JPH0292938A - Hollow polymer particle - Google Patents

Abstract

PURPOSE:To obtain hollow polymer particles, consisting of at least two polymer layers, having holes in the interior thereof, excellent in hiding power, gloss, film strength, adhesion, etc., and suitable as coating materials for paper, fiber, etc., and various coatings, etc. CONSTITUTION:Hollow polymer particles having at least two polymer layers of an inner layer consisting of a crosslinked polymer consisting of polymerization units expressed by formula I (R<1> is H or methyl; X is n-functional organic group, etc.; n is 2 or 3), formula II (R<2> is H or methyl; Y is phenyl, etc.), formula III (R<3> and R<5> are H or methyl; R<4> is H, carboxyl, etc.; R<6> is H, 1-18C alkyl, etc.) and, as necessary, polymerization units expressed by formula IV (R<7> is H or methyl) and an outer layer consisting of an uncrosslinked polymer consisting of one or more polymerization units selected from formulas II, III and IV, 0.15-20mum average particle diameter, 0.2-0.8 average ratio of the equivalent hollow diameter to the equivalent diameter, 20-90wt.% content of portions insoluble in toluene and 0.1-1g/10min melt flow rate.

Description

[Detailed description of the invention]

<Industrial Application Field> The present invention relates to a hollow polymer particle having a novel structure consisting of at least two polymer layers and having pores inside. More specifically, the present invention relates to hollow polymer particles useful as a light scattering agent, light scattering aid, or microcapsule in coating agents for paper, fibers, leather, etc., and various paints. <Prior art> Polymer particles having pores inside the particles can be used as microcapsule particles by containing various substances in the inner pores, or as light scattering agents by making the inner pores hollow. It is used as an organic material such as hollow polymer particles. Conventionally, as a method for producing polymer particles having inner pores,
The following methods are known. CI) A method of incorporating a blowing agent into polymer particles and then foaming the blowing agent. (II) A method in which a volatile substance such as butane is encapsulated in a polymer, and the volatile substance is then gasified and swollen. (I[l) A method in which a polymer is melted and a jet of gas such as air is blown thereto to seal in air bubbles. (IV) A method of infiltrating an alkali-swellable substance into the interior of polymer particles to swell the alkali-swellable substance. (V) A method of creating a w/o/w type monomer emulsion and conducting polymerization. (Vl) A method of polymerizing 7-mer in a suspension solution in which a pigment is suspended in an unsaturated polyester solution. (■) A two-step crosslinking method in which crosslinked polymer particles are used as seeds, and polymers with different compatibility are polymerized and crosslinked onto the seeds. (■) A method of manufacturing by polymerization shrinkage of a polymer. <Problems to be Solved by the Invention> However, in these production methods, it is difficult to control production conditions or to stably produce polymer particles having desired internal pores. In addition, conventional hollow fine particles had the required physical properties of hiding when added as a light-scattering agent to a coating film-forming substance, but they had poor gloss, coating strength, elasticity, adhesion, water resistance, and resistance. The balance of physical properties such as alkalinity, solvent resistance, and weather resistance was poor. In particular, in conventional methods for producing polymer particles with internal pores, it was necessary to use a shell polymer with a high glass transition temperature in order to develop internal pores in the polymer particles. This method had a fatal problem in that hollow polymer particles with good quality could not be obtained. An object of the present invention is to provide novel hollow polymer particles. Another object of the present invention is to provide excellent hiding properties as well as gloss,
The object of the present invention is to provide hollow polymer particles with an excellent balance of physical properties such as coating strength, elasticity, adhesiveness, water resistance, alkali resistance, solvent resistance, and weather resistance. Still another object of the present invention is to provide hollow polymer particles having adhesive properties that cannot be obtained by conventional methods. Yet another object of the present invention is to provide an industrially advantageous method for producing the novel hollow polymer particles of the present invention. Further objects and advantages of the invention will become apparent from the description below. Means for Solving the Problems> According to the present invention, the above objects and advantages of the present invention are provided by hollow polymer particles having at least two polymer layers, (1) having an average particle diameter of 0. (2) the average ratio of equivalent hollow diameter to equivalent particle size for each particle is in the range of 0.2 to 0.8, and (3) the proportion of toluene-insoluble portion is in the range of 20 to 20 μm. (4) Melt flow rate under the conditions of 180°C and 10 kgf/cm" is 0.1 = l g/IO+n
(5) The inner layer of the two-layer polymer layer has the following formula X is an n-functional organic group or a bond, and n is the number 2 or 3, provided n R1 may be the same or different, and when X is a bond, n is 2, a polymerized unit represented by the following formula (b), where R1 is a hydrogen atom or a methyl group, , and Y is a phenyl group, a phenyl group substituted with a halogen atom, an alkyl group or a vinyl group, a halogen atom, a cyano group, an alkanoyloxy group having 1 to 18 carbon atoms, an alkoxy group, a pyridyl group. , pyridylalkyl, aminoalkoxy, or amide group, a polymerized unit represented by the following formula (c), where R3 and R8 are the same or different and are a hydrogen atom or a methyl group, and R4 is a hydrogen atom, a carboxyl group, or a methyl group. is a carboxylate group, and R6 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a hydroxyalkyl group having 2 to 10 carbon atoms, or a small group selected from glycidyl, amino, cyano, and a carbon-carbon double bond. and optionally, a polymerized unit represented by the following formula (d), where R7 is a hydrogen atom or a methyl group, (6) The outer layer of the two-layered polymer has the formula (b), (
This is achieved by hollow polymer particles characterized by being made of a non-crosslinked polymer comprising at least one polymer unit selected from the group consisting of C) and (d). According to the present invention, the hollow polymer particles (Q) of the present invention include (m-1) polymerized units of the above formulas (a), (b), (c) and optionally further polymerized units of (d). consisting of a crosslinked polymer with an average particle diameter of 0.05 to 15μ
Hollow polymer particles within the range of m (hereinafter sometimes referred to as pre-hollow polymer particles CP), and (m-2) the following formula (b 1) where R2 and Y are defined in the above formula (b). The same is true for the monomer represented by the above formula % and the following formula (cl), where R3, R', R', and R'' are defined as the monomer represented by the above formula %, and the following formula (di) CHI -CR'-CH-CHz (d
1) Here, the definition of R7 is the same as in the above formula (d). At least one monomer selected from the group consisting of monomers represented by Emulsifier and/or not more than 5 parts by weight per 100 parts by weight of body (m −2)
Alternatively, it can be produced by subjecting it to polymerization in an aqueous medium at a pH of less than 7 in the presence of a dispersant. Pre-hollow polymer particles (P) used in the above method
As described above, is composed of the polymerized units of the above formulas (a), (b), and (C) and optionally the polymerized units of (d), and has an average particle diameter in the range of 0.105 to 15 μm. Pre-hollow polymer particles (P) are, for example, disclosed in JP-A-61-62
510 and JP-A No. 61-66710, etc., and the method (■) shown in the conventional technical section and JP-A-61-Sho.
-87734, JP-A-61-86941, JP-A-6
It can be suitably manufactured by the method (■) shown in the conventional technical section proposed in No. 2-127336, JP-A No. 62-156387, etc. By using pre-hollow polymer particles obtained by such a method, the hollow polymer particles (Q) of the present invention having particularly excellent hiding properties can be produced. In particular, according to the method (■), it is easy to control the inner diameter and outer diameter of the obtained pre-hollow polymer particles (P), and by using it, it is possible to improve not only the hiding property but also the solvent resistance and heat resistance. It is also possible to produce the hollow polymer particles of the present invention which are excellent in the following. The method (■) is particularly preferred. Of the methods (■), the method disclosed in Japanese Patent Application Laid-open No. 127336/1988 is most preferred. According to this method, further excellent polymerization stability and productivity can be achieved in the polymerization of pre-hollow polymer particles (P). Thus, according to the invention, the pre-hollow polymer particles (
P) is the following formula (a l), X is an n-functional organic group or a bond, and n is a number of 2 or 3, provided that n R'+! A monomer represented by the following formula (bl) Y, which may be the same or different, and when X is a bond, n is 2, where R2 is a hydrogen atom or a methyl group, and and Y is a phenyl group, a phenyl group substituted with a halogen atom, an alkyl group or a vinyl group, a halogen atom, a cyano group, an alkanoyloxy group having 1 to 18 carbon atoms, an alkoxy group, pyridyl, pyridyl A monomer represented by the following formula (cl) 3 R6 which is an alkyl, aminoalkoxy or amide group, where R3 and R' are the same or different and are a hydrogen atom or a methyl group, and R1 is a hydrogen atom or a carboxyl group. or a carboxylate group, R' is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a hydroxyalkyl group having 2 to 10 carbon atoms, or is selected from glycidyl, amino, cyano, and a carbon-carbon double bond. is an organic group having at least one member or -equivalent base, and optionally the following formula (d l) CHz-C-CH-CHz...(di
), where R7 is a hydrogen atom or a methyl group, and a monomer mixture (m-1) of the following is combined with another polymer (m-1) having a composition different from that of the polymer from this monomer mixture. In the presence of particles (hereinafter sometimes referred to as different polymer (S)), 1 - of the other polymer particles per 100 parts by weight of the monomer mixture (m-1)
It can be produced by polymerizing in an aqueous medium using 100 parts by weight. Examples of the monomer represented by the above formula (al) include divinyl-based monomers or trivinyl-based monomers such as hashinylbenzene, ethylene glycol dimethacrylate, l,3-butylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and allyl methacrylate. Examples include monomers. Particularly preferred are divinylbenzene, ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate. Examples of the monomer represented by the above formula (bl) include styrene, σ-methylstyrene, p-methylstyrene,
Aromatic vinyl monomers such as ethylstyrene, hinyltoluene, halogenated styrene, and hinylna-7talene; propylene, ■-butene, l-pentene, 1-hexene, 2-
σ-olefins such as methyl-1-pentene and 4-methyl-■-pentene; vinyl halides such as vinyl fluoride and hinyl bromide; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; vinyl acetate; vinyl propionate; Organic acids such as vinyl stearate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, and vinyl imbutyl ether; amide monomers such as acrylamide, methacrylamide, and N-methylol methacrylamide; alkenyls such as vinyl pyridine and propenyl pyridine. Pyridines; examples include aminoalkyl vinyl ethers such as aminoethyl vinyl ether and dimethylaminoethyl vinyl ether. Examples of the monomer represented by the above formula (cl) include acrylic acid, methacrylic acid, crotonic acid, maleic acid,
Unsaturated mono- or dicarboxylic acid monomers such as maric acid and itaconic acid, or their dicarboxylic acid anhydrides, methyl diacrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, butyl methacrylate , (meth)acrylic acid ester monomers such as lauryl methacrylate; dicarboxylic acid monoesters or diesters such as crotonate esters, monomethyl itaconate, and dimethyl maleate; 2-hydroxyethyl acrylate, 2-hydroxypropyl ( Meta)
Hydroxyalkyl esters of ethylenically unsaturated carboxylic acids such as acrylate and β-hydroxyethyl (meth)acrylate; amino groups of ethylenically unsaturated carboxylic acids such as methylaminoethyl (meth)acrylate and dimethylaminopropyl (meth)acrylate Containing alkyl esters; cyano group-containing alkyl esters of ethylenically unsaturated carboxylic acids such as cyanomethyl acrylate and 2-cyanoethyl acrylate; methylaminoethyl (
meth) acrylamide, dimethylaminoethyl (meth)
Examples include aminoalkylamides of ethylenically unsaturated carboxylic acids such as acrylamide, and glycidyl esters of ethylenically unsaturated carboxylic acids such as glycidyl (meth)acrylate. Examples of the monomer represented by the above formula (a l) include aliphatic conjugated diene monomers such as 1,3-butadiene, 2-methyl-1,3-butadiene, and 2-chloro-1,3-butadiene. The body can be exemplified. In addition, as the polymer (heterogeneous polymer (S)) having the above-mentioned properties used when producing pre-hollow polymer particles (P) from these monomers, seven polymers (
A polymer that is different from the polymer m-1) and that is easily dissolved or swelled in the above monomer is preferably used. Specifically, examples of such different polymers include polystyrene, carboxy-modified polystyrene, carboxy-modified styrene-butadiene copolymer, styrene-butadiene copolymer, styrene-acrylic ester copolymer, etc.
Examples include styrene methacrylic ester copolymer, acrylic ester copolymer, methacrylic ester copolymer, carboxy-modified styrene acrylic ester copolymer, carboxy-modified styrene methacrylic ester copolymer, carboxy-modified acrylic ester copolymer and carboxy-modified methacrylic ester copolymer. Among these, polystyrene or styrene components are particularly
Styrene copolymers containing at least % by weight are preferred. The pre-hollow polymer particles (P) are the above (a l) and (b
The above-mentioned heterogeneous polymer (
S) l-100 parts by weight, preferably 2 to 50 parts by weight, more preferably 5 to 20 parts by weight, and is produced by subjecting them to polymerization in an aqueous medium. If the amount of the different polymer used is less than 1 part by weight, the effect of forming inner pores will be small, and if the amount of the different polymer used exceeds 100 parts by weight, the formation of inner pores will tend to be suppressed, which is not preferable. Therefore, a particularly preferable method for producing pre-hollow polymer particles (P) is to use monomers ( Based on the total of al), (bl), (C1) and (d l), 1 to 80% by weight of monomer (al), monomer (
20 to 99% by weight of a wood-loving supertumer selected from b l) and (C1) and another copolymerizable hexamer O selected from monomers (bl), (C1) and (dl).
This method uses a monomer mixture consisting of ~70% by weight. Examples of the hydrophilic seven-mer selected from monomers (b1) and (c1) include vinylpyridine, glycidyl acrylate, glycidyl methacrylate, methyl acrylate, ethyl acrylate, methyl methacrylate, acrylonitrile, and acrylamide. , methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, acrylic acid, methacrylic acid, itaconic acid, fumaric acid, sodium styrene sulfonate, vinyl acetate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-hydroxyethyl methacrylate, Examples include 2-hydroxypropyl methacrylate. Among these, those preferably used include unsaturated carboxylic acids such as methacrylic acid, methyl methacrylate, vinylpyridine, and 2-hydroxyethyl methacrylate. The solubility of these hydrophilic hexamers in water is preferably 0.5% by weight or more, particularly 0.5% by weight or more. Further, the other copolymerizable monomers selected from the monomers (bl), (cl), and (di) can be used without being particularly limited to vi, but include aromatic vinyl compounds such as those exemplified above. , ethylenically unsaturated carboxylic acid alkyl esters, vinyl cyanates, aliphatic conjugated dienes, and particularly styrene, methacrylic acid alkyl esters having an alkyl group having 3 or more carbon atoms, and methacrylic acid having an alkyl group having 2 or more carbon atoms. Acid alkyl esters are preferred. A more preferable composition of the monomer mixture (m-1) is:
Monomer (al) (crosslinking monomer) 2 to 60% by weight, monomer (bl) and (cl) selected from 40 to 98% by weight of a wood-loving upper layer, and monomer (bl), ( cl
) and (dl). If the amount of wood-philic material used is too small, the phase separation of the different polymers (S) may be insufficient, or the different polymers may be exposed on the surface of the polymer particles, resulting in the formation of inner pores. This is not desirable because it tends to lead to uncertainty. In addition, if the amount of crosslinking additive used is too small, the strength of the particles during polymerization will be insufficient and the entire particle will shrink.
Problems such as insufficient strain due to polymerization shrinkage inside the particles, resulting in no internal pores being formed, or even if polymer particles having internal pores are formed, the strength of the shell is reduced, tend to occur. On the other hand, if the amount of crosslinking monomer used is too large, different types of polymers tend to be excluded to the outside of the polymer particles formed during polymerization, and as a result, the resulting polymer particles are not perfectly spherical and have irregularities. This results in some lumpy particle problems. A preferred embodiment of the method for producing pre-hollow polymer particles (P) is as follows. This preferred embodiment is based on the polymerization technique disclosed in JP-A No. 62-127336, in which (a) a monomer mixture and optionally an oily substance are absorbed into fine particles of a different type of polymer (seed polymer). , then a method of polymerizing the monomer mixture, or (b) a monomer mixture and, if necessary, an oily substance,
This is a method in which a different type of polymer is dissolved to form an oily solution, this oily solution is finely dispersed in water to produce an oil-in-water emulsion, and then the above-mentioned upper additive component is polymerized. As mentioned above, the presence of an oily substance together with a different type of polymer makes it easier to control the diameter of the inner pores of the polymer particles. When the foreign polymer (S) is used in the form of particles by the method (a) above, the foreign polymer (S) functions as a seed polymer particle and the monomer mixture and oily substance are absorbed therein. Preferably, the polymer has good absorption of monomer mixtures and oily substances. For this reason, it is preferable to use a heteropolymer having a small molecular weight; for example, the number average molecular weight is 20,000 or less, preferably 10,000 or less, and more preferably 700 to 7,000. Note that the number average molecular weight here refers to dissolving a different type of polymer in its good solvent and using the resulting solution using a conventional method such as gel permeation chromatography (GPC), an osmotic pressure molecular weight measuring device, or a vapor pressure lowering molecular weight measuring device. It can be obtained by measuring using the method described below. If the number average molecular weight of the different polymer is greater than 20.000, there will be a large amount of monomer that will not be absorbed by the seed polymer particles, and this will polymerize separately with the seed polymer particles in the aqueous dispersion, resulting in fine particles that will not form polymer particles with internal pores. This not only tends to be produced in large amounts, but also causes the problem that the polymerization system becomes unstable. Further, the particle diameter of the different polymer used as the seed polymer particles is preferably 0.3 to 0.8 times the outer diameter of the intended pre-hollow polymer particles (P). There are no particular restrictions on the method for producing such a dissimilar polymer used as seed polymer particles, but for example, it can be produced using a production method such as emulsion polymerization or suspension polymerization using a relatively large amount of a chain transfer agent. . In addition, when using a different kind of polymer as the seed polymer particles, by pre-absorbing a highly lipophilic substance having a solubility in water of 10-s weight % or less into the seed polymer particles, the monomers for the seed polymer particles can be absorbed. The absorption capacity of mixtures and oily substances can be increased. When using a method of absorbing a highly lipophilic substance into the seed polymer particles as described above, favorable results can be obtained even when the number average molecular weight of the different polymer exceeds 20,000. Examples of the highly lipophilic substance include l-chlordodecane, octanoyl peroxide, and 3.5°5-trimethylhexanoyl peroxide. In order to absorb these highly lipophilic substances into the seed polymer particles, for example, an aqueous dispersion in which the highly lipophilic substance is finely dispersed is prepared, and this dispersion is mixed with an aqueous dispersion of the seed polymer particles. The highly lipophilic substance and the seed polymer particles may be brought into contact with each other. The particle size of the pre-hollow polymer particles (P) having inner pores obtained when seed polymer particles are used is the particle size of the particles that have become enlarged by absorbing polymerizable particles and oily substances. roughly matches. Therefore, by adjusting the particle size of the seed polymer particles and the relative usage amount of the seed polymer particles with respect to the monomer mixture and the oily substance, it is possible to control the particle size of the pre-hollow particles having internal pores. can. Specifically, in the production of pre-hollow polymer particles (P) having inner pores, 0, 1 to
In order to obtain pre-hollow polymer particles with a particle size of 0.6 μm, seed polymer particles with a particle size of 0.06 to 0.40 μm may be used. Another advantage of using seed polymer particles is that the particle size is 1
Another advantage is that when producing polymer particles having internal pores with a small particle size of .mu.m or less, small-sized heptomer droplets can be easily and stably formed. When using a different type of polymer in the method (b) above,
The molecular weight of the different polymer is not particularly limited, and those having a number average molecular weight of 20,000 or more can be preferably used. In this manufacturing method (b), an oily substance can be used if necessary. Such an oily substance has a solubility in water of 0.2m! There is no particular restriction as long as the oil is lipophilic and has a lipophilicity of % or less, and any vegetable oil, animal oil, mineral oil, or synthetic oil can be used. In this production method (b), pre-hollow polymer particles having inner pores can be obtained without using an oily substance, but the diameter of the inner pores can be adjusted by using an oily substance and adjusting the amount used. You can definitely hunt roll. Examples of the oily substance include lard oil, olive oil,
Examples include coconut oil, castor oil, cottonseed oil, kerosene, benzene, toluene, xylene, butane, pentane, hexane, cyclohexane, carbon disulfide, and carbon tetrachloride. Further, as the oily substance, high boiling point oils such as eugenol, geraniol, cyclamenaldehyde, citronellal, dioctyl tuclate, and dibutyl phthalate can also be used. With these high boiling point oils,
Curved polymer particles containing perfume, plasticizer, etc. in the core are obtained. The amount of oily substance used is usually 0 to 1.000 parts by weight, preferably 0 to 300 parts by weight, per 100 parts by weight of the monomer mixture.
Parts by weight. Incidentally, inert solvents which are normally contained in those supplied as crosslinkable materials can also be included as oily substances here. If the amount of the oily substance used is too large, there will be a relative shortage of the heptamer component and the thickness of the outer shell of the polymer will become thin, causing the problem that the strength of the capsule will be insufficient and it will be easily crushed. In addition, the concept of the oily substance includes the already mentioned monomer (a
l), (bl), (c 1) and (di). In this case, in the polymerization step, by stopping the polymerization with the monomer remaining inside the produced polymer particles, the remaining monomer can be used as an oily substance. In this case, the polymerization yield must be kept at 97% or less, preferably 95% or less. For this purpose, methods such as adding a small amount of polymerization inhibitor to polymerize, lowering the temperature of the reaction system during polymerization, or adding a polymerization terminator during polymerization to stop polymerization can be adopted. . In addition, in this production method (b), capsule-shaped polymer particles containing an oily substance or water-containing hollow polymer particles obtained by replacing the oily substance with water as described above are separated from the aqueous dispersion and subjected to drying treatment. By this, pre-hollow polymer particles having spaces inside are obtained. The pre-hollow polymer particles (P) obtained using the above polymerization technique have the following advantages. (i) The manufacturing process is simple and has excellent productivity. (d) Production control is easy, and pre-hollow polymer particles having the desired outer and inner diameters can be obtained. (ij) Since the pH of the aqueous dispersion of pre-hollow polymer particles can be freely selected, it can be used without any restriction as a polymer dispersion to be formed on the surface of the pre-hollow polymer particles. (iv) Using these pre-hollow polymer particles as the pre-hollow polymer particles (P) in the method of the present invention, the obtained hollow polymer particles of the present invention have - far superior hiding properties,
Indicates gloss, adhesion, and coating strength. According to the present invention, by the method described above, the average particle diameter is 0.05 to 15 μm, preferably 0.15 to 10 μm.
of pre-hollow polymer particles (P) can be advantageously produced. Particles having an average particle diameter of less than 0.05 μm are difficult to produce, and even if they can be produced, they are not preferred because they contain at least a portion of polymer particles that do not have hollow spaces. On the other hand, when the outer diameter exceeds 15 μm, the particle size distribution becomes broad, and the hollow polymer particles of the present invention obtained by using these as pre-hollow polymer particles (P) have uniform particle sizes. I don't like it. The ratio of the inner diameter to the outer diameter of the pre-hollow polymer particles (P) is preferably 0.25 to 0.9 times. If it is 0.25 times or more, it is preferable because hollow polymer particles with even better physical properties, which are the object of the present invention, can be obtained.On the other hand, if it exceeds 0.9 times, the pre-hollow polymer particles (P) Manufacturing becomes difficult,
This is not preferable for industrial production. Further, the pre-hollow polymer particles CP) preferably have a room temperature toluene insoluble content of 80% by weight or more, and the glass transition temperature Tg is 150° C. or more or cannot be measured. As described above, the pre-hollow polymer particles (P) in the present invention have a composition of a crosslinked polymer consisting of polymerization sites (a), (b), (c) and optionally (d). Preferable pre-hollow polymer particles (P) in the present invention are:
According to the preferred manufacturing method described above, (i)! i Based on the total of polymerized units a), (b), (c) and (d), 20 to 99% by weight of hydrophilic polymerized units selected from polymerized units (b) and (c), polymerized unit (a) ) and 0 to 70% by weight of other copolymerizable units selected from polymerized units (b), (C), and (d), and (ii) the above-mentioned copolymer. A polymer with a composition different from that of a polymer (S
), (ii) It has a composition of 1-100 parts by weight of the above polymer (■) per 100 parts by weight of the above polymer (i). More preferably, component (i) consists of 40 to 98% by weight of hydrophilic polymerized units, 2 to 60% by weight of polymerized units (a), and 0 to 70% by weight of other copolymerizable polymerized units. (i) Type I of hydrophilic polymerized units in the component;
Although not particularly limited, it preferably consists of polymerized units derived from unsaturated carboxylic acid and/or other hydrophilic monomers. The hydrophilic polymerized units in component (i) are more preferably composed of unsaturated carboxylic acids and/or other wood-philic monomers, and whose composition ratio is derived from unsaturated carboxylic acids. It consists of 70% by weight and 30 to 99% by weight of other polymerized units derived from hydrophilic polymers. According to the present invention, by using pre-hollow polymer particles (P) having these preferable or even more preferable component (i), hollow fine particles with even better physical properties as the object of the present invention can be produced. It's loud. As described above, the hollow polymer particles (Q) of the present invention are made by combining pre-hollow polymer particles (P) with monomers (m-2), that is, monomers (bl), (cl) and (d l) A total of 100 pre-hollow polymer particles (P) and monomers (m-2) as a mixture with at least one selected from the group consisting of
It can be produced by polymerizing in an aqueous medium at a pH of less than 7 in the presence of 5 parts by weight or less of an emulsifier and/or a dispersant. Monomer (bl) used as monomer (m-2), (
As c1) and (di), the same ones as mentioned above for pre-hollow polymer particles CP) can be used. Among the monomers (bl), those preferable as component (m-2) include aromatic vinyl monomers such as styrene and p-methylstyrene; vinyl shea 7 compounds such as acrylonitrile; vinyl fluoride, etc. These include vinyl halides; organic acid vinyls such as vinyl acetate; and amide monomers such as acrylamide. Particularly preferred is styrene. The amount of monomer (bl) used is preferably 0 to 99.5% by weight, more preferably 10% by weight based on the total of components (m-2).
~99.5% by weight, particularly preferably 20-99.5Ii
The amount is %. It is preferable from the viewpoint of light scattering properties and gloss imparted to the hollow polymer particles of the present invention. Preferred monomers (cl), including component (m-2), include unsaturated mono- or dicarboxylic acids such as acrylic acid, methacrylic acid, and itaconic acid; methyl (meth)acrylate, and (meth)acrylic acid; (meth)acrylic acid ester monomers such as ethyl acid, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; dicarboxylic acid mono- or diesters such as monomethyl itaconate and dimethyl maleate; 2-hydroxy These include hydroxyalkyl esters of ethylenically unsaturated carboxylic acids such as ethyl (meth)acrylate; glycidyl esters of ethylenically unsaturated carboxylic acids such as glycylate and dil (meth)acrylate; Particularly preferred are (meth)acrylic acid, itaconic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and (meth)acrylate.
2-ethylhexyl acrylate, 2-hydroxyethyl (meth)acrylate. The amount of monomer (cl) used is preferably 0.5 to 100% by weight, more preferably 0.5 to 90% by weight, particularly preferably 0.5 to 80% by weight based on the total of component (m-2). %
It is. In addition, as the monomer (cl), an unsaturated carboxylic acid such as (meth)acrylic acid or itaconic acid is preferably used in an amount of 0.5 to 50% by weight, more preferably 1% by weight based on the total of component (m-2). It is preferable to use up to 40% by weight, particularly preferably 2 to 30% by weight, since polymerization stability can be obtained. Also, instead of 1 part of the monomer (cl), 1 carboxyl group
The molecular weight of each unsaturated carboxylic acid monomer is 100
The above unsaturated carboxylic acids can also be used. Examples of these are shown below in the form of general formulas. Use of this unsaturated carboxylic acid further improves the strength and adhesive properties of the hollow polymer particles of the present invention. R1! R, 13 (where Rl ISR+ 2, R13 is H or an alkyl group having 1 to 20 carbon atoms) is an aromatic or cyclic alkyl group such as Y OOH, and Y is H or CH) (above 2 In the above two formulas, R, , R, is H or an alkyl group having 1 to 20 carbon atoms. , R11 is H or an alkyl group having 1 to 12 carbon atoms, EO is an ethylene oxide group, and .PO is a propylene oxide group). Among the monomers (dl), 1,3-butadiene is particularly preferable as well as component (m-2). The amount of monomer (d1) used is based on the total of component (m-2), preferably 0 to 80% by weight, more preferably 0 to 80% by weight.
60% by weight, particularly preferably 0 to 50% by weight. It is preferable from the viewpoint of the strength, adhesiveness, and balance of weather resistance, light radiation resistance, and heat resistance of the hollow polymer particles of the present invention. The calculated Tg of the copolymer of the heptamer mixture (m-2) used in the production of the hollow polymer particles of the present invention is preferably 40 to 150°C. A temperature of 40 to 100°C is particularly preferable when strength, adhesiveness, pigment binding properties, etc. are strongly required for the particles, and a temperature of 7°C is particularly preferable when high gloss and light scattering properties are required.
Particularly preferred is 0 to 150°C. The polymerization step is carried out in the presence of 5 parts by weight or less of an emulsifier and/or dispersant per 100 parts by weight of the total weight of the pre-hollow polymer particles (P) and the monomer mixture (m-2), under conditions where the pH is less than 7, and water is added. carried out in the medium. Monomer or monomer mixture (m-2) on the surface of the pre-hollow polymer particles (P)
to form a polymer coating with an average particle diameter of 0.15 to 2.
Hollow polymer particles (Q) of the present invention having a diameter in the range of 0 μm are formed. In the polymerization process, monomers or monomer mixtures (m-
The addition method of 2) is a method of stirring and mixing the pre-hollow polymer particles (P) and the monomer or heptamer mixture (m-2) and polymerizing them, or a method of adding the heptad-mer mixture (m-2) to the pre-hollow polymer particles ( There is an incremental polymerization method in which P) is supplied continuously or in portions to a polymerization system in which P) is present, and polymerization is carried out. Efficiently deposit polymerizable 7-mer on the surface of pre-hollow polymer particles.
Increment polymerization is preferred for stable copolymerization. As emulsifiers and/or dispersants (suspending agents),
Any of anionic, nonionic, cationic, and amphoteric types can be used. These can be used alone or in combination of two or more. Examples of emulsifiers include rosinate salts such as potassium rosinate and sodium rosinate; aliphatic sodium and potassium salts such as potassium oleate, potassium laurate, sodium laurate, sodium stearate, and potassium stearate, and sodium lauryl sulfate. Sulfuric ester salts of aliphatic alcohols such as; anionic emulsifiers such as alkylaryl sulfonates such as sodium dodecylbenzenesulfonate, sodium dialkyl sulfosuccinates, and formalin condensate salts of naphthalene sulfonic acid; alkyl ester types of polyethylene glycol, alkyl Nonionic emulsifiers such as ether type and alkylphenyl ether type are preferred. Among them, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium dioctylsulfosuccinate, formalin condensate salt of naphthalenesulfonic acid, and alkylphenyl ether type polyethylene glycol are preferable. Examples of cationic emulsifiers include quaternary ammonium salt type emulsifiers, and when the aqueous dispersion is made into a cationic emulsifier, they are used alone or in combination with a nonionic emulsifier. Examples of dispersants include hydrophilic synthetic polymer substances such as polyacrylic acid, polymethacrylic acid, polyvinyl sulfonic acid, polyvinyl alcohol, polyvinylpyrrolidone, and polyethylene glycol; natural hydrophilic polymer substances such as gelatin and water-soluble starch; Examples include hydrophilic semi-synthetic polymeric substances such as carboxymethylcellulose. The amount of emulsifier and/or dispersant used is 5 parts by weight or less, preferably 2 parts by weight or less, more preferably 1 part by weight or less. If the amount exceeds 5 parts by weight, the production efficiency of the hollow polymer particles of the present invention decreases due to the generation of new particles during polymerization, and furthermore, the hiding power and gloss decrease, which is not preferable. Examples of polymerization initiators include organic hydroperoxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide, and sugar-containing birophosphoric acid formulations.
Redonx initiators in combination with reducing agents, such as sulfoxylate formulations and mixed formulations of sugar-containing pyrophosphate formulations/sulfoxylate formulations; and persulfates such as potassium persulfate and ammonium persulfate; Azobisisobutyronitrile, benzoyl peroxide, lauroyl peroxide, etc. can be used. Preferably, a persulfate such as potassium persulfate or ammonium persulfate, azobisisobutyronitrile, or benzoyl peroxide is combined with a reducing agent if necessary. Particularly preferred are persulfates such as potassium persulfate and ammonium persulfate. These polymerization initiators tend to have radicals concentrated on the surface of pre-hollow polymer particles (
Formation of a film by component m-2) is performed efficiently. The amount of polymerization initiator is preferably 0.05 to 2! with respect to the total amount of pre-hollow polymer particles (P) and monomer or monomer mixture (m-2). ! Amount part, more preferably 0.05~
It is 0.8 parts by weight. When used within this range, hollow polymer particles of the present invention having excellent water resistance and alkali resistance can be obtained. The polymerization temperature is usually 5 to 95°C, particularly preferably 50 to 90°C. Other chain transfer agents may be used in combination if necessary. Examples of chain transfer agents include mercaptans such as m-dodecyl mercaptan, octyl mercaptan, n-tetradecyl mercaptan and hexyl mercaptan, and halogen compounds such as carbon tetrachloride and ethylene bromide. In the emulsion polymerization of the present invention, the polymerization stability and the particle size distribution of the hollow polymer particles of the present invention are determined by the pH of the polymerization system.
It depends to a large extent on the inner diameter/outer diameter ratio. When the pH is lower than 7, the above items are satisfactory and the desired hollow particles of the present invention can be obtained. When the pH exceeds 7, the above items are similarly satisfactory if the monomer or monomer mixture (m-2) does not contain a polymerizable unsaturated carboxylic acid, but if the monomer or monomer mixture (m-2) does not contain a polymerizable unsaturated carboxylic acid. In this case, there is a tendency for polymerization stability to decrease, which is not preferable. As the pre-hollow polymer particles (P), the above-mentioned JP-A-62-1
When using the aqueous dispersion of hollow fine particles obtained by the method disclosed in Publication No. 27336, since its pH is 7 or less, the monomer of the polymer to be formed on the surface of the hollow fine particles can be used without restriction, and is extremely effective. preferable. Thus, according to the present invention, as described above, hollow polymer particles having at least two polymer layers, (1) have an average particle diameter in the range of 0.15 to 20 μm, and (2) each The average ratio of equivalent hollow diameter to equivalent particle diameter for the particles is in the range of 0.2 to 0.8, (3) the proportion of toluene-insoluble portion is 20 to 90% by weight, (4) 180°C, The melt flow rate under the condition of 100 kgf/cm" is O, l -1 g/min, (5) The inner layer of the above two polymer layers is expressed by the following formula (a), (
b), (C) and optionally (d), and (6) the outer layer of the two-layered polymer has the formula (b), (
The hollow polymer particles of the present invention are provided, characterized in that they are made of a non-crosslinked polymer comprising at least one type of polymer unit selected from the group consisting of c) and (d). The average particle diameter of the hollow polymer particles (Q) of the present invention is in the range of 0.15 to 20 μm, as described above. Those with an average particle diameter of less than 0.15 μm have poor hiding properties when used as a light scattering aid, and those with an average particle diameter of more than 20 μm have poor polymerization stability, and monomer (m-2) during polymerization.
New powder derived only from
Various physical properties such as gloss and gloss cannot be balanced. The average particle diameter of the hollow polymer particles (Q) of the present invention is preferably in the range of 0.2 to 2 μm. Further, the average value of the ratio of equivalent hollow diameter to equivalent particle diameter for each particle is in the range of 0.2 to 0.8. If this ratio is less than 0.2, the hiding property will be considerably poor, which is not preferable, and if it exceeds 0.8, the balance between hiding property, adhesiveness, gloss, and strength will be poor, which is not preferable. Preferably, this ratio is between 0.4 and 0.75. The equivalent hollow diameter means the diameter of a hollow portion when converted into a sphere, and similarly, the equivalent particle diameter means the diameter of a particle when the particle is converted into a sphere. The average value of these ratios is determined, for example, for 50 randomly selected particles. The hollow polymer particles of the present invention have a toluene-insoluble portion of 20 to 90% by weight, preferably 20 to 80% by weight.
It is. Also, the melt flow rate is O,l”1g/1
0 m1n (180°0.10 kgf/cm"), preferably 0.1 to 0°8 g/10 m1n. Also, the compositions of the inner layer and outer layer of the polymer are as described above, and their ratios is preferably 5 to 2,000 parts by weight of the inner layer per 100 parts by weight of the outer layer, more preferably 10 to 1,000 parts by weight of the inner layer per 100 parts by weight of the outer layer.The outer layer preferably has a Tg of 40 to 150°C. The hollow polymer particles of the present invention have a portion that dissolves in tetrahydrofuran, and the molecular weight of the portion is determined by high performance liquid chromatography as a tetrahydrofuran solution. In the distribution, the number average molecular weight is 700 ~
20.000 in an amount of 1 to 80% by weight, based on the sum of the parts dissolved in the tetrahydro7 run. The hollow polymer particles of the present invention are produced as an aqueous dispersion according to the above production method. There is no limit to the solid content of the aqueous dispersion of hollow polymer particles of the present invention, but considering the solid content of the formulation for each use, it is usually 1.
It is preferably 0 to 65%. Note that it can be confirmed that the polymer particles of the aqueous dispersion of hollow polymer particles of the present invention have pores, for example, by using a transmission electron microscope or by measuring specific gravity. The aqueous dispersion of hollow polymer particles obtained in the present invention can be powdered by drying. Powderization can be performed by a commonly used method for powdering an aqueous dispersion. For example, spray drying at 130 to 180°C, tray drying in a hot air atmosphere at, for example, 50 to 70°C, or fluidized bed drying at room temperature to 70°C. The solid content of the aqueous dispersion before drying is preferably 20% or more. The particle size of the obtained powder of the aqueous dispersion of the present invention is approximately the same as the particle size of the aqueous dispersion used. The hollow polymer particles and the aqueous dispersion thereof of the present invention exhibit an excellent balance of physical properties such as hiding power, gloss, adhesiveness, water resistance, solvent resistance, and heat resistance. Therefore, it is useful for example in plastic pigments (organic resin pigments), paints, paper coatings, inks, adhesives, pressure-sensitive adhesives, primers, leather treatment agents, resin/rubber additives, carpets, and breathable paints. It can be applied to civil engineering and construction materials such as metal coating agents, lubricants, and sealants, can sealants, thermal recording paper overcoating agents, paper whitening additives, etc. In addition, by utilizing the encapsulation property, the inner pores of polymer particles can contain fragrances, medicines, pesticides, dyes, detergents, oils and fats, foods, enzymes, liquid crystals, rust preventives, catalysts, flame retardants, etc.
Depending on the application, active ingredients such as anti-aging agents and adhesives can be encapsulated by means such as dipping treatment, reduced pressure treatment, pressure dipping treatment, etc. Depending on the useful ingredients contained inside, it can be used for various purposes such as pharmaceuticals and cosmetics. The physical properties of the (hollow) polymer particles of the following Examples and Comparative Examples and the properties when used in coating films were measured by the methods shown below. ((Method for measuring physical properties of polymer particles)) (1) Measurement of particle diameter and inner pore diameter: Transmission electron microscope (JEM-10 manufactured by JEOL Ltd.)
Measured from an electron micrograph using 0sX). (2) MFT (minimum film forming temperature): Measured using a thermal gradient type film forming temperature measuring device (manufactured by Rigaku Kogyo Co., Ltd.). (3) Number average molecular weight; (Sample preparation) ■ Treat the aqueous dispersion-like polymer particles with an ion exchange resin (Amberlite 1R120 manufactured by Organo Co., Ltd.),
Adjust pH to approximately 2. (2) Add 30 II and 112 parts of tetrahydrofuran to 100 mg of polymer solid content, and leave to stand at room temperature for 24 hours to dissolve the polymer. ■ Pre-filter (AP2 manufactured by Nippon Millibore Industries Co., Ltd.)
5-1000) and microfilter (Fuji Film (
Insoluble matter was removed using Microfilter FR-1oo) manufactured by Co., Ltd., and the sample was diluted 3 times with tetrahydrofuran and used as a sample. (Measurement conditions) ■ Measuring device: High performance liquid chromatograph HLC-802A manufactured by Toyo Soda Co., Ltd. ■ Column: TSK Gel G6000 manufactured by Toyo Soda Co., Ltd.
S-G6000S-G5000HS-G4000HS-
G4000H5 (*in no particular order), ■ Fluid solvent: Tetrahydrofuran, ■ Flow rate: 1. Om < 1/min, ■ Pressure = 84 kg/am'', The number average molecular weight in terms of polystyrene was measured under the above conditions. (4) Measurement of toluene insoluble content; (Procedure) ■ Dry the latex on a glass plate. ■ Take about 0.15 g of the dried polymer into a 1001RQ Erlenmeyer flask and accurately weigh it. (A g) ■ Add 50 d of solvent (toluene) using an autobuilette and shake at 60°C for 30 minutes. ■ Toyo Roshi. No. 2 (JIS-P38012 type), and the filtrate is processed for 1 hour at 23.00 Orpm in an ultracentrifuge (Hitachi Department 55P-2). (* At this time, it is not dissolved in toluene. The polymer precipitates, and the polymer dissolved in toluene is present in the transparent supernatant.) ■ Collect 10 mβ of the supernatant using a whole pipette,
Pour into an aluminum plate (Bg) that has been accurately weighed in advance. ■ Evaporate the solvent to dryness on a hot plate, and after cooling, accurately weigh the polymer with the aluminum plate. (Cg) ■ Calculate the solvent insoluble content from the following formula. (CB)X5X 100 Toluene insoluble content (%) -100- (5) MFR (MeltFlowRate); (
Sample Preparation) Polymer particles in the form of an aqueous dispersion were dried and powdered on a glass plate to prepare a sample. (Measurement conditions)...Measurement was carried out in accordance with JIS K7210. ■ Measuring equipment: Melt indexer made by Takara Kogyo Co., Ltd. ■ Temperature: 180°C ■ Load: 10 kgf ((test conditions for coating film)) (6) Hiding rate; Hiding rate test paper (made by Japan Test Panel Industry Co., Ltd.) ) to 6
After applying with a mill applicator and drying for 5 days at 20°C and 60% RH, the gloss at 45° and 10° was measured on the black and white parts of the test paper using a Murakami gloss meter, and the ratio was calculated using the formula below. Calculated. (JIs K-5400) (7) 60 parts specular gloss (glass plate): After applying the prepared paint for several days, apply it to the glass plate with a 3 mil applicator and dry with a trowel at 20°C and 60% RH for 5 days. Afterwards, it was measured using a Murakami glossy needle. (8) Water resistance; After drying the glass plate coating film prepared in (7) for one day, it was immersed in water at room temperature for 14 days, and visually determined. (Judgment) ◎: No blistering or pristalling of the coating film. ○: No blistering of the coating film, some pristalling. △: There is some blistering and blistering in the coating film. ×: Significant blistering of the coating film and excessive pristalling. (9) Solvent resistance: After drying the glass plate coating film prepared in (7) for one day, it was immersed in toluene at room temperature for 24 hours, and visually judged. (Judgment) ○: Blistering of coating film, no pristering. △: There is some blistering in the coating film and some blistering. ×: Significant blistering of the coating film, and a lot of pristalling. (10) Heat resistance: The glass plate coating prepared in (7) was placed in a thermostat kept at 100°C and left for one day, then placed indoors for one hour and visually evaluated. (Judgment) ○: No blistering of the coating film, no pristering. △2 No blistering of the coating film, with pristalling. ×: There is blistering of the coating film, and there is pristalling. (11) Adhesion; (Adhesion) Apply the prepared paint to the flexible board twice with a brush (2
00g/cm, and after drying for 5 days, remove with a razor 2
A square millimeter square was made and a peel test was performed using cellophane tape. (J I 5A-6 (12) Film strength; 0.5 mm coating film dried for 5 days was
It was punched out and evaluated using an autograph. (20℃, 6
0% RH) [Example] Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. In addition, in the following description, "%" and "part" represent weight % and weight part. (1) Production of heterogeneous polymer (S): 80 parts of styrene, 17 parts of methyl methacrylate, methacrylic r! 3 parts of a and 7 parts of t-dodecyl mercaptan, 0.5 parts of sodium lauryl sulfate and 1.0 parts of potassium persulfate in 200 parts of water.
The polymer particles were placed in an aqueous solution containing a portion of the polymer and polymerized at 70° C. for 4 hours with stirring to obtain polymer particles. The polymer particles had an average particle diameter of 0.2 μm and a number average molecular weight of 6.000 in terms of polystyrene by CYPC. This is designated as S-1. Production of heterogeneous polymers (S-2 to 7): Polymerization was carried out under the same conditions as S-1 except that the monomer compositions shown in Table 1 were used to obtain heterogeneous polymers S-2 to 7. Production of heterogeneous polymer (S-8): Heterogeneous polymer S was added to an aqueous solution prepared by dissolving 062 parts of sodium lauryl sulfate and 0.7 parts of potassium persulfate in 200 parts of water.
2 parts of solid content of -5 were added, the temperature was raised to 75°C without stirring, and 85 parts of styrene, 7 parts of methyl methacrylate, 8 parts of acrylic acid and 7 parts of t-dodecylmercaptan were added continuously over 5 hours. After addition, polymerization is carried out, and after the completion of addition, 85
The temperature was raised to ℃ and aging was performed for 2 hours. The obtained polymer particles had an average particle diameter of 2 μm and a polystyrene-equivalent number average molecular weight of 6.500 by GPC. This will be referred to as S-8. In addition, the meanings of the abbreviations in the above Table 1 and the following table are as follows. DVB Divinylbenzene E DMA Ethylene glycol dimethacrylate S
T Styrene AN Acrylonitrile BD Butadiene AA Acrylic acid MAA Methacrylic acid EA Ethyl acrylate BA Butyl acrylate 2EHA 2-ethylhexyl acrylate MMA Methyl methacrylate 2HEMA 2-hydroxyethyl methacrylate acryester HH DBS Sodium dodecylbenzenesulfonate PO
ENPE polyoxyethylene nonyl phenyl ether (2) Production of pre-hollow polymer particles (P): Using an aqueous dispersion of a different type of polymer (S-1) as a seed polymer particle, 10 parts of this polymer particle in terms of solid content, 0.1 part of polyoxyethylene nonylphenyl ether, 0.3 part of sodium lauryl sulfate, 0.5 part of potassium persulfate, and 39 parts of water
0 parts were charged into a reaction vessel. To this, 75 parts of methyl methacrylate, 2.0 parts of divinylbenzene (same as pure product equivalent)
When a mixture of 1 part and 5 parts of acrylic acid was added and stirred at 30°C for 1 hour, the substance was almost completely absorbed into the seed polymer particles. When this was polymerized at 70° C. for 5 hours with stirring, a dispersion of capsule particles containing water inside the particles was obtained with a polymerization yield of 99%. When this dispersion was observed under a dry transmission electron microscope, it was found that the polymer particles were
They were perfectly spherical hollow polymer particles with a transparent center. This hollow particle has an outer diameter of 0.40 μm and an inner diameter of 0.40 μm.
It was 30 μm. This was designated as P-1. The thus obtained pre-hollow polymer particles CP) were used as seeds in the production of hollow polymer particles (Q) of the present invention described below. Production of pre-hollow polymer particles (P-2 to 6.8.9.l. 13): Using the sample number and usage amount listed in Table 2 as the different polymer (S), and using the sample number and usage amount listed in Table 2. Polymerization was carried out in the same manner as P-1, except that 100 parts by weight of a seven-mer mixture having the seven-mer composition (m-1) described above was used and the amount of emulsifier was adjusted, and P-2 to 6.8,9 .11.13 was obtained. However, P-5 and 6 are different polymers S-
The former was made to absorb 10 parts of toluene and the latter was made to absorb 15 parts of dibutyl phthalate into 12 and 13 parts of No. 2, and then polymerized. The polymerization results are shown in Table 2. Production of pre-hollow polymer particles (P-7): heterogeneous polymer (
S-8) aqueous dispersion, 2 parts as solid content, polyvinyl alcohol (Gohsenol GH20, Nippon Synthetic Chemical Co., Ltd.)
Co., Ltd.), 2 parts of 3.5.5-)limethylhexanoyl peroxide (Verloyl 3551, manufactured by NOF Corporation) as a polymerization initiator, and 500 parts of water were charged into a reaction vessel. To this was added a mixture of 50 parts of 4-vinylpyridine, 2 parts of divinylbenzene, 28 parts of styrene, 20 parts of butyl acrylate, and 100 parts of toluene, and the mixture was stirred at 40°C for 2 hours to mix the above 7-mer and solvent into seed polymer particles. After absorption, polymerization was performed at 70°C with stirring for 15 hours, and a dispersion of toluene-containing capsule particles was obtained with a polymerization yield of 98%. The polymerization results are shown in Table 2. Production of pre-hollow polymer particles P-10, 12 2 The same method as P-7 except that the seven-mer composition and the amount of oily substance toluene used in the production method of P-7 were changed to those shown in Table 1. Polymerization was carried out to obtain P-10,12. Production of hollow polymer particles (Q): Example 1 20 parts solid content of the hollow particle aqueous dispersion P-1 prepared by the above method was used as seed particles, 127 parts water, 0.7 parts potassium persulfate. A portion of the mixture was placed in a 2α reaction vessel, the temperature was raised to 85°C under nitrogen atmosphere, and the following seven-mer emulsion was continuously added dropwise over a period of 3 hours. Monomer emulsion: water
40 parts, butyl acrylate 5 parts, methyl methacrylate 89 parts, methacrylic acid 5 parts, N-methylolmethacrylamide 1 part and sodium dodecylbenzenesulfonate 0.3 parts After completion of the dropwise addition, the temperature was maintained for 2 hours, and then cooled. . There was no coagulum in the resulting dispersion. When the particle size of the dispersion was measured with a nanosizer (Coulter Co., model N-4),
It was 0.63 μm. When the obtained dispersion was dried and transmission was observed using an electron microscope, it was found that the surface of the pre-hollow polymer particles was coated with a polymer layer. The hollow particles had an outer diameter of 0.63 μm and an inner diameter of 0.30 μm. Further, no new particles were generated, and all particles had hollow spaces. Manufacturing requirements and results are shown in Table 3. Example 2.3.6, Comparative Examples 1 to 5 In Example 1, some conditions were changed to Example 2.3 in Table 3.
．． Polymerization was carried out in exactly the same manner as in Example 1, except that the conditions were changed to those described in the columns of 6 and Comparative Examples 1 to 5. Example 4 In a 100Q stainless steel pressure container, 150 parts of water, 1.0 part of potassium persulfate, 0.4 part of sodium bisulfite, 0.5 part of sodium dodecylbenzenesulfonate, and polyoxyethylene nonylphenyl ether (EO-30 0.1 part (mol) and 40 parts of the above P-3 (in terms of solid content) as seed particles, and while stirring, under a nitrogen atmosphere,
The temperature was raised to 0°C, and the following seven-mer mixture was continuously added dropwise over 12 hours. Monomer mixture; styrene 75 parts, 1.3
-Butadiene 15 parts, methacrylic acid 5 parts and acryester HH
After addition of 5 parts of the monomer, the mixture was aged at 80° C. for 5 hours, and then cooled. There was no coagulum in the resulting dispersion. The particle diameter of the dispersion was 0.55 μm. The outer diameter of the polymer particles after drying was 0.54 μm. Hollow particles had an inner diameter of 0.30 μm, and no new particles were generated. Examples 5.7 and 8 In Example 4, some conditions were changed to Examples 5 and 7 in Table 3.
．． Polymerization was carried out in exactly the same manner as in Example 4, except that the conditions were changed to those described in column 8. Example 9 Hollow particle aqueous dispersion P-9 was used as seed particles, solid content 500 m, water 1400 parts, sodium dodecylbenzenesulfonate 0.7 parts, polyoxyethylene nonylphenyl ether (EO-30 mol) 0 .1 part was placed in reaction vessel 2a. To this, 5 parts of n-butyl acrylate,
A mixture of 89 parts of methyl methacrylate and 6 parts of methacrylic acid was added and stirred at 40° C. for 1 hour, so that the heptamer mixture was almost completely absorbed into the seed hollow polymer particles. To this were added 1.0 part of benzoyl peroxide and 0.5 part of sodium bisulfite, the temperature was raised to 70°C, polymerization was carried out for 5 hours, and then cooled. The resulting dispersion was free of coagulum and the outer diameter of the polymer particles after drying was 0-41 p m
The particles were hollow particles with an inner diameter of 0.30 μm, and no new particles were generated. Comparative Examples 6 and 7 The following ordinary polymer particle dispersion was used in place of the pre-hollow polymer particle (P) dispersion of Example 1, and the particle diameter of the obtained polymer particles was 0. 64μm
There was no inner hole. This is referred to as Comparative Example 6. Seed polymer particle dispersion P'-1; an aqueous dispersion produced by conventional emulsion polymerization. Particle size 0.40 μm, pH 7.2, solid content 40%. The composition is butyl acrylate/methyl methacrylate/styrene/acrylic acid-45/10/42/3, and there are no internal pores. Comparative Example 7 was obtained by changing the type and amount of polymer particles used in the seed in the above method to those shown in Table 3 and below. Seed polymer particle dispersion P'-2; an aqueous dispersion produced by conventional suspension polymerization. Particle size 4pm, pH 7.8, solid content 45%. Composition is ethyl acrylate/styrene/acrylic acid-20
/79/l and there are no internal pores. Comparative Examples 9, 1O and 11 Hollow polymer particles of P-1 and commercially available polymer fine particles (Rohm, a 0P-84 (P'-
3)) and Asahi Kasei Plastic Pigment AK88
Comparative Examples 9, 10 and 11 are examples in which the physical properties of the coating film were evaluated using 01 (P'-4), respectively. Comparative Example 8 Hollow particle aqueous dispersion P'-3 was used as seed particles, and 200 parts of solid content, 460 parts of water, and 0.5 parts of potassium persulfate were placed in a 2Q reaction vessel, and the temperature was raised under a nitrogen atmosphere. 85℃
The next monomer emulsion was continuously added dropwise over 3 hours to polymerize. Monomer emulsion: water
40 parts styrene 95
Part methyl methacrylate 5 parts Sodium dodecylbenzenesulfonate 0.3 parts Polyoxyethylene nonylphenyl ether 0.1 g After the dropwise addition was completed, the temperature was maintained for 2 hours and then cooled. The polymer particles after drying were hollow particles with an outer diameter of 0.62 μm and an inner diameter of 0.30 μm, and no new particles were generated. The heptad composition of the different polymer (S), the monomer composition (m-1) of the pre-hollow polymer particles (P), the heptad composition (m-2) of the hollow polymer particles (Q), and (m-2) 100
of the polymerized units (a), (b), (c), (d) defined in the claims, from the amount of pre-hollow polymer particles (P) and foreign polymer (S) used per part % was calculated and recorded in Table 3.

[Application example]

Each of the aqueous dispersions of Examples 1 to 9 and Comparative Examples 1 to 11 was used in a solid content of 60 parts, rutile was a 71% aqueous dispersion of titanium dioxide in a solid content of 40 ffi, and an acrylic copolymer emulsion (13 pieces synthesized) was used as a binder. Manufactured by Rubber Co., Ltd., JSRAE3
15) in terms of solid content. 2.2.4-) riftyl-1,3-bentanediol monoisobutyrate (Texanol C5-12 manufactured by Chitsuso Co., Ltd.) 7 parts, ethylene glycol 3 parts, β-su7talenesulfonic acid formalin condensate sodium A formulation consisting of 2 parts of salt, 1.5 parts of hydroxyethylcellulose, and 150 parts of water was blended and stirred until the viscosity was constant. Each paint formulation was prepared in this manner. The above-mentioned various paints were applied on a Molest hiding power chart and a glass plate to form a film of the same thickness and air-dried for 3 days. Table 4 shows the physical properties of these coatings. still,
The test conditions are as follows. Examples 1 to 9 had excellent hiding properties, gloss, adhesion,
Shows water resistance, solvent resistance, heat resistance, and strength. For example, compared to Comparative Example 6.7, which was polymerized using non-hollow polymer particles, it showed extremely excellent hiding power and gloss, and also showed a plastic pigment (Comparative Example-11),
Commercially available hollow polymer particles (P'-3) (Comparative Example 1O), prototype hollow polymer particles (first hollow polymer particles (P-1)
) Plain particles (Comparative Example 9) and hollow polymer particles consisting of a two-layer polymer (Comparative Example 8) in which neither the inner layer nor the outer layer are crosslinked polymers have good hiding properties, gloss, adhesion, water resistance, Solvent resistance and heat resistance were insufficient. In particular, the hollow fine particles of Examples 1 to 5 and 7 to 9 have much better hiding properties, gloss, water resistance, etc., and are particularly preferable and worthy of special mention. In Comparative Example 1, the inner diameter/outer diameter ratio of the polymer particles of the obtained aqueous dispersion was smaller than 0.2, and the hiding property was extremely poor, which is not preferable. In Comparative Example 2.5, the particle size of the obtained aqueous dispersion was 20 μm.
m, the polymerization stability is poor, new particles are generated, and the hiding power, gloss, and resistance are also poor, which is not preferable. In Comparative Example 3, the particle diameter was less than 0.15 μm, the polymerization stability was poor, and the generation of new particles was observed, and the hiding property and
Water resistance etc. are significantly inferior. In Comparative Example 4, the toluene insoluble content exceeded 90% and the VFR
is less than 0.1, and the inner diameter/outer diameter ratio exceeds 0.8, and the gloss and strength of the coating film are significantly inferior. Comparative Examples 6, 7.11 are solid polymer particles,
Concealability is significantly poor. Comparative Example 8 is a hollow polymer particle made of a non-crosslinked two-layer polymer, has the same characteristics as Comparative Example 1O, and has similar inferior physical properties. Comparative Example 9 is a hollow polymer particle made of a crosslinked layer polymer, and the coating film has significantly poor gloss and strength, and is also poor in other durability. Comparative Example 1O is a hollow polymer particle made of a non-crosslinked layer polymer, and the coating film has significantly poor solvent resistance, heat resistance, and water resistance, as well as poor gloss and strength. The hollow fine particles obtained by the method of the present invention are in the form of an aqueous dispersion, and can be used as they are, or can be dried and used as a powder. Particularly in the case of solvent-based paints, powder is preferable. Drying can be carried out by normal means, but for example, using a spray dryer (Ashizawaniro Atomizer Co., Ltd., Mobil Minor type spray dryer), 5 kg of an aqueous dispersion with a solid content of approximately 40% is dried at an inlet temperature. 130～
At 180° C. and a drop rate of 1.5 kg/hr, 2 kg of powder could be produced in 3.5 hours. <Effects of the Invention> The hollow polymer particles of the present invention have the above-mentioned unique particle structure, and have excellent hiding properties, gloss, water resistance, solvent resistance, heat resistance, adhesion, and coating strength. In addition, it is used as a pigment due to its high concealability and light weight. For example, they can be widely used in paints, paper coatings, inks, carpets, internal additives for paper, etc., and are useful because of the above-mentioned characteristics that ordinary hollow particles cannot exhibit. In addition, by taking advantage of the capsule function, it is possible not only to contain substances such as solvents, plasticizers, fragrances, inks, agricultural chemicals, and medicines, but also to have the advantage of being able to freely modify the surface of the hollow polymer particles. Therefore, there is currently no technology for modifying the adhesion of commercially available hollow polymer particles, and this invention, which has hardly been applied, is being considered more specifically for the above uses and/or various application fields. and can be applied. Furthermore, according to the present invention, hollow polymer particles can be polymerized in a simple process in an aqueous medium, resulting in good stability and industrial production. Next, preferred embodiments of the present invention will be described. 1. Hollow polymer particles (Q) having at least two polymer layers, (1) having an average particle diameter in the range of 0.15 to 20 μm, (2) equivalent hollow diameter vs. The average ratio of equivalent particle diameters is in the range of 0.2 to 0.8, (3) the proportion of the toluene-insoluble portion is 20 to 90% by weight, and (4) the conditions are 180°C and 10 kgf/cm. (5) The inner layer of the two-layer polymer layer has a melt flow rate of 0.1-1 g/10 min, and (5) the inner layer of the above two-layered polymer layer has a structure in which the following formula X is an n-functional organic group or a bond, and and n is a number of 2 or 3, provided that n R's may be the same or different, or I; when X is a bond, n is 2, a polymerized unit represented by The following formula (b) where R: is a hydrogen atom or a methyl group, and 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 polymerized unit represented by the following formula (c), which is a cyano group, an alkanoyloxy group having 1 to 18 carbon atoms, an alkoxy group, pyridyl, pyridylalkyl, aminoalkoxy, or an amide group, where R3 and R1 are the same or different; , a hydrogen atom or a methyl group, R4 is a hydrogen π ion, a carboxyl group or a carboxylate group, and R@ is a hydrogen atom, an alkyl group having 1-18 carbon atoms, or a hydroxyalkyl group having 2-10 carbon atoms. or is an organic group having at least one member selected from glycidyl, amino, cyano, and carbon-carbon double bonds, or is an equivalent base, and optionally, the following formula (d) R7 is a hydrogen atom or a methyl group, and (6) the outer layer of the two-layer polymer has the above formula (b), (
Hollow polymer particles comprising a non-crosslinked polymer comprising at least one type of polymer unit selected from the group consisting of c) and (d). 2. The hollow polymer particles of the above 1 having an average particle diameter in the range of 0.2 to 2 μm. 3. The hollow polymer particles of 1 above, wherein the average ratio of equivalent hollow diameter to equivalent particle diameter for each particle is in the range of 0.4 to 0.75. 4. The hollow polymer particles of 1 above, in which the proportion of the toluene-insoluble portion is 20 to 80% by weight. 5. Tg of the outer layer of the above two polymer layers is 40 to 150°C
The hollow polymer particles of l above. 6. The hollow polymer particles of 1 above, wherein the inner layer of the two polymer layers does not have a Tg of 150° C. or lower. 7. Melt 7 under the conditions of 180°C and lOkgf/cm”
Hollow polymer particles of 1 above, having a 0-rate of 0.1 to 0.8 g/l Om + n. 8. The inner layer of the two-layer polymer layer contains 1 to 80 weight units of polymer unit (a) based on the total of polymer unit (a), polymer unit (b), polymer unit (C), and polymer unit (d). %, 20 to 99% by weight of hydrophilic polymerized units selected from polymerized units (b) and polymerized units (C), non-hydrophilic polymerized units of polymerized units (b) or polymerized units (c), and polymerized units ( The hollow polymer particles of 1 above, which are crosslinked polymers comprising 0 to 70% by weight of other copolymerizable polymer units selected from d). 9. The outer layer of the two-layer polymer contains 0 to 99.5% by weight of the polymerized unit (b), based on the total of the polymerized unit (b), the polymerized unit (c), and the polymerized unit (d), and the polymerized unit ( c) is 0.
The hollow polymer particles of 1 above, which are non-crosslinked polymers comprising 5 to 100% by weight and 0 to 80% by weight of polymerized units (d). 10. The outer layer of the two-layer polymer layer has the above formula (c) in which R6 is a hydrogen atom and/or R6 is a carboxyl group
The hollow polymer particles of 1 above are composed of a non-crosslinked polymer containing 0.5 to 50% by weight of polymerized units. 11. The outer layer of the two-layer polymer layer contains 20 to 99.5% by weight of polymerized units of the above formula (b), where Y is a phenyl group or is substituted with an alkyl group and t is a phenyl group. The hollow polymer particles according to 1 above, which are composed of a non-crosslinked polymer. 12. The polymer component constituting the hollow polymer particles has a portion that dissolves in tetrahydrofuran, and this portion has a number average molecular weight of 700 to 20.000 in the molecular weight distribution measured by high performance liquid chromatography as a tetrahydrofuran solution. 1 to 80% by weight based on the total amount dissolved in tetrahydrofuran. 13. The hollow polymer particles of 1 above, wherein the ratio of the inner layer to the outer layer of the two polymer layers is 5 to 2000 parts by weight of the inner layer per 100 parts by weight of the outer layer. 14, (A) Hollow particles made of a crosslinked polymer consisting of polymerized units of the above formulas (a), (b), (C) and optionally (d), and whose average particle diameter is in the range of 0.05 to 15 μm. Polymer particles (P) and (B) the following formula (bl), where the definitions of R2 and Y are the same as in the above formula (b), a monomer represented by and the following formula (cl), an emulsifier and/ or pH in an aqueous medium in the presence of a dispersant.
Hollow polymer particles (Q) according to the above item 1, which are produced by polymerization under conditions where ? is smaller than 7. 15. The hollow polymer particles CP) have the following formula (al), where Rゝ, R4, R8, and R' are defined as monomers represented by the above formula % formula %, and the following formula (dl) CH , child CR'-CH=CH, (d l') where R
The definition of 7 is the same as the above formula (d), at least one monomer (m-2) selected from the group consisting of monomers represented by (C) the hollow polymer particles (P) and monomer (m-2)
5 parts by weight or less per 100 parts by weight of R'
The definitions of , A monomer mixture (m-1) represented by the formula (a)
100 of the monomer mixture in the presence of other polymer (S) particles having a composition different from that of the copolymer from this monomer mixture.
The hollow polymer particles (Q) of I4 above are produced by polymerization in an aqueous medium using 1 to 100 parts by weight of the other polymer (S) particles per part by weight.

Claims (1)

[Claims] 1. Hollow polymer particles having at least two polymer layers, which (1) have an average particle diameter in the range of 0.15 to 20 μm, (2) correspond to each particle. The average ratio of hollow diameter to equivalent particle diameter is in the range of 0.2 to 0.8, (3) the proportion of toluene-insoluble portion is 20 to 90% by weight, and (4) 180°C, 10 kgf/cm^ The melt flow rate under the conditions of 2 is 0.1 to 1 g/10 min, (5) The inner layer of the above two polymer layers is the following formula (a) ▲There are mathematical formulas, chemical formulas, tables, etc.▼... ...(a) Here, R^1 is a hydrogen atom or a methyl group, X is an n-functional organic group or a bond, and n is a number of 2 or 3, provided that n R^1 may be the same or different, and
In the case of a bond, n is 2.The polymerized unit is represented by the following formula (b) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(b) Here, R^2 is a hydrogen atom or is a methyl group, and Y
is a phenyl group, a phenyl group substituted with a halogen atom, an alkyl group or a vinyl group, a halogen atom, a cyano group, an alkanoyloxy group having 1 to 18 carbon atoms, an alkoxy group, pyridyl, pyridylalkyl, amino A polymerized unit represented by the following formula (c), which is an alkoxy or amide group ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(c) Here, R^3 and R^5 are the same or different. , a hydrogen atom or a methyl group, R^4 is a hydrogen atom, a carboxyl group or a carboxylate group, and R^6 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or a hydroxyalkyl group having 2 to 10 carbon atoms. or is an organic group having at least one member selected from glycidyl, amino, cyano and carbon-carbon double bonds, or is one equivalent of a base, and optionally, a polymerized unit represented by the following formula ( d) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(d) Here, R^7 is a hydrogen atom or a methyl group, and consists of a crosslinked polymer consisting of the polymerized unit represented by, and ( 6) The outer layer of the two-layer polymer has the above formulas (b) and (c
Hollow polymer particles comprising a non-crosslinked polymer comprising at least one polymer unit selected from the group consisting of ) and (d).