KR100691858B1 - Resin composition for cellular phone - Google Patents

Resin composition for cellular phone Download PDF

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Publication number
KR100691858B1
KR100691858B1 KR1020050094527A KR20050094527A KR100691858B1 KR 100691858 B1 KR100691858 B1 KR 100691858B1 KR 1020050094527 A KR1020050094527 A KR 1020050094527A KR 20050094527 A KR20050094527 A KR 20050094527A KR 100691858 B1 KR100691858 B1 KR 100691858B1
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weight
resin composition
acrylate
resin
acrylic
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KR1020050094527A
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Korean (ko)
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황영상
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주식회사 디에프씨
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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
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C08L83/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Abstract

Provided is a resin composition for a mobile phone which is excellent in self-restoration, scratch resistance, cosmetic resistance, impact resistance and abrasion resistance. The resin composition comprises 10-30 wt% of an acrylic resin copolymer; 5-15 wt% of a silicone modified acrylic resin having a hydroxyl functional group; 1.0-5.0 wt% of a polyester-hydroxy modified polysiloxane compound; 0.5-3.0 wt% of an alkoxysilane compound; 0.1-0.5 wt% of a catalyst; 25-50 wt% of a resin diluent; and 20-40 wt% of an isocyanate curing agent. Preferably, the silicon modified acrylic resin has a hydroxyl number of 10-100 mg KOH/g and a weight average molecular weight of 3,000-50,000 and contains 5-40 wt% of silicon; and the polyester-hydroxy modified polysiloxane compound has a hydroxyl number of 30-120 mg KOH/g and a weight average molecular weight of 1,000-30,000 and contains 20-60 wt% of silicon.

Description

핸드폰용 수지 조성물{Resin composition for cellular phone}Resin composition for cellular phone

본 발명은 핸드폰의 표면 코팅제에 있어서 고객의 불만인 긁힘으로 인한 스크래치가 발생되거나 낙구 시 깨짐, 표면손상, 외부환경 노출 시의 오염, 지속적인 장기 사용 시 눌림 등에 의한 자국 발생 등의 문제를 개선한 우수한 핸드폰용 표면 코팅제에 관한 것으로서, 더욱 상세하게는 분자 내에 실리콘, 아크릴을 함유시킴으로써 이소시아네이트와 반응 시 아크릴, 실리콘, 우레탄의 사다리구조를 갖게 함으로써, 기존의 수지 조성물에서는 갖지 못하던 도막의 자기복원성을 비롯하여 우수한 내침염성, 내스크래치성, 내화장품성, 내충격성, 내마모성이 우수한 수지조성물 제조방법에 관한 것이다. The present invention is excellent in improving the problems such as scratches caused by the customer's dissatisfied scratches on the surface coating of the mobile phone, cracks when falling, surface damage, contamination when exposed to the external environment, pressing due to long-term use, etc. The present invention relates to a surface coating agent for mobile phones, and more particularly, by containing silicone and acryl in a molecule to have a ladder structure of acryl, silicone, and urethane when reacting with isocyanate, thereby providing excellent self-resilience of the coating film which is not available in conventional resin compositions. The present invention relates to a method for producing a resin composition having excellent stain resistance, scratch resistance, cosmetic resistance, impact resistance, and wear resistance.

본 발명에 따른 핸드폰용 수지 조성물은 이러한 특성으로 인하여 사용 중의 오염, 긁힘, 눌림, 깨짐 등의 표면 손상을 현저히 감소시켜 핸드폰이 외부환경에의 지속적인 노출과 장기 사용 시 내구성을 유지할 수 있다. Due to these characteristics, the resin composition for a mobile phone according to the present invention can significantly reduce surface damage such as contamination, scratches, crushing, and cracking during use, so that the mobile phone can maintain its durability when exposed to the external environment and its long-term use.

핸드폰은 표면보호 외관향상을 목적으로 대부분 유광 및 무광수지를 코팅 처리하여 제조하게 된다. 이러한 핸드폰 표면 보호 코팅제로서의 종래의 기술을 살펴 보면 일반 소부형 타입의 수성 또는 유성 우레탄레진을 코팅하거나 광경화 타입의 우레탄-아크릴레이트수지, 에폭시-아크릴레이트수지를 도포하여 핸드폰외관을 보호하는 상기의 목적을 이루려고 하고 있으나 기존의 사용되는 수지조성물의 분자구조로 인한 도막물성 특성상 핸드폰을 장기간 사용 시 크고 작은 스크래치 등의 흠집 발생이 매우 높으며 외부환경 및 파손에 의한 빈번한 접촉에 의하여 표면도막의 오염, 벗겨짐 눌림이 쉽게 되는 편이며, 사용 시 부주의로 인하여 바닥 등에 낙구 시 도막의 표면 깨짐, 손상이 자주 보고되고 있는 실정이다.Cell phones are mostly manufactured by coating glossy and matt resins for the purpose of improving surface protection. Looking at the conventional technology as such a mobile phone surface protective coating agent is to coat the water-based or oil-based urethane resin of the general small-type type or photocurable type urethane-acrylate resin, epoxy-acrylate resin to protect the appearance of the mobile phone However, due to the nature of the coating film due to the molecular structure of the resin composition used, scratches such as large and small scratches are very high when the cellular phone is used for a long period of time. Peeling is easily pressed, and the surface crack and damage of the coating film are frequently reported when falling on the floor due to careless use.

이와 같은 문제점을 개선하기 위하여서 일본 공개특허공보 제 2000-293895호에서는 표면 처리된 실리카와 광경화 타입의 아크릴레이트를 이용하여 내스크래치성의 향상을 이룰 수 있었으나, 실리카의 도입으로 표면외관의 광 특성이 저하되고 표면오염이 더욱 심화되는 결과를 나타내는 문제점을 드러내었다.In order to improve such a problem, Japanese Laid-Open Patent Publication No. 2000-293895 uses the surface-treated silica and the photocurable acrylate to improve scratch resistance, but the introduction of silica improves the optical properties of the surface appearance. It has been shown to cause problems that result in lowering and intensifying surface contamination.

이를 개선하기 위해 일본 공개특허공보 평 11-293159호에서는 불소계 화합물을 첨가한 아크릴하드코팅제를 제시하였으나, 불소계 화합물을 첨가함으로써 내 오염성 개선의 목적은 이룰 수 있었으나, 반면에 막의 경도가 저하되어 표면 긁힘 등의 문제점을 나타내며 다층 코팅 시 베이스코트와의 상용성이 극도로 저하되어 현실적으로 적용이 어렵게 되었다. In order to improve this, Japanese Laid-Open Patent Publication No. 11-293159 proposes an acrylic hard coating agent to which a fluorine-based compound is added. However, by adding a fluorine-based compound, the purpose of improving the contamination resistance can be achieved. In addition, the compatibility with the base coat is extremely reduced when the multilayer coating is applied, making it difficult to apply in reality.

이와 같은 이유로 인하여 상기의 지적한 물성의 향상 및 개선을 위해 고품질의 고기능을 요하는 핸드폰 코팅용 수지조성물의 연구가 필요한 실정이다.For this reason, there is a need for research on resin compositions for cellular phone coatings that require high quality and high functionality for improving and improving the physical properties.

상기와 같은 종래기술의 문제점을 해결하고자 본 발명을 연구 개발한 것으로서, 본 발명에서는 핸드폰 표면코팅용 수지조성물로써 도막의 자기복원성, 내스크래치성, 내침염성, 내화장품성, 내충격성, 내마모성을 부여하여 뛰어난 자기복원성을 비롯하여 외부환경에 의한 스크래치 등의 긁힘 현상, 벗겨짐 현상, 오염, 표면손상, 마모, 깨짐 등을 방지할 뿐만 아니라 표면질감이 뛰어난 핸드폰 표면코팅용 수지조성물을 제공함에 발명의 기술적 과제를 두고 본 발명을 완성한 것이다.In order to solve the problems of the prior art as described above, the present invention has been researched and developed, and in the present invention, as a resin composition for coating a mobile phone surface, self-resilience, scratch resistance, impregnation resistance, cosmetic resistance, impact resistance, and wear resistance of coatings are given. The present invention provides a resin composition for coating the surface of a mobile phone with excellent surface texture as well as preventing scratches, peeling, contamination, surface damage, abrasion, and cracking, etc. The present invention has been completed.

휴대폰은 기능, 품질의 향상에도 불구하고 휴대폰 외관 및 표면코팅에 현재 사용되고 있는 수지는 장기간 사용 시 표면에 긁힘 현상을 방지하는 내스크래치성과, 유기용제 및 화장품등에 의한 내약품성, 그리고 외부 환경요인에 의한 표면오염, 얼룩방지 등의 내오염성과 품질, 내마모성, 내충격성이 현저히 떨어지는 문제점을 갖고 있어 고객의 불만요소로 나타나며 제품의 품질 저하로 이어지고 있을 뿐만 아니라 핸드폰을 장기 사용 시 표면질감도 뛰어나고 스스로 자기복원성을 갖는 핸드폰 표면코팅제가 요구되게 되었다.Despite improvements in functionality and quality of mobile phones, the resins currently used for cell phone exteriors and surface coatings are scratch-resistant to prevent scratches on the surface for long periods of time, chemical resistance by organic solvents and cosmetics, and external environmental factors. It has the problem of pollution, quality, abrasion resistance and impact resistance such as surface contamination, stain prevention, etc., which is notable to customer's dissatisfaction and leads to deterioration of product quality. It also has excellent surface texture and long term self-resilience. Cell phone surface coatings having been required.

본 발명에서는 이와 같은 문제점을 개선하고 고객의 요구를 충족시킬 수 있는 새로운 핸드폰용 수지의 개발 및 적용을 이루고자 하였다.In the present invention, to improve the above problems and to achieve the development and application of a new mobile phone resin that can meet the needs of customers.

본 발명의 목적은 상기한 바와 같은 종래의 핸드폰용 표면 코팅제의 문제점을 해결하기 위하여 안출된 것으로서 핸드폰 표면도막의 자기복원성을 나타나게 함은 물론 표면물성을 향상시켜 긁힘에 의한 스크래치방지, 오염, 충격, 벗겨짐, 눌 림, 마모현상을 방지하게 하여 우수한 핸드폰용 수지 조성물을 제공함에 있다.The purpose of the present invention is to solve the problems of the conventional surface coating agent for mobile phones as described above, as well as to show the self-resilience of the surface coating of the mobile phone, as well as to improve the surface properties of scratches, contamination, impact, The present invention provides an excellent cell phone resin composition by preventing peeling, pressing and abrasion.

상기와 같은 문제를 해결하기 위해서 핸드폰 표면의 하우징 외관에 얇은 코팅층을 형성하여 내 스크래치성, 내침염성, 내화장품성, 내충격성, 내마모성 및 자기복원성을 이루려는 연구가 진행되어 왔다. In order to solve the above problems, studies have been made to form a thin coating layer on the exterior of the mobile phone surface to achieve scratch resistance, dye resistance, cosmetic resistance, impact resistance, wear resistance and self-resilience.

상기한 목적을 달성하기 위하여 본 발명의 핸드폰 표면 코팅용 수지조성물은 아크릴 수산기가 30~300mg KOH/g, 아크릴 산가가 2~20mg KOH/g, 중량평균분자량이 3000~30000, 유리전이온도가 -50℃~20℃인 아크릴수지 공중합화합물 10~30중량%, 히드록시 관능기를 갖는 실리콘변성 아크릴수지 5~15중량%, 폴리에스테르-히드록시 변성 폴리 실록산화합물 1.0~5.0중량%, 알콕시 실란화합물 0.5~3.0중량%, 촉매 0.1~0.5중량%, 수지희석제로 25~50중량%, 이소시아네이트 경화제를 20~40중량%로 이루어진 핸드폰 표면코팅용 수지 조성물을 그 특징으로 한다.In order to achieve the above object, the resin composition for coating a cell phone surface of the present invention has an acrylic hydroxyl value of 30 to 300 mg KOH / g, an acrylic acid value of 2 to 20 mg KOH / g, a weight average molecular weight of 3000 to 30000, and a glass transition temperature of- 10 to 30% by weight of acrylic resin copolymer compound at 50 ° C to 20 ° C, 5 to 15% by weight of silicone modified acrylic resin having hydroxy functional group, 1.0 to 5.0% by weight of polyester-hydroxy modified polysiloxane compound, alkoxy silane compound 0.5 It is characterized by a resin composition for cell phone surface coating, consisting of -3.0% by weight, 0.1-0.5% by weight of catalyst, 25-50% by weight of resin diluent, and 20-40% by weight of isocyanate curing agent.

이하 본 발명을 상세하게 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.

본 발명에 따른 아크릴 수지는 라디칼 개시제에 의하여 반응이 개시되며 솔루션 중합법에 의해 반응온도 80~120℃에서 반응이 이루어져 제조되며 중량평균분자량 3000~30000, 수산기가 30~300, 산가 2~20, -50℃~20℃의 유리전이온도, 고형분 40~70중량%를 가지게 함으로써 핸드폰용 표면코팅제로서 실리콘 및 이소시아네이트 경화제와의 원활한 상용성 및 경화시스템을 유지하게 하고 도막의 투명성 및 접착성 및 내약품성을 나타나게 할 수 있다.The acrylic resin according to the present invention is initiated by a radical initiator, the reaction is produced by a solution polymerization method at a reaction temperature of 80 ~ 120 ℃, the weight average molecular weight 3000 ~ 30000, hydroxyl value 30 ~ 300, acid value 2 ~ 20, It has a glass transition temperature of -50 ℃ ~ 20 ℃ and a solid content of 40 ~ 70% by weight to maintain smooth compatibility with silicone and isocyanate curing agents and hardening system as a surface coating agent for mobile phones, and transparency, adhesion and chemical resistance of coating film. Can be displayed.

본 발명에 따른 아크릴수지 공중합화합물로는 비관능성 아크릴모노머로, 부틸아크릴레이트, 부틸메타크릴레이트, 이소부틸아크릴레이트, 시클로헥실메타아크 릴레이트, 2-에틸헥실아크릴레이트, 시클로헥실아크릴레이트, 시클로헥실메타아크릴레이트, 라우릴아크릴레이트, 라우릴메타아크릴레이트, 아이소데실아크릴레이트, 아이소데셀메타아크릴레이트, 이소보닐아크릴레이트가 혼합 또는 단독으로 아크릴수지 공중합화합물 중에 40~60중량% 함유되는 것이 바람직하다.The acrylic resin copolymer according to the present invention is a non-functional acrylic monomer, butyl acrylate, butyl methacrylate, isobutyl acrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, cyclo It is preferable that hexyl methacrylate, lauryl acrylate, lauryl methacrylate, isodecyl acrylate, isodecel methacrylate, and isobornyl acrylate are mixed or singly contained in the acrylic resin copolymer in an amount of 40 to 60% by weight. Do.

수산기함유 아크릴모노머로는 2-히드록시에틸아크릴레이트, 2-히드록시에틸메타아크릴레이트, 2-히드록시프로필아크릴레이트, 2-히드록시프로필메타아크릴레이트가 아크릴수지 조성물에 30~40중량% 함유되는 것이 바람직하다. 카르복실기함유 아크릴모노머로는 아크릴산, 메타아크릴산이 사용되며 아크릴수지 조성물 중 0.5~2중량% 사용하는 것이 바람직하다.  As the hydroxyl group-containing acrylic monomer, 30 to 40% by weight of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate are contained in the acrylic resin composition. It is preferable to be. Acrylic acid and methacrylic acid are used as a carboxyl group-containing acrylic monomer, and it is preferable to use 0.5-2 weight% of an acrylic resin composition.

본 발명에서는 핸드폰 표면외관 코팅 수지조성물의 자기복원성을 나타나게 함은 물론 내스크래치성 및 내침염성, 내화장품성, 내충격성 내마모성을 향상시키려는 목적을 두고 있으나, 아크릴 공중합 수지로는 한계가 있으므로 상기에 제시한 아크릴공중합수지 조성물 외에 실리콘변성 아크릴수지, 히드록시기를 함유한 폴리에스테르변성 폴리실록산 화합물에 다관능성 실란화합물과 이소시아네이트 경화제를 첨가하여 도막을 경회시킴으로 인하여 폴리우레탄-실리콘-아크릴의 삼차원의 사다리구조를 갖게 함으로써 자기복원성, 내스크래치성, 내침염성, 내화장품성, 내충격성, 내마모성을 향상시킬 수가 있다.In the present invention, it is intended to improve the scratch resistance and stain resistance, cosmetic resistance, impact resistance and abrasion resistance, as well as to show the self-resilience of the surface coating coating composition of the mobile phone, but the acrylic copolymer resin is presented above because there is a limit. By adding a polyfunctional silane compound and an isocyanate curing agent to a silicone-modified acrylic resin and a polyester-modified polysiloxane compound containing a hydroxy group in addition to the acrylic copolymer resin composition, the coating film is traversed to give a three-dimensional ladder structure of polyurethane-silicone-acrylic. Self-resilience, scratch resistance, needle resistance, cosmetic resistance, impact resistance and abrasion resistance can be improved.

히드록시 관능기를 갖는 실록산변성 아크릴수지로는 수산기가 20~50mg KOH/g 의 아크릴변성 실록산구조로 이루어져 있으며 5~15중량% 첨가가 적당하다. 만일 본 화합물이 5중량% 이하로 첨가될 때는 내스크래치성이 저하되게 되며 15중량% 이상일 경우에는 아크릴수지와의 상용성 및 분산성, 레벨링성 등 도막물성이 저하되는 경향이 나타나게 된다.The siloxane-modified acrylic resin having a hydroxy functional group is composed of an acrylic-modified siloxane structure having a hydroxyl group of 20 to 50 mg KOH / g, and 5 to 15% by weight is appropriate. If the present compound is added at 5% by weight or less, the scratch resistance is lowered. If the compound is 15% by weight or more, the coating film properties such as compatibility and dispersibility and leveling property with acrylic resins are deteriorated.

폴리에스테르-히드록시 변성 폴리실록산화합물로는 실록산 구조를 반복단위로 갖는 폴리실록산 화합물에 측쇄 또는 말단에 폴리에스테르와 히드록시 관능기가 변성되어 있는 구조를 나타내며 1.0~5.0중량% 첨가가 적당하다. 1.0중량% 이하 일 경우에는 내오염성, 내침염성이 저하되게 되며, 5.0중량% 이상일 경우에는 아크릴수지와의 상용성 및 레벨링성이 떨어지게 된다. As the polyester-hydroxy modified polysiloxane compound, a polysiloxane compound having a siloxane structure as a repeating unit shows a structure in which a polyester and a hydroxy functional group are modified at the side chain or terminal, and 1.0 to 5.0% by weight is appropriate. If the amount is less than 1.0% by weight, fouling resistance and stain resistance are reduced, and when the amount is 5.0% by weight or more, compatibility with the acrylic resin and leveling property are inferior.

알콜시 실란화합물로는 테트라메톡시실란, 메틸트리메톡시실란, 테트라에톡시실란, 메틸트리에톡시실란을 단독 또는 혼합 사용하며 0.5~3.0중량%가 적당하다. 1중량% 이하일 경우에는 도막의 가교도가 저하되게 되며 3.0중량% 이상일 경우에는 도막의 가교도가 증가되어 내충격성이 저하되게 된다. As the silane compound in alcohol, tetramethoxysilane, methyltrimethoxysilane, tetraethoxysilane and methyltriethoxysilane are used alone or in combination, and 0.5 to 3.0% by weight is appropriate. When it is 1% by weight or less, the degree of crosslinking of the coating film is lowered, and when it is 3.0% by weight or more, the degree of crosslinking of the coating film is increased, thereby reducing the impact resistance.

경화촉진제로서의 촉매로는 0.1~0.5중량%가 적당하며 디부틸틴옥테이트, 징크옥테이트, 틴옥테이트, 티타늄클로라이드화합물, 황산, 염산, 질산, 인산을 단독 또는 혼합 사용할 수 있다.As a catalyst for curing accelerators, 0.1 to 0.5% by weight is suitable, and dibutyltinate, zincate, tinate, titanium chloride compounds, sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid may be used alone or in combination.

수지희석제로는 방향족유기용제인 톨루엔, 크실렌, 알킬벤젠시클로핵사논, 시클로핵산, 메틸이소부틸케톤, 메틸셀루솔부아세테이트, 에틸셀루솔부아세테이트, 부틸셀루솔브아세테이트, 부틸아세테이트, 3-메틸-1 프로판올, 희석용제로 단독 또는 혼합 사용할 수 있다.As the resin diluent, toluene, xylene, alkylbenzenecyclonucleone, cyclonucleic acid, methyl isobutyl ketone, methyl cellulose sol acetate, ethyl cellulose sol acetate, butyl cellulose sorbate, butyl acetate, 3-methyl-1 propanol It can be used alone or mixed as a diluting solvent.

희석양은 수지전체 중량에 25~50중량%가 적합하다.Dilution amount is 25 to 50% by weight based on the total weight of the resin.

경화제로는 이소시아네이트구조르 갖는 지방족이소시아네이트를 사용하며 헥 사메틸렌디이소시아네이트, 이소보닐디이소시아네이트, 메틸렌디이소시아네이트, 아이소포론디이소시아네이트, 시클로헥실디이소시아네이트를 단독 또는 혼합 사용할 수 있으며 20~40중량%로 혼합하여 사용하는 것이 적합하다.As the curing agent, an aliphatic isocyanate having an isocyanate structure is used, and hexamethylene diisocyanate, isobornyl diisocyanate, methylene diisocyanate, isophorone diisocyanate, cyclohexyl diisocyanate can be used alone or mixed, and mixed at 20 to 40% by weight. It is suitable to use.

본 발명 수지조성물의 건조 및 경화과정을 통하여 아크릴, 실리콘, 우레탄의 삼차원 사다리 구조를 갖게 함으로써 자기복원성은 물론, 우수한 내스크래치성, 내침염성, 내화장품성, 내충격성, 내마모성을 나타내는 핸드폰용 표면수지 코팅 수지 조성물을 그 특징으로 한다.The resin composition of the present invention has a three-dimensional ladder structure of acrylic, silicone, urethane through the drying and curing process of the resin composition, surface resistance for mobile phones showing excellent scratch resistance, impregnating resistance, cosmetic resistance, impact resistance, wear resistance It is characterized by the coating resin composition.

이하 본 발명을 구체적인 실시예를 들어 상세히 설명하고자 한다.Hereinafter, the present invention will be described in detail with reference to specific examples.

(실시예 1)(Example 1)

아크릴수지 공중합화합물 230g에 아크릴변성 실리콘화합물 80g, 에스테르변성 폴리실록산 화합물 20g, 메틸트리에톡시실란 1.5g, 촉매0.3g, 희석제 360g, 이소시아네이트 경화제 300g을 넣고 2시간 혼합 교반하여 수지 조성물을 제조 후 스프레이 건조, 경화 등을 거쳐 핸드폰용 표면코팅 도막을 얻었다.80 g of acrylic modified silicone compound, 20 g of ester modified polysiloxane compound, 1.5 g of methyl triethoxysilane, 0.3 g of catalyst, diluent 360 g, and 300 g of isocyanate curing agent were added to 230 g of the acrylic resin copolymer compound to prepare a resin composition, followed by mixing and stirring, followed by spray drying. And the surface coating coating film for mobile phones was obtained through hardening.

(실시예 2)(Example 2)

아크릴수지 공중합화합물 230g에 아크릴변성 실리콘화합물 75g, 에스테르변성 폴리실록산 화합물 25g, 메틸트리에톡시실란 1.5g, 촉매0.3g, 희석제 360g, 이소시아네이트 경화제 300g을 넣고 2시간 혼합 교반하여 수지 조성물을 제조 후 스프레이 건조, 경화 등을 거쳐 핸드폰용 표면코팅 도막을 얻었다.To 230 g of the acrylic resin copolymer compound, 75 g of acrylic modified silicone compound, 25 g of ester modified polysiloxane compound, 1.5 g of methyl triethoxysilane, 0.3 g of catalyst, 360 g of diluent, and 300 g of isocyanate curing agent were mixed and stirred for 2 hours to prepare a resin composition, followed by spray drying. And the surface coating coating film for mobile phones was obtained through hardening.

(실시예 3)(Example 3)

아크릴수지 공중합화합물 230g에 아크릴변성 실리콘화합물 85g, 에스테르변성 폴리실록산 화합물 15g, 메틸트리에톡시실란 1.5g, 촉매0.3g, 희석제 360g, 이소시아네이트 경화제 300g을 넣고 2시간 혼합 교반하여 수지 조성물을 제조 후 스프레이 건조, 경화 등을 거쳐 핸드폰용 표면코팅 도막을 얻었다.Add 230 g of acrylic resin copolymer compound to 85 g of acrylic modified silicone compound, 15 g of ester-modified polysiloxane compound, 1.5 g of methyl triethoxysilane, 0.3 g of catalyst, 360 g of diluent, and 300 g of isocyanate curing agent. And the surface coating coating film for mobile phones was obtained through hardening.

(비교예 1)(Comparative Example 1)

아크릴수지 공중합화합물 230g에 에스테르변성 폴리실록산 화합물 20g, 메틸트리에톡시실란 1.5g, 촉매 0.3g, 희석제 360g, 이소시아네이트 경화제 300g을 넣고 2시간 혼합 교반하여 수지 조성물을 제조 후 스프레이 건조, 경화 등을 거쳐 핸드폰용 표면코팅 도막을 얻었다.20 g of the ester-modified polysiloxane compound, 1.5 g of methyl triethoxysilane, 0.3 g of catalyst, 360 g of diluent, and 300 g of isocyanate curing agent were added to 230 g of the acrylic resin copolymer, and the mixture was stirred for 2 hours to prepare a resin composition, followed by spray drying and curing. A surface coating coating film was obtained.

(비교예 2)(Comparative Example 2)

아쿠릴수지 공중합화합물 230g에 아크릴변성 실리콘화합물 100g, 메틸트리에톡시실란 1.5g, 촉매 0.3g, 희석제 360g, 이소시아네이트 경화제 300g을 넣고 2시간 혼합 교반하여 수지 조성물을 제조 후 스프레이 건조, 경화 등을 거쳐 핸드폰용 표면코팅 도막을 얻었다.100 g of acrylic modified silicone compound, 1.5 g of methyltriethoxysilane, 0.3 g of catalyst, 360 g of diluent, and 300 g of isocyanate curing agent were added to 230 g of the acryl resin copolymer compound, and then mixed and stirred for 2 hours to prepare a resin composition, followed by spray drying and curing. A surface coating film for mobile phones was obtained.

(비교예 3)(Comparative Example 3)

아크릴수지 공중합화합물 330g에 메틸트리에톡시실란 1.5g, 촉매 0.3g, 희석제 360g, 이소시아네이트 경화제 300g을 넣고 2시간 혼합 교반하여 수지 조성물을 제조 후 스프레이 건조, 경화 등을 거쳐 핸드폰용 표면코팅 도막을 얻었다.1.5 g of methyl triethoxysilane, 0.3 g of catalyst, 360 g of diluent, and 300 g of isocyanate curing agent were added to 330 g of the acrylic resin copolymer compound, and the mixture was stirred for 2 hours to prepare a resin composition, followed by spray drying and curing to obtain a surface coating film for mobile phones. .

상기 실시예와 비교예에 따라 얻어진 도막에 대한 물성측정결과는 표1에 나 타난 바와 같다.Physical property measurement results of the coating film obtained according to the above Examples and Comparative Examples are as shown in Table 1.

내스크래치성의 경우 연필 경도법으로 1kgf, 45°측정 조건하에서 평가하였으며, 내침염성의 경우 유성펜을 시편에 칠한 후 50℃×95%×1Hrs 방치 후 헝겊에 메탄올을 묻혀 닦은 후 외관표면 검사를 통하여 측정하였다. 내화장품성의 경우 자외선 차단크림(니베아 선 스프레이SPF 20)을 붓에 묻혀 시편에 도포, 상온에서 10분 동안 방치, 크림이 뭉친 부분을 다시 붓으로 칠한 후 80℃×80% 항온항습기에 24시간 방치 후 수세로 크림제거한 뒤 상온에서 4시간 방치 후 2mmX-Cutting 하여 테이프 탈착여부를 측정하였다. 내충격성의 경우 500g의 추를 낙구시켜 깨짐 정도를 평가하였다. 자기복원성은 연필지우개에 500g 하중으로 시편위에 올린 후 150회 왕복하여 소재노출여부를 측정하였다.The scratch resistance was evaluated under the conditions of 1kgf and 45 ° by the pencil hardness method.In the case of the stain resistance, the oil-based pen was applied to the specimen, and after leaving 50 ℃ × 95% × 1Hrs, the cloth was wiped with methanol and then measured by the external surface inspection. It was. For cosmetics, apply a sunscreen cream (NIVEA sun spray SPF 20) to the specimen and apply it to the specimen, leave it for 10 minutes at room temperature, and apply the cream back together with a brush and leave it at 80 ℃ × 80% constant temperature and humidity for 24 hours. After removing the cream with water and left for 4 hours at room temperature and 2mmX-Cutting to measure the tape detachment. In case of impact resistance, a weight of 500 g was dropped, and the degree of cracking was evaluated. Self-resilience was measured on the specimen with a 500g load on a pencil eraser and then reciprocated 150 times to determine whether the material was exposed.

항목Item 실시예1Example 1 실시예2Example 2 실시예3Example 3 비교예1Comparative Example 1 비교예2Comparative Example 2 비교예3Comparative Example 3 내스크래치성 Scratch resistance 2H2H 1∼2H1 ~ 2H 1∼2H1 ~ 2H BB B∼HBB to HB B∼HBB to HB 내침염섬 Internal salinity 우수(5)Excellent (5) 양호(4)Good (4) 양호(4)Good (4) 불량(1)Poor (1) 미흡(2)Poor (2) 미흡(2)Poor (2) 내화장품성 Cosmetic resistance 우수(◎)Excellent (◎) 우수(◎)Excellent (◎) 우수(◎)Excellent (◎) 미흡(△)Poor (△) 미흡(△)Poor (△) 미흡(△)Poor (△) 내충격성 Impact resistance ◎◎ ◎◎ ◎◎ 깨짐발생Crack 미흡(△)Poor (△) 미흡(△)Poor (△) 자기복원성 Self-resilience 소재노출없음No material exposure 소재노출없음No material exposure 소재노출없음No material exposure 노출발생Exposure 노출발생Exposure 노출발생Exposure

상기 표1의 결과로부터 본 발명에 따라 히드록시- 카르복실기 변성 아크릴공중합화합물와 아크릴변성실리콘 수지화합물, 폴리에스테르-히드록시 변성 폴리실록산 화합물, 알콕시 실란화합물, 경화촉진제 및 이소시아네이트를 함유하는 수지조성물로 이루어진 핸드폰용 표면코팅제의 경우 내스크래치성, 내침염성, 내화장품성, 내충격성, 자기복원성이 매우 우수함을 알 수 있다.According to the present invention from the results of Table 1, a mobile phone comprising a resin composition containing a hydroxy-carboxy-modified acrylic copolymer and an acrylic-modified silicone resin compound, a polyester-hydroxy-modified polysiloxane compound, an alkoxy silane compound, a curing accelerator and an isocyanate In the case of the surface coating agent, it can be seen that scratch resistance, dye resistance, cosmetic resistance, impact resistance, and self-resilience are very excellent.

이상에서 살펴본 바와 같이 본 발명은 수지조성물로서 표면의 도막을 형성하는데 있어서, 상기 표1에 의하여 알 수 있는 바와 같이 본 발명의 핸드폰용 표면 코팅제의 도막물성 중 내스크래치성, 내침염성, 내화장품성, 내마모성, 내충격성이 월등히 개선됨을 알 수 있었으며 이를 적용하여 핸드폰 표면의 고품질 유지를 위한 수지로서 유용하게 사용할 수 있다.As described above, in the present invention, in forming a coating film on the surface as a resin composition, scratch resistance, impregnating resistance, and cosmetic resistance among the coating film properties of the surface coating agent for a mobile phone of the present invention, as can be seen from Table 1 above. It was found that the wear resistance and impact resistance were greatly improved, and it can be usefully used as a resin for maintaining high quality of the surface of a mobile phone by applying it.

Claims (8)

아크릴수지 공중합화합물 10~30중량%, 히드록시 관능기를 갖는 실리콘변성 아크릴수지 5~15중량%, 폴리에스테르-히드록시 변성 폴리 실록산화합물 1.0~5.0중량%, 알콕시 실란화합물 0.5~3.0중량%, 촉매 0.1~0.5중량%, 수지희석제로 25~50중량%, 이소시아네이트 경화제를 20~40중량%로 이루어진 것을 특징으로 하는 핸드폰용 수지 조성물.10-30% by weight of acrylic resin copolymer compound, 5-15% by weight of silicone modified acrylic resin having hydroxy functional group, 1.0-5.0% by weight of polyester-hydroxy modified polysiloxane compound, 0.5-3.0% by weight of alkoxy silane compound, catalyst 0.1 to 0.5% by weight, 25 to 50% by weight of the resin diluent, 20-40% by weight of isocyanate curing agent, the resin composition for mobile phones. 제 1항에 있어서,The method of claim 1, 아크릴수지 공중합화합물로는 아크릴 수산기가 30~300mg KOH/g, 아크릴 산가가 2~20mg KOH/g, 중량평균분자량이 3000~30000, 유리전이온도가 -50℃~20℃인 아크릴수지 공중합화합물로서 비관능성 아크릴레이트인 부틸아크릴레이트, 부틸메타그릴레이트, 이소부틸아크릴레이트, 시클로헥실아크릴레이트, 2-에틸헥실아크릴레이트, 2-에틸헥실메타아크릴레이트, 시클로헥실아크릴레이트, 시클로헥실메타아크릴레이트, 아이소데실아크릴레이트, 아이소데실메타아크릴레이트, 이소보닐아크릴레이트, 라우릴아크릴레이트, 라우릴메타아크릴레이트가 혼합 또는 단독으로 40~60중량%, 수산기함유 아크릴모노머가 30~40중량%, 카르복실산 함유 아그릴모노머가 1~5중량% 함유하는 것을 특징으로 하는 핸드폰용 수지 조성물.The acrylic resin copolymer is an acrylic resin copolymer having an acrylic hydroxyl value of 30 to 300 mg KOH / g, an acrylic acid value of 2 to 20 mg KOH / g, a weight average molecular weight of 3000 to 30000, and a glass transition temperature of -50 ° C to 20 ° C. Butyl acrylate, butyl methacrylate, isobutyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, Isodecyl acrylate, isodecyl methacrylate, isobornyl acrylate, lauryl acrylate, lauryl methacrylate is mixed or alone 40 to 60% by weight, hydroxyl group-containing acrylic monomer 30 to 40% by weight, carboxyl The resin composition for mobile phones containing 1-5 weight% of acid containing aglycol monomers. 제 1항에 있어서,The method of claim 1, 실리콘 변성 아크릴수지는 수산기가 10~100mg KOH/g, 실리콘 함량이 5~40중량%, 중량평균분자량이 3000~50000인 것을 사용하는 것을 특징으로 하는 핸드폰용 수지 조성물.Silicone-modified acrylic resin is a resin composition for mobile phones, characterized in that the hydroxyl value of 10 ~ 100mg KOH / g, the silicon content of 5 to 40% by weight, the weight average molecular weight of 3000 to 50000. 제 1항에 있어서,The method of claim 1, 폴리에스테르-히드록시 변성 폴리 실록산화합물은 수산기가 30~120mg KOH/g, 실리콘 함량이 20~60중량%, 중량평균분자량이 1000~30000인 것을 사용하는 것을 특징으로 하는 핸드폰용 수지 조성물.The polyester-hydroxy modified polysiloxane compound has a hydroxyl value of 30 to 120 mg KOH / g, a silicon content of 20 to 60% by weight, and a weight average molecular weight of 1000 to 30000. 제 1항에 있어서,The method of claim 1, 알콕시 실란화합물은 테트라메톡시실란, 메틸트리메톡시실란, 테트라에톡시실란, 메틸트리에톡시실란을 단독 또는 혼합 사용하는 것을 특징으로 하는 핸드폰용 수지 조성물.The alkoxy silane compound uses tetramethoxysilane, methyltrimethoxysilane, tetraethoxysilane, and methyltriethoxysilane alone or in a mixture. 제 1항에 있어서,The method of claim 1, 경화촉진 촉매로는 디부틸틴옥테이트, 징크옥테이트, 틴옥테이트, 티타늄틀로라이드 화합물, 황산, 염산, 질산, 인산을 단독 또는 혼합 사용하는 것을 특징으 로 하는 핸드폰용 수지 조성물.A curing accelerator catalyst is a resin composition for mobile phones, characterized in that the dibutyl tin octane, zinc octate, tin octanate, titanium fluoride compound, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid alone or mixed. 제 1항에 있어서,The method of claim 1, 수지희석제로는 톨루엔, 크실렌, 알킬벤젠, 시클로핵사논, 시클로핵산, 메틸이소부틸케톤, 메틸셀루솔부아세테이트, 에틸셀루솔부아세테이트, 3-메틸-1 프로판올, 부틸아세테이트를 단독 또는 혼합 사용하는 것을 특징으로 하는 핸드폰용 수지 조성물.As the resin diluent, toluene, xylene, alkylbenzene, cyclonuxanone, cyclonucleic acid, methyl isobutyl ketone, methyl cellulose sol acetate, ethyl cellulose sol acetate, 3-methyl-1 propanol, butyl acetate are used alone or in combination. Resin composition for mobile phones made. 제 1항에 있어서,The method of claim 1, 경화제로는 이소시아네이트 구조를 갖는 지방족이소시아네이트인 헥사메틸렌디이소시아네이트, 이소보닐디이소시아네이트, 메틸렌디이소시아네이트, 아이소포론디이소시아네이트, 시클로헥실디이소시아네이트를 단독 또는 혼합 사용하는 것을 특징으로 하는 핸드폰용 수지 조성물.A resin composition for mobile phones comprising hexamethylene diisocyanate, isobornyl diisocyanate, methylene diisocyanate, isophorone diisocyanate, and cyclohexyl diisocyanate alone or in combination as a curing agent.
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US9308616B2 (en) 2013-01-21 2016-04-12 Innovative Finishes LLC Refurbished component, electronic device including the same, and method of refurbishing a component of an electronic device
KR20200029898A (en) * 2018-09-11 2020-03-19 주식회사 케이씨씨 Ink Composition
KR20230027444A (en) 2021-08-19 2023-02-28 단국대학교 산학협력단 Coating method for restoration of damaged structures

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US9308616B2 (en) 2013-01-21 2016-04-12 Innovative Finishes LLC Refurbished component, electronic device including the same, and method of refurbishing a component of an electronic device
KR20200029898A (en) * 2018-09-11 2020-03-19 주식회사 케이씨씨 Ink Composition
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