JP3418445B2 - Aqueous dispersion of synthetic resin particles - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to water repellency, lubricity, and mold release.
Excellent in anti-fouling property, anti-fouling property, etc.
Ester and other plastic film surface modifiers,
Carrier powders such as iron powder and ferrite used for
Synthetic resin particles useful for coating agents, paints, resin modifiers, etc.
The present invention relates to an aqueous dispersion of [0002] 2. Description of the Related Art Conventionally, polydialkyl
On one end of a polymeric silicon compound such as
A silicon macromonomer into which a silyl group has been introduced;
Of vinyl macromonomer with copolymerizable vinyl monomer
Coalescence is provided. Such a copolymer is water repellent,
It has excellent lubricity and mold release properties.
Plastic film surface modifiers such as esters and electrons
Carrier coat of iron powder or ferrite used for photography
It is used as an agent. The above copolymers may cause environmental pollution.
Supplied as a dispersion using an aqueous solvent with little
It is desirable. [0003] SUMMARY OF THE INVENTION
In the conventional copolymer, the copolymer is used as an aqueous dispersion.
If provided, excellent coating physical properties and excellent film forming properties
At the same time. What happens
In order to obtain excellent coating film properties, the copolymer glass
Although a high transition point (Tg) is required, aqueous dispersions
If it is provided as, increase the Tg of the copolymer
And, unlike the solvent type, the film forming property is reduced. So the copolymer
Ensures film-forming properties when provided as an aqueous dispersion
Therefore, it is necessary to set Tg low to some extent.
Setting the Tg low as described above causes the deterioration of the coating film properties.
And the degree of freedom of the copolymer composition is reduced.
Aqueous dispersions of copolymers have higher silicon content than solvent-based dispersions.
Characteristics such as water repellency and low surface energy
Not. [0004] SUMMARY OF THE INVENTION The present invention relates to the above-mentioned conventional problems.
As a means to solve the problem, synthetic resin particles in an aqueous medium
An aqueous dispersion in which particles are dispersed, wherein said synthetic resin particles
IsHaving a double structure consisting of a core layer and a shell layer, wherein the core layer and the shell
What is a layer?Silicon macromocon with vinyl group introduced at one end
Nomer A polymer or said silicon macromonomer A
And a vinyl copolymerizable with the silicon macromonomer A
From a copolymer with monomer BAnd the Tg of the shell layer is
Is set to be lower than the Tg of the
The weight ratio of conmacromonomer A is determined by comparing the core layer and the shell layer.
All silicon macromolecules in the constituent polymer or copolymer
Set to the range of 50-100 for Nomer ASynthetic tree
An aqueous dispersion of fat particles is provided. The present invention will be described in detail below. [Silicon macromonomer A] The silicon macromonomer A used in the present invention and
Has the following structure. Embedded image And / or Embedded image Where R₁, R_ThreeIs a hydrogen atom or a methyl group, R_Two, R
_FourIs a phenyl group, a methyl group or an ethyl group, and n is 10
Is an integer of ~ 400, and m is an integer of 1 or more. The present invention
The silicon macromonomer usually has a molecular weight of 400
Approximately 30,000 are used.
Two or more types of monomer may be used as a mixture. [Vinyl monomer B] The vinyl monomer B used in the present invention is the above-mentioned silicone monomer.
It is copolymerizable with the chromanomer A.
Examples of the vinyl monomer include methyl acrylate and ethyl acrylate.
Acrylate, n-butyl acrylate, iso-butyl acrylate
Acrylate, 2-ethylhexyl acrylate, cyclohexane
Xyl acrylate, tetrahydrofurfuryl acryle
Methyl methacrylate, ethyl methacrylate,
n-butyl methacrylate, iso-butyl methacrylate,
2-ethylhexyl methacrylate, stearyl methacrylate
, Lauryl methacrylate, methyl vinyl ether
, Ethyl vinyl ether, n-propyl vinyl ether
, N-butyl vinyl ether, iso-butyl vinyl ether
Styrene, α-methylstyrene, acrylonitrile
, Methacrylonitrile, vinyl acetate, vinyl chloride, salt
Vinylidene fluoride, vinyl fluoride, vinylidene fluoride, 2-hydro
Xyethyl acrylate, 2-hydroxyethyl methacrylate
Rate, 2-hydroxypropyl acrylate, 2-hydro
Xypropyl methacrylate, allyl alcohol, gly
Sidyl acrylate, glycidyl methacrylate,
Sidyl allyl ether, acrylic acid, methacrylic acid,
Taconic acid, crotonic acid, maleic acid, maleic anhydride,
Citraconic acid, acrylamide, methacrylamide, N
-Methylol acrylamide, N-methylol methacryl
Luamide, dimethylaminoethyl acrylate, dimethyl
Luminoethyl methacrylate, ethylene, propylene
, Isoprene, chloroprene, butadiene and the like.
Two or more of the above vinyl monomers may be used in combination. [Synthetic resin particles] In the synthetic resin particles of the present invention, the silicon
The mixing ratio of the monomer A and the vinyl monomer B is usually 9
It is set in the range of 5: 5 to 5:95. Also core layer and shell layer
Is usually in the range of 10:90 to 90:10.
Is set. The shell in the copolymer that normally constitutes the shell layer
The weight ratio of the recon macromonomer A is such that the core layer and the shell layer
Silicon macromolecules in polymers or copolymers comprising
It is set in the range of 50 to 100 with respect to the monomer A.
The Tg of the core layer of the synthetic resin particles of the present invention is usually 25 ° C. or higher.
Preferably, the temperature is set to 30 ° C. or higher, and the Tg of the shell layer is usually 15 ° C.
C. or less, preferably 10 ° C. or less, and the Tg is
Types and types of conmacromonomer A and vinyl monomer B
And the copolymer composition ratio. [Production of aqueous dispersion of synthetic resin particles] The aqueous dispersion of synthetic resin particles of the present invention is prepared by an emulsion polymerization method.
Manufactured. To explain the outline, first, the core layer is formed.
Monomer or raw material of the polymer or copolymer
The monomer mixture is dispersed in water using a surfactant,
Raw material monomer or raw material monomer depending on the reactive polymerization initiator
Emulsion polymerization of the mixture to produce a core layer, followed by a shell layer
Monomer or raw material of polymer or copolymer
The surfactant used when producing the core layer using the monomer mixture
Using a surfactant or a new surfactant
Dispersed in the above emulsion polymer, by a water-soluble polymerization initiator
Emulsion polymerization of the raw material monomer or raw material monomer mixture
A shell layer is formed on the outer periphery of the core layer. In this way, the core layer
An aqueous dispersion of the synthetic resin particles of the present invention comprising a shell layer is produced.
Is done. [Surfactant] Used in the production of the aqueous dispersion of the synthetic resin particles of the present invention
As a surfactant, ordinary anionic, nonionic,
It is a cationic surfactant. For example, anionic interface
As an activator, higher alcohol sulfate (Na salt or the like)
Or amine salt), alkyl allyl sulfonate (Na
Salt), alkyl naphthalene sulfonate, alkyl naphthalene
Phthalene sulfonate condensate, alkyl phosphate
G, dialkyl sulfosuccinate, rosin soap, etc.
Yes, non-ionic surfactants are polyoxyethylene
Alkyl ether, polyoxyethylene alkyl
Knol ether, polyoxyethylene alkyl ester
, Polyoxyethylene alkylamine, polyoxyethylene
Tylene alkyl amide, sorbitan alkyl ester
, Polyoxyethylene sorbitan alkyl ester, etc.
There is. Trimethylamido as a cationic surfactant
Noethylalkylamide halogenide, alkylpyridini
Sulfate, alkyltrimethylammonium halogeni
And others. These surfactants can be used as a mixture of two or more.
May be used. The above examples also do not limit the present invention.
No. The amount of the surfactant used is the raw material monomer or
0.1 to 10 weights per 100 parts by weight of the raw material monomer mixture
It is about a part by volume. The amount of water as a polymerization medium is 30
About 100 parts by weight. [Water-soluble polymerization initiator] Used in the production of the aqueous dispersion of the synthetic resin particles of the present invention
As the water-soluble polymerization initiator, ammonium persulfate, persulfur
Potassium, sodium persulfate, sodium perborate,
Inorganic peroxides such as hydrogen oxide, cumene hydroperoxide
Sid, tertiary butyl peroxymaleic acid, koha
Citrate peroxide, tertiary butyl hydroperoxide
Organic peroxides such as oxides and 2,2'-azobis [2-
(N-benzylamidino) propane] dihydrochloride, 2,
2'-azobis [2- (N-allylamidino) propa
Dihydrochloride, 2,2'-azobis (2-amidinopro
Bread) dihydrochloride, 2,2'-azobis [2- {N- (2
-Hydroxyethyl) amidino {propane] dihydrochloride,
2,2'-azobis [2-methyl-N- [1,1-bis
(Hydroxymethyl) -2-hydroxyethyl] propyl
Onamide, 2,2'-azobis [2-methyl-N-
(2-Hydroxyethyl)] azo such as propionamide
There are compounds. Sodium sulfite as the water-soluble polymerization initiator
, Sodium bisulfite, sodium hyposulfite, Asco
Redox opening using a reducing agent such as sodium rubinate
An initiator system may be applied. The water-soluble polymerization initiator and
One or two or more reducing agents may be used in combination. Also above
The examples also do not limit the invention. [Emulsion polymerization] Emulsifies the polymer or copolymer constituting the core layer and shell layer
When polymerizing, the raw material monomer or raw material monomer mixture
The concentration is usually about 20 to 65% by weight.
The polymerization initiator concentration is usually the raw material monomer or raw material
It is about 0.01 to 5% by weight based on the body mixture. milk
During chemical polymerization, water and surfactant are charged into the reactor.
The raw material monomer or raw material monomer mixture
And a method of emulsion polymerization using a water-soluble polymerization initiator.
Enclosing method), the above-mentioned raw material monomer or raw material monomer mixture several times
And then emulsion-polymerized with a water-soluble polymerization initiator.
Raw material monomer or raw material monomer mixture
A method of continuously dropping a compound over a predetermined time (continuous method)
The above-mentioned raw material monomer or raw material monomer mixture is applied.
The compound is emulsified in a predetermined amount of aqueous surfactant solution to prepare
And the pre-emulsified liquid is prepared by a batch method, a split method, or
May be charged into the reactor by a continuous method. The above emulsification
In the case of polymerization, the surfactant and water used to manufacture the core layer
Soluble polymerization initiators and surfactants and
And the same type of water-soluble polymerization initiator,
Alternatively, different types may be used. In the case of core layer production
And the case of shell layer production is the raw material monomer or raw material monomer
Use the same or different mixture charging method
It may be modal. Polymerization applied in the above emulsion polymerization
The temperature range depends on the type of raw material monomers and water-soluble polymerization initiator used.
It is set appropriately depending on the type, but usually in the range of 30 to 90 ° C.
Is set. [Third component] If desired, an aqueous dispersion of the synthetic resin particles of the present invention
Components may be added. As such a third component
Is water-soluble epoxy resin, water-soluble melamine resin, water-soluble
Blocked isocyanate, having hydrolyzable silyl group
Cross-linking agents such as compounds, calcium carbonate, titanium oxide, oxidation
Filling iron, chromium oxide, blast furnace slag, fly ash, etc.
Material, polyvinyl alcohol, methylcellulose, carbo
Protective materials for xylmethylcellulose, polyacrylates, etc.
Lloyd or thickener, UV absorber, anti-aging agent, etc.
May be added. Addition of the third component before emulsion polymerization, milk
It is carried out during chemical polymerization or after emulsion polymerization. [0013] The synthetic resin particles of the present invention are made of silicon macromonomer.
Water repellency, lubricity, release properties, antifouling properties
Etc., and has excellent coating film properties.
Excellent film-forming properties even when provided as an aqueous dispersion
You. Such features of the present inventionThe Tg of the shell layer is replaced by the Tg of the core layer.
thanIt becomes more remarkable by lowering. Further shell layer
Weight ratio of the silicon macromonomer A in the core layer and the shell
All silicon polymers in the polymer or copolymer that constitute the layer
Set in the range of 50 to 100 for chromanomer ADo
Thus, the above characteristics of silicon are effectively exhibited. [0014] The present invention will be described below with reference to Examples and Comparative Examples.
Will be described in more detail. Note that in Examples and Comparative Examples,
Used as raw materials, water-soluble polymerization initiators and binders
Surfactants are indicated by the following abbreviations. MMA: methyl methacrylate, n-BA: n-butyl
Acrylate, 2-HEMA: 2-hydroxyethyl methacrylate, FM-0725: Chisso Corporation Silicon Macro Mono
Mer Molecular weight 10,000 X-22-5002: Silicon made by Shin-Etsu Chemical Co., Ltd.
Macromonomer molecular weight 422.8 KPS: potassium persulfate, DBS: dodecylbenzenes
Sodium sulfonate (Evaluation method of aqueous dispersion of synthetic resin particles) Evaluation of aqueous dispersion of synthetic resin particles obtained in each Example
The value was determined in the following manner. -Film preparation: The obtained aqueous dispersion of synthetic resin particles is
It was taken on a glass plate and dried at 20 ° C. for one day. -Film-forming property: The state of the obtained film was visually observed. Conclusion
Fruits are ○ (good), △ (cracks partially occur), × (whole)
Cracks occurred). ・ Surface energy: using the above film, Nakarai
The cissing of the Tesque wetting index standard solution was determined by visual observation.
Different. [Example 1] Stirrer, thermometer, condenser, nitrogen gas inlet tube, dripping
100 flasks of pure water in a 500 ml flask equipped with
Charged parts (hereinafter simply referred to as parts), DBS, 0.5 parts
And add 1 part of KPS at 80 ° C under nitrogen atmosphere
Was. Then, 5 parts of MMA and X-
22-5002, 5 parts of pure water 5 parts and DBS, 0.3
The pre-emulsified liquid emulsified with 5 parts is continuously reacted for 1 hour.
The mixture was dropped into the reactor and aged for 2 hours. Next, the raw material for forming the shell layer
X-22-5002, 90 parts of pure water 45 parts and
The pre-emulsified liquid emulsified with 3.15 parts of DBS was added for 3 hours.
Or continuously dropped into the reactor and aged for another 2 hours
Was. Then cool to room temperature and adjust to pH 7 with aqueous ammonia
Thus, an aqueous dispersion of synthetic resin particles was obtained. Raw material monomer composition
Are shown in Table 1. An aqueous dispersion of the obtained synthetic resin particles
Table 3 shows the evaluation results. [Embodiment 2] In the same reactor as in Example 1, 100 parts of pure water, DBS, 0.
5 parts were charged and KPS, 1 at a temperature of 80 ° C. under a nitrogen atmosphere.
Parts were added. Next, MMA, 25 was used as a raw material for forming the core layer.
Part and n-BA, 5 parts with pure water 15 parts and DBS,
Pre-emulsified liquid emulsified with 1.05 parts
It was continuously dropped into the reactor and aged for 2 hours. Next, the shell layer
MMA, 20 parts and n-BA, 10
Parts and X-22-5002, 40 parts by pure water 35 parts and
And pre-emulsified liquid emulsified with 2.45 parts of DBS for 2.5 hours
Drops continuously into the reactor over a period of time and ages for another 2 hours
I let it. Then cool to room temperature and adjust to pH 7 with aqueous ammonia
This was adjusted to obtain an aqueous dispersion of synthetic resin particles. Raw material monomer
The composition is shown in Table 1. The aqueous content of the obtained synthetic resin particles
Table 3 shows the evaluation results of the liquid dispersion. [Embodiment 3] In the same reactor as in Example 1, 100 parts of pure water, DBS, 0.
5 parts were charged and KPS, 1 at a temperature of 80 ° C. under a nitrogen atmosphere.
Parts were added. Next, MMA, 50 was used as a raw material for forming the core layer.
Was emulsified with 25 parts of pure water and 1.75 parts of DBS.
The emulsion was continuously dropped into the reactor over a period of 2 hours.
Aged for hours. Next, MMA, 1 was used as a raw material for forming a shell layer.
7.5 parts and n-BA, 20 parts and FM-072
5.12.5 parts of pure water 25 parts and DBS, 1.75 parts
The pre-emulsified liquid emulsified in the reactor continuously for 2 hours
The mixture was added dropwise and aged for 2 hours. Then cool to room temperature
Adjust the pH to 7 with aqueous ammonia and adjust the aqueous
A dispersion was obtained. Table 1 shows the monomer composition of the raw materials. Also gain
Table 3 shows the evaluation results of the obtained aqueous dispersions of synthetic resin particles.
You. [Embodiment 4] In the same reactor as in Example 1, 100 parts of pure water, DBS, 0.
5 parts were charged and KPS, 1 at a temperature of 80 ° C. under a nitrogen atmosphere.
Parts were added. Next, MMA, 40 was used as a raw material for forming a core layer.
Parts and n-BA, 5 parts and 2-HEMA, 5 parts
Pre-emulsification emulsified with 25 parts of water and 1.75 parts of DBS
The solution was continuously dropped into the reactor over 2 hours and aged for 2 hours.
Was completed. Next, 10 parts of MMA was used as a raw material for forming the shell layer.
And n-BA, 5 parts, 2-HEMA, 5 parts, FM-07
25, 5 parts and X-22-5002, 25 parts of pure water 2
Pre-emulsified liquid emulsified with 5 parts and DBS, 1.75 parts
Dropping into the reactor continuously over 2 hours, for another 2 hours
Aged. Then cool to room temperature and pH with ammonia water
7, to obtain an aqueous dispersion of synthetic resin particles. Raw material
Table 1 shows the monomer composition. The water of the obtained synthetic resin particles
Table 3 shows the evaluation results of the aqueous dispersion. [Embodiment 5] In the same reactor as in Example 1, 100 parts of pure water, DBS, 0.
5 parts were charged and KPS, 1 at a temperature of 80 ° C. under a nitrogen atmosphere.
Parts were added. Next, MMA, 60 was used as a raw material for forming the core layer.
Part and n-BA, 10 parts with pure water 35 parts and DBS,
Pre-emulsified liquid emulsified with 2.45 parts over 2.5 hours
It was continuously dropped into the reactor and aged for 2 hours. Next, the shell layer
30 parts of X-22-5002 and 30 parts of pure water 1
Pre-emulsified liquid emulsified with 5 parts and 1.05 parts DBS
Drops into the reactor continuously over 1.5 hours, followed by an additional 2
Aged for hours. Then cool to room temperature and use ammonia water
The pH was adjusted to 7 to obtain an aqueous dispersion of synthetic resin particles. material
Is shown in Table 1. Also obtained synthetic resin particles
Table 3 shows the results of the evaluation of the aqueous dispersion of Embodiment 6 In the same reactor as in Example 1, 100 parts of pure water, DBS, 0.
5 parts were charged and KPS, 1 at a temperature of 80 ° C. under a nitrogen atmosphere.
Parts were added. Next, MMA, 55 was used as a raw material for forming the core layer.
Parts and X-22-5002, 15 parts with 35 parts of pure water and
And pre-emulsified liquid emulsified with 2.45 parts of DBS for 2.5 hours
Drop in the reactor continuously over a period of time and ripen for 2 hours
Was. Next, 5 parts of MMA and n-
BA, 10 parts, X-22-5002, 15 parts pure
Pre-emulsification emulsified with 15 parts of water and 1.05 parts of DBS
The liquid was continuously dropped into the reactor over 1.5 hours,
For 2 hours. Then cool to room temperature and ammonia
The pH was adjusted to 7 with water to obtain an aqueous dispersion of synthetic resin particles.
Table 1 shows the monomer composition of the raw materials. Also obtained synthetic resin
Table 3 shows the evaluation results of the aqueous dispersion of particles. [Embodiment 7] In the same reactor as in Example 1, 100 parts of pure water, DBS, 0.
5 parts were charged and KPS, 1 at a temperature of 80 ° C. under a nitrogen atmosphere.
Parts were added. Next, MMA, 80 was used as a raw material for forming a core layer.
Part and n-BA, 10 parts with pure water 45 parts and DBS,
3.Continue the pre-emulsified liquid emulsified with 15 parts for 2 hours
The mixture was dropped into the reactor and aged for 2 hours. Next, shell layer formation
X-22-5002, 10 parts of pure water 5 parts
Pre-emulsified liquid emulsified with DBS and 0.35 parts for 2 hours
And continuously aged for 2 hours.
I let you. Then cool to room temperature and adjust to pH 7 with ammonia water
And an aqueous dispersion of synthetic resin particles was obtained. Raw monomer group
The results are shown in Table 1. Aqueous dispersion of the obtained synthetic resin particles
Table 3 shows the evaluation results of the liquid. [Comparative Example A] In the same reactor as in Example 1, 100 parts of pure water, DBS, 0.
5 parts were charged and KPS, 1 at a temperature of 80 ° C. under a nitrogen atmosphere.
Parts were added. Next, MMA, 5 parts and X-22-50
02,95 parts milk with 50 parts pure water and 3.5 parts DBS
The liquefied product was continuously dropped into the reactor over 4 hours.
Aged for 2 hours. Then cool to room temperature and add ammonia water
The pH was adjusted to 7 to obtain an aqueous resin dispersion. Raw material monomer
The composition is shown in Table 2. Evaluation of the obtained aqueous resin dispersion
Table 3 shows the results. [Comparative Example B] In the same reactor as in Example 1, 100 parts of pure water, DBS, 0.
5 parts were charged and KPS, 1 at a temperature of 80 ° C. under a nitrogen atmosphere.
Parts were added. Next, MMA, 2 was used as a raw material for forming the core layer.
2.5 parts, n-BA, 7.5 parts and X-22-500
2.20 parts milk with 25 parts pure water and 1.75 parts DBS
The preliminarily emulsified liquid is continuously introduced into the reactor for 2 hours.
The mixture was dropped and aged for 2 hours. Next, as a raw material for forming a shell layer, M
MA, 22.5 parts and n-BA, 7.5 parts, and X
22-5002, 20 parts of pure water 25 parts and DBS,
Pre-emulsified liquid emulsified with 1.75 parts continuously for 2 hours
The mixture was dropped into the reactor and aged for 2 hours. afterwards
Cool to room temperature, adjust the pH to 7 with aqueous ammonia, and use synthetic resin
An aqueous dispersion of the particles was obtained. Table 2 shows the monomer composition of the raw materials.
You. Evaluation results of the aqueous dispersion of the obtained synthetic resin particles
Are shown in Table 3. [Comparative Example C] In the same reactor as in Example 1, 100 parts of pure water, DBS, 0.
5 parts were charged and KPS, 1 at a temperature of 80 ° C. under a nitrogen atmosphere.
Parts were added. Next, MMA, 67.5 parts, n-BA, 2
0 parts and FM-0725, 12.5 parts 50 parts pure water
Pre-emulsified liquid emulsified with DBS and 3.5 parts in 4 hours
The mixture was dropped continuously into the reactor and aged for 2 hours. So
After cooling to room temperature, adjust to pH 7 with ammonia water and synthesize
An aqueous dispersion of resin particles was obtained. Table 2 shows the monomer composition of the raw materials.
Shown in Evaluation of the obtained aqueous dispersion of synthetic resin particles
Table 3 shows the results. [Comparative Example D] In the same reactor as in Example 1, 100 parts of pure water, DBS, 0.
5 parts were charged and KPS, 1 at a temperature of 80 ° C. under a nitrogen atmosphere.
Parts were added. Next, MMA, 10
Part, n-BA, 5 parts, 2-HEMA, 5 parts, FM-07
25, 5 parts and X-22-5002, 25 parts of pure water 2
Pre-emulsified liquid emulsified with 5 parts and DBS, 1.75 parts
Drops continuously into the reactor over 2 hours and matures for 2 hours
I let you. Next, 40 parts of MMA as a shell layer forming raw material and
n-BA, 5 parts and 2-HEMA, 5 parts, purified water 25 parts
And pre-emulsified liquid emulsified with 1.75 parts of DBS at 2:00
Drops continuously into the reactor over a period of time and ages for another 2 hours
I let it. Then cool to room temperature and adjust to pH 7 with aqueous ammonia
This was adjusted to obtain an aqueous dispersion of synthetic resin particles. Raw material monomer
The composition is shown in Table 2. The aqueous content of the obtained synthetic resin particles
Table 3 shows the evaluation results of the liquid dispersion. [Comparative Example E] In the same reactor as in Example 1, 100 parts of pure water, DBS, 0.
5 parts were charged and KPS, 1 at a temperature of 80 ° C. under a nitrogen atmosphere.
Parts were added. Next, MMA, 50 parts, n-BA, 5 parts,
2-HEMA, 10 parts, FM-0725, 5 parts and X
22-5002, 25 parts of pure water and DBS,
The pre-emulsified liquid emulsified with 3.5 parts is continuously fed for 4 hours.
Was dropped into a reactor and aged for 2 hours. Then to room temperature
After cooling, adjust the pH to 7 with ammonia water
A liquid dispersion was obtained. Table 2 shows the monomer composition of the raw materials. Also
Table 3 shows the evaluation results of the obtained aqueous dispersions of synthetic resin particles.
Show. [Comparative Example F] In the same reactor as in Example 1, 100 parts of pure water, DBS, 0.
5 parts were charged and KPS, 1 at a temperature of 80 ° C. under a nitrogen atmosphere.
Parts were added. Next, MMA, 50 was used as a raw material for forming the core layer.
And 20 parts of X-22-5002, 35 parts of pure water and
And pre-emulsified liquid emulsified with 2.45 parts of DBS for 2.5 hours
Drop in the reactor continuously over a period of time and ripen for 2 hours
Was. Next, MMA, 10 parts and n
-BA, 10 parts and X-22-5002, 10 parts pure
Pre-emulsification emulsified with 15 parts of water and 1.05 parts of DBS
The liquid was continuously dropped into the reactor over 1.5 hours,
For 2 hours. Then cool to room temperature and ammonia
The pH was adjusted to 7 with water to obtain an aqueous dispersion of synthetic resin particles.
Table 2 shows the monomer composition of the raw materials. Also obtained synthetic resin
Table 3 shows the evaluation results of the aqueous dispersion of particles. [Comparative Example G] In the same reactor as in Example 1, 100 parts of pure water, DBS, 0.
5 parts were charged and KPS, 1 at a temperature of 80 ° C. under a nitrogen atmosphere.
Parts were added. Next, MMA, 80 parts, n-BA, 10 parts
And X-22-5002, 10 parts of pure water 50 parts and
Preliminary emulsified liquid emulsified with 3.5 parts of DBS for 4 hours
The mixture was continuously dropped into the reactor and aged for 2 hours. afterwards
Cool to room temperature, adjust the pH to 7 with aqueous ammonia, and use synthetic resin
An aqueous dispersion of the particles was obtained. Table 2 shows the monomer composition of the raw materials.
You. Evaluation results of the aqueous dispersion of the obtained synthetic resin particles
Are shown in Table 3. [Example of use of crosslinking agent] 100 parts of the resin obtained in Example 4 and Comparative Examples D and E
Water-soluble melamine manufactured by Mitsui Cyanamid Co., Ltd.
One-part curing type synthesis by adding 350 and 4 parts of resin cymer
Resin particle aqueous dispersions were obtained (4 ', D', and E ', respectively).
). The obtained one-part curable synthetic resin particle aqueous dispersion is
Then, place on a glass plate and dry at 20 ° C for 1 hour.
It was further dried at 150 ° C. for 30 minutes. this
Using film to evaluate film forming properties and surface energy
Was.Table 4 shows the results. [0030] [Table 1] [0031] [Table 2][0032] [Table 3] [0033] [Table 4] [0034] According to the present invention, the synthetic resin particles are coated in a shell layer.of
TgHas a two-layer structure so that the Tg is lower than the Tg of the core layer.
Excellent film forming properties and coating film propertiesOf the shell layerShi
Recon MacromonomerA weight ratio of the core layer and the shell layer
All silicone macromolecules of the polymer or copolymer
Set the range between 50 and 100 for Nomer A.And to
Than,Capable of effectively expressing the characteristics of silicon
In conventional silicon macromonomer polymers,
An aqueous dispersion of synthetic resin particles of excellent performance that could not be obtained
Can be obtained.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hironori Hata 8-3 Ninocho, Mizuho-ku, Nagoya-shi, Aichi Prefecture Inside Natco Paint Co., Ltd. (72) Inventor Ken Satoru Mochizuki 1-3-6 Nakamagome, Ota-ku, Tokyo Ricoh Co., Ltd. (72) Inventor Fumihiro Sasaki 1-3-6 Nakamagome, Ota-ku, Tokyo, Japan Stock Company Ricoh (72) Inventor Hidefumi Gobara 1-3-6 Nakamagome, Ota-ku, Tokyo, Japan (56) References JP-A-5-194911 (JP, A) JP-A-5-140255 (JP, A) JP-A-1-315451 (JP, A) JP-A-4-175343 (JP) JP-A-2-308801 (JP, A) JP-A-64-51475 (JP, A) JP-A-59-80460 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB Name) C08F 290/00-290/14 C08F 299/00-299/08 C09D 1/00- 201/10

Claims (1)

(57) [Claim 1] An aqueous dispersion in which synthetic resin particles are dispersed in an aqueous medium, the synthetic resin particles comprising a core layer and a shell layer.
The core layer and the shell layer each have a vinyl group-introduced vinyl group at one end, or a polymer of the silicon macromonomer A, and the silicon macromonomer A can be copolymerized with the silicon macromonomer A. Do a copolymer of vinyl monomer B, such Ri, Tg of the shell layer is ne lower than the Tg of the core layer
Silicon macromonomer for the shell layer
The weight ratio of A is a polymer constituting the core layer and the shell layer or
Is 5 relative to the total silicon macromonomer A in the copolymer.
Synthetic resin characterized by being set in the range of 0 to 100
Aqueous dispersion of particles