EP0331421A2
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EP
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Hollow polymer particles, process for production thereof, and use thereof as pigment
Assignee: JSR Corp
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Filing: 1989-02-28
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Granted: —
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Expires: 2009-02-28
Abstract
Abstract Hollow polymer particles having at least two polymer layers, wherein (1) the particles have an average particle diameter in the range of 0.15 to 20 micrometers, (2) each of the particles has an average equivalent hollow diameter/equivalent particle diameter in the range of 0.2 to 0.8, (3) the proportion of a toluene-insoluble portion of the particles is 20 to 90 % by weight, (4) the polymer particles have a melt flow rate at 180 °C under 10 kgf/cm² of 0.1 to 1 g/10min., (5) the inside layer of the two polymer layers is composed of a crosslinked polymer and (6) the outside layer of the two polymer layers is composed of a non-crosslinked polymer. This invention also provides hollow crosslinked polymer particles wherein the proportion of a toluene-insoluble portion of the particles exceeds 85 % by weight, the melt flow rate of the polymer particles at 180 °C under 10 kgf/cm² is less than 0.2 g/10 min., and the outside layer is composed of a crosslinked polymer. The hollow polymer particles are useful, for example, as a pigment and for a paper coating composition and a general-purpose coating composition.
Inventors
- 👤 Nobuo Kawahashi
- 👤 Fujio Sakurai
- 👤 Hiroshi Tadenuma
Bibliographic Details
Application Number
—
Jurisdiction
EP
Data Source
google_patents
Last Synchronized
2026-11-08 16:14
CPC Classifications
D; D21; D21H; D21H21/00; D21H21/50; D21H21/52; D21H21/54; C; C08; C08F; C08F265/00; C08F265/04; C08F271/00; C08F271/02; C08F291/00; C09; C09D; C09D151/00; C09D151/003; Y; Y10; Y10S; Y10S525/00; Y10S525/902; Y10T; Y10T428/00; Y10T428/29; Y10T428/2982; Y10T428/2991; Y10T428/2998
Claims Analysis
Total Claims: 22
Claim 1
Independent Claim
357 words
Hollow polymer particles having at least two polymer layers, wherein (1) the particles have an average particle diameter of 0.15 to 20 micrometers, (2) each of the particles has an average equivalent hollow diameter/equivalent particle diameter of 0.2/1 to 0.8/1. (3) the proportion of toluene-insoluble material in the particles is 20 to 90% by weight, (4) the polymer particles have a melt flow rate at 180°C under 10 kgf/cm² of 0.1 to 1 g/10 min., (5) the inner of said at least two polymer layers is composed of a crosslinked polymer composed of (a) recurring units represented by the following formula wherein R¹ represents a hydrogen atom or a methyl group, X represents an n -functional organic group or a bond, and n is 2 or 3, provided that n R¹'s may be identical or different and when X is a bond, n is 2, (b) recurring units represented by the following formula wherein R² represents a hydrogen atom or a methyl group, and Y represents a phenyl group optionally substituted by halo, alkyl or vinyl, a halogen atom, a cyano group, an alkanoyloxy group having 1 to 18 carbon atoms, an alkoxy group, a pyridyl group, a pyridyl-alkyl group, an aminoalkoxy group or an amide group, (c) recurring units represented by the following formula wherein R³ and R⁵ are identical or different, and each represents a hydrogen atom or a methyl group, R⁴ represents a hydrogen atom, a carboxyl group or a carboxylate group, and R⁶ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a hydroxyalkyl group having 2 to 10 carbon atoms, an organic group containing at least one member selected from a glycidyl group, an amino group, a cyano group and a carbon-carbon double bond, or one equivalent of a cation group, and (d) optionally, recurring units represented by the following formula wherein R⁷ represents a hydrogen atom or a methyl group, and (6) the outer of said at least two polymer layers is composed of a non-crosslinked polymer composed of at least one type of recurring units selected from the recurring units of fomulae (b), (c) and (d).
Claim 2
Dependent Claim
357 words
Hollow polymer particles having at least two polymer layers, wherein (1) the particles have an average particle diameter of 0.15 to 20 micrometers, (2) each of the particles has an average equivalent hollow diameter/equivalent particle diameter of 0.2/1 to 0.8/1. (3) the proportion of toluene-insoluble material in the particles is 20 to 90% by weight, (4) the polymer particles have a melt flow rate at 180°C under 10 kgf/cm² of 0.1 to 1 g/10 min., (5) the inner of said at least two polymer layers is composed of a crosslinked polymer composed of (a) recurring units represented by the following formula wherein R¹ represents a hydrogen atom or a methyl group, X represents an n -functional organic group or a bond, and n is 2 or 3, provided that n R¹'s may be identical or different and when X is a bond, n is 2, (b) recurring units represented by the following formula wherein R² represents a hydrogen atom or a methyl group, and Y represents a phenyl group optionally substituted by halo, alkyl or vinyl, a halogen atom, a cyano group, an alkanoyloxy group having 1 to 18 carbon atoms, an alkoxy group, a pyridyl group, a pyridyl-alkyl group, an aminoalkoxy group or an amide group, (c) recurring units represented by the following formula wherein R³ and R⁵ are identical or different, and each represents a hydrogen atom or a methyl group, R⁴ represents a hydrogen atom, a carboxyl group or a carboxylate group, and R⁶ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a hydroxyalkyl group having 2 to 10 carbon atoms, an organic group containing at least one member selected from a glycidyl group, an amino group, a cyano group and a carbon-carbon double bond, or one equivalent of a cation group, and (d) optionally, recurring units represented by the following formula wherein R⁷ represents a hydrogen atom or a methyl group, and (6) the outer of said at least two polymer layers is composed of a non-crosslinked polymer composed of at least one type of recurring units selected from the recurring units of fomulae (b), (c) and (d).
Claim 3
Dependent Claim
22 words
Hollow polymer particles according to claim 1 in which the outer polymer layer has a glass transition temperature of 40 to 150°C.
Claim 4
Dependent Claim
26 words
Hollow polymer particles according to claim 1 or 2 in which the inner polymer layer does not have a glass transition temperature at 150°C or below.
Claim 5
Dependent Claim
93 words
Hollow polymer particles according to claim 1, 2 or 3 in which the inner polymer layer is composed of a crosslinked polymer consisting of 1 to 80% by weight of recurring units (a), 20 to 99% by weight of hydrophilic recurring units selected from recurring units (b) and recurring units (c) and 0 to 70% by weight of other copolymerizable recurring units selected from non-hydrophilic recurring units of (b) or (c) and the recurring units (d), the proportions being based on the total weight of the recurring units (a), (b), (c) and (d).
Claim 6
Dependent Claim
70 words
Hollow polymer particles according to any one of the preceding claims in which the outer polymer layer is composed of a non-crosslinked polymer consisting of 0 to 99.5% by weight of the recurring units (b), 0.5 to 100% by weight of recurring units (c) and 0 to 80% by weight of recurring units (d), the proportions being based on the total weight of the recurring units (b), (c) and (d).
Claim 7
Dependent Claim
48 words
Hollow polymer particles according to any one of the preceding claims in which the outer polymer layer is composed of a non-crosslinked polymer contianing 0.5 to 50% by weight of recurring units of formula (c) in which R⁶ is a hydrogen atom and/or R⁴ is a carboxyl group.
Claim 8
Dependent Claim
47 words
Hollow polymer particles according to any one of the preceding claims in which the outer polymer layer is composed of a non-crosslinked polymer containing 20 to 99.5% by weight of recurring units of formula (b) in which Y is a phenyl group or an alkyl-substituted phenyl group.
Claim 9
Dependent Claim
69 words
Hollow polymer particles according to any one of the preceding claims in which the polymer components constituting the hollow polymer particles comprise a portion which is soluble in tetrahydrofuran of which 1 to 80% by weight is a component having a number average molecular weight of 700 to 20,000 as determined from the molecular weight distribution of the tetrahydrofuran-soluble portion measured by high-performance liquid chromatography on a tetrahydrofuran solution.
Claim 10
Dependent Claim
37 words
Hollow polymer particles according to any one of the preceding claims in which the proportion of the inner polymer layer is 5 to 2000 parts by weight per 100 parts by weight of the outer polymer layer.
Claim 11
Dependent Claim
143 words
Hollow crosslinked polymer particles having at least two polymer layers, wherein (1) the particles have an average particle diameter of 0.15 to 20 micrometers, (2) each of the particles has an average equivalent hollow diameter/equivalent particle diameter of 0.2/1 to 0.8/1, (3) the proportion of toluene-insoluble material in the particles exceeds 85% by weight, (4) the melt flow rate of the polymer particles at 180°C under 10 kgf/cm² is less than 0.2 g/10 min., (5) the inner layer of the two polymer layers is composed of a crosslinked polymer as defined in any one of claims 1, 3, 4 and 9, and (6) the outer layer is composed of a crosslinked polymer consisting of at least the recurring units of formula (a) in claim 1 and optionally recurring units selected from the recurring units of formulae (b), (c) and (d) in claim 1.
Claim 12
Dependent Claim
76 words
Hollow crosslinked polymer particles according to claim 10 in which the outside polymer layer is composed of a crosslinked polymer consisting of 0.5 to 99.5% by weight of recurring units (a), 0 to 99.5% by weight of recurring units (b), 0.5 to 99.5% by weight of recurring units (c), and 0 to 80% by weight of recurring units (d), the proportions being based on the total weight of the recurring units (a), (b), (c) and (d).
Claim 13
Dependent Claim
29 words
Hollow crosslinked polymer particles according to claim 10 or 11 in which the outer layer is composed of a crosslinked polymer otherwise as defined in claim 6 or 7.
Claim 14
Dependent Claim
64 words
Hollow crosslinked polymer particles according to claim 10, 11 or 12 in which the polymer components comprise a portion which is soluble in tetrahydrofuran of which 20 to 95% by weight is a component having a number average molecular weight of 700 to 20,000 as determined from the molecular weight distribution of the tetrahydrofuran-soluble portion measured by high-performance liquid chromatography on a tetrahydrofuran solution.
Claim 15
Dependent Claim
175 words
A process for producing hollow polymer particles as claimed in any one of claims 1 to 9, which comprises subjecting (A) hollow pre-polymer particles having an average particle diameter of 0.05 to 15 micrometers and the same composition as said inner polymer layer, and (B) as monomer at least one monomer selected from; a monomer represented by the following formula wherein R² and Y are as defined in claim 1, a monomer represented by the following formula (c1) wherein R³ to R⁶ are as defined in claim 1, and a monomer represented by the following formula (d1) CH₂=CR⁷-CH=CH₂ (d1) wherein R⁷ is as defined in claim 1, to polymerization in the presence of not more than 5 parts by weight, per 100 parts by weight of the hollow pre-polymer particles (A) and monomer (B), of an emulsifying agent and/or a dispersing agent in an aqueous medium to form a polymeric film derived from monomer (B) on the surface of the hollow pre-polymer particles (A) and thereby form the outer layer of said hollow polymer particles.
Claim 16
Dependent Claim
152 words
A process for producing hollow crosslinked polymer particles as claimed in any one of claims 10 to 13, which comprises subjecting (A) hollow pre-polymer particles having an average particle diameter of 0.05 to 15 micrometers and the same composition as said inner polymer layer, and (B) as monomer a monomer represented by the following formula (a1) wherein R¹, X and n are as defined in claim 1, and optionally at least one monomer of formulae (b1), (c1) and (d1) as defined in claim 14 to polymerization in an aqueous medium in the presence of not more than 5 parts by weight, per 100 parts by weight of the hollow pre-polymer particles (A) and (B), of an emulsifying agent and/or a dispersing agent to form a polymeric film derived from monomer (B) on the surface of the hollow pre-polymer particles (A) and thereby form said outer layer of said hollow crosslinked polymer particles.
Claim 17
Dependent Claim
25 words
A process according to claim 14 or 15 in which the polymerization of monomer (B) is carried out at a pH of less than 7.
Claim 18
Dependent Claim
79 words
A process according to claim 14, 15 or 16 in which the hollow pre-polymer particles (A) have been produced by polymerizing a monomeric mixture composed of monomers (a1), (b1) and (c1) and optionally (d1) in an aqueous medium in the presence of other polymer particles (S) having a different composition from the copolymer of the monomeric mixture, the proportion of the other polymer particles (S) being 1 to 100 parts by weight per 100 parts of the monomeric mixture.
Claim 19
Dependent Claim
15 words
A pigment comprising hollow particles as claimed in any one of claims 1 to 13.
Claim 20
Dependent Claim
78 words
A paper coating composition comprising hollow particles as claimed in any one of claims 1 to 13, a mineral inorganic pigment and a pigment binder, the hollow particles accounting for 1 to 50% by weight of the total weight of the hollow particles and the mineral inorganic pigment, and the proportion of the pigment binder being 3 to 30 parts by weight per 100 parts of the total weight of the hollow particles and the mineral inorganic pigment.
Claim 21
Dependent Claim
43 words
A paper coating composition according to claim 19 which further comprises non-hollow polymer particles in an amount of not more than 25% by weight based on the total weight of the hollow particles, the mineral inorganic pigment and the non-hollow polymer particles combined.
Claim 22
Dependent Claim
59 words
A coating composition comprising 3 to 95 parts by weight of hollow particles as claimed in any one of claims 1 to 13, 5 to 97 parts by weight of a pigment binder and 0 to 700 parts by weight, per 100 parts of the total weight of the hollow particles and the pigment binder, of an inorganic filler.
References Cited (Backward Citations)
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