JP3337607B2 - Powder composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a powder composition comprising a polymer and a powder, and a coating material containing the same. More specifically, the present invention relates to a powder composition excellent in powder dispersibility and a coating material excellent in film properties.

[0002]

2. Description of the Related Art Compositions in which powder materials, especially pigments and polymers are blended, are widely used for paints, paints and the like, and are useful as coating materials for paints and the like. The major problems in using the composition of polymers and powder materials for coating materials are surface properties such as polarity and wettability of polymers, and polymers such as thermal expansion coefficient, viscoelasticity, and thermal conductivity. It is the physical properties of itself and their compatibility in powder materials. Often the difference in physical properties between polymers and powder materials is large, and when a composition containing both is used as a paint or coating material, there is a problem that the strength of the film is reduced due to agglomeration of the powder and the like. There was a case. In addition, there are many cases where a problem occurs in the dispersibility of the powder material in the coexistence of the polymer, for example, the powder material agglomerates due to a difference in surface characteristics.

In order to improve the compatibility between such polymers and the powder material, especially the dispersibility of the powder material, a polymer which has a high affinity for the powder and which does not adversely affect the dispersibility of the powder. Have been developed. For example, a polymer obtained by polymerizing a monomer having a powder affinity group such as a phosphoric acid group, such as acryloxyphosphate, is exemplified.

However, in these polymers, compatibility between surface characteristics such as surface polarity and wettability, and
It was not easy to adjust the compatibility between physical properties such as the coefficient of thermal expansion. That is, although it is possible to match the surface properties of the polymer and the powder, it is also difficult to match the physical properties such as the coefficient of thermal expansion of both at the same time. Powder agglomeration and the like occurred, and the dispersibility of the powder was insufficient. When such a powder composition is used as a coating material, there is a problem that the coating properties such as coating strength and glass transition point are inferior.

[0005] Therefore, there has been a demand for the development of a powder composition which has a good affinity between a polymer and a powder and gives a coating material having excellent film properties.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of such circumstances, and has a high affinity between a powder and a polymer, has excellent powder dispersibility, and has excellent film properties. It is an object of the present invention to provide a powder composition which gives a coating material excellent in quality.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a multilayer polymer structure having an outer shell made of a copolymer containing a polymerizable monomer having a specific functional group as a copolymer component. It has been found that the above problem can be solved by using, and the present invention has been achieved.

That is, the present invention provides a powder composition comprising a polymer and a powder, wherein the polymer has the following A:
Vinyl monomers selected from the group and the following (1) to (6)
Characterized in that it is a multilayer polymer structure having an outer shell made of a copolymer with a functional group-containing monomer having at least one kind of functional group selected from the functional group group shown in (1) and an inner core made of a vinyl polymer. Powder composition.

(Group A: acrylic compounds, styrenes,
Dienes, vinyl chloride, vinyl alcohol)

(1)

[0011]

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[In the formula, X represents an —NH— group which may be substituted with an oxygen atom or a hydrocarbon group. R ¹ represents a divalent hydrocarbon group. M is selected from the group consisting of groups represented by the following formulas. Here, R ² and R ³ each represent a hydrogen atom or a hydrocarbon group. ]

[0013]

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(2) -XCH ₂ CH (OH) CH ₂ OH wherein X represents an —NH— group which may be substituted by an oxygen atom or a hydrocarbon group. ]

(3)

[0016]

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[In the formula, Y represents an oxygen atom or a hydrogen atom or a nitrogen atom to which a hydrocarbon group may be added. R ² and R ³ each represent a hydrogen atom or a hydrocarbon group. ]

(4) -R ² SO ₃ H wherein R ² represents a hydrogen atom or a hydrocarbon group. ]

(5)

[0020]

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[In the formula, R ⁴ represents a hydrocarbon group having an epoxy group. ]

(6) -CN

[0023] The present invention also relates to a coating material containing the powder composition.

In the present invention, the functional groups shown in the above (1) to (6) are used as the outer shell, that is, the polarity of the polymer surface,
It affects surface properties such as wettability and surface tension. By changing the type and number of these functional groups, the surface properties can be freely adjusted in a wide range.
Therefore, the chemical affinity between the polymer and the powder can be increased. In addition, by appropriately selecting the vinyl polymer forming the inner core, the physical properties such as the coefficient of thermal expansion, viscoelasticity, and thermal conductivity can be adapted to the physical properties of the coexisting powder. Therefore, by using such a multi-layered polymer structure, it is possible to prevent the polymer from being separated or dropped from the powder due to the difference in surface characteristics and physical properties between the polymer and the powder, and to suppress the aggregation of the powder. Thus, the dispersibility of the powder in the powder composition can be improved. Thus, a coating material having excellent coating properties such as coating strength and glass transition point can be obtained.

[0025]

Embodiments of the present invention will be described below.

(1) Powder composition of the present invention The powder composition of the present invention comprises a polymer and a powder, wherein the polymer comprises a vinyl monomer selected from the group A and the ( It is composed of a copolymer with a functional group-containing monomer having at least one type of functional group selected from the group of functional groups shown in 1) to (6) (hereinafter, referred to as functional groups (1) to (6), respectively). It is a multilayer polymer structure having an outer shell and an inner core made of a vinyl polymer.

Here, the functional groups (1) to (6) of the functional group-containing monomer constituting the outer shell will be described. First, the functional group (1) is represented by the following general formula.

[0028]

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Here, in the formula, X represents an —NH— group which may be substituted with an oxygen atom or a hydrocarbon group. R ¹ represents a divalent hydrocarbon group. The hydrocarbon group is preferably a linear or branched divalent hydrocarbon group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms. M is selected from the group consisting of groups represented by the following formulas. here,
R ² and R ³ each represent a hydrogen atom or a hydrocarbon group. The hydrocarbon group is preferably a linear or branched one having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms.

[0030]

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Specific examples of such a functional group (1) include a phosphoethoxycarbonyl group, a phenoxyphosphoethoxycarbonyl group, a phosphobisethoxycarbonyl group, a dimethylaminomethoxycarbonyl group, a dimethylaminoethoxycarbonyl group, and a diethylaminoethylcarbonyl group. , A hydroxyethoxycarbonyl group, a hydroxypropoxycarbonyl group, a sulfopropoxycarbonyl group, a sulfo-1,1-dimethylethylaminocarbonyl group, and the like.

The functional group (2) has a general formula: —XCH ₂
CH (OH) CH ₂ OH. Here, in the formula, X represents an —NH— group which may be substituted with an oxygen atom or a hydrocarbon group. The hydrocarbon group is preferably a linear or branched divalent hydrocarbon group having 1 to 20 carbon atoms, more preferably about 1 to 12 carbon atoms. Specific examples of such a functional group (2) include 2, 3
-Dihydroxypropoxy group, 2,3-dihydroxypropylamino group and the like.

The functional group (3) is represented by the following general formula.

[0034]

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In the formula, Y represents an oxygen atom or a hydrogen atom or a nitrogen atom to which a hydrocarbon group may be added. R ² and R ³ each represent a hydrogen atom or a hydrocarbon group. Such a hydrocarbon group is preferably a straight-chain or branched one having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms. Specific examples of such a functional group include an alkylamino group such as a dimethylamino group, an alkylammonium group such as a dimethylammonium group, an amino group, and a hydroxyl group.

The functional group (4) has the general formula: -R^TwoSO_Three
H, wherein R ^TwoIs a hydrogen atom or charcoal
Represents a hydride group. Preferably, the hydrocarbon group is carbon
1 to 20, more preferably 1 to 12 carbon atoms
You. Specific examples of such functional groups include sulfophenyl
And the like.

The functional group (5) is represented by the following general formula.

[0038]

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Here, in the formula, R ⁴ represents a hydrocarbon group having an epoxy group. The hydrocarbon group preferably has 2 to 20 carbon atoms, more preferably about 2 to 12 carbon atoms. Examples of such a functional group include a 3,4-epoxycyclohexyloxycarbonyl group and an epoxypropoxycarbonyl group.

The functional group-containing monomer of the present invention having a functional group selected from the functional groups (1) to (6) including the functional group and the cyano group (6) described above includes a double bond or a triple bond. It is not particularly limited as long as it is a polymerizable monomer having a bond, but is preferably represented by the following general formula (I) or (I)
It is a compound represented by I).

[0041]

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Here, in the formulas (I) and (II), Z is a hydrogen atom, — (CH ₂ ) _r —CH ₃ , —COO (CH ₂ ) _r —
CH ₃ represents a phenyl group or a cyano group which may have a substituent, and r represents 0 or an integer of 1 to 17. Q represents any one of the functional groups (1) to (6). n is preferably 0 or an integer of 1 to 20, more preferably 0 or 1.
And represents an integer of 0 to 16, more preferably 0 or an integer of 1 to 12.

Specific examples of such a functional group-containing monomer include acryloxyphosphate, methacryloxyphosphate, acryloxyethylphosphate, methacryloxyethylphosphate, methacryloxyethylphenylacid phosphate, sulfopropyl acrylate, sulfopropyl methacrylate, -Acrylamide-2-methylpropanesulfonic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, allyl alcohol, propargyl alcohol, allylamine, propargylamine, glyceryl monoallyl ether, Glyceryl diallyl ether, acrylic Diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminomethyl acrylate, dimethylaminoethyl methacrylate, diallyldimethylammonium chloride, glycidyl acrylate, glycidyl methacrylate, 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexyl methacrylate, allyl glycidyl ether,
Butadiene monooxide, acrylonitrile, methacrylonitrile and the like. One or two of these
More than species are selected.

The vinyl-based monomer selected from the group A constituting the copolymer together with the functional group-containing monomer will be described. The group A is a group consisting of acrylic compounds, styrenes, dienes, vinyl chloride, and vinyl alcohol. Examples of the acrylic compounds include (meth) acrylic acid, (meth) acrolein, and alkyl (meth) acrylate. Ester, (meth) acrylamide and the like. Among them, examples of the alkyl (meth) acrylate include methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, 2-ethylhexyl acrylate, and 2-ethylhexyl methacrylate. Examples of styrenes include styrene, α-methylstyrene, divinylbenzene, and the like. Examples of dienes include butadiene and isoprene. One or more of the vinyl monomers of the present invention can be appropriately selected from these.

The preferred ratio of the functional group-containing monomer to the vinyl monomer in the outer shell is 1: 999 in molar ratio.
9: 3: 7, more preferably 1: 999 to 1:
9 If the proportion of the functional group-containing monomer is too small, the contribution to the surface properties may be reduced, and if it is too large, the surface properties may be impaired.

The vinyl polymer constituting the inner core of the multilayer polymer structure is not particularly limited, but is preferably a vinyl monomer selected from the above-mentioned group A, like the vinyl monomer constituting the outer shell. Is a polymer of a different monomer from that used in the above. One or more kinds of such vinyl monomers can be selected from the group A. By using different monomers for the outer shell and the inner core, a multilayer structure in which each layer has different physical properties can be obtained, and a coating having a non-uniform multilayer structure can be formed. A strong film can be obtained over time for the coating material.

The polymer constituting the outer shell and inner core may contain optional components contained in ordinary polymer materials. Examples of such optional components include a plasticizer, a colorant, an oxidation stabilizer, and an ultraviolet absorber.

The multilayer polymer structure of the present invention is a spherical structure having an outer shell made of the above-described copolymer and an inner core made of a vinyl polymer, and preferably has an average particle size of about 0.05 to 1 μm. It is granular. Here, the outer shell in the present invention refers to a polymer layer that forms a surface layer of a spherical structure, but the entire surface of the structure does not necessarily have to be covered with the outer shell. part,
Specifically, it is sufficient to occupy 30% or more of the surface area. In the present invention, the inner core refers to a polymer layer that forms a nucleus of a spherical structure, but it is not necessary that the inner surface has no exposed portion on the surface of the structure. For example, the inner core is exposed to about 50% of the surface area. It may be.

In the multilayer polymer structure of the present invention,
One unit of the spherical structure covered by the outer shell may include one or more inner cores. Further, the outer shell and the inner core do not necessarily have to be clearly separated, and for example, the polymer forming the outer shell and the polymer forming the inner core may be partially bonded to each other. Further, the entire outer shell does not necessarily have to be outside the inner core. For example, the outer shell and the inner core may be partially embedded in each other.

In the multilayer polymer structure of the present invention, in addition to the case where the constituent layers are two layers of the outer shell and the inner core, a polymer layer is further provided between the outer shell and the inner core to form three or more layers. It may be configured. The polymer constituting such an intermediate polymer layer can be appropriately selected from the above-mentioned vinyl monomers which can constitute the outer shell or inner core. The number of constituent layers is not particularly limited as long as it is two or more, but two layers are most preferable in consideration of the disadvantages in production and the advantages of film surface characteristics derived from such a structure. In such polymers, the outer shell affects the surface properties of the formed film, and the inner core affects the film properties itself.

One example of the structure of the multilayer polymer structure of the present invention is schematically shown in FIG. Specifically, for example, FIG.
(A), (B) or (C). FIG. 1A shows a so-called core-shell type polymer structure having one inner core inside an outer shell covering the entire structure surface. FIG. 1B is a shot-type polymer structure having a plurality of inner cores inside an outer shell. FIG.
(C) is an eyeball type polymer structure in which the inner layer (inner core or intermediate polymer layer) of the outer shell is partially exposed on the surface. A structure combining these structures may be used. Among these, a particularly preferable one has the structure shown in FIG. 1A or FIG. 1B, and has two constituent layers. In the case of the core-shell type polymer of FIG. 1A having two layers, the average diameter of the inner core is preferably about 0.03 to 0.7 μm.

The above-mentioned multilayer polymer structure is obtained by polymerizing one or more vinyl monomers selected from the group A to form an inner core, and then forming one or more vinyl monomers selected from the group A. It can be produced by polymerizing a monomer different from the vinyl monomer forming the inner core and the functional group-containing monomer to form an outer shell.

The specific polymerization method is not particularly limited, and may be, for example, a method of performing polymerization while coating a mixture of monomers in a phase inversion state (polymerizing a surface and another surface while polymerizing from one surface to the inside). To form a polymer film by polymerizing the monomers in a film form, and further polymerizing the monomers in a layered form on the polymer film to form a multilayer structure film, and crushing this film. ,
Examples include a method of producing a polymer structure having a multilayer structure by emulsion polymerization over multiple stages. The most preferable of these is a method based on multi-stage emulsion polymerization.

As a preferred method for producing a multilayer polymer structure by emulsion polymerization, one or more vinyl monomers selected from Group A are emulsion-polymerized to form an inner core, and then the above-mentioned A is formed in the presence of the inner core. Emulsion polymerization of at least one vinyl monomer selected from the group, which is different from the vinyl monomer forming the inner core, and at least one of the functional group-containing monomers to form an outer shell around the inner core; Forming method. Emulsion polymerization can be carried out according to a conventionally known conventional method. That is, an emulsifier, a monomer, and a dispersion medium are emulsified in advance by stirring or the like, and a polymerization initiator is added to the emulsifier to perform polymerization. Further, the step of forming the outer shell can be further divided into multiple stages. That is, after forming the inner core, first, in the presence of the inner core, one or more vinyl-based monomers selected from the group A and different from the vinyl-based monomer forming the inner core are emulsion-polymerized. One or more of the functional group-containing monomers may be emulsion-polymerized to form an outer shell around the inner core.

In the case of a multilayer polymer structure having three or more layers,
First, before forming the inner core and then the outer shell,
By further including a new emulsion polymerization step, a multilayer polymer structure having an arbitrary number of constituent layers can be obtained. For example, by further including an emulsion polymerization step between the inner core forming step and the outer shell forming step, a multilayer polymer structure having an intermediate layer between the inner core and the outer shell can be obtained.

Further, the multilayer polymer structure used in the present invention forms an inner core by emulsion polymerization of at least one vinyl monomer selected from the group A, and then forms a hydroxyl group and a halogen in the presence of the inner core. After forming a copolymer by emulsion-polymerizing a polymerizable monomer having an atom, an amino group, or a phenyl group and the vinyl-based monomer, concentrated sulfuric acid, chloromethoxymethane, and trimethylamine are added to the copolymer. It can also be obtained by reacting a selected reagent to form an outer shell around the inner core.

That is, as a method of forming the outer shell, in addition to a method of emulsion-polymerizing a functional group-containing monomer together with a vinyl monomer, the above-mentioned specific polymerizable monomer and the vinyl monomer are emulsion-polymerized. By taking the method of reacting the reagent, the outer shell (1)
Functional groups shown in (6) to (6) can be introduced. Examples of the polymerizable monomer having a phenyl group include styrenes such as styrene, bromostyrene, and divinylbenzene. Examples of the polymerizable monomer having a halogen atom include vinyl chloride and allyl bromide.
Examples of the polymerizable monomer having a hydroxyl group include vinyl alcohol. Examples of the polymerizable monomer having an amino group include allylamine. The amount of the reagent used is not particularly limited and is determined according to a desired multilayer polymer structure.
0 to 200 mol%.

The emulsifiers used for the emulsion polymerization include sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium alkyldiphenyletherdisulfonate, sodium alkylnaphthalenesulfonate,
Anionic surfactants such as sodium dialkyl sulfosuccinate, sodium stearate, potassium oleate, sodium oleate, sodium dioctyl sulfosuccinate, sodium polyoxyethylene alkyl ether sulfate and sodium polyoxyethylene alkyl phenyl ether sulfate; polyoxyethylene Lauryl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene oleyl phenyl ether,
Nonionic surfactants such as polyoxyethylene nonyl phenyl ether and oxyethylene oxypropylene block polymer; cationic surfactants such as lauryl trimethyl ammonium chloride and stearyl trimethyl ammonium chloride; and the like. The amount of these used is appropriately determined according to a conventional method, but it is preferable to use, for example, about 0.1 to 10 parts by weight based on 100 parts by weight of the total solids.

Water is usually used as the dispersion medium. Examples of the polymerization initiator include peroxides such as hydrogen peroxide, persulfates such as ammonium persulfate and potassium persulfate, azo initiators such as azobisisobutyronitrile, cumene hydroperoxide and t-butyl hydroperoxide. Redox initiators in combination with organic peroxides such as oxides or their persulfates, or peroxides, metal ions such as iron ions, reducing agents such as sodium sulfoxylate, sodium pyrosulfite, L-ascorbic acid, etc. And the like. The amount of these used is determined according to a conventional method, but it is preferable to use, for example, about 0.1 to 4 parts by weight based on 100 parts by weight of the total solids. Further, a chain transfer agent such as mercaptan can be added to adjust the molecular weight. The polymerization temperature is about 30 to 90 ° C, and the polymerization time is preferably about 1 to 10 hours, depending on the amount of the monomer used.

The powder used in the powder composition of the present invention comprises:
It is not particularly limited as long as it is an aggregate of powdery and granular materials, and the shape of the powdery and granular materials may be any of spherical, fibrous, scale-like, and plate-like. Preferably, the average particle size is 10μ.
m or less, more preferably an organic or inorganic particulate matter having an average particle size of 0.1 to 10 μm.

As such organic or inorganic particulate matter,
For example, titanium oxide, yellow iron oxide, black iron oxide, lead yellow,
Inorganic pigments such as zinc oxide, red iron blue, ultramarine blue, ultramarine blue, chromium oxide, chromium hydroxide; organic pigments such as quinacridone yellow, quinacridone red, copper phthalocyanine, benzidine yellow; yellow No. 4 Al, red 213 Al, red 230
Lakes of organic dyes such as Al; minerals such as talc, sericite and mica; mineral processed powders such as titanium mica and titanium oxide baked mica; synthetic powders such as silica gel, calcium silicate and calcium carbonate; .

The powder composition of the present invention comprises the above-mentioned multilayer polymer structure and powder, and each of the multilayer polymer structure and powder may be used alone. Two or more kinds may be used in combination. Also,
The content ratio of the powder to the multilayer polymer structure is preferably 1:99 to 99: 1, more preferably 1: 9 to 9: 1.

(2) Coating Material of the Present Invention The coating material of the present invention contains the powder composition of the present invention. Specific examples of the coating material include paints, paints, paints, rust inhibitors and the like. The coating material of the present invention may contain, in addition to the powder composition comprising the powder and the multilayer polymer structure, optional components usually used in powder-dispersed products according to the intended use. Such optional components include plasticizers such as diethyl adipate, diisopropyl adipate, triethyl citrate and diisopropyl succinate, solvents such as water and alcohol, ultraviolet absorbers, antioxidants, preservatives, defoamers, Dispersing agents, dispersing aids and the like are included. Further, a conventional film-forming agent or the like may be contained.

The preferable content of the powder and the multilayer polymer structure in the coating material of the present invention varies depending on the use of the powder composition.
%, More preferably 5 to 60% by weight, the multilayer polymer structure 2 to 50% by weight, more preferably 3 to 20% by weight. The method for producing the coating material may be a conventional method.

[0065]

EXAMPLES The present invention will be described in detail below with reference to examples, but it goes without saying that the present invention is not limited to these examples.

[0066]

[Production Example 1] (1) Inner nucleus forming step 100 parts by weight of water and 3 parts by weight of sodium lauryl sulfate were charged into a reaction vessel, and the temperature was raised to 70 ° C. while stirring and purging with nitrogen by nitrogen bubbling. On the other hand, in advance, 63.6 parts by weight of methyl methacrylate, 26.8 parts by weight of 2-ethylhexyl acrylate, 1.5 parts by weight of diethylene glycol monobutyl ether, 0.7 parts by weight of diethylene glycol monoethyl ether, 1.6 parts by weight of n-dodecyl mercaptan The parts were dissolved and mixed to prepare a core / monomer liquid for inner core formation. Twenty percent of the core monomer solution was added to the reactor, and then 0.5 part by weight of potassium persulfate was dissolved and added to 15 parts by weight of water to initiate polymerization. After the reaction was carried out for 45 minutes, the remaining core monomer liquid was added dropwise, and the reaction was carried out for 4 hours after the completion of the dropwise addition.

(2) Outer Shell Forming Step A solution obtained by dissolving 0.1 part by weight of potassium persulfate in 15 parts by weight of water was added to the reaction solution of the polymerization reaction, and a shell monomer solution [acrylic Acid 4 parts by weight, α-methylstyrene 8.6 parts by weight, styrene 2 parts by weight, diethylene glycol monobutyl ether 1.2 parts by weight, diethylene glycol monoethyl ether 0.3 parts by weight, n-
Dodecyl mercaptan 0.5 part by weight, methacryloxyethyl phosphate 0.5 part by weight, and methacryloxyethyl phenyl acid phosphate 0.5 part by weight] were added dropwise, and the mixture was reacted for 4 hours after completion of the dropwise addition. 90 ° C
And reacted for 1 hour. After cooling, the reaction solution was neutralized with aqueous ammonia to obtain an aqueous dispersion 1 of a multilayer polymer structure. This was frozen, and a frozen section was observed under an electron microscope. The average particle size was 0.5 μm, and the inner core particle size was 0.3.
It was found to be an 8 micron core-shell multilayer polymer structure.

[0068]

Production Example 2 0.5 part by weight of methacryloxyethyl phosphate and 0.5 part by weight of methacryloxyethyl phenyl acid phosphate of Production Example 1 were mixed with 0.5 part by weight of sulfopropyl methacrylate and 2-acrylamide-2.
An aqueous dispersion 2 of a multilayer polymer structure was obtained in the same manner as in Production Example 1, except that 0.5 part by weight of -methylpropanesulfonic acid was used. Observation with a frozen section revealed that this was a shot-type multilayer polymer structure containing an average of 3.7 polymers having an average particle size of 0.45 microns and an inner layer having an average particle size of 0.1 microns.

[0069]

Preparation Example 3 0.5 parts by weight of methacryloxyethyl phosphate and 0.5 parts by weight of methacryloxyethyl phenyl acid phosphate of Preparation Example 1 were combined with 2 parts by weight of hydroxyethyl methacrylate, 2 parts by weight of hydroxypropyl acrylate, and hydroxypropyl methacrylate. An aqueous dispersion 3 of a multilayer polymer structure was obtained in the same manner as in Production Example 1, except that 1 part by weight of the acrylate was used. Observation with a frozen section revealed that this was a core-shell type multilayer polymer structure having an average particle size of 0.6 μm and an inner core having an average particle size of 0.48 μm.

[0070]

Production Example 4 The procedure of Production Example 1 was repeated except that 0.5 part by weight of methacryloxyethyl phosphate and 0.5 part by weight of methacryloxyethyl phenylacid phosphate were replaced by 5 parts by weight of allylamine. An aqueous dispersion 4 of a multilayer polymer structure was obtained. Observation with a frozen section revealed that this was a core-shell type multilayer polymer structure having an average particle size of 0.41 μm and an inner core having an average particle size of 0.3 μm.

[0071]

Production Example 5 0.5 part by weight of methacryloxyethyl phosphate and 0.5 part by weight of methacryloxyethyl phenyl acid phosphate of Production Example 1 were replaced with 2 parts by weight of glyceryl monoallyl ether and 2 parts by weight of glyceryl diallyl ether. In the same manner as in Production Example 1, an aqueous dispersion 5 of a multilayer polymer structure was obtained. Observation with a frozen section revealed that this was a core-shell type multilayer polymer structure having an average particle size of 0.29 μm and an inner core having an average particle size of 0.25 μm.

[0072]

Production Example 6 0.5 part by weight of methacryloxyethyl phosphate and 0.5 part by weight of methacryloxyethyl phenyl acid phosphate of Production Example 1 were combined with 2 parts by weight of diethylaminoethyl methacrylate, 2 parts by weight of dimethylaminomethyl acrylate, and An aqueous dispersion 6 of a multilayer polymer structure was obtained in the same manner as in Production Example 1, except that 1 part by weight of dimethylaminoethyl methacrylate was used. Observation with a frozen section revealed that this was a core-shell type multilayer polymer structure having an average particle size of 0.29 μm and an inner core having an average particle size of 0.25 μm.

[0073]

Production Example 7 Same as Production Example 1, except that 0.5 parts by weight of methacryloxyethyl phosphate and 0.5 parts by weight of methacryloxyethyl phenyl acid phosphate of Production Example 1 were replaced with 4 parts by weight of diallyldimethylammonium chloride. Thus, an aqueous dispersion 7 of a multilayer polymer structure was obtained. According to observation by frozen section, this product had an average particle size of 0.
It was found to be a core-shell type multilayer polymer structure having a diameter of 42 microns and an inner core having an average particle diameter of 0.32 microns.

[0074]

Preparation Example 8 0.5 parts by weight of methacryloxyethyl phosphate and 0.5 parts by weight of methacryloxyethyl phenyl acid phosphate of Preparation Example 1 were replaced with 2 parts by weight of glycidyl acrylate and 2 parts by weight of 3,4-epoxycyclohexyl acrylate. Except for the above, an aqueous dispersion 8 of a multilayer polymer structure was obtained in the same manner as in Production Example 1. Observation with a frozen section revealed that this was a core-shell type multilayer polymer structure having an average particle size of 0.37 μm and an inner core having an average particle size of 0.28 μm.

[0075]

Production Example 9 The procedure of Production Example 1 was repeated except that 0.5 parts by weight of methacryloxyethyl phosphate and 0.5 parts by weight of methacryloxyethylphenyl acid phosphate were replaced by 2 parts by weight of acrylonitrile and 2 parts by weight of methacrylonitrile. An aqueous dispersion 9 of a multilayer polymer structure was obtained in the same manner as in Example 1. Observation with a frozen section revealed that this was a core-shell type multilayer polymer structure having an average particle size of 0.41 μm and an inner core having an average particle size of 0.34 μm.

[0076]

Production Example 10 Production Example 1 was repeated except that 0.5 parts by weight of methacryloxyethyl phosphate and 0.5 parts by weight of methacryloxyethyl phenylacid phosphate were replaced by 5 parts by weight of styrene and 5 parts by weight of divinylbenzene. In the same manner as in Example 1, an aqueous dispersion of the multilayer polymer structure was obtained. However, this was not neutralized with ammonia. To this, 10 parts by weight of concentrated sulfuric acid was added, heated at 90 ° C. for 2 hours, and then neutralized to obtain a dispersion 10 of the multilayer polymer structure of the present invention. According to the observation by the frozen section, this one had an average particle size of 0.98 μm and the inner core had an average particle size of 0.8.
It was found to be a 1 micron core-shell multilayer polymer structure.

[0077]

Production Example 11 Production Example 1 was repeated except that 0.5 part by weight of methacryloxyethyl phosphate and 0.5 part by weight of methacryloxyethyl phenyl acid phosphate were replaced by 5 parts by weight of styrene and 5 parts by weight of divinylbenzene. In the same manner as in Example 1, an aqueous dispersion of the multilayer polymer structure was obtained. However, this was not neutralized with ammonia. One part by weight of concentrated sulfuric acid and 10 parts by weight of chloromethoxymethane were added thereto, and the mixture was heated at 90 ° C. for 2 hours, then neutralized, further added with 20 parts by weight of trimethylamine, and heated at 90 ° C. for 2 hours. This was neutralized with citric acid and dialyzed to obtain a dispersion 11 of the multilayer polymer structure of the present invention. Observation with a frozen section revealed that this was a core-shell type multilayer polymer structure having an average particle size of 0.87 μm and an inner core having an average particle size of 0.74 μm.

[0078]

Formulation Example 1 Paint 1 was prepared according to the following formulation. That is, the following formulation components were weighed into a ball mill, and the resulting mixture was subjected to a ball mill for 48 hours, and the ball was filtered off with a strainer to obtain a paint. (Prescription component) Aqueous dispersion of multilayer polymer structure of Production Example 1:
50 parts by weight (including 18 parts by weight of the multilayer polymer structure), 30 parts by weight of titanium oxide, and diethyl adipate:
10 parts by weight, water: 10 parts by weight.

[0079]

Formulation Example 2 Paint 2 was prepared according to the following formulation. That is, the following formulation components were weighed into a ball mill, and the resulting mixture was subjected to a ball mill for 48 hours, and the ball was filtered off with a strainer to obtain a paint. (Prescription component) Aqueous dispersion of multilayer polymer structure of Production Example 2:
50 parts by weight (including 21 parts by weight of the multilayer polymer structure), bengara: 30 parts by weight, diisopropyl adipate: 10 parts by weight, water: 10 parts by weight.

[0080]

Formulation Example 3 Paint 3 was prepared according to the following formulation. That is, the following formulation components were weighed into a ball mill, and the resulting mixture was subjected to a ball mill for 48 hours, and the ball was filtered off with a strainer to obtain a paint. (Prescription component) Aqueous dispersion of multilayer polymer structure of Production Example 3:
50 parts by weight (including 20 parts by weight of the multilayer polymer structure), 30 parts by weight of yellow iron oxide, and triethyl citrate:
10 parts by weight, water: 10 parts by weight.

[0081]

Formulation Example 4 Paint 4 was prepared according to the following formulation. That is, the following formulation components were weighed into a ball mill, and the resulting mixture was subjected to a ball mill for 48 hours, and the ball was filtered off with a strainer to obtain a paint. (Prescription component) Aqueous dispersion of multilayer polymer structure of Production Example 4:
50 parts by weight (including 21 parts by weight of the multilayer polymer structure), 30 parts by weight of chromium hydroxide, 10 parts by weight of diisopropyl succinate, and 10 parts by weight of water.

[0082]

Formulation Example 5 Paint 5 was prepared according to the following formulation. That is, the following components were kneaded with a kneader and rolled to obtain a paint. (Prescription component) Aqueous dispersion of multilayer polymer structure of Production Example 5:
40 parts by weight (including 19 parts by weight of the multilayer polymer structure), black iron oxide: 30 parts by weight, talc: 20 parts by weight,
Diethyl adipate: 10 parts by weight.

[0083]

[Formulation Example 6] Paint 1 was prepared according to the following prescription. That is, the following formulation components were weighed and kneaded in a kneader, and rolled to obtain a paint. (Prescription component) Aqueous dispersion of multilayer polymer structure of Production Example 1:
20 parts by weight (of which 20 parts by weight of the multilayer polymer structure), an aqueous dispersion of methyl acrylate (methyl acrylate 1)
0% by weight): 20 parts by weight, titanium oxide: 50 parts by weight, water: 10 parts by weight.

[0084]

Example 1, Comparative Example 1 <Film Strength Test> Using each composition obtained in Formulation Examples 1 to 6, a film was formed on glass with a 10-mil doctor blade. The coating was cycled from -10 ° C to 4 for 48 hours.
Place in an aging box that changes between 0 ° C for 3 months,
The state of peeling of the film was observed (Example 1). As a comparison, the same formulation as in Formulation Examples 1 to 6 except that the aqueous dispersions of the multilayer polymer structure in Formulation Examples 1 to 6 were each replaced with an aqueous methyl acrylate dispersion (containing 10% by weight of methyl acrylate). The obtained composition was used (Comparative Example 1). Table 1 shows the results. From this result, it is understood that the powder composition of the present invention has better temporal adhesion than the comparative example.

[0085]

[Table 1]

[0086]

Example 2, Comparative Example 2 <Aging Test> Samples prepared in Example 1 (Formulation Examples 1 to 4)
(Composition No. 6) was filled in a test tube so as to have a height of 10 cm, left at 40 ° C., and observed one month later (Example 2). As a comparison, similarly to Comparative Example 1, a composition using an aqueous dispersion of methyl acrylate instead of the aqueous dispersion of a multilayer polymer structure was observed in the same manner (Comparative Example 2). Table 2 shows the results. From these results, it can be seen that the powder composition of the present invention is excellent in powder dispersion stability.

[0087]

[Table 2]

[0088]

According to the present invention, a powder composition having good powder dispersibility can be obtained, and by using this, a coating material having excellent film properties such as film strength can be obtained.

[Brief description of the drawings]

FIG. 1 is a schematic view showing the structure of a multilayer polymer structure used in the present invention, wherein (A) is a core-shell type polymer structure, (B) is a shot type polymer structure, and (C) is an eyeball type. 1 shows a polymer structure.

[Explanation of symbols]

 1 ... outer shell 2 ... inner core

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-2-140203 (JP, A) JP-A-1-201313 (JP, A) JP-A-62-119271 (JP, A) JP-A-6-119271 93189 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 51/00 C08F 251/00-291/18 C08K 3/00 C09D 5/06 C09D 151/00

Claims (8)

(57) [Claims] 1. A powder composition comprising a polymer and a powder, wherein the polymer is at least one selected from the group consisting of a vinyl monomer selected from the following group A and the group represented by the following functional groups (1) to (6). A powder composition characterized by being a multilayer polymer structure having an outer shell made of a copolymer with a functional group-containing monomer having a kind of functional group and an inner core made of a vinyl polymer. (Group A: acrylic compounds, styrenes, dienes, vinyl chloride, vinyl alcohol) (1) [In the formula, X represents an —NH— group which may be substituted with an oxygen atom or a hydrocarbon group. R ¹ represents a divalent hydrocarbon group. M is selected from the group consisting of groups represented by the following formulas. Here, R ² and R ³ each represent a hydrogen atom or a hydrocarbon group. ] ₍₂₎ -XCH in _{2 CH (OH) CH 2 OH} [ wherein, X represents an oxygen atom or optionally substituted -NH- group by a hydrocarbon group. (3) [In the formula, Y represents an oxygen atom or a nitrogen atom to which a hydrogen atom or a hydrocarbon group may be added. R ² and R ³
Represents a hydrogen atom or a hydrocarbon group, respectively. _{^{] (4) -R 2 SO 3}} H [ wherein, R ² represents a hydrogen atom or a hydrocarbon group. (5) [In the formula, R ⁴ represents a hydrocarbon group having an epoxy group. ] (6) -CN 2. The powder composition according to claim 1, wherein the functional group-containing monomer is a compound represented by the following general formula (I) or (II). Embedded image [In the formulas (I) and (II), Z is a hydrogen atom,-(C
H _{2) r} -CH _3, represents _{-COO (CH 2) r -CH 3} , which may have a substituent phenyl group or a cyano group, r represents an integer of 0 or 1 to 17. Q is the above (1) to (6)
Represents any of the functional groups. n represents 0 or an integer of 1 to 20. ] 3. The polymer according to claim 1, wherein the vinyl polymer constituting the inner core is a polymer of a vinyl monomer selected from the group A and different from the vinyl monomer constituting the outer shell. Powder composition. 4. The powder composition according to claim 1, wherein the powder is an organic or inorganic particulate having an average particle size of 10 μm or less. 5. The multilayer polymer structure forms an inner core by emulsion polymerization of at least one vinyl monomer selected from the group A, and then forms an inner core in the presence of the inner core. It is obtained by forming an outer shell around the inner core by emulsion polymerization of one or more kinds of vinyl monomers different from the vinyl monomer forming the inner core and one or more of the functional group-containing monomers. The powder composition according to claim 1, wherein the powder composition is obtained. 6. The multilayer polymer structure forms an inner core by emulsion polymerization of at least one vinyl monomer selected from the group A, and then forms an inner core in the presence of the inner core. At least one kind of vinyl monomer different from the vinyl monomer forming the inner core is emulsion-polymerized, and one or more of the functional group-containing monomers are emulsion-polymerized to form an outer shell around the inner core. The powder composition according to claim 1, which is obtained by performing the following. 7. The multilayer polymer structure forms an inner nucleus by forming an inner nucleus by emulsion polymerization of at least one vinyl monomer selected from the group A, and then forms a hydroxyl group and a halogen atom in the presence of the inner nucleus. After forming a copolymer by emulsion polymerization of a polymerizable monomer having an amino group or a phenyl group and the vinyl monomer, the copolymer is selected from the group consisting of concentrated sulfuric acid, chloromethoxymethane, and trimethylamine. The powder composition according to claim 1, which is obtained by reacting a reagent to be formed to form an outer shell around the inner core. 8. A coating material containing the powder composition according to claim 1.