KR890013100A - Hollow polymer particles, preparation method thereof and use as pigment - Google Patents

Abstract

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Description

Hollow polymer particles, preparation method thereof and use as pigment

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Claims (27)

As hollow polymer particles having at least two polymer layers, (1) the average particle diameter is in the range of 0.15-20 μm, (2) the average ratio of the equivalent hollow diameter to the equivalent particle diameter in each particle is in the range of 0.2-0.8, (3) toluene The insoluble content ratio is 2-90% by weight, (4) the melt flow rate is 0.1-1 g / 10 min under conditions of 180 ° C. and 10 Kgf / cm ² , and (5) the inner layer of the polymer layer of the two layers is Formula (a) [Wherein R ¹ is a hydrogen atom or a methyl group, X is an n-functional organic group or a bond number, n is a number of 2 or 3, provided that n R ¹ are the same or different from each other Good or n is 2 when X is a bond water, the polymerization unit represented by following formula (b) [Wherein R ² is a hydrogen atom or a methyl group, Y is a phenyl group, a phenyl group substituted with a halogen atom, an alkyl group or a vinyl group, or a halogen atom, a cyano group, an alkanoyloxy group having 1 to 18 carbon atoms, an alkoxy group, a pyridyl group , A pyridylalkyl group, an aminoalkoxy or an amide group], the following formula (c) [Wherein R ³ and R ⁵ are the same as or different from each other, and are a hydrogen atom or a methyl group, R ⁴ is a hydrogen atom, a carboxyl group or a carboxylate group, R ⁶ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, and a carbon number 2 to A hydroxyalkyl group of 10 or an organic group having at least one selected from glycidyl, amino, cyano and carbon-carbon double bonds, or one equivalent of a base, and optionally Formula (d) (Wherein R ⁷ is a hydrogen atom or a methyl group) to a crosslinked polymer, and (6) the outer layer of the polymer layer of the two layers is represented by the formulas (b), (c), (d) Hollow polymer particles characterized in that the non-crosslinked polymer consisting of at least one polymer unit selected from the group consisting of. The hollow polymer particle according to claim 1, wherein the Tg of the outer layer of the two-layer polymer layer is 40-150 ° C. The hollow polymer particle according to claim 1, wherein the Tg of the inner layer of the polymer layer of the two layers does not exist at 150 ° C or less. The inner layer of the polymer layer of the two layers is characterized in that the polymerization unit (a) is based on the total of the polymerization unit (a), the polymerization unit (b), the polymerization unit (c) and the polymerization unit (d). 20-99% by weight of hydrophilic polymer unit selected from 1-80% by weight, polymerized unit (b) and polymerized unit (c), non-hydrophilic polymerized unit and polymerized unit (d) of polymerized unit (b) or polymerized unit (c) Hollow polymer particles, characterized in that the cross-linked polymer of 0 to 70% by weight of the other copolymerizable polymer unit selected from. The outer layer of the polymer of the said two layers is 0-99.5 weight% of polymerization units (b) and a polymerization unit based on the sum total of a polymerization unit (b), a polymerization unit (c), and a polymerization unit (d). (c) a hollow polymer particle, characterized in that it is a non-crosslinked polymer comprising 0.5-100% by weight and polymerized units (d) 0-80% by weight. The outer layer of the two-layer polymer layer is a non-crosslinked polymer according to claim 1, containing 0.5-50% by weight of a polymer unit of the formula (c) wherein R ⁷ is a hydrogen atom and / or R ⁴ is a carboxyl group. Hollow polymer particles, characterized in that. The hollow layer according to claim 1, wherein the outer layer of the two-layer polymer layer is a non-crosslinked polymer containing 20-99.5% by weight of the polymerized unit of formula (b) wherein Y is phenyl or an alkyl group. Polymer particles. The molecular weight distribution according to claim 1, wherein the polymer component constituting the hollow polymer particles has a part dissolved in tetrahydrofuran, and in this molecular weight distribution measured by high performance liquid chromatography as a tetrahydrofuran solution, the number average molecular weight is A hollow polymer particle comprising 1 to 80% by weight of a component of 700 to 20,000 based on the total of the parts dissolved in tetrahydrofuran. The hollow polymer particle according to claim 1, wherein the ratio of the inner layer to the outer layer of the two polymerized layers is 5-2000 parts by weight of the inner layer per 100 parts by weight of the outer layer. Hollow polymer particles having at least two polymer layers, wherein (1) the average particle diameter is in the range of 0.15-20 μm, (2) the average ratio of the equivalent hollow diameter to the equivalent particle diameter for each particle is in the range of 0.2-0.8, (3) The ratio of the toluene insoluble portion is 85% by weight or more, (4) the melt flow rate is less than 0.2 kg / 10 minutes under the conditions of 180 ° C. and 10 Kgf / cm ² , and (5) the inner layer of the polymer layer of the two layers It becomes the crosslinked polymer which has the same composition as the crosslinked polymer of the inner layer of the hollow polymer particle of Claim 1, and (6) The outer layer of the polymer layer of the said two layers contains the polymer unit of Formula (a) of Claim 1, The crosslinked hollow polymer particles, which optionally comprises a polymer further containing a polymerized unit selected from the group consisting of formulas (b), (c) and (d) of claim 1. The polymer layer according to claim 10, wherein the inner layers of the polymer layers of the two layers are formed based on the total of the polymerization unit (a), the polymerization unit (b), the polymerization unit (c) and the polymerization unit (d). Based on 1-80% of the polymerization unit (a), 20-95% by weight of the hydrophilic polymerization unit selected from the polymerization unit (b) and the polymerization unit (c), A crosslinked hollow polymer particle comprising 0-70% by weight of a copolymerizable other polymerized unit selected from an aqueous polymerized unit and a polymerized unit (d). The polymer according to claim 10, wherein the outer layer of the two-layer polymer layer is based on the total of the polymerized unit (a), the polymerized unit (b), the polymerized unit (c) and the polymerized unit (d). A crosslinked hollow polymer particle comprising 99.5% by weight of polymerized units (b) 0-99.5% by weight, polymerized units (c) 05-99.5% by weight and polymerized units (d) 0-80% by weight. The outer layer of the two-layer polymer layer is a crosslinked polymer according to claim 10, wherein the outer layer of the polymer layer contains 0.5-50% by weight of a polymer unit of formula (c) wherein R ⁶ is a hydrogen atom and / or R ⁴ is a carboxyl group. Crosslinked hollow polymer particles, characterized in that. 11. The crosslinked polymer according to claim 10, wherein the outer layer of the two-layer polymer layer contains 20-99.5% by weight of the polymerized unit of formula (b), wherein Y is a phenyl group or a phenyl group substituted with an alkyl group. Crosslinked hollow polymer. The number average molecular weight in the molecular weight distribution of Claim 10 which has the part which the polymer component which comprises a hollow polymer particle melt | dissolves in tetrahydrofuran, and this part measured by high performance liquid chromatography as a tetrahydrodifuran solution. 20-95 weight% of this 700-20,000 component is contained based on the sum total of the part melted in tetrahydrofuran, The crosslinked hollow polymer particle characterized by the above-mentioned. 11. The crosslinked hollow polymer particle according to claim 10, wherein the ratio of the inner layer and the outer layer of the two-layer polymer cake is 5-2000 parts by weight of the inner layer per 100 parts by weight of the outer layer. (a) Free hollow polymer particles comprising a crosslinked polymer having an average particle diameter in the range of 0.05 m-15 μm and having the same composition as the crosslinked polymer of the inner layer of the hollow polymer particles of claim 1, and (b) the following formula (b1) [Where R ² is a hydrogen atom or a methyl group, Y is a phenyl group or a halogen atom, a cyano group, an alkanoyloxy group having 1 to 18 carbon atoms, an alkoxy group, a pyridyl group, a pyridylalkyl group, an aminoalkoxy group or an amide group] Monomer represented by the following formula (C1) [Wherein R ³ and R ⁴ are the same as or different from each other, and are a hydrogen atom or a methyl group, R ⁴ is a hydrogen atom, a carboxyl group or a carboxylate group, R ⁶ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, and a carbon number 2-10 is a hydroxy alkyl group or an organic group having at least one selected from glycidyl, amino, cyano, and carbon-carbon double bonds, or one equivalent of base; and, if necessary, the following formula (d1) Here, the monomer mixture (m-2) of the monomer represented by R <^7> is a hydrogen atom or a methyl group, (c) 100 weight of the total weight of the said free hollow polymer particle (A) and monomer mixture (m-2) In the presence of 5 parts by weight or less of emulsifier and / or dispersant per part, the polymer is polymerized in an aqueous medium to produce a polymer film of the monomer mixture (m-2) on the surface of the free hollow polymer particles (A), thereby producing an average particle size. The hollow polymer particle of Claim 1 is produced, Comprising: The hollow polymer particle of Claim 1 characterized by the above-mentioned. 18. The process of claim 17, wherein the polymerization is carried out under conditions of pH less than 7. 18. The method of claim 17, wherein the free hollow polymer particles are of formula (a1) (Wherein R ¹ , X and n are as defined in claim 1), the monomer represented by formula (b1), the monomer represented by formula (c1), and, if necessary, formula (d1) 1-100 weight of said other polymer (S) particles per 100 weight part of said monomer mixtures in presence of the other polymer (S) particle which has a monomer mixture (m-1) which shows a composition different from the copolymer obtained from this monomer mixture. A process characterized in that it is prepared by polymerization in an aqueous medium using a negative proportion. (A) The free hollow polymer particle which becomes a crosslinked polymer which has an average particle diameter in the range of 0.05-10.5 micrometer, and has the same composition as the crosslinked polymer of the inner layer of the hollow polymer particle of Claim 2, and (B) following formula (a1) [Wherein R ¹ is a hydrogen atom or a methyl group, X is a functional organic group or a bond number, n is a number of 2 or 3, provided that n R ^{1 s} may be the same or different from each other, and X is a bond number Where n is 2, and optionally a monomer mixture (m-) with at least one of the monomer of formula (b1) of claim 3 and the monomer of formula (d1) of formula (c1). 2) '(c) polymerizing the monomer mixture (m-2) of the free hollow polymer particles (A) in an aqueous medium in the presence of up to 5 parts by weight of an emulsifier and / or a dispersant, The hollow polymer particle of claim 10, wherein a hollow film particle having an average particle size in the range of 0.15-20 µm is produced by generating a polymer film of the monomer (m-2) 'on the surface of the free hollow polymer particle (A). How to prepare. 21. The method of claim 20, wherein said polymerization is carried out under conditions of pH less than 7. The said free hollow polymer particle is a monomer represented by the said Formula (a1), the monomer represented by the said (b1), the monomer represented by the said Formula (c1), and if necessary, are represented by Formula (d1). 1-100 of said other weight body (S) particles per 100 weight part of said monomer mixtures in presence of the other polymer (S) particle which has a monomer mixture (m-1) which shows a monomer composition different from the copolymer obtained from this monomer mixture. A process characterized in that the polymerization is carried out in an aqueous medium using a proportion by weight. A pigment comprising the hollow polymer particles of claim 1. The hollow polymer particles, the mineral inorganic pigment and the pigment binder according to claim 1 or 10, wherein the hollow polymer particles occupy 1-50% by weight of the total amount of the hollow polymer particles and the mineral inorganic pigment, and the pigment binder The coating composition for paper is contained 3-30 weight part per 100 weight part of total amounts of the said hollow polymer particle and the said mineral inorganic pigment. The coating composition for paper according to claim 24, further comprising non-hollow polymer particles in an amount of 25% by weight or less of the total amount of the hollow polymer particles, the mineral inorganic pigment, and the non-hollow polymer particles. The general coating composition comprising the polymer particle 3-95 midway portion, the pigment binder 5-97 midway portion, and 0-700 parts by weight of the inorganic filler per 100 parts by weight of the total amount of the hollow polymer particles and the pigment binder. . Use of the polymer particles according to claim 1 as a pigment. ※ Note: The disclosure is based on the initial application.