KR101219602B1 - Polypropylene-based resin composition for a light diffusion plate, a light diffusion plate containing the same and manufacturing method thereof - Google Patents

Polypropylene-based resin composition for a light diffusion plate, a light diffusion plate containing the same and manufacturing method thereof Download PDF

Info

Publication number
KR101219602B1
KR101219602B1 KR1020120100988A KR20120100988A KR101219602B1 KR 101219602 B1 KR101219602 B1 KR 101219602B1 KR 1020120100988 A KR1020120100988 A KR 1020120100988A KR 20120100988 A KR20120100988 A KR 20120100988A KR 101219602 B1 KR101219602 B1 KR 101219602B1
Authority
KR
South Korea
Prior art keywords
light
particles
particle
polypropylene resin
diffusion plate
Prior art date
Application number
KR1020120100988A
Other languages
Korean (ko)
Inventor
하현대
Original Assignee
세원정공 주식회사
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 세원정공 주식회사 filed Critical 세원정공 주식회사
Priority to KR1020120100988A priority Critical patent/KR101219602B1/en
Application granted granted Critical
Publication of KR101219602B1 publication Critical patent/KR101219602B1/en

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10Homopolymers or copolymers of propene
    • C08L23/12Polypropene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/16Solid spheres
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/02Diffusing elements; Afocal elements
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00Composition 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
    • C08L2666/66Substances characterised by their function in the composition

Abstract

PURPOSE: A polypropylene-based resin composition is provided to provide a light-diffusion plate which has excellent light transmittance, high luminance, impact resistance, and weathering ability without generating yellowing phenomena. CONSTITUTION: A polypropylene-based resin composition comprises 0.1-10 parts by weight of light diffusion agent based on 100 parts by weight of base resin. The base resin comprises 60-70 weight% of random propylene resin and 30-40 weight% of impact polypropylene resin. The light diffusing agent is one or a mixture of compounds selectee from a calcium carbonate particle, a barium sulfate particle, a titanium oxide particle, an aluminum hydroxide particle, a silica particle, a glass particle, a mica particle, a magnesium oxide particle, a zinc oxide particle, an acryl-based crosslinked particle, a silicon-based crosslinked particle, or a styrene-based crosslinked particle. [Reference numerals] (AA) Incident light; (BB) Transmitted light; (CC) Scattered light; (DD) Diffusing agent

Description

광확산판용 폴리프로필렌계 수지 조성물, 이를 포함하는 광확산판 및 그 제조방법{Polypropylene-based resin composition for a light diffusion plate, a light diffusion plate containing the same and manufacturing method thereof}Polypropylene-based resin composition for a light diffusion plate, a light diffusion plate comprising the same and a method for manufacturing the same {Polypropylene-based resin composition for a light diffusion plate, a light diffusion plate containing the same and manufacturing method

본 발명은 광확산판용 폴리프로필렌계 수지 조성물, 이를 포함하는 광확산판 및 그 제조방법에 관한 것으로, 보다 상세하게는 랜덤 폴리프로필렌 수지, 임팩트 폴리프로필렌 수지 및 광확산제를 포함하는 수지 조성물을 압출성형 하여 쉬트 형태로 제조함으로써 가격이 저렴하면서도 내광성이 매우 우수하여 황변현상이 발생하지 않을 뿐만 아니라, 광투과성 및 광확산성이 우수하고 휘도가 높으며, 내충격성 및 내후성 등의 기계적 물성이 향상된 광확산판을 제공하는 것이다.The present invention relates to a polypropylene resin composition for light diffusing plates, a light diffusing plate comprising the same and a method for manufacturing the same, and more particularly, to extrude a resin composition comprising a random polypropylene resin, an impact polypropylene resin and a light diffusing agent. It is inexpensive and has excellent light resistance because it is molded and manufactured in the form of sheet, so that yellowing does not occur, and it has excellent light transmittance and light diffusivity, high luminance, and light diffusion with improved mechanical properties such as impact resistance and weather resistance. To provide a plate.

광확산판은 간판, 조명기구, 자동차 방향지시등의 보호 커버, 디스플레이용 직하형 백라이트 유닛(BLU)에 적용되는 확산판 및 표시 판넬과 같은 광학용으로 사용되고 있다. 일반적으로 광확산판은 점 또는 선 광원을 균일한 면 광원으로 나타나게 하는 쉬트 형태의 것으로서, 후면의 조명등 또는 내용물이 외부에서는 보이지 않으면서 균일한 밝기를 구현하기 위하여 우수한 광투과도와 광확산도가 요구된다. Light diffusion plates are used for optical applications such as signage plates, lighting fixtures, protective covers for automobile direction indicators, diffuser plates and display panels applied to direct-type backlight units (BLUs) for displays. In general, the light diffusion plate has a sheet shape that makes a point or line light source appear as a uniform surface light source, and excellent light transmittance and light diffusivity are required in order to realize uniform brightness without the back light or contents being visible from the outside. .

그리고 광확산판의 구체적인 용도에 따라 요구되는 기계적·광학적 물성에도 차이가 있는바, 간판과 같이 외부에 직접 노출된 경우에는 충격에 의한 강도 및 태양광, 온도, 습도 등에 의한 변형 또는 변색이 없고 내후성이 충족되어야 한다. 한편, 실내 조명기구용의 경우에는 내충격성, 내후성보다는 디자인 및 심미적 관점에서 여러 가지 형태의 모양을 만들 수 있도록 성형성이 우수하여야 한다. In addition, there is a difference in the mechanical and optical properties required according to the specific use of the light diffusion plate. When directly exposed to the outside, such as a signboard, there is no deformation or discoloration due to impact strength, sunlight, temperature, humidity, etc. Should be met. On the other hand, in the case of indoor lighting fixtures should be excellent in moldability to create a variety of shapes from the design and aesthetic point of view rather than impact resistance, weather resistance.

특히, 최근에 각광받고 있는 LED 채널간판의 경우에는 형광등과 네온에 비하여 높은 밝기의 휘도와 에너지 절감 효과가 있고, 다양한 연출기법으로 세련된 이미지 구현이 가능하며, 화재발생의 위험 및 보수비용이 적게 드는 등 경제적이고 효율적인 간판으로서, LED 채널간판에 적용되는 광확산판은 LED 조명의 광원을 노출시키지 않아 눈부심을 방지하면서도 조도조절이 가능하여 조명기기의 효율성을 극대화할 수 있도록 높은 수준의 광투과성 및 광확산성이 요구된다. 이러한 광확산판은 상기 용도에 따라 통상적으로 아크릴계, 폴리카보네이트계, 폴리스티렌계 또는 폴리프로필렌계와 같은 열가소성 수지에 광확산제 등의 첨가제가 혼합되어 쉬트 형태로 성형된다.In particular, LED channel signages, which have been in the spotlight recently, have higher brightness and energy saving effect than fluorescent lamps and neons, and can realize sophisticated images by various production techniques, and reduce the risk of fire occurrence and maintenance cost. As an economical and efficient signboard, the light diffusion plate applied to the LED channel signboard does not expose the light source of the LED light, preventing glare and adjusting the illumination while maximizing the efficiency of the lighting equipment. Diffusion is required. Such a light diffusing plate is usually molded into a sheet form by mixing an additive such as a light diffusing agent into a thermoplastic resin such as acrylic, polycarbonate, polystyrene, or polypropylene.

광확산판의 주재로 많이 사용되고 있는 아크릴계 수지로서는 투명성, 내광성 및 광투과성이 양호한 폴리메틸메타크릴레이트(PMMA)가 있는데, 종래기술에서는 PMMA 주재에 광확산제로서 실리콘 입자를 분산시킨 광확산판을 제조하여 광확산성과 광투과성 간에 존재하는 일반적인 트레이드-오프 관계에도 불구하고 광확산성 및 광투과성을 동시에 향상시켰으나, 기계적 강도와 내흡습성 및 내열성에 한계가 있었고, 따라서 그 용도가 제한적일 수밖에 없었다(특허문헌 1).As an acrylic resin widely used as a main material of the light diffusion plate, polymethyl methacrylate (PMMA) having good transparency, light resistance, and light transmittance is known. In the related art, a light diffusion plate in which silicon particles are dispersed as a light diffusion agent in a PMMA material is used. In spite of the general trade-off relationship between the light diffusion and the light transmission, the light diffusion and light transmittance were simultaneously improved, but the mechanical strength, hygroscopicity and heat resistance were limited, and thus the use was limited. Document 1).

한편, 아크릴계 수지에 비하여 내광성은 떨어지나 내열성이 우수한 폴리카보네이트계 수지를 광확산판의 매트릭스 수지로 사용하거나(특허문헌 2), 폴리카보네이트계 수지에 광확산제를 혼합하고, 여기에 내광성을 부여하기 위한 내광제로서 자외선 흡수 스펙트럼에서 극대 파장이 290~330nm인 자외선 흡수제를 첨가한 폴리카보네이트계 광확산성 수지 조성물이 보고되어 있지만(특허문헌 3), 상업화 측면에서 생산 원가가 비싸고, 상대적으로 내후성 및 성형가공성이 좋지 않아 다양한 형태로 만들기 어려운 단점을 가지고 있다.On the other hand, polycarbonate resin having a lower light resistance than acrylic resin but excellent in heat resistance is used as a matrix resin of a light diffusion plate (Patent Document 2), or a light diffusing agent is mixed with a polycarbonate resin to impart light resistance thereto. Although a polycarbonate-based light diffusing resin composition containing an ultraviolet absorber having a maximum wavelength of 290 to 330 nm in the ultraviolet absorption spectrum has been reported (Patent Document 3) in terms of commercialization, the production cost is high in terms of commercialization, and the weather resistance and It has a disadvantage that it is difficult to make various forms because of poor molding processability.

따라서 최근에는 생산 원가가 싸면서도 가공성이 양호한 폴리스티렌계 수지가 광확산판의 주재로 사용되고 있고(특허문헌 4), 폴리스티렌 수지의 내충격성을 보강하기 위하여 고무 변성 폴리스티렌계 수지를 이용한 광확산판도 공지되어 있다(특허문헌 5). 그러나 이러한 폴리스티렌계 수지는 표면광택도, 내후성 및 내열성이 떨어지고 중합공정이 복잡하여 경제적이지 못하다는 문제점이 있다.Therefore, recently, polystyrene-based resins having low production cost and good processability have been used as the main material of light diffusion plates (Patent Document 4), and light diffusion plates using rubber-modified polystyrene resins are also known to reinforce the impact resistance of polystyrene resins. There is (patent document 5). However, such polystyrene-based resins have a problem in that surface glossiness, weather resistance and heat resistance are poor, and the polymerization process is complicated and economical.

한편, 폴리프로필렌 수지는 비중(밀도)이 0.9~0.92(g/cm3)로 범용 플라스틱 중 가장 가볍고 투명하며 PMMA 수준의 내후성을 가지고 있어 실내뿐만 아니라 옥외용으로 적합하고, 재활용성도 우수한 환경친화적 소재로 알려져 있다. 그러나 프로필렌 단량체 단위로만 이루어진 중합체인 호모 폴리프로필렌 수지는 저온 충격강도가 약하여 최근에는 프로필렌 단량체 단위에 에틸렌 또는 부틸렌 등의 올레핀계 단량체를 도입한 폴리프로필렌계 공중합체 수지가 많이 사용되고 있는 실정이다. 그 대표적인 것으로는 프로필렌 단량체와 에틸렌 단량체를 공중합하여 양 단량체의 배열을 무질서하게 형성한 랜덤 폴리프로필렌 수지, 호모 폴리프로필렌 수지에 에틸렌-프로필렌 공중합체 반복단위가 블록을 형성하고 있는 구조로서 저온 충격강도가 개선된 임팩트 폴리프로필렌 수지가 있다. 또한, 에틸렌-프로필렌 공중합체와 PMMA를 블렌드 하여 광확산판의 매트릭스 수지로 사용한 예도 있으나, 상대적으로 내광성이 떨어져 황변현상이 발생할 우려가 있고, 광확산성이 현저하게 낮은 문제점을 갖고 있었다.(특허문헌 6)On the other hand, polypropylene resin has a specific gravity (density) of 0.9 to 0.92 (g / cm 3 ), which is the lightest, most transparent, and PMMA-grade weather resistant of general purpose plastics. Known. However, homopolypropylene resin, which is a polymer composed only of propylene monomer units, has a low low-temperature impact strength, and thus, polypropylene copolymer resins in which olefin monomers such as ethylene or butylene are introduced into propylene monomer units have recently been used. Typical examples thereof are random polypropylene resins in which copolymers of propylene monomers and ethylene monomers are randomly formed and random polypropylene resins and homo polypropylene resins form blocks of repeating units of ethylene-propylene copolymers. There is an improved impact polypropylene resin. In addition, the ethylene-propylene copolymer and PMMA may be blended to be used as the matrix resin of the light diffusing plate, but there is a possibility that yellowing may occur due to relatively low light resistance, and the light diffusibility is remarkably low. Document 6)

특허문헌 1. 일본공개특허공보 평1-172801호Patent Document 1. Japanese Patent Application Laid-Open No. 1- 172801 특허문헌 2. 일본공개특허공보 평11-158364호Patent Document 2. Japanese Patent Application Laid-Open No. 11-158364 특허문헌 3. 일본공개특허공보 제2006-117822호Patent Document 3. Japanese Laid-Open Patent Publication No. 2006-117822 특허문헌 4. 한국공개특허공보 제2007-0085938호Patent Document 4. Korean Patent Publication No. 2007-0085938 특허문헌 5. 한국등록특허공보 제10-995784호Patent Document 5. Korean Registered Patent Publication No. 10-995784 특허문헌 6. 한국등록특허공보 제10-823438호Patent Document 6. Korean Registered Patent Publication No. 10-823438

따라서 본 발명은 상기와 같은 문제점을 감안하여 안출된 것으로, 본 발명의 목적은 랜덤 폴리프로필렌 수지, 임팩트 폴리프로필렌 수지 및 광확산제를 포함하는 수지 조성물을 압출성형 하여 쉬트 형태로 제조함으로써 가격이 저렴하면서도 내광성이 매우 우수하여 황변현상이 발생하지 않을 뿐만 아니라, 광투과성 및 광확산성이 우수하고 휘도가 높으며, 내충격성 및 내후성 등의 기계적 물성이 향상된 광확산판을 제공하고자 하는 것이다.Accordingly, the present invention has been made in view of the above problems, and an object of the present invention is to provide a sheet form by extrusion molding a resin composition comprising a random polypropylene resin, an impact polypropylene resin, and a light diffusing agent, thereby reducing the cost. However, the excellent light resistance does not cause yellowing, but also provides a light diffusion plate having excellent light transmittance and light diffusivity, high brightness, and improved mechanical properties such as impact resistance and weather resistance.

상기한 바와 같은 목적을 달성하기 위한 본 발명은 랜덤 폴리프로필렌 수지 60~70 중량%와 임팩트 폴리프로필렌 수지 30~40 중량%를 블렌드한 주재 수지 100 중량부에 대하여 광확산제 0.1~10 중량부를 포함하는 광확산판용 폴리프로필렌계 수지 조성물을 제공한다.The present invention for achieving the above object includes 0.1 to 10 parts by weight of a light diffusing agent based on 100 parts by weight of the main resin blended from 60 to 70% by weight of random polypropylene resin and 30 to 40% by weight of impact polypropylene resin. It provides a polypropylene resin composition for light diffusion plate.

또한, 상기 광확산제는 탄산칼슘 입자, 황산바륨 입자, 산화티탄 입자, 수산화알루미늄 입자, 실리카 입자, 유리 입자, 마이카 입자, 산화마그네슘 입자, 산화아연 입자, 아크릴계 가교입자, 실리콘계 가교입자, 및 스티렌계 가교입자로 이루어지는 군으로부터 선택된 어느 하나 또는 2 이상의 것을 혼합하여 사용하는 것을 특징으로 한다.In addition, the light diffusing agent is calcium carbonate particles, barium sulfate particles, titanium oxide particles, aluminum hydroxide particles, silica particles, glass particles, mica particles, magnesium oxide particles, zinc oxide particles, acrylic crosslinked particles, silicone crosslinked particles, and styrene It is characterized by using any one or two or more selected from the group consisting of crosslinked particles.

또한, 상기 광확산제 입자는 평균 입경이 2~30 μm인 것을 특징으로 한다.In addition, the light diffusing agent particles are characterized in that the average particle diameter of 2 ~ 30 μm.

또한, 상기 광확산판용 폴리프로필렌계 수지 조성물은 자외선 안정제, 산화방지제, 대전방지제, 난연제, 및 안료로 이루어지는 군으로부터 선택된 어느 하나 또는 2 이상의 첨가제를 추가로 포함하는 것을 특징으로 한다.In addition, the polypropylene resin composition for the light diffusion plate is characterized in that it further comprises any one or two or more additives selected from the group consisting of UV stabilizers, antioxidants, antistatic agents, flame retardants, and pigments.

본 발명은 상기 폴리프로필렌계 수지 조성물을 포함하는 광확산판을 제공한다.The present invention provides a light diffusing plate comprising the polypropylene resin composition.

또한, 상기 폴리프로필렌계 광확산판이 적용된 조명기구 보호 커버, 옥외용 간판, 또는 LED 채널간판을 제공한다.The present invention also provides a luminaire protective cover to which the polypropylene light diffusion plate is applied, an outdoor signage, or an LED channel sign.

본 발명은 i) 랜덤 폴리프로필렌 수지, 임팩트 폴리프로필렌 수지 및 광확산제를 이축 압출기의 호퍼에 공급하는 단계; ii) 공급된 원료를 이축 압출기에서 용융·혼련하는 단계; 및 iii) 용융·혼련된 블렌드물을 압출성형 하여 평판 쉬트를 제조하는 단계;를 포함하는 광확산판의 제조방법을 제공한다.The present invention comprises the steps of: i) supplying a random polypropylene resin, impact polypropylene resin and light diffusing agent to the hopper of a twin screw extruder; ii) melting and kneading the supplied raw material in a twin screw extruder; And iii) extruding the melted and kneaded blend to produce a flat sheet.

본 발명에서 제조되는, 랜덤 폴리프로필렌 수지, 임팩트 폴리프로필렌 수지 및 광확산제를 포함하는 광확산판은 가격이 저렴하면서도 내광성이 매우 우수하여 황변현상이 발생하지 않을 뿐만 아니라, 광투과성 및 광확산성이 우수하고 휘도가 높으며, 내충격성 및 내후성 등의 기계적 물성이 향상되어 조명기구 보호 커버 또는 옥외용 간판뿐만 아니라, LED 채널간판 등에도 적용이 가능하다.The light diffusing plate produced in the present invention, including a random polypropylene resin, an impact polypropylene resin and a light diffusing agent is inexpensive and has excellent light resistance, so that yellowing does not occur, as well as light transmittance and light diffusivity. It is excellent in brightness, high in mechanical properties such as impact resistance and weather resistance is improved, it can be applied to LED channel signage as well as luminaire protective cover or outdoor signage.

도 1은 본 발명에 따른 폴리프로필렌계 광확산판의 개념도.
도 2는 본 발명에 따른 광확산판이 적용된 옥외용 간판을 나타내는 사시도.
도 3은 본 발명에 따른 광확산판이 적용된 조명기구를 나타내는 사시도.
도 4는 본 발명에 따른 광확산판이 적용될 수 있는 LED 채널간판.
1 is a conceptual diagram of a polypropylene light diffuser plate according to the present invention.
Figure 2 is a perspective view showing an outdoor signage to which the light diffusion plate according to the present invention is applied.
3 is a perspective view showing a light fixture to which the light diffusion plate according to the present invention is applied.
Figure 4 is an LED channel sign that can be applied to the light diffusion plate according to the present invention.

이하에서는 본 발명에 따른 랜덤 폴리프로필렌 수지와 임팩트 폴리프로필렌 수지를 블렌드한 주재 수지 및 광확산제를 포함하는 수지 조성물, 이를 포함하는 광확산판 및 그 제조방법에 관하여 상세히 설명하기로 한다.Hereinafter, a resin composition comprising a main resin and a light diffusing agent blended with a random polypropylene resin and an impact polypropylene resin according to the present invention, a light diffusion plate including the same, and a method of manufacturing the same will be described in detail.

본 발명에서는 종래 PMMA 또는 폴리카보네이트계와 같이 가격이 비싼 광확산판을, 성능이 우수하면서도 가격이 저렴한 광확산판으로 대체할 목적으로 수지 가격이 저렴하면서도 타카시공, 절단, 절삭, 조각, 연마 등의 후가공성이 양호하여 다양한 형태로 제작 가능한 랜덤 폴리프로필렌 수지와 임팩트 폴리프로필렌 수지를 블렌드한 폴리프로필렌계 수지를 광확산판의 주재 수지로 채택한 것이다. In the present invention, in order to replace the expensive light diffuser plate, such as PMMA or polycarbonate, with a light diffuser plate having excellent performance and low cost, the resin is inexpensive and the Takagi construction, cutting, cutting, engraving, polishing, etc. Polypropylene-based resin blended with a random polypropylene resin and an impact polypropylene resin that can be produced in various forms due to its good post-processability is adopted as the main resin of the light diffusion plate.

먼저, 본 발명에 따른 광확산판용 수지 조성물을 구성하는 주재 수지의 일 성분으로서 랜덤 폴리프로필렌 수지를 사용하는바, 랜덤 폴리프로필렌 수지는 투명성이 우수하고 호모 폴리프로필렌 수지에 비하여 유연성이 높아 성형품을 다양한 형태로 제작할 수 있고, 가격이 저렴하면서도 성형가공성이 뛰어나 압출성형 및 사출성형에 적합하며, 내후성도 높아서 종래 PMMA 주재의 조명기구 커버 또는 간판을 대체할 수 있다.First, random polypropylene resin is used as one component of the main resin constituting the resin composition for a light diffusion plate according to the present invention. The random polypropylene resin has a high transparency and a high flexibility compared to the homo polypropylene resin, thereby forming a variety of molded articles. It can be manufactured in the form, low cost but excellent molding processability is suitable for extrusion molding and injection molding, high weather resistance can replace the conventional lighting fixture cover or signage of PMMA.

그러나 랜덤 폴리스티렌 수지는 투명도가 높지만 호모 폴리프로필렌 수지에 비해서는 강성이 떨어지는 단점이 있고, 강성이 뛰어난 호모 폴리프로필렌 수지는 내충격성이 낮은 단점이 있으므로, 본 발명에서는 이를 보완하기 위하여 임팩트 폴리프로필렌 수지를 병용하여 사용한다. 임팩트 폴리프로필렌 수지는 호모 폴리프로필렌 수지에 에틸렌-프로필렌 공중합체 반복단위가 블록을 형성하고 있는 블록 공중합체로서 에틸렌-프로필렌 공중합체가 고무상을 나타내는 특성으로 인하여 호모 폴리프로필렌 수지에 비하여 내충격성이 향상되는 것으로 알려져 있다.However, the random polystyrene resin has a high transparency but has a disadvantage of inferior rigidity as compared to the homo polypropylene resin, and the excellent homo polypropylene resin has a disadvantage of low impact resistance. Use in combination. Impact polypropylene resin is a block copolymer in which the ethylene-propylene copolymer repeating unit forms a block in the homo polypropylene resin, and the impact resistance is improved compared to the homo polypropylene resin due to the characteristic that the ethylene-propylene copolymer exhibits a rubber phase. It is known to become.

본 발명의 광확산판 주재 수지는 기본적으로 랜덤 폴리프로필렌 수지 60~70 중량%와 임팩트 폴리프로필렌 수지 30~40 중량%를 블렌드 하여 구성되는 것으로서, 랜덤 폴리프로필렌 수지와 블렌드 되는 임팩트 폴리프로필렌 수지의 비율이 30 중량% 미만이면 양호한 내충격성을 얻기 어렵고, 40 중량%를 초과하면 투명성 및 내광성이 떨어지고, 광선투과율도 감소하여 우수한 광확산성을 기대하기 힘들다.The light diffusion plate main resin of the present invention is basically composed of 60 to 70 wt% of a random polypropylene resin and 30 to 40 wt% of an impact polypropylene resin, and the ratio of the impact polypropylene resin blended with the random polypropylene resin. If it is less than 30% by weight, it is difficult to obtain good impact resistance, and if it exceeds 40% by weight, transparency and light resistance are poor, light transmittance also decreases, and it is difficult to expect excellent light diffusivity.

본 발명은 상기 광확산판 주재 수지에 광확산제를 혼합함으로써 광투과성 및 광확산성을 향상시키게 되는 것이다.The present invention improves light transmittance and light diffusivity by mixing a light diffusing agent into the light diffusing plate base resin.

광확산제는 광확산판 주재 수지와 굴절률이 다른 무기계 또는 유기계의 투명입자를 사용할 수 있는데, 무기계 입자로는 탄산칼슘 입자, 황산바륨 입자, 산화티탄 입자, 수산화알루미늄 입자, 실리카 입자, 유리 입자, 마이카 입자, 산화마그네슘 입자, 산화아연 입자를 사용할 수 있고, 유기계 입자로는 아크릴계 가교입자, 실리콘계 가교입자 또는 스티렌계 가교입자를 사용할 수 있으며, 상기 유기계 입자 및 무기계 입자를 단독 또는 2 이상의 것을 혼합하여 사용할 수도 있다. 바람직하기로는 내광성이 우수한 유기계의 아크릴계 가교입자, 실리콘계 가교입자 또는 스티렌계 가교입자를 사용한다.The light diffusing agent may be an inorganic or organic transparent particle having a different refractive index than that of the light diffusion plate main resin, and the inorganic particles may be calcium carbonate particles, barium sulfate particles, titanium oxide particles, aluminum hydroxide particles, silica particles, glass particles, Mica particles, magnesium oxide particles, and zinc oxide particles may be used, and as the organic particles, acrylic crosslinked particles, silicon crosslinked particles, or styrene crosslinked particles may be used, and the organic particles and inorganic particles may be mixed alone or in combination of two or more. Can also be used. Organic acrylic crosslinked particles, silicone crosslinked particles or styrene crosslinked particles having excellent light resistance are preferably used.

상기 광확산제는 광확산판 주재 수지 100 중량부에 대하여 0.1~10 중량부를 혼합하는바, 광확산제의 함량이 0.1 중량부 미만이면 광확산 효과가 미미하며, 10 중량부를 초과하면 광확산 효과는 향상되는 반면, 휘도가 저하되므로, 광확산제는 상기 범위 내에서 조절하는 것이 바람직하다.The light diffusing agent mixes 0.1 to 10 parts by weight with respect to 100 parts by weight of the light diffusing plate base resin, the light diffusion effect is insignificant if the content of the light diffusing agent is less than 0.1 parts by weight, the light diffusion effect is greater than 10 parts by weight Is improved while the brightness is lowered, it is preferable to adjust the light diffusing agent within the above range.

또한, 상기 광확산제는 광확산판 주재 수지와의 상용성 및 분산성을 고려하여 입자 형태로 혼합하는데, 광확산제 입자의 평균 입경은 2~30 μm인 것이 바람직하다. 광확산제 입자의 평균 입경이 2 μm미만이면 광확산판의 황변 형상이 발생할 우려가 있고, 30 μm를 초과하면 광확산제 입자의 크기가 너무 커서 광확산판 주재 수지와의 분산성 및 혼화성이 떨어져 광확산 효과를 기대하기 어렵다. 상기 광확산제는 스티렌계 가교입자로서 평균 입경 8~20 μm의 메틸메타크릴레이트-스티렌 공중합체 입자, 아크릴계 가교입자로서 평균 입경 5~30 μm의 PMMA 입자 또는 평균 입경 2~5 μm인 실리콘계 가교입자를 단독 또는 함께 사용하는 것이 더욱 바람직하다.In addition, the light diffusing agent is mixed in the form of particles in consideration of compatibility and dispersibility with the light diffusing plate base resin, the average particle diameter of the light diffusing agent particles is preferably 2 ~ 30 μm. If the average particle diameter of the light diffusing agent particles is less than 2 μm, yellowing of the light diffusing plate may occur. It is difficult to expect a light diffusion effect apart from this. The light diffusing agent is a styrene-based crosslinked particle having an average particle diameter of 8-20 μm of methyl methacrylate-styrene copolymer particles, an acryl-based crosslinking particle having PMMA particles having an average particle diameter of 5-30 μm, or an average particle diameter of 2-5 μm. More preferably, the particles are used alone or together.

한편, 본 발명에 따른 광확산판용 폴리프로필렌계 수지 조성물에는 자외선 안정제, 산화방지제, 대전방지제, 난연제, 및 안료로 이루어지는 군으로부터 선택된 어느 하나 또는 2 이상의 첨가제를 추가로 포함할 수 있는바, 그 종류 및 함량에 대해서는 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자에게 널리 알려져 있으므로 그에 따라 적절히 사용하면 된다.On the other hand, the polypropylene resin composition for light diffusing plate according to the present invention may further include any one or two or more additives selected from the group consisting of UV stabilizers, antioxidants, antistatic agents, flame retardants, and pigments, the kind And the content is well known to those of ordinary skill in the art to which the present invention belongs may be used accordingly accordingly.

본 발명은 상기 광확산판용 폴리프로필렌계 수지 조성물을 포함하는 광확산판을 제공한다. 도 1에 본 발명에 따른 폴리프로필렌계 광확산판에 의하여 입사광이 산란되고, 광확산판에 포함된 광확산제의 광확산 효과에 의하여 빛이 확산 및 투과되는 개념도를 나타내었다.The present invention provides a light diffusion plate comprising the polypropylene resin composition for light diffusion plate. 1 shows incident light scattered by the polypropylene-based light diffusing plate according to the present invention, and light is diffused and transmitted by the light diffusing effect of the light diffusing agent included in the light diffusing plate.

또한, 본 발명은 i) 랜덤 폴리프로필렌 수지, 임팩트 폴리프로필렌 수지 및 광확산제를 이축 압출기의 호퍼에 공급하는 단계; ii) 공급된 원료를 이축 압출기에서 용융·혼련하는 단계; 및 iii) 용융·혼련된 블렌드물을 압출성형 하여 평판 쉬트를 제조하는 단계;를 포함하는 광확산판의 제조방법을 제공한다.In addition, the present invention comprises the steps of i) supplying a random polypropylene resin, impact polypropylene resin and light diffusing agent to the hopper of the twin screw extruder; ii) melting and kneading the supplied raw material in a twin screw extruder; And iii) extruding the melted and kneaded blend to produce a flat sheet.

이하 구체적인 실시예를 상세히 설명한다.
Hereinafter, specific embodiments will be described in detail.

(( 실시예Example 1) One)

랜덤 폴리프로필렌 수지 700kg, 임팩트 폴리프로필렌 수지 300kg 및 광확산제로 평균 입경이 8 μm인 메틸메타크릴레이트-스티렌 공중합체 입자 10kg, 평균 입경이 5 μm인 PMMA 입자 5kg, 평균 입경이 2 μm인 실리콘계 가교입자 5kg을 이축 압출기의 호퍼부에 공급하였다. 공급된 원료를 이축 압출기에서 용융·혼련하고, 그 용융·혼련된 블렌드물을 압출성형 함으로써 2 mm 두께의 평판 쉬트로 광확산판을 제조하였다.
700 kg of random polypropylene resin, 300 kg of impact polypropylene resin, and 10 kg of methyl methacrylate-styrene copolymer particles having an average particle diameter of 8 μm with a light diffusing agent, 5 kg of PMMA particles having an average particle diameter of 5 μm, and silicone-based crosslinking having an average particle diameter of 2 μm 5 kg of particles were fed to the hopper portion of the twin screw extruder. The supplied raw material was melted and kneaded in a twin screw extruder, and the melt-kneaded blend was extruded to prepare a light diffusion plate with a flat sheet of 2 mm thickness.

(( 실시예Example 2) 2)

랜덤 폴리프로필렌 수지 600kg, 임팩트 폴리프로필렌 수지 400kg 및 광확산제로 평균 입경이 2 μm인 실리콘계 가교입자 10kg을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 광확산판을 제조하였다.
A light diffusion plate was manufactured in the same manner as in Example 1, except that 600 kg of random polypropylene resin, 400 kg of impact polypropylene resin, and 10 kg of silicone-based crosslinked particles having an average particle diameter of 2 μm were used as the light diffusing agent.

(( 비교예Comparative example 1) One)

랜덤 폴리프로필렌 수지 800kg, 임팩트 폴리프로필렌 수지 200kg 및 광확산제로 평균 입경이 5 μm인 PMMA 입자 0.5kg을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 광확산판을 제조하였다.
A light diffusion plate was manufactured in the same manner as in Example 1, except that 800 kg of random polypropylene resin, 200 kg of impact polypropylene resin, and 0.5 kg of PMMA particles having an average particle diameter of 5 μm were used as the light diffusing agent.

(( 비교예Comparative example 2) 2)

랜덤 폴리프로필렌 수지 500kg, 임팩트 폴리프로필렌 수지 500kg 및 광확산제로 평균 입경이 1 μm인 실리콘계 가교입자 15kg을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 광확산판을 제조하였다.
A light diffusion plate was manufactured in the same manner as in Example 1, except that 500 kg of random polypropylene resin, 500 kg of impact polypropylene resin, and 15 kg of silicone-based crosslinked particles having an average particle diameter of 1 μm were used as the light diffusing agent.

(( 시험예Test Example ))

상기 실시예 1, 2 및 비교예 1, 2로부터 제조된 광확산판의 광학적 성질 및 기계적 물성을 아래 방법에 의하여 측정하였다. The optical and mechanical properties of the light diffusion plates prepared in Examples 1 and 2 and Comparative Examples 1 and 2 were measured by the following method.

(1) 전광선 투과율 및 광확산도(haze)는 ASTM D1003 방법에 따라 헤이즈미터를 이용하여 측정하였다.(1) Total light transmittance and light haze were measured using a haze meter according to the ASTM D1003 method.

(2) 광확산율은 변각 광도계를 이용하여 수광각 0˚의 광선 투과율I0, 수광각 70˚의 광선투과율 I70을 측정하고, 다음 식에 의해 계산하였다.(2) The light diffusivity was measured using a variable photometer, and the light transmittance I 0 at the light receiving angle of 0 ° and the light transmittance I 70 at the light receiving angle of 70 ° were measured and calculated by the following equation.

광확산율(%) = (I70/I0) X 100Light diffusivity (%) = (I 70 / I 0 ) X 100

(3) 내광성은 ATLAS-UVCON을 이용하여 60℃에서 72시간 동안 자외선을 조사한 후, YI(Yellow Index) 변화량을 측정하였다.(3) Light resistance after irradiating ultraviolet rays at 60 ° C. for 72 hours using ATLAS-UVCON, and measured YI (Yellow Index) change.

(4) 휘도는 휘도계를 이용하여 단위면적당 나오는 빛의 밝기(cd/m2)로 계산하였다.(4) Luminance was calculated as the brightness (cd / m 2 ) of light emitted per unit area using a luminance meter.

(5) 충격강도는 통상의 Izod 충격시험기로 측정하였다.(5) Impact strength was measured by a conventional Izod impact tester.

구분division 전광선
투과율
(%)
Light rays
Transmittance
(%)
광확산도
(haze)
(%)
Light diffusivity
(haze)
(%)
광학산율
(%)
Optical scatter
(%)
△YI△ YI 휘도
(cd/m2)
Luminance
(cd / m 2 )
Izod
충격강도
(J/m)
Izod
Impact strength
(J / m)
내후성
Weatherability
실시예 1Example 1 61.361.3 99.199.1 30.230.2 0.70.7 6,1006,100 65.365.3 우수Great 실시예 2Example 2 60.560.5 99.099.0 28.528.5 0.80.8 6,0006,000 63.163.1 우수Great 비교예 1Comparative Example 1 48.248.2 98.598.5 21.521.5 2.42.4 5,4505,450 51.551.5 양호Good 비교예 2Comparative Example 2 46.346.3 98.098.0 19.419.4 2.52.5 5,4005,400 50.350.3 양호Good

상기 표 1에서 보는 바와 같이, 본 발명에 따라 제조된 실시예 1, 2의 광확산판은 비교예 1, 2의 광확산판에 비하여 전광선 투과율, 광확산도(haze), 광확산율이 높고, 특히 YI 변화량이 극히 적어 내광성이 탁월하므로 장기간 옥외에 사용하여도 황변현상이 발생할 우려가 거의 없을 뿐만 아니라, 상대적으로 휘도도 높아 광학적 물성이 우수하며, 내충격성 및 내후성 등의 기계적 물성도 모두 우수함을 확인할 수 있다.As shown in Table 1, the light diffusing plates of Examples 1 and 2 prepared according to the present invention have a higher total light transmittance, a light haze, and a light diffusing rate than the light diffusing plates of Comparative Examples 1 and 2, In particular, since there is very little YI change and excellent light resistance, there is little fear of yellowing phenomenon even when used outdoors for a long time. You can check it.

따라서 본 발명에 따른 광확산판은 조명기구 보호 커버 또는 옥외용 간판뿐만 아니라, LED 채널간판 등에도 적용이 가능하다.Therefore, the light diffusion plate according to the present invention can be applied to LED channel signs, as well as luminaire protective cover or outdoor signage.

1. 간판 2. 폴리프로필렌계 확산판
3. 조명기구 4. 폴리프로필렌계 광확산 보호 커버
1. Signage 2. Polypropylene diffusion plate
3. Lighting equipment 4. Polypropylene light diffusion protection cover

Claims (7)

랜덤 폴리프로필렌 수지 60~70 중량%와 임팩트 폴리프로필렌 수지 30~40 중량%를 블렌드한 주재 수지 100 중량부에 대하여 탄산칼슘 입자, 황산바륨 입자, 산화티탄 입자, 수산화알루미늄 입자, 실리카 입자, 유리 입자, 마이카 입자, 산화마그네슘 입자, 산화아연 입자, 아크릴계 가교입자, 실리콘계 가교입자, 및 스티렌계 가교입자로 이루어지는 군으로부터 선택된 어느 하나 또는 2 이상의 것을 혼합하여 사용하는 광확산제 0.1~10 중량부를 포함하는 광확산판용 폴리프로필렌계 수지 조성물.Calcium carbonate particles, barium sulfate particles, titanium oxide particles, aluminum hydroxide particles, silica particles, glass particles, based on 100 parts by weight of the base resin blended from 60 to 70% by weight of random polypropylene resin and 30 to 40% by weight of impact polypropylene resin. And 0.1 to 10 parts by weight of a light diffusing agent used by mixing any one or two or more selected from the group consisting of mica particles, magnesium oxide particles, zinc oxide particles, acrylic crosslinked particles, silicone crosslinked particles, and styrene crosslinked particles. Polypropylene resin composition for light diffusion plates. 삭제delete 제1항에 있어서, 상기 광확산제 입자는 평균 입경이 2~30 μm인 것을 특징으로 하는 광확산판용 폴리프로필렌계 수지 조성물.The polypropylene resin composition for light diffusing plate according to claim 1, wherein the light diffusing agent particles have an average particle diameter of 2 to 30 µm. 제1항에 있어서, 자외선 안정제, 산화방지제, 대전방지제, 난연제, 및 안료로 이루어지는 군으로부터 선택된 어느 하나 또는 2 이상의 첨가제를 더욱 포함하는 것을 특징으로 하는 광확산판용 폴리프로필렌계 수지 조성물.The polypropylene resin composition for light diffusion plate according to claim 1, further comprising any one or two or more additives selected from the group consisting of an ultraviolet stabilizer, an antioxidant, an antistatic agent, a flame retardant, and a pigment. 제1항, 제3항 및 제4항 중 어느 한 항의 광확산판용 폴리프로필렌계 수지 조성물을 포함하는 광확산판.The light-diffusion plate containing the polypropylene resin composition for light-diffusion plates of any one of Claims 1, 3, and 4. 제5항의 광확산판이 적용된 조명기구 보호 커버, 옥외용 간판, 또는 LED 채널간판.Lighting fixture protection cover, outdoor signage, or LED channel signage applied to the light diffusion plate of claim 5. 삭제delete
KR1020120100988A 2012-09-12 2012-09-12 Polypropylene-based resin composition for a light diffusion plate, a light diffusion plate containing the same and manufacturing method thereof KR101219602B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020120100988A KR101219602B1 (en) 2012-09-12 2012-09-12 Polypropylene-based resin composition for a light diffusion plate, a light diffusion plate containing the same and manufacturing method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1020120100988A KR101219602B1 (en) 2012-09-12 2012-09-12 Polypropylene-based resin composition for a light diffusion plate, a light diffusion plate containing the same and manufacturing method thereof

Publications (1)

Publication Number Publication Date
KR101219602B1 true KR101219602B1 (en) 2013-01-31

Family

ID=47841382

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1020120100988A KR101219602B1 (en) 2012-09-12 2012-09-12 Polypropylene-based resin composition for a light diffusion plate, a light diffusion plate containing the same and manufacturing method thereof

Country Status (1)

Country Link
KR (1) KR101219602B1 (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105733088A (en) * 2014-05-13 2016-07-06 上海宇明光电材料技术有限公司 Preparation method of modified plastic for LED tube
KR101893688B1 (en) * 2017-04-10 2018-08-30 한화토탈 주식회사 Polypropylene resin composition having excellent Light diffusing property
CN109135066A (en) * 2016-12-09 2019-01-04 天津中天精科科技有限公司 A kind of polypropylene material for daily necessities
CN109486041A (en) * 2018-11-01 2019-03-19 广东基地光电有限公司 A kind of fire-retardant PP diffuser plate and preparation method thereof
CN109535563A (en) * 2018-12-04 2019-03-29 佛山市巨齿鲨科技有限公司 A kind of environment-friendly composite material and the preparation method and application thereof
KR101973598B1 (en) * 2018-09-04 2019-04-29 박용필 Polypropylene resin composition for a light diffusing plate and a light diffusing plate containing the same
CN110791020A (en) * 2018-08-02 2020-02-14 东莞市亨嘉橡塑科技有限公司 Transparent flame-retardant photodiffusion polypropylene material and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100547363B1 (en) * 2000-07-15 2006-01-26 에스케이 주식회사 Polyolefin resin composition having a good matt property, impact strength and transparency for blow molding and an article using it
KR101135698B1 (en) * 2009-12-16 2012-04-13 호남석유화학 주식회사 Polypropylene resin composition having ultra high transparency and the molded article

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100547363B1 (en) * 2000-07-15 2006-01-26 에스케이 주식회사 Polyolefin resin composition having a good matt property, impact strength and transparency for blow molding and an article using it
KR101135698B1 (en) * 2009-12-16 2012-04-13 호남석유화학 주식회사 Polypropylene resin composition having ultra high transparency and the molded article

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105733088A (en) * 2014-05-13 2016-07-06 上海宇明光电材料技术有限公司 Preparation method of modified plastic for LED tube
CN109135066A (en) * 2016-12-09 2019-01-04 天津中天精科科技有限公司 A kind of polypropylene material for daily necessities
CN109135065A (en) * 2016-12-09 2019-01-04 天津中天精科科技有限公司 A kind of preparation method of the polypropylene material for daily necessities
KR101893688B1 (en) * 2017-04-10 2018-08-30 한화토탈 주식회사 Polypropylene resin composition having excellent Light diffusing property
CN110791020A (en) * 2018-08-02 2020-02-14 东莞市亨嘉橡塑科技有限公司 Transparent flame-retardant photodiffusion polypropylene material and preparation method thereof
KR101973598B1 (en) * 2018-09-04 2019-04-29 박용필 Polypropylene resin composition for a light diffusing plate and a light diffusing plate containing the same
CN109486041A (en) * 2018-11-01 2019-03-19 广东基地光电有限公司 A kind of fire-retardant PP diffuser plate and preparation method thereof
CN109535563A (en) * 2018-12-04 2019-03-29 佛山市巨齿鲨科技有限公司 A kind of environment-friendly composite material and the preparation method and application thereof
CN109535563B (en) * 2018-12-04 2021-11-05 佳润科技(惠州)有限公司 Environment-friendly composite material and preparation method and application thereof

Similar Documents

Publication Publication Date Title
KR101219602B1 (en) Polypropylene-based resin composition for a light diffusion plate, a light diffusion plate containing the same and manufacturing method thereof
KR101231718B1 (en) Resin composition for a light diffusion plate, a light diffusion plate containing the same and manufacturing method thereof
KR102035546B1 (en) A light diffusing polymer composition, method of producing the same, and articles made therefrom
JP6215327B2 (en) Light diffusing polymer composition, method for producing the same, and article made therefrom
JP2021101011A (en) Transparent resin composition, resin molded body, lamp cover, lamp cover for vehicles, combination lamp cover, and vehicle
US20180052260A1 (en) High efficiency diffusion lighting coverings
CN113286850A (en) Polymer composition comprising particles and a colorant, method for the production thereof and use thereof
CN103709713A (en) Light diffusion material
US10907039B2 (en) (Meth)acrylic composition comprising particles, its method of preparation, its use and object comprising it
US9557445B2 (en) Optical diffusion blend materials for LED lighting
KR101372295B1 (en) Light diffusing polystyrene resin composition and monolayer light diffusing sheet containing the same
US9547108B2 (en) Optical diffusion blend materials for LED lighting
CN109791217B (en) (meth) acrylic composition comprising particles, method for preparing same and use thereof as masterbatch
KR101952833B1 (en) Polystyrene-based high-luminance light diffusing monolayer sheet having improved light-shielding effect
KR101973598B1 (en) Polypropylene resin composition for a light diffusing plate and a light diffusing plate containing the same
US10345493B2 (en) Optical diffusion blend materials for LED lighting
CN101285897A (en) Light diffusing plate resin composition and light diffusing plate
JP4970451B2 (en) Light diffusion resin composition and light diffusion plate
KR101479169B1 (en) Polypropylene-based light diffusion resin composition for LED and light diffusion plate
KR101331348B1 (en) Light diffusion polycarbonate resin comprsing high­density polyolefine system
KR100837348B1 (en) Composition for backlight unit optical member of display device and backlight unit optical member
KR20060021112A (en) Multi-layered light diffuser developed warpage and liquid crystal display using the same
CN113286845A (en) Polymer composition suitable for injection moulding comprising particles and colorants, method for the production thereof and use thereof
KR20050070435A (en) Resin composition with excellent light diffusivity
CN111630104A (en) (meth) acrylic polymer composition comprising particles, method for the preparation thereof and use thereof as masterbatch

Legal Events

Date Code Title Description
A201 Request for examination
A302 Request for accelerated examination
E902 Notification of reason for refusal
E701 Decision to grant or registration of patent right
GRNT Written decision to grant
FPAY Annual fee payment

Payment date: 20160105

Year of fee payment: 4

FPAY Annual fee payment

Payment date: 20190103

Year of fee payment: 7

FPAY Annual fee payment

Payment date: 20191231

Year of fee payment: 8