KR101579276B1 - Resin composition, hard-coating agent, film, and method for production of molded article - Google Patents
Resin composition, hard-coating agent, film, and method for production of molded article Download PDFInfo
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- 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
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- C08J2433/00—Characterised by the use 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; Derivatives of such polymers
- C08J2433/04—Characterised by the use 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; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use 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; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
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- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/02—Polyamines
Abstract
본 발명의 수지조성물은, 2개 이상의 아크릴로일기를 갖는 다관능 중합성 화합물 및 아크릴로일기에 부가반응 가능한 화합물을 함유하는 것을 특징으로 한다.The resin composition of the present invention is characterized by containing a multifunctional polymerizable compound having two or more acryloyl groups and a compound capable of addition reaction with an acryloyl group.
Description
본 발명은, 수지조성물, 하드코팅제, 필름 및 성형체의 제조방법에 관한 것이다.The present invention relates to a resin composition, a hard coating agent, a film, and a method for producing a molded article.
종래부터, 가전제품의 멤브레인 스위치나 자동판매기의 견본캔 등에 있어서, 열경화형 수지를 도공한 필름이 사용되어 왔다.BACKGROUND ART [0002] Conventionally, a film coated with a thermosetting resin has been used in a membrane switch of an electric appliance or a sample can of a vending machine.
또한, 열경화형 수지에 비해 내찰과상성이 우수한 자외선 경화형 수지를 도공·경화시킨 성형용 필름이 보급되어 왔다. 특히, 휴대전화, 휴대 음악 플레이어, 터치패널 등의 전자기기 하우징이나 자동차 내장재는, 경도, 내찰과상성, 내오염성, 광택감 등이 요구되기 때문에, 이러한 용도에 자외선 경화형 수지를 도공·경화시킨 성형용 필름이 응용되기 시작하였다(특허문헌 1 ~ 3 참조).In addition, a molding film coated and cured with an ultraviolet curable resin excellent in abrasion resistance as compared with a thermosetting resin has been widely used. Particularly, since electronic housings and automobile interior materials such as cellular phones, portable music players, and touch panels are required to have hardness, abrasion resistance, stain resistance, glossiness, and the like, Films have begun to be applied (see Patent Documents 1 to 3).
특허문헌 1: 국제공개 제00/34396호 팜플렛Patent Document 1: International Publication No. 00/34396 pamphlet
특허문헌 2: 일본특허공개공보 제2005-8717호Patent Document 2: Japanese Patent Application Laid-Open No. 2005-8717
특허문헌 3: 일본특허공개공보 제2004-305863호Patent Document 3: Japanese Patent Application Laid-Open No. 2004-305863
열경화형 수지를 도공한 필름은 경도나 내찰과상성이 낮아 손상이 잘 되며 외관이 현저하게 열화되어 버린다. 한편, 자외선 경화형 수지를 도공·경화시킨 성형용 필름은, 강직하며 균열이 생기기 쉽기 때문에, 성형성이 부족하여, 비교적 평탄한 구조체의 성형에만 이용할 수 있었다.The film coated with the thermosetting resin has a low hardness and abrasion resistance, so that the film is easily damaged and the appearance deteriorates remarkably. On the other hand, a molding film coated and cured with an ultraviolet curable resin is rigid and easily cracked, so that the moldability is insufficient and it can be used only for molding of a relatively flat structure.
본 발명은 이러한 점을 감안하여 이루어진 것으로서, 경도나 내찰과상성이 높고, 또한 성형성도 양호한 수지조성물, 하드코팅제, 필름 및 성형체의 제조방법을 제공하는 것을 목적으로 한다.SUMMARY OF THE INVENTION The present invention has been made in view of the above points, and it is an object of the present invention to provide a resin composition, a hard coating agent, a film, and a method of producing a molded article having high hardness and abrasion resistance and good moldability.
이하, 본 발명에 대해서 상세히 설명한다.Hereinafter, the present invention will be described in detail.
(1) 본 발명의 수지조성물(1) The resin composition of the present invention
본 발명의 수지조성물은, 2개 이상의 아크릴로일기를 갖는 다관능 중합성 화합물 및 아크릴로일기에 부가반응 가능한 화합물을 함유하는 것을 특징으로 한다.The resin composition of the present invention is characterized by containing a multifunctional polymerizable compound having two or more acryloyl groups and a compound capable of addition reaction with an acryloyl group.
본 발명의 수지조성물은, 1차 경화된 상태에서는 성형하여도 균열이 잘 생기지 않는 유연성을 갖는 동시에, 점착성이 생기기 어렵다. 또한, 본 발명의 수지조성물은 2차 경화된 상태에서는 경도나 내찰과상성이 우수하다.The resin composition of the present invention has flexibility that does not cause cracking even when molded in the primary cured state, and tackiness is hardly caused. In addition, the resin composition of the present invention is excellent in hardness and abrasion resistance in the secondary cured state.
참고로, 1차 경화란, 아크릴로일기로의 부가반응을 의미한다. 또한, 2차 경화란, 자외선이나 전자선 등의 활성에너지선을 조사하는 것에 의한 라디칼 중합이다.For reference, primary curing means an addition reaction to an acryloyl group. Secondary curing is radical polymerization by irradiating active energy rays such as ultraviolet rays or electron beams.
본 발명에 관한 2개 이상의 아크릴로일기를 갖는 다관능 중합성 화합물은, 라디칼 반응성이 매우 높고, 속경성(速硬性)과 고경도인 점에서 우위성이 있다. 2개 이상의 아크릴로일기를 갖는 다관능 중합성 화합물로서는, 예컨대 1,4-부탄디올 디아크릴레이트, 1,6-헥산디올 디아크릴레이트, 네오펜틸글리콜 디아크릴레이트, 폴리에틸렌글리콜 디아크릴레이트, 히드록시피발산 네오펜틸글리콜 디아크릴레이트, 디시클로펜타닐 디아크릴레이트, 카프로락톤 변성 디시클로펜테닐 디아크릴레이트, 에틸렌옥사이드 변성 인산 디아크릴레이트, 아릴화 시클로헥실 디아크릴레이트, 이소시아누레이트 디아크릴레이트, 트리메티롤 프로판 트리아크릴레이트, 디펜타에리트리톨 트리아크릴레이트, 프로피온산 변성 디펜타에리트리톨 트리아크릴레이트, 펜타에리트리톨 트리아크릴레이트, 프로필렌 옥사이드 변성 트리메티롤 프로판 트리아크릴레이트, 트리스(아크릴옥시에틸) 이소시아누레이트, 디펜타에리트리톨 펜타아크릴레이트, 프로피온산 변성 디펜타에리트리톨 펜타아크릴레이트, 디펜타에리트리톨 헥사아크릴레이트, 카프로락톤 변성 디펜타에리트리톨 헥사아크릴레이트 등을 들 수 있다.The multifunctional polymerizable compound having two or more acryloyl groups according to the present invention is superior in radical reactivity, quick hardness and high hardness. Examples of the multifunctional polymerizable compound having two or more acryloyl groups include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, Diacylpentanyl diacrylate, caprolactone-modified dicyclopentenyl diacrylate, ethylene oxide-modified phosphoric acid diacrylate, arylated cyclohexyl diacrylate, isocyanurate diacrylate , Trimethylolpropane triacrylate, dipentaerythritol triacrylate, propionic acid-modified dipentaerythritol triacrylate, pentaerythritol triacrylate, propylene oxide-modified trimethylolpropane triacrylate, tris (acryloxyethyl ) Isocyanurate, dipentaerythritol penta Propylenic acid-modified dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, caprolactone-modified dipentaerythritol hexaacrylate, and the like.
관능기수가 많은 아크릴레이트일수록 표면경도가 높아져 바람직하다. 이들은 단독 혹은 2종 이상을 혼합해서 사용해도 된다. 2개 이상의 아크릴로일기를 갖는 다관능 중합성 화합물은, 모노머여도 되고 프리폴리머여도 되며, 또한, 우레탄아크릴레이트, 에폭시아크릴레이트, 폴리에스테르아크릴레이트 등이어도 된다.The acrylate having a large number of functional groups is preferable because the surface hardness is increased. These may be used alone or in combination of two or more. The multifunctional polymerizable compound having two or more acryloyl groups may be either a monomer or a prepolymer, or may be a urethane acrylate, an epoxy acrylate, or a polyester acrylate.
본 발명에서 이용하는 아크릴로일기에 부가반응 가능한 화합물은, 2개 이상의 아크릴로일기를 갖는 다관능 중합성 화합물과 부가반응 가능한 화합물이다. 이러한 부가반응에 의해 수지조성물이 1차 경화(B 스테이지화)되기 때문에, 수지조성물의 점착성이 소실되거나 감소된다. 이것을 이용하여, 수지조성물을 필름에 도포한 후에 부가반응이 촉진되는 조건을 부여함으로써, 필름간의 블록킹이나 성형시에서의 필름과 금형의 블록킹을 방지할 수 있다. 아크릴로일기에 부가반응 가능한 화합물은, 구핵성(求核性)을 갖는 화합물이면 되는데, 구체적으로는 아민 화합물이 바람직하다.The compound capable of addition reaction with an acryloyl group used in the present invention is a compound capable of addition reaction with a polyfunctional polymerizable compound having two or more acryloyl groups. Since the resin composition is first cured (B-staged) by this addition reaction, the tackiness of the resin composition is lost or reduced. By using this, it is possible to prevent blocking between films or blocking of a film and a mold at the time of molding by giving conditions under which the addition reaction is accelerated after the resin composition is applied to a film. The compound capable of addition reaction with an acryloyl group may be any compound having a nucleophilic (nucleophilic) property, and specifically, an amine compound is preferable.
아민 화합물로서는, 1급 또는 2급 아민을 갖는 것, 예컨대, 메틸아민, 에틸렌디아민, 디에틸렌트리아민, 트리에틸렌테트라민, 테트라에틸렌펜타민, 펜타에틸렌헥사민, 헥사메틸렌디아민, 아닐린, 페네틸아민, 아만타딘, 피페라진이나, 아미노기를 함유한 실란 커플링제 등의 저분자량 아민을 들 수 있다. 본 발명에서의 저분자량 아민이란, 예컨대, DETA(디에틸렌트리아민), TETA(트리에틸렌테트라민), PEHA(펜타에틸렌헥사민) 등의 에틸렌디아민 유도체를 의미하고, 그 분자량은, 예컨대, 50 ~ 400의 범위가 적합하다. 또한, 아민 화합물로서는 아민을 반복해서 구조로서 갖는 폴리아민을 이용할 수도 있다. 저분자량 아민과 폴리아민을 병용함으로써 수지조성물의 경화성을 용이하게 조정할 수 있다. 또한, 저분자량 아민과 폴리아민을 병용하면, 수지조성물이 1차 경화의 상태에 있을 때에, 점착성이 한층 생기기 어렵다. 폴리아민의 분자량은, 예컨대 1만 ~ 20만의 범위가 적합하다.Examples of the amine compound include compounds having a primary or secondary amine such as methylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine, aniline, phenethyl Amine, amantadine, piperazine, and a silane coupling agent containing an amino group. The low molecular weight amine in the present invention means an ethylene diamine derivative such as DETA (diethylene triamine), TETA (triethylene tetramine), PEHA (pentaethylene hexamine), etc. Its molecular weight is, for example, 50 A range of ~ 400 is suitable. As the amine compound, a polyamine having an amine repeatedly in its structure may be used. The curing property of the resin composition can be easily adjusted by using the low molecular weight amine and the polyamine in combination. Further, when a low molecular weight amine and a polyamine are used in combination, it is difficult for the resin composition to have more tackiness when it is in the primary curing state. The molecular weight of the polyamine is suitably in the range of, for example, 10,000 to 200,000.
아민 화합물의 사용량은, 사용하는 아민 화합물의 아민가(amine number)에 의존하는데, 2개 이상의 아크릴로일기를 갖는 다관능 중합성 화합물 100 중량부에 대하여, 0.1 ~ 50 중량부의 범위가 바람직하고, 0.5 ~ 30 중량부의 범위가 더욱 바람직하며, 5 ~ 25 중량부의 범위가 특히 바람직하다. 수지조성물의 1차 경화가 불충분할 경우, 아민 화합물의 배합량을 늘리거나, 아민 화합물 중에 차지하는 폴리아민의 비율을 높게 함으로써, 경화성을 향상시킬 수 있다. 한편, 수지조성물의 포트 라이프(pot life)가 짧을 경우에는, 아민 화합물의 배합량을 줄이거나, 아민 화합물 중에 차지하는 폴리아민의 비율을 낮게 함으로써 포트 라이프를 연장할 수 있다. 또한, 아민가가 큰 화합물일수록 아민 화합물의 반응성이 크고, 아민 화합물의 첨가량을 줄일 수 있으며, 표면 물성도 양호해서 바람직하다.The amount of the amine compound to be used depends on the amine number of the amine compound to be used, but is preferably in the range of 0.1 to 50 parts by weight, more preferably 0.5 to 50 parts by weight based on 100 parts by weight of the polyfunctional polymerizable compound having two or more acryloyl groups, To 30 parts by weight, and particularly preferably 5 to 25 parts by weight. When the primary curing of the resin composition is insufficient, the curing property can be improved by increasing the amount of the amine compound or increasing the proportion of the polyamine occupied in the amine compound. On the other hand, when the pot life of the resin composition is short, the pot life can be extended by reducing the compounding amount of the amine compound or decreasing the proportion of the polyamine occupied in the amine compound. Further, a compound having a large amine value is preferable because the reactivity of the amine compound is large, the amount of the amine compound to be added can be reduced, and the surface properties are good.
상기 아크릴로일기에 부가반응 가능한 화합물과 함께 감온성 촉매를 배합함으로써, 1차 경화성과 수지조성물의 포트 라이프의 양립이 용이해진다. 즉, 감온성 촉매는 상온에서는 촉매활성이 없기(또는 낮기) 때문에, 수지조성물의 포트 라이프를 길게 할 수 있고, 고온에서는 급속히 활성을 발휘하기 때문에 1차 경화성을 향상시킬 수가 있다. 또한, 감온성 촉매를 배합하면 수지조성물이 1차 경화의 상태에 있을 때에 점착성이 한층 생기기 어렵다.By blending a thermosensitive catalyst together with a compound capable of addition reaction to the acryloyl group, compatibility between the primary curing property and the pot life of the resin composition becomes easy. That is, since the thermosensitive catalyst has no catalyst activity (or low temperature) at room temperature, the pot life of the resin composition can be lengthened, and the primary curing property can be improved because the catalyst exhibits rapid activity at high temperature. Further, when the thermosensitive catalyst is blended, it is difficult for the resin composition to be more viscous when the resin composition is in the primary curing state.
감온성 촉매의 구체예로서, 강염기인 DBU(디아자비시클로운데센)나 DBN(디아자비시클로노넨) 염이 특히 바람직하다. DBU나 DBN 염은, 각종 용제와의 상용성도 우수하여, 종래의 3급 아민이나 무기계의 염기성 촉매를 이용하는 것보다 더욱 온화한 조건에서 반응수율의 향상을 도모할 수 있다.As specific examples of the thermosensitive catalyst, DBU (diazabicyclo undecene) and DBN (diazabicyclononene) salts which are strong bases are particularly preferable. DBU and DBN salts are excellent in compatibility with various solvents and can be improved in reaction yield under milder conditions than those using conventional tertiary amines or inorganic basic catalysts.
DBU나 DBN 염으로서는, 예컨대, DBU-페놀염, DBU-옥틸산염, DBU-올레인산염, DBU-p-톨루엔술폰산염, DBU-기산염, DBN-페놀염, DBN-옥틸산염, DBN-올레인산염, DBN-p-톨루엔술폰산염, DBN-기산염메틸아민 등을 들 수 있고, 기타 아미딘 염기나 구아니딘 염기의 염 등을 들 수 있다. 또한, 유기용제에 가용으로 탈(脫)프로톤 작용하는 강염기염이면 이용할 수가 있다. 이들 감온성 촉매는 단독 혹은 2종 이상을 혼합하여 사용해도 된다. 또한, 아크릴로일기에 부가반응을 촉진할 수 있는 촉매이면, 상기 감온성 촉매에 한정되지 않으며, 촉매활성을 발휘할 수 있는 수단과 함께 이용할 수가 있다.Examples of DBU and DBN salts include salts of DBU-phenol salts, DBU-octylates, DBU-olefins, DBU-p-toluenesulfonates, DBU-salts, DBN-phenol salts, DBN- , DBN-p-toluenesulfonate, DBN-methylamine methylamine, and the like, and salts of other amidine bases and guanidine bases. Further, a strong base salt which can be used as a deaspontone in an organic solvent can be used. These thermosensitive catalysts may be used alone or in combination of two or more. The catalyst capable of accelerating the addition reaction to the acryloyl group is not limited to the above-mentioned temperature-sensitive catalyst but can be used together with a means capable of exhibiting catalytic activity.
감온성 촉매의 배합량은 2개 이상의 아크릴로일기를 갖는 다관능 중합성 화합물 100 중량부에 대하여, 5 ~ 20 중량부의 범위가 바람직하다. 이 범위 내인 것에 의해, 수지조성물이 1차 경화의 상태에 있을 때에, 점착성이 한층 생기기 어렵다.The blending amount of the thermosensitive catalyst is preferably in the range of 5 to 20 parts by weight based on 100 parts by weight of the multifunctional polymerizable compound having two or more acryloyl groups. Within this range, when the resin composition is in the primary curing state, the tackiness is less likely to occur.
본 발명의 수지조성물은, 자외선이나 전자선 등의 활성에너지선을 조사함으로써 2차 경화된다. 자외선 경화를 행할 경우, 초고압 수은등, 고압 수은등, 저압 수은등, 카본아크, 메탈할라이드램프 등을 이용하여, 100 ~ 400nm, 바람직하게는 200 ~ 400nm의 파장영역에서, 50 ~ 300mJ/cm2의 에너지를 갖는 자외선을 조사할 수가 있다. 경화 저해를 방지하기 위해 질소가스 등의 불활성 가스하에서 조사를 행해도 된다.The resin composition of the present invention is secondarily cured by irradiating active energy rays such as ultraviolet rays or electron beams. When ultraviolet curing is carried out, an energy of 50 to 300 mJ / cm 2 is applied in a wavelength range of 100 to 400 nm, preferably 200 to 400 nm, by using an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, It is possible to irradiate the ultraviolet ray having the ultraviolet ray. Irradiation may be carried out under an inert gas such as nitrogen gas in order to prevent curing inhibition.
자외선에 의해 경화시키는 경우, 2개 이상의 아크릴로일기를 갖는 다관능 중합성 화합물 100 중량부에 대하여, 자외선 경화형 개시제를 3 ~ 10 중량부 첨가하는 것이 바람직하다. 첨가량을 3중량 이상으로 함으로써 열경화후에 점착성이 잘 남지 않으며, 10 중량부 이하로 함으로써 과도한 경화반응을 억제하여 성형성을 확보할 수가 있다.In the case of curing by ultraviolet rays, it is preferable to add 3 to 10 parts by weight of an ultraviolet curing initiator to 100 parts by weight of the polyfunctional polymerizable compound having two or more acryloyl groups. When the addition amount is 3 parts by weight or more, the adhesiveness does not remain well after heat curing. When the addition amount is 10 parts by weight or less, excessive curing reaction can be suppressed and moldability can be ensured.
자외선 경화형 개시제로서는, 예컨대, 1-히드록시시클로헥실페닐케톤, 2,2-디메톡시-2-페닐아세트페논, 크산톤, 플루오레논, 벤즈알데히드, 플루오렌, 안트라퀴논, 트리페닐아민, 카바졸, 3-메틸아세트페논, 4-클로로벤조페논, 4,4'-디메톡시벤조페논, 4,4'-디아미노벤조페논, 미히라케톤(Michler's ketone), 벤조인프로필에테르, 벤조인에틸에테르, 벤질디메틸케탈, 1-(4-이소프로필페닐)-2-히드록시-2-메틸프로판-1-온, 1-[4-(2-히드록시에톡시)-페닐]-2-히드록시-2-메틸-1-프로판-1-온, 2-히드록시-1-[4-[4-(2-히드록시-2-메틸-프로피오닐)-벤질]-페닐]-2-메틸-프로판-1-온, 2-히드록시-2-메틸-1-페닐프로판-1-온, 티오크산톤, 디에틸티오크산톤, 2-이소프로필티오크산톤, 2-클로로티오크산톤, 2-메틸-1-[4-(메틸티오)페닐]-2-몰포리노-프로판-1-온, 2,4,6-트리메틸벤조일디페닐포스핀옥사이드, 비스-(2,6-디메톡시벤조일)-2,4,4-트리메틸펜틸포스핀옥사이드 등을 들 수 있고, 시판품으로서는 Irgacure 127, 184, 369, 651, 500, 819, 907, 2959(이상, 치바·재팬사 제품, 상품명) 등을 들 수 있다. 이러한 자외선 경화형 개시제는 2종 이상을 병용해도 된다.Examples of the ultraviolet curable initiator include 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, Benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- [4- (2- hydroxyethoxy) -phenyl] -2- Methyl-propan-1-one, 2-hydroxy-1- [4- [4- (2- hydroxy- 2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2- chlorothioxanthone, 2- Methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, and commercially available products include Irgacure 127, 184, 369, 651, 500, 819, 907, 2959 (Trade names, products of Chiba, Japan). These ultraviolet curing initiators may be used in combination of two or more.
또한, 수지조성물을 전자선에 의해 경화시킬 경우, 공지된 전자선 조사장치를 이용할 수 있다. 전자선의 조사량은 10 ~ 200kGy가 바람직하고, 30 ~ 100kGy가 보다 바람직하다. 10kGy 이상으로 함으로써 수지조성물을 확실하게 경화시킬 수 있고, 200kGy 이하로 함으로써 전자선 조사장치로의 부하를 저감할 수 있어 경제적이다.When the resin composition is cured by electron beams, a known electron beam irradiation apparatus can be used. The dose of the electron beam is preferably 10 to 200 kGy, more preferably 30 to 100 kGy. By setting it to 10 kGy or more, the resin composition can be reliably cured, and when it is 200 kGy or less, the load on the electron beam irradiating apparatus can be reduced, which is economical.
(2) 본 발명의 하드코팅제(2) Hard coating agent of the present invention
본 발명의 하드코팅제는, 상기 (1)의 수지조성물을 포함하는 것을 특징으로 한다. 본 발명의 하드코팅제를 이용하여 형성한 하드코트층은, 1차 경화된 상태에서는 성형하여도 균열이 잘 생기지 않는 유연성 갖는 동시에 점착성이 잘 생기지 않는다. 또한, 본 발명의 하드코팅제를 이용하여 형성한 하드코트층은 2차 경화된 상태에서는 경도나 내찰과상성이 우수하다.The hard coating agent of the present invention is characterized by containing the resin composition of the above (1). The hard coat layer formed by using the hard coating agent of the present invention has flexibility that does not easily crack even when molded in the primary hardened state, and the hard coat layer is not easily adhered. The hard coat layer formed by using the hard coating agent of the present invention is excellent in hardness and abrasion resistance in the secondary hardened state.
본 발명의 하드코팅제는, 상기 (1)의 수지조성물 그대로여도 되고, 적절히 그 밖의 성분을 첨가해도 된다.The hard coating agent of the present invention may be either the resin composition of the above (1) or other components as appropriate.
(3) 본 발명의 필름(성형용 필름)(3) The film (molding film)
본 발명의 필름은, 필름기재(基材) 상에 상기 (1)의 수지조성물로 이루어진 하드코트층이 형성된 것을 특징으로 한다.The film of the present invention is characterized in that a hard coat layer composed of the resin composition of (1) is formed on a film substrate.
본 발명의 필름은, 예컨대, 하드코트층이 1차 경화된 상태에 있는 것으로 할 수 있다. 본 발명의 필름을 구성하는 하드코트층은 균열이 잘 생기지 않는 유연성을 갖는다. 이에 따라, 본 발명의 필름은 하드코트층에 균열을 일으키기 않고, 의장성이 우수한 딥 드로잉이나 복잡한 구조로 성형할 수가 있다.In the film of the present invention, for example, it can be considered that the hard coat layer is in a first cured state. The hard coat layer constituting the film of the present invention has flexibility so that cracks do not occur easily. Thus, the film of the present invention can be formed into a deep drawing or a complicated structure having excellent designability without causing cracks in the hard coat layer.
또한, 본 발명의 필름을 구성하는 하드코트층은, 2차 경화되어 있지 않은 상태에서도 점착성이 잘 생기지 않으므로, 필름간의 블록킹이나 성형시에서의 필름과 금형의 블록킹을 방지할 수 있다. 또한, 2차 경화후의 하드코트층은 경도나 내찰과상성이 우수하다.Further, since the hard coat layer constituting the film of the present invention does not have good adhesiveness even when the film is not cured secondarily, blocking between the films and blocking of the film and the mold at the time of molding can be prevented. The hard coat layer after the secondary curing is excellent in hardness and abrasion resistance.
본 발명의 필름은, 하드코트층보다 상층에 보호층을 구비하는 것이 바람직하다. 1차 경화된 상태에 있는 하드코트층이 충분한 경도를 가지고 있지 않아도, 보호층을 구비함으로써, 예컨대, 필름을 성형할 때에 하드코트층에 손상 등이 잘 생기지 않는다. 보호층은, 예컨대, 용매에 용해 또는 분산된 수지를 하드코트층에 도포한 후, 용매를 휘발시킴으로써 형성할 수 있다. 이렇게 함으로써, 점착제가 부착된 필름 등으로 이루어진 보호층을 이용하는 경우와 같이, 점착제가 하드코트층 표면에 남아, 외관상 문제가 생길 우려가 없다.The film of the present invention preferably has a protective layer above the hard coat layer. Even when the hard coat layer in the primary hardened state does not have sufficient hardness, the hard coat layer is not easily damaged, for example, when the film is formed by providing the protective layer. The protective layer can be formed, for example, by applying a resin dissolved or dispersed in a solvent to a hard coat layer and then volatilizing the solvent. By doing so, there is no fear that the pressure-sensitive adhesive remains on the surface of the hard coat layer, as in the case of using a protective layer made of a film or the like with a pressure-sensitive adhesive attached thereto, thereby causing no apparent problem.
보호층을 형성하기 위해 이용되는 수지는, 1차 경화상태의 하드코트층을 보호할 수 있을 만큼의 경도를 가지고, 하드코트층과의 밀착성이 양호하며, 하드코트층으로부터 박리될 때에 표면에 남지 않는 수지가 더욱 바람직하다. 이러한 수지로서, 예컨대, 폴리비닐알코올(PVA), 폴리에틸렌 옥사이드(PEO), 폴리비닐알코올 변성의 폴리비닐 아세탈수지, 폴리아크릴산 나트륨 등을 들 수 있고, 용매에 분산된 수지로서, 초산비닐에멀젼, 에틸렌 초산비닐(EVA)에멀젼, 아크릴에멀젼, 아크릴스티렌에멀젼, 염화비닐리덴에멀젼, 우레탄에멀젼, 분산형 불소수지 등을 들 수 있다. 이 중에서도 폴리비닐알코올이 바람직하다.The resin used for forming the protective layer has a hardness enough to protect the hard coat layer in the primary hardened state and has good adhesion with the hard coat layer and remains on the surface when peeled from the hard coat layer Is more preferable. Examples of such a resin include polyvinyl alcohol (PVA), polyethylene oxide (PEO), polyvinyl acetal resin denatured with polyvinyl alcohol, and sodium polyacrylate. Resins dispersed in a solvent include vinyl acetate emulsion, ethylene Vinyl acetate (EVA) emulsion, acrylic emulsion, acryl styrene emulsion, vinylidene chloride emulsion, urethane emulsion, and dispersion type fluorine resin. Of these, polyvinyl alcohol is preferred.
또한, 보호층을 형성하는 수지에 염료, 안료, 소광제, 대전방지제, 소포제, 레벨링제, 증점제, pH 조정제, 내수화제, 가교제 등을 첨가해도 된다. 하드코트층 상에 형성된 보호층은 ２차 경화 전에 적절히 제거할 수 있다.Further, dyes, pigments, quenching agents, antistatic agents, antifoaming agents, leveling agents, thickening agents, pH adjusting agents, water resistance agents, crosslinking agents and the like may be added to the resin forming the protective layer. The protective layer formed on the hard coat layer can be appropriately removed before the second hardening.
본 발명의 필름은, 예컨대, 필름기재에 이형(離型)처리를 실시하여, 하드코트층을 전사 가능한 전사필름으로 할 수 있다. 이 경우, 다른 부재(다른 필름이어도 됨)의 표면에 하드코트층을 전사할 수 있다. 이형처리로서는, 예컨대 실리콘 처리 등을 들 수 있다.In the film of the present invention, for example, a film base material may be subjected to a release treatment to form a transfer film capable of transferring the hard coat layer. In this case, the hard coat layer can be transferred to the surface of another member (which may be another film). Examples of the mold-releasing treatment include silicone treatment and the like.
본 발명의 필름은, 예컨대, 몰드재(型材)에 가압되어 성형된 것이어도 된다. 본 발명의 필름을 구성하는 하드코트층은 성형하여도 균열이 잘 생기지 않는다.The film of the present invention may be molded, for example, by being pressed onto a mold material. The hard coat layer constituting the film of the present invention is not easily cracked even when molded.
본 발명의 필름은, 예컨대, 하드코트층이 활성에너지선에 의해 2차 경화된 상태에 있어도 된다. 이 상태일 때, 하드코트층은 경도나 내찰과상성이 우수하다.For example, the film of the present invention may be in a state in which the hard coat layer is secondarily cured by an active energy ray. In this state, the hard coat layer is excellent in hardness and abrasion resistance.
본 발명의 필름에서의 필름기재로서는, 예컨대, 폴리에틸렌 테레프탈레이트 필름, 폴리부틸렌 테레프탈레이트 필름, 폴리에틸렌 나프탈레이트 필름, 폴리에틸렌 필름, 폴리프로필렌 필름, 셀로판, 디아세틸셀룰로오스 필름, 트리아세틸셀룰로오스 필름, 아세틸셀룰로오스 부틸레이트 필름, 폴리염화비닐 필름, 폴리염화비닐리덴 필름, 폴리비닐알코올 필름, 에틸렌-초산비닐 공중합체 필름, 폴리스티렌 필름, 폴리카보네이트 필름, 폴리메틸펜텐 필름, 폴리술폰필름, 폴리에테르에테르케톤 필름, 폴리에테르술폰 필름, 폴리에테르이미드 필름, 폴리이미드 필름, 불소수지 필름, 나일론 필름, 아크릴수지 필름 등을 들 수 있다.Examples of the film substrate in the film of the present invention include a polyethylene terephthalate film, a polybutylene terephthalate film, a polyethylene naphthalate film, a polyethylene film, a polypropylene film, a cellophane, a diacetylcellulose film, a triacetylcellulose film, Polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyetheretherketone film, A polyether imide film, a polyimide film, a fluororesin film, a nylon film, and an acrylic resin film.
또, 필름기재와 수지조성물과의 밀착성을 향상시키기 위해, 필름기재에 대하여 샌드블라스트법이나 용제처리법 등에 의한 표면의 요철화 처리, 혹은 코로나 방전처리, 크롬산처리, 화염처리, 열풍처리, 오존·자외선 조사처리 등 표면의 산화처리와 같은 표면처리를 실시해도 된다.In order to improve the adhesion between the film substrate and the resin composition, the surface of the film substrate is subjected to a surface irregularization treatment such as a sand blasting method or a solvent treatment method, a corona discharge treatment, a chromic acid treatment, a flame treatment, a hot air treatment, A surface treatment such as an oxidation treatment of the surface such as an irradiation treatment may be performed.
수지조성물의 필름기재로의 도포방법에 대해서는 특별히 제한은 없으며, 공지된 방법, 예컨대, 그라비아 코트법, 바 코트법, 나이프 코트법, 롤 코트법, 블레이드 코트법, 다이 코트법 등을 이용할 수 있다. 예컨대, 건조·경화 처리후의 막두께가 1 ~ 200㎛가 되도록 도공하고, 건조·경화 처리한다.There is no particular limitation on the method of applying the resin composition to the film base, and known methods such as gravure coating method, bar coating method, knife coating method, roll coating method, blade coating method and die coating method can be used . For example, it is coated so as to have a thickness of 1 to 200 mu m after the drying and curing treatment, followed by drying and curing treatment.
(4) 본 발명의 성형체의 제조방법(4) Method for producing molded article of the present invention
본 발명의 성형체의 제조방법은, 상기 (3)의 필름을 몰드재에 가압하고, 탈형(脫型)후, 활성에너지선에 의해 상기 하드코트층을 2차 경화시키는 것을 특징으로 한다.The method for producing a molded article of the present invention is characterized in that the film of the above (3) is pressed onto a mold material and is de-molded, followed by secondary hardening of the hard coat layer with an active energy ray.
본 발명에 따르면, 성형시에 하드코트층이 깨지는 경우가 잘 생기지 않는다. 또한, 하드코트층은 2차 경화되어 있지 않은 상태에서도 점착성이 잘 생기지 않으므로, 필름간의 블록킹이나 성형시에서의 필름과 금형의 블록킹을 방지할 수 있다. 또한, 2차 경화후의 하드코트층은 경도나 내찰과상성이 우수하다.According to the present invention, the hard coat layer is not easily broken at the time of molding. In addition, since the hard coat layer does not adhere well even when the film is not cured secondarily, blocking between the films and blocking of the film and the mold at the time of molding can be prevented. The hard coat layer after the secondary curing is excellent in hardness and abrasion resistance.
본 발명에 관한 필름 성형체(6; 성형체)의 제조방법의 구체예를 도 1의 (a)-(d)에 근거하여 설명한다. 우선, 필름기재(9)에 수지조성물(1)을 도포한다(도 1의 (a)). 이때, 수지조성물(1)은 액체상태이다. 그 다음으로, 수지조성물(1)을 가열·건조에 의해 열경화시켜, 하드코트층(2)을 형성하고, 성형용 필름(5)을 얻는다(도 1의 (b)). 이 때, 하드코트층(2)은 고체이며 1차 경화된 상태에 있다. 이어서, 몰드재(도시생략)에 성형용 필름(5)을 가압하고, 탈형후(도 1의 (c)), 자외선을 조사하여 하드코트층(2)을 2차 경화시키면 필름 성형체(6)가 얻어진다(도 1의 (d)).A specific example of a method for producing the film formed article (6; molded article) according to the present invention will be described with reference to Figs. 1 (a) to 1 (d). First, the resin composition 1 is applied to the film base 9 (Fig. 1 (a)). At this time, the resin composition (1) is in a liquid state. Next, the resin composition 1 is thermally cured by heating and drying to form the hard coat layer 2 to obtain a molding film 5 (Fig. 1 (b)). At this time, the hard coat layer 2 is solid and is in a primary hardened state. 1 (c)), the hard coat layer 2 is secondarily cured by irradiating ultraviolet rays to form the film molded
도 1의 (a)-(d)는 필름 성형체의 제조방법을 나타내는 설명도이다.1 (a) to 1 (d) are explanatory diagrams showing a method for producing a film-formed article.
본 발명의 실시형태를 설명한다.An embodiment of the present invention will be described.
(실시예 1)(Example 1)
(a) 수지조성물(하드코팅제)의 제조(a) Production of resin composition (hard coating agent)
표 1 ~ 표 3에 나타낸 각 성분을 배합하여, 실시예 1-1 ~ 1-18 및 비교예 1 ~ 2의 수지조성물을 제조하였다. 또, 표 1 ~ 표 3은 고형분 환산에서의 배합량을 나타낸다. 수지조성물은, A제, B제의 2제식이며, A제, B제를 각각 제조하였다. A 제는, 표 1 ~ 표 3에서의 A제란에 기재된 성분을 포함하며, MEK(메틸에틸케톤)를 용매로 하는 고형분 40중량%의 용액이다. B제는, 표 1 ~ 표 3에서의 B제란에 기재된 성분을 포함하며, 톨루엔을 용매로 하는 용액이다.Each of the components shown in Tables 1 to 3 was blended to prepare the resin compositions of Examples 1-1 to 1-18 and Comparative Examples 1 and 2. Tables 1 to 3 show blending amounts in terms of solid content. The resin composition was an A-type and B-type two-component, and A-type and B-type were respectively prepared. The agent A is a solution containing 40 wt% of a solid component containing MEK (methyl ethyl ketone) as a solvent and containing the components described in the column A of Tables 1 to 3. The agent B is a solution containing the components described in the column B in Tables 1 to 3 and containing toluene as a solvent.
수지조성물을 사용할 때에는 A제와 B제를 중량비 1:1로 혼합한다. 또, B제의 고형분비는, A제와 B제를 중량비 1:1로 혼합했을 때에 수지조성물의 배합비가 고형분 환산으로 표 1 ~ 표 3에 나타낸 배합비가 되도록 설정되어 있다.When using the resin composition, the A agent and the B agent are mixed at a weight ratio of 1: 1. The solid content ratio of the component B is set such that the compounding ratio of the resin composition when mixing the component A and the component B in a weight ratio of 1: 1 is the composition ratio shown in Tables 1 to 3 in terms of solid content.
참고로, 표 1 ~ 표 3에서 U-15HA는 (주)신나카무라카가쿠고교 제품인 우레탄아크릴레이트의 상품명이다. 빔 세트 371은 (주)아라카와카가쿠고교 제품인 아크릴아크릴레이트의 상품명이다. 아로닉스 M7300K는 (주)토아고세이 제품인 폴리에스테르아크릴레이트의 상품명이다.For reference, in Tables 1 to 3, U-15HA is a trade name of urethane acrylate manufactured by Shin Nakamura Kagaku Kogyo Co., Ltd. The beam set 371 is a trade name of acrylic acrylate manufactured by Arakawa Chemical Industries, Ltd. Aronix M7300K is a trade name of polyester acrylate manufactured by TOAGOSEI CO., LTD.
DPHA(디펜타에리트리톨헥사아크릴레이트), U-15HA, 빔 세트 371 및 아로닉스 M7300K는, 각각 2개 이상의 아크릴로일기를 갖는 다관능 중합성 화합물에 해당한다.DPHA (dipentaerythritol hexaacrylate), U-15HA, Beam set 371 and Aronix M7300K correspond to polyfunctional polymerizable compounds having two or more acryloyl groups, respectively.
또한, Irg 2959는 치바·재팬의 제품인 UV 개시제의 상품명이다. BYK 310은, (주)빗크케미·재팬의 제품인 레벨링제의 상품명이다.Irg 2959 is a trade name of a UV initiator, a product of Chiba Japan. BYK 310 is a trade name of leveling agent which is a product of Birch Chemie Japan.
또한, DETA(디에틸렌트리아민), TETA(트리에틸렌테트라민) 및 PEHA(펜타에틸렌헥사민)는 각각 저분자량 아민에 해당한다.Further, DETA (diethylenetriamine), TETA (triethylenetetramine) and PEHA (pentaethylene hexamine) correspond to low molecular weight amines, respectively.
또한, 폴리멘트 NK-350 및 폴리멘트 NK-380은, 각각 (주)니혼쇼쿠바이 제품인 폴리아민의 상품명이다.Further, Polymer NK-350 and Polymer NK-380 are trade names of polyamines manufactured by Nihon Shokubai Co., Ltd.
또한, U-CAT SA 1은, (주) 산아프로 제품인 DBU-페놀염의 상품명이다. U-CAT SA 102는, (주) 산아프로 제품인 CBU-옥틸산염의 상품명이다. U-CAT 1102는, (주) 산아프로 제품인 DBN-옥틸산염의 상품명이다.U-CAT SA 1 is a trade name of DBU-phenol salt which is a product of San-a Co., Ltd. U-CAT SA 102 is a trade name of CBU-octylate, manufactured by SAN-A Co., Ltd. U-CAT 1102 is a trade name of DBN-octylate, a product of San-a Co., Ltd.
U-CAT SA 1, U-CAT SA 102 및 U-CAT 1102는, 각각 감온성 촉매에 해당한다.U-CAT SA 1, U-CAT SA 102 and U-CAT 1102 correspond to a thermosensitive catalyst, respectively.
(b) 필름 및 성형체의 제조(b) Production of film and molded article
상기 (a)에서 제조한 수지조성물을, 두께 100㎛의 PET 필름((주)도요보세키 제품, 상품명:코스모 샤인 A4300-188)에, 경화후의 막두께가 5㎛가 되도록 도포하였다.The resin composition prepared in (a) above was applied to a PET film (trade name: Cosmo Shine A4300-188, product of Toyo Boseki Co., Ltd.) having a thickness of 100 占 퐉 so that the film thickness after curing became 5 占 퐉.
다음으로, 도포한 수지조성물을 110℃에서 3분간 건조시켜(1차 경화시켜), 고체의 하드코트층을 형성하고, 성형용 필름을 얻었다. 다음으로, 이 성형용 필름을 몰드재에 가압하고, 탈형하였다. 이후, 자외선 조사기를 이용해서, 자외선을 200mJ/cm2의 강도로 조사하여, 하드코트층의 자외선 경화(2차 경화)를 행하고, 필름 성형체를 완성하였다.Next, the applied resin composition was dried (primary curing) at 110 캜 for 3 minutes to form a solid hard coat layer, and a molding film was obtained. Next, this molding film was pressed onto the mold material and demolded. Thereafter, the hard coat layer was irradiated with ultraviolet rays at an intensity of 200 mJ / cm 2 using an ultraviolet light irradiator, and ultraviolet curing (secondary curing) was performed to complete the film mold.
(c) 수지조성물 및 성형용 필름의 평가(c) Evaluation of resin composition and molding film
상기 (a) ~ (b)에서 제조한 수지조성물 및 성형용 필름에 대해서, 외관, 포트 라이프, 점착성, 성형성 및 연필경도를 시험하였다. 시험방법 및 평가기준은 다음과 같다.The appearance, pot life, tackiness, moldability and pencil hardness of the resin composition and the molding film prepared in the above (a) to (b) were tested. Test methods and evaluation criteria are as follows.
(외관) 육안으로 도포막 외관을 관찰하였다. 도포막이 클리어하면 ○로 평가하고, 백화되어 있으면 ×로 평가하였다.(Appearance) The appearance of the coated film was visually observed. When the coating film was cleared, it was evaluated as?, And when it was whitened, it was evaluated as?.
(포트라이프) 수지조성물이 상온하에서 겔화될 때까지의 시간을 측정하였다.(Portlife) The time until the resin composition gelated at room temperature was measured.
(점착성) PET 필름에 수지조성물을 도포하고, 110℃에서 3분간 건조시킨 후, 검지손가락으로 수지조성물을 만져 판단하였다. 판단기준은 다음과 같이 하였다. 또, 비교예 2에 대해서만 수지조성물이 ２차 경화된 후에 있어서도 동일하게 시험을 실시하였다.(Tackiness) The resin composition was applied to a PET film, dried at 110 캜 for 3 minutes, and then evaluated by touching the resin composition with the index finger. The criteria were as follows. Also, the test was carried out in the same manner even after the resin composition was secondarily cured only in Comparative Example 2.
5: 완전히 점착성 없음5: Not completely tacky
4: 거의 점착성 없음4: Almost no tacky
3: 대체로 점착성 없음3: Generally not tacky
2: 약간 점착성 있음2: slightly sticky
1: 점착성 잔존1: stickiness remaining
(성형성) 성형용 필름(하드코트층은 1차 경화된 상태)을 성형용 금형에 가압하여, 크랙이 생기지 않으면 ○로 평가하고, 크랙이 생기면 ×로 평가하였다. 또, 비교예 2에 대해서만은 2차 경화후의 성형용 필름에 대해서도 마찬가지로 시험을 실시하였다.(Moldability) The molding film (the hard coat layer was in a primary cured state) was pressed against the molding die. When the mold was not cracked, the evaluation was evaluated as & cir & In addition, only the molding for Comparative Example 2 was subjected to the same test for the secondarily cured molding film.
(연필경도) 성형용 필름(하드코트층은 2차 경화된 상태)에 대하여, JIS K5400에 준거하여 연필경도시험을 실시하였다. 시험은, 연필경도가 2H인 경우와 H인 경우에 실시하였다. 또한, 각각의 연필경도에 있어서 5회 시험을 실시하였다. 5회 중, 하드코트층에 손상이 생기지 않은 횟수를 상기 표 1 ~ 표 3에 기재한다.(Pencil hardness) The molding film (the hard coat layer was in a secondary cured state) was subjected to a pencil hardness test according to JIS K5400. The test was conducted when the pencil hardness was 2H and when the pencil hardness was H. In addition, five pencil hardness tests were carried out. The number of times the hard coat layer was not damaged during 5 times is shown in Tables 1 to 3 above.
상기 표 1 ~ 표 3에 평가결과를 나타낸다. 표 1 ~ 표 3에 나타낸 바와 같이, 실시예 1-1 ~ 1-18에 대해서는, 하드코트층의 외관은 양호하고, 수지조성물의 포트 라이프는 길고, 1차 경화된 상태의 하드코트층에는 점착성이 생기지 않고, 성형용 필름의 성형성도 양호하였다. 또한, 2차 경화된 상태의 하드코트층은 경도가 높았다.The evaluation results are shown in Tables 1 to 3 above. As shown in Tables 1 to 3, in Examples 1-1 to 1-18, the appearance of the hard coat layer was favorable, the pot life of the resin composition was long, and the hard coat layer in the primary hardened state had adhesiveness And the moldability of the molding film was good. Further, the hard coat layer in the secondary hardened state had a high hardness.
특히, 저분자량 아민과 폴리아민을 병용한 실시예 1-1은, 저분자량 아민과 폴리아민 중 한쪽만을 배합한 실시예 1-8 ~ 1-9 보다, 점착성이 한층 생기기 어려웠다. 또한, 감온성 촉매를 배합한 실시예 1-1은, 감온성 촉매를 배합하지 않은 실시예 1-10에 비해, 점착성이 한층 생기기 어려웠다.In particular, in Example 1-1 in which a low molecular weight amine and a polyamine were used in combination, adhesiveness was more difficult to be obtained than in Examples 1-8 to 1-9 in which only one of low molecular weight amine and polyamine was blended. In addition, Example 1-1 in which a thermosensitive catalyst was blended was less likely to have adhesiveness than Example 1-10 in which a thermosensitive catalyst was not blended.
(실시예 2)(Example 2)
기본적으로는 상기 실시예 1의 (a) ~ (b)와 마찬가지로 하여 성형용 필름을 제조하였다. 단, 본 실시예 2에서는 하드코트층을 형성하고, 이것을 1차 경화시킨 후, 하드코트층에 PVA를 도포하고, 보호층을 형성하였다. 이후, 상기 실시예 1과 마찬가지로 하여 필름 성형체를 얻었다. 마지막으로, 보호층을 박리하였다. 본 실시예 2에서는, 하드코트층 상에 보호층이 형성된 상태에서 성형을 실시하였으므로, 하드코트층에 손상이 잘 생기지 않았다. 또한, 보호층을 박리한 후, 하드코트층의 표면에는 전혀 자국이 남아 있지 않았다.Basically, a molding film was produced in the same manner as in Example 1 (a) to (b). However, in Example 2, a hard coat layer was formed, and after hardening the hard coat layer, PVA was applied to the hard coat layer to form a protective layer. Thereafter, a film molded article was obtained in the same manner as in Example 1 above. Finally, the protective layer was peeled off. In Example 2, since molding was performed in a state in which the protective layer was formed on the hard coat layer, the hard coat layer was not easily damaged. After the protective layer was peeled off, no marks remained on the surface of the hard coat layer.
(실시예 3)(Example 3)
기본적으로는 상기 실시예 1의 (a) ~ (b)와 마찬가지로 하여 성형용 필름을 제조하였다. 단, 본 실시예 3에서는 하드코트층을 형성하고, 이것을 1차 경화시킨 후, 하드코트층 상에 점착제가 부착된 필름을 부착하여 보호층을 형성하였다. 이후, 상기 실시예 1과 마찬가지로 하여 필름 성형체를 얻었다. 마지막으로, 보호층을 박리하였다. 본 실시예 3에서는, 하드코트층 상에 보호층이 형성된 상태에서 성형을 실시하였으므로, 하드코트층에 손상이 잘 생기지 않았다. 다만, 보호층을 박리한 후, 하드코트층의 표면에는 약간 점착제가 남아 있었다.Basically, a molding film was produced in the same manner as in Example 1 (a) to (b). However, in Example 3, a hard coat layer was formed, and after curing the hard coat layer, a film having an adhesive attached thereto was formed on the hard coat layer to form a protective layer. Thereafter, a film molded article was obtained in the same manner as in Example 1 above. Finally, the protective layer was peeled off. In Example 3, molding was performed in a state where the protective layer was formed on the hard coat layer, so that the hard coat layer was not damaged well. However, after the protective layer was peeled off, a little pressure-sensitive adhesive remained on the surface of the hard coat layer.
(실시예 4)(Example 4)
기본적으로는 상기 실시예 1의 (a) ~ (b)와 마찬가지로 하여, 성형용 필름을 제조하였다. 단, 본 실시예에서는 수지조성물을 도포하는 필름기재로서, 이형 PET 필름((주)도요보세키 제품, 상품명: TN110)을 이용하였다. 상기 이형 PET 필름은 이형처리가 실시되어 있어, 이후에, 수지조성물로 이루어진 층(하드코트층)을 용이하게 이형시킬 수가 있다.Basically, a molding film was produced in the same manner as in Example 1 (a) to (b). However, in this embodiment, a release PET film (trade name: TN110 available from Toyo Boseki Co., Ltd.) was used as a film substrate to which the resin composition was applied. The release PET film is subjected to releasing treatment so that the layer (hard coat layer) comprising the resin composition can be easily released thereafter.
본 실시예의 성형용 필름은 전사필름으로서 사용할 수 있다. 전사필름은 예컨대, 아래와 같이 사용할 수 있다. 먼저, 성형용 필름 중, 하드코트층이 형성된 쪽을 성형재료쪽에 맞닿게 하여, 성형을 행한다. 이때, 하드코트층은 1차 경화된 상태이다. 다음으로, 이형 PET 필름을 제거한다. 이때, 성형재료의 표면에 하드코트층이 부착되어 있다. 다음으로, 자외선을 조사하고 하드코트층을 2차 경화시킨다. 또한, 본 실시예의 성형용 필름은 인몰드 사출성형에 이용할 수도 있다.The molding film of this embodiment can be used as a transfer film. The transfer film can be used, for example, as follows. First, among the molding films, the side where the hard coat layer is formed is brought into contact with the molding material side, and molding is performed. At this time, the hard coat layer is in a primary hardened state. Next, the release PET film is removed. At this time, a hard coat layer is attached to the surface of the molding material. Next, ultraviolet rays are irradiated and the hard coat layer is secondarily cured. The molding film of this embodiment can also be used for in-mold injection molding.
또, 본 발명은 상기 실시예에 조금도 한정되는 것은 아니며, 본 발명을 일탈하지 않는 범위에서 다양한 양태로 실시할 수 있음은 말할 필요도 없다.It is needless to say that the present invention is not limited to the above-described embodiments, but can be carried out in various forms without departing from the scope of the present invention.
1 : 수지조성물
2 : 하드코트층
5 : 성형용 필름
6 : 필름 성형체
9 : 필름기재1: Resin composition
2: Hard coat layer
5: Molding film
6: Film molding body
9: Film substrate
Claims (14)
상기 아크릴로일기에 부가반응 가능한 화합물로서, 분자량이 50 내지 400인 저분자량 아민과 분자량이 1만 내지 20만인 폴리아민을 함유하는 것을 특징으로 하는, 수지조성물.A polyfunctional polymerizable compound having at least two acryloyl groups and a compound capable of addition reaction with an acryloyl group,
Wherein the compound capable of addition reaction with the acryloyl group contains a low molecular weight amine having a molecular weight of 50 to 400 and a polyamine having a molecular weight of 10,000 to 200,000.
감온성 촉매를 더 함유하는 것을 특징으로 하는 수지조성물.The method according to claim 1,
And a thermosensitive catalyst.
감온성 촉매로서 DBN-옥틸산염을 함유하며,
다관능 중합성 화합물 100 중량부에 대해, 상기 저분자량 아민 및 폴리아민의 합계 함유량이 15 내지 50 중량부이고, 상기 DBN-옥틸산염의 함유량이 10 내지 20 중량부인 것을 특징으로 하는 수지 조성물.3. The method of claim 2,
Containing DBN-octylate as a thermosensitive catalyst,
Wherein the total content of the low molecular weight amine and the polyamine is 15 to 50 parts by weight and the content of the DBN-octylate is 10 to 20 parts by weight based on 100 parts by weight of the multifunctional polymerizable compound.
상기 하드코트층이 1차 경화된 상태에 있는 것을 특징으로 하는 필름.6. The method of claim 5,
Wherein the hard coat layer is in a first cured state.
상기 하드코트층보다 상층에 보호층을 구비하는 것을 특징으로 하는 필름.6. The method of claim 5,
And a protective layer on the upper layer than the hard coat layer.
상기 보호층은, 용매에 용해 또는 분산된 수지를 상기 하드코트층에 도포한 후, 상기 용매를 휘발시킴으로써 형성된 것을 특징으로 하는 필름.8. The method of claim 7,
Wherein the protective layer is formed by applying a resin dissolved or dispersed in a solvent to the hard coat layer and then volatilizing the solvent.
상기 보호층을 형성하는 수지로서, 폴리비닐알코올을 함유하는 것을 특징으로 하는 필름.9. The method of claim 8,
A film comprising polyvinyl alcohol as the resin for forming the protective layer.
상기 필름기재에 이형(離型)처리가 실시되어 있고, 상기 하드코트층을 전사할 수 있는 것을 특징으로 하는 필름.6. The method of claim 5,
Wherein the film substrate is subjected to a releasing treatment to transfer the hard coat layer.
몰드재(型材)에 가압되어, 성형된 것을 특징으로 하는 필름.6. The method of claim 5,
Is pressed onto a mold material and molded.
상기 하드코트층이 활성에너지선에 의해 2차 경화된 상태에 있는 것을 특징으로 하는 필름.6. The method of claim 5,
Wherein the hard coat layer is in a state of being secondarily cured by an active energy ray.
A process for producing a molded article, characterized in that the film according to claim 5 is pressed onto a mold material, and after the mold is demolded, the hard coat layer is secondarily cured by an active energy ray.
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| KR101291937B1 (en) | 2011-04-15 | 2013-07-31 | (주)엘지하우시스 | Hard-coating composition and sheet for forming hard-coating with excellent low temperature formability and slip property |
| CN103631459B (en) * | 2012-08-26 | 2016-12-21 | 宝宸（厦门）光学科技有限公司 | Touch-control sensing layer and manufacture method thereof |
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| WO2021140875A1 (en) * | 2020-01-08 | 2021-07-15 | リケンテクノス株式会社 | Coating material for forming b-stage coating film, b-stage coating film, and method for producing b-stage coating film |
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| JPH1192546A (en) * | 1997-09-22 | 1999-04-06 | Toyo Ink Mfg Co Ltd | Curable resin composition |
| JP2000017030A (en) * | 1998-07-02 | 2000-01-18 | Dainippon Ink & Chem Inc | Active energy ray curable aqueous resin composition |
| JP3984488B2 (en) * | 2001-03-27 | 2007-10-03 | 日本ペイント株式会社 | Curable coating composition and coating film forming method |
| US6897264B2 (en) * | 2001-12-21 | 2005-05-24 | Dainippon Ink And Chemicals, Inc. | Curable mixtures |
| CA2414719C (en) * | 2001-12-21 | 2009-07-21 | Dainippon Ink And Chemicals, Inc. | Curable resin compositions and process for preparing oligomers containing acrylate groups and substituted methacrylate groups |
| EP1593728B1 (en) * | 2004-05-03 | 2012-05-09 | Rohm And Haas Company | Michael addition compositions |
| US7799943B2 (en) * | 2005-06-24 | 2010-09-21 | Rohm And Haas Company | Method for promoting Michael addition reactions |
| JP5186768B2 (en) * | 2006-06-16 | 2013-04-24 | 東洋インキＳｃホールディングス株式会社 | Antistatic curable composition, cured film and laminate |
-
2009
- 2009-03-24 TW TW098109467A patent/TWI449713B/en not_active IP Right Cessation
- 2009-03-24 KR KR1020107023668A patent/KR101579276B1/en not_active IP Right Cessation
- 2009-03-24 CN CN200980110485.7A patent/CN101981068B/en not_active Expired - Fee Related
- 2009-03-24 JP JP2009072151A patent/JP5654207B2/en not_active Expired - Fee Related
- 2009-03-24 WO PCT/JP2009/055833 patent/WO2009119588A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003051139A (en) | 2000-11-29 | 2003-02-21 | Sony Corp | Sheet member for forming optical transmission layer and manufacturing method for optical recording medium |
| JP2005505653A (en) | 2001-10-12 | 2005-02-24 | アシュランド インコーポレイテッド | Self-initiated polyfunctional acrylate |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201000499A (en) | 2010-01-01 |
| JP2010084120A (en) | 2010-04-15 |
| TWI449713B (en) | 2014-08-21 |
| KR20100139060A (en) | 2010-12-31 |
| CN101981068B (en) | 2014-10-29 |
| JP5654207B2 (en) | 2015-01-14 |
| WO2009119588A1 (en) | 2009-10-01 |
| CN101981068A (en) | 2011-02-23 |
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