METHOD FOR PREPARING FINE PARTICLES HAVING ENCLOSED VOIDS WITH IMPROVED STAIN RESISTANCE CONTAINING FUNCTIONAL PHOSPHORIC ACID MONOMER AND COMPOSITION COMPRISING THE PARTICLES

• Main Authors: KIM JI YUN, CHAE MIN JI, CHOI SI ON, KIM NAM WOO, KIM HYUN JI
• Format: Patent
• Language: English; Korean
• Published: 03.01.2023
• Subjects: ADHESIVES; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F,C08G; CHEMICAL PAINT OR INK REMOVERS; CHEMISTRY; COATING COMPOSITIONS, e.g. PAINTS, VARNISHES ORLACQUERS; COMPOSITIONS BASED THEREON; CORRECTING FLUIDS; DYES; FILLING PASTES; GENERAL PROCESSES OF COMPOUNDING; INKS; MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVINGCARBON-TO-CARBON UNSATURATED BONDS; METALLURGY; MISCELLANEOUS APPLICATIONS OF MATERIALS; MISCELLANEOUS COMPOSITIONS; NATURAL RESINS; ORGANIC MACROMOLECULAR COMPOUNDS; PAINTS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; POLISHES; THEIR PREPARATION OR CHEMICAL WORKING-UP; USE OF MATERIALS THEREFOR; WOODSTAINS; WORKING-UP

The present invention relates to a method for producing fine particles with internal pores with improved fouling resistance containing a functional phosphoric acid monomer and a composition containing the particles. In the multi-step emulsion polymerization method for producing microparticles with internal pores using a core polymer containing carboxylic acid, a polymerization initiator, a primary intermediate shell monomer, and a secondary hard shell monomer, the primary middle shell monomer includes a polyfunctional monomer that is a crosslinkable monomer having two or more double bonds, and during the process of forming the secondary hard shell, a functional monoethylenically unsaturated monomer having a phosphate group and a secondary hard shell monomer are additionally added to the fine particles and polymerized to remove residual polymerization initiator. The microparticles with internal pores manufactured according to the present invention not only have excellent fouling resistance, but also have the advantage of minimizing the reversal phenomenon between the hydrophilic core and hydrophobic shell and the generation of defective particles, preventing destruction of the shell film due to swelling, and increasing monodisperse efficiency by controlling the ratio of monoethylenically unsaturated monomers of different compositions containing a crosslinking agent during polymerization of the primary middle shell polymer. In addition, at the end of the reaction, all remaining polymerization initiators are reacted by adding the functional monomer containing a phosphate group and the hard shell monomer, thereby the surface of the particle improves adsorption with latex while preventing subsequent secondary polymerization. Therefore, it has the advantage of increasing adhesion and stain resistance, increasing stain resistance, and making the shape of the particles more even. 본 발명은 기능성 인산계 단량체를 함유한 내오염성이 향상된 내부기공을 갖는 미세입자의 제조방법 및 그 입자를 포함하는 조성물에 관한 것으로, 카르복시산을 함유하는 코어 중합체, 중합 개시제, 1차 중간쉘 단량체 및 2차 경질쉘 단량체를 이용하여 내부기공을 갖는 미세입자를 제조하는 다단계 유화중합 방법에 있어서, 상기 1차 중간쉘 단량체는 2개 이상의 이중결합을 가지는 가교성 단량체인 다관능성 단량체를 포함하고, 2차 경질쉘을 형성하는 과정 중 미세입자에 인산기를 가진 기능성 모노에틸렌계 불포화 단량체 및 2차 경질쉘 단량체를 추가 투입 및 중합하여 잔류 중합 개시제를 소거하는 것을 특징으로 한다. 본 발명에 의하여 제조된 내부기공을 갖는 미세입자는 내오염성이 우수할 뿐만 아니라, 1차 중간쉘 중합체의 중합시 가교제가 포함된 조성이 다른 모노에틸렌계 불포화 단량체의 비율을 조절하여, 친수성 코어와 소수성 쉘의 역전현상 및 불량입자의 발생을 최소화하고, 팽윤으로 인한 쉘 피막의 파괴를 방지하며, 단분산 효율을 높이는 장점이 있다. 또한, 반응 마지막에 인산기가 포함된 기능성 단량체와 경질쉘 단량체의 첨가로 남은 중합 개시제를 모두 반응시켜 이후 부수적인 중합이 일어나지 않도록 막으면서 입자의 표면이 라텍스와의 흡착을 향상시켜 부착성 및 내오염성을 증가시켜 얼룩저항성을 높이고 입자의 형태를 더욱 고르게 할 수 있는 장점이 있다.