-02-22 | 2008-02-22 | Adhesive resin for foamed sheet using interreactive copolymer and foamed sheet using the same |
| PCT/KR2008/001054 WO2008103008A1 (en) | 2007-02-22 | 2008-02-22 | Adhesive resin for expansion sheet using mutually reactive copolymers and expansion sheet using their adhesive |
| CN2008800001327A CN101541907B (en) | 2007-02-22 | 2008-02-22 | Adhesive resin for expansion sheet using mutually reactive copolymers and expansion sheet using their adhesive |
| TW097106319A TWI374923B (en) | 2007-02-22 | 2008-02-22 | Adhesive resin for expansion sheet using mutually reactive copolymers and expansion sheet using their adhesive |
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| KR101559925B1 (en) | 2013-05-10 | 2015-10-14 | 김시원 | Composition Of The Adhesion Pad having Adhesion Removable Performance |
| KR20190036190A (en) * | 2017-09-27 | 2019-04-04 | (주)애니원 | Impact-absorbing adhesive tape having improved durability in an environment with a high temperature and a high humidity |
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| JP2011149009A (en) * | 2009-12-25 | 2011-08-04 | Nitto Denko Corp | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
| KR20120003815A (en) * | 2010-07-05 | 2012-01-11 | 닛토덴코 가부시키가이샤 | Active energy ray-curable pressure-sensitive adhesive for re-release and dicing die-bonding film |
| TWI612089B (en) | 2016-11-15 | 2018-01-21 | 財團法人工業技術研究院 | Crosslinked copolymer and ionic exchange film |
| CN111333768B (en) * | 2018-12-18 | 2022-03-29 | 浙江海虹控股集团有限公司 | Acrylic resin thermal expansion foaming microsphere and preparation method thereof |
| CN114207033B (en) * | 2019-08-01 | 2024-04-02 | 株式会社钟化 | Thermosetting resin composition, thermosetting resin film, thermosetting film, laminate, and printed wiring board and method for producing same |
| CN112724306B (en) * | 2019-10-28 | 2022-07-12 | 中国石油化工股份有限公司 | Microspherical ionomer with cross-linked structure and preparation method and application thereof |
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Also Published As
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| CN101541907B (en) | 2011-06-01 |
| TWI374923B (en) | 2012-10-21 |
| CN101541907A (en) | 2009-09-23 |
| WO2008103008A1 (en) | 2008-08-28 |
| JP2010519379A (en) | 2010-06-03 |
| JP5235904B2 (en) | 2013-07-10 |
| TW200904926A (en) | 2009-02-01 |
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