JPH036236A - Reactive resin particle - Google Patents

Abstract

PURPOSE:To prepare highly reactive resin particles even at a low temp. in an aq. medium by causing resin particles having a specific particle diameter to carry a specific chelate group. CONSTITUTION:Reactive resin particles, having a mean particle diameter of 0.01-100mum and carrying a chelate group of formula 1 (wherein R1 is H or 1-3C alkyl; X is oxygen, sulfur, or NR2, wherein R2 is H, 1-3C alkyl, or phenyl; and (n) is 1-3), are obtd., e.g. by the emulsion or suspension polymn. of an alpha,beta- ethylenically unsatd. monomer contg. said chelate group or of said monomer with another polymerizable monomer (e.g. acrylic acid or methacrylic acid), and can be crosslinked, if necessary.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a novel reactive resin particle, and more specifically, it is useful in the fields of paints, inks, adhesives, medicine, pharmaceutical materials, polymer flocculants, etc. This invention relates to reactive resin particles.

<Prior art> Reactive resin particles are used in industrial fields such as paints, inks, and adhesives, as flow regulators, extenders, or additives to improve physical properties, and as functional carrier materials for medical and pharmaceutical products. It is widely used and attracts attention. Particularly in recent years, demands for low pollution and resource conservation have been increasing in the above fields, and there has been a shift from conventional compositions based on organic media to compositions that use water as a medium and react at low temperatures. Highly desired. However, conventional reactive resin particles mainly undergo reactions in organic media, and the functional groups supported on the resin particles are mainly hydroxyl groups, carboxyl groups, amino groups, epoxy groups, and incyanate groups. It is. These functional groups form chemical bonds with other functional groups through dehydration condensation or addition polymerization, but in both reaction systems, the presence of water hinders the reaction, and the above requirements are not necessarily met. is the current situation.

<Problems to be Solved by the Invention> An object of the present invention is to provide novel reactive resin particles that have high reactivity even at low temperatures and in an aqueous medium.

<Means for Solving the Problems> According to the present invention, resin particles having an average particle size of 0.01 to 100 μm are formed by the following general formula (1) (wherein R is a hydrogen atom). or represents an alkyl group having 1 to 3 carbon atoms, X represents an oxygen atom, a sulfur atom, or -NR2-, provided that R2 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group; Reactive resin particles are provided, which are characterized in that they carry a chelate group represented by (representing an integer of 3 to 3).

The present invention will be explained in more detail below.

The reactive resin particles of the present invention are characterized by having a specific particle size and carrying a specific chelate group.

In the present invention, the supported chelate group can be represented by the following general formula (1), where R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X represents an oxygen atom, a sulfur atom, or -NR2-, where R2 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group. Moreover, n represents an integer of 1 to 3. When the number of carbon atoms in R and R2 is 4 or more, it may become unstable in an aqueous medium. The chelate group represented by the general formula (I) is extremely stable in an aqueous medium, and includes amino groups, aldehyde groups, isocyanate groups, diazonium salts, metals such as tin, zinc, lead, aluminum, and titanium; It is known to react with compounds such as unsaturated carbonyl compounds and melamine-formaldehyde resins. Regarding the reaction of chelate group, F, Del R
ector,, star-Borne and High
her 5olids Coatings Symp,
, Feb. 3-5, 1988.

In the present invention, in order to support the chelate group represented by the general formula (1), α, β
- The ethylenically unsaturated monomer is polymerized alone or together with other polymerizable monomers by known polymerization methods such as emulsion polymerization, suspension polymerization, or NAD polymerization, or the polymer having the chelate group is used as a surfactant. and/or in the presence of a polymeric surfactant.

This can be carried out by a forced emulsification method in which mechanical emulsification is performed in an aqueous or non-aqueous medium.

Examples of the α,β-ethylenically unsaturated monomer having a chelate group include acetoacetoxyethyl (meth)acrylate, acetoacetoxypropyl (meth)acrylate, acetoacetoxybutyl (meth)acrylate, and acetoacetoxyethylthio(meth)acrylate. ) acrylate,
acetoacetoxypropylthio(meth)acrylate,
Examples include acetoacetoxybutylthio(meth)acrylate, acetoacetoxyethyl(meth)acrylic amide, acetoacetoxypropyl(meth)acrylic amide, acetoacetoxybutyl(meth)acrylic sanamide, and the like. To produce the α,β-ethylenically unsaturated monomer having the chelate group, an acrylic acid or methacrylic acid derivative having a hydroxyl group, a thiol group, or an amino group (including an imino group), diketene or acetoacetic acid, and It can be easily obtained by a method of reacting. In addition, other polymerizable monomers that may be used as desired in addition to the α,β-ethylenically unsaturated monomer include, for example, acrylic acid and methacrylic acid.

Examples include itaconic acid, maleic acid, fumaric acid, and esters thereof, and may also include styrene, vinyltoluene, acrylonitrile, vinyl acetate, and the like. In addition, especially when using acrylic esters and methacrylic esters here, the following general formula (II
) 3 (wherein R3 represents a hydrogen atom or a methyl group, and R4 represents an alkyl group having 1 to 15 carbon atoms, a hydroxyl group, or an epoxy group) is preferable, and when R4 in the formula 1 is an alkyl group, 1 For example, methyl (meth)acrylate,
(meth)ethyl acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)acrylate
Examples include lauryl acrylate, and in the formula R
When 4 is a hydroxyl group or an epoxy group, for example (meta)
Examples include 2-hydroxypropyl acrylate, 2-hydroxyethyl (meth)acrylate, glycidyl acrylate, and glycidyl methacrylate.

On the other hand, the polymer having a chelate group can be easily obtained, for example, by reacting a polymer having a hydroxyl group, a thiol group, or an amino group (including an imino group) with a diketone or acetoacetic acid.

In the present invention, if the average particle size of the reactive resin particles obtained by each of the above methods is less than 0.01 μm, the viscosity of the system during production will increase and workability will decrease;
If more than
．． It is necessary to set it as the range of 01-100 micrometers. In order to adjust the particle size of the reactive resin particles within the above range, it can be carried out by the method generally used in the above manufacturing method. In other words, the type and amount of surfactant, dispersion stabilizer, and polymeric surfactant to be used (1) Dispersion medium, type of monomer, and synthesis conditions such as dropping rate and polymerization temperature are appropriately selected. be able to.

Furthermore, the reactive resin particles of the present invention can be crosslinked if necessary, for example, by using a known monomer having two or more radically polymerizable ethylenically unsaturated groups in the molecule. Crosslinking can be carried out by the method described in the following. Examples of the monomer having an ethylenically unsaturated group include a polymerizable unsaturated monocarboxylic acid ester of a polyhydric alcohol, a polymerizable unsaturated alcohol ester of a polybasic acid, or a monomer having an ethylenically unsaturated group.
Examples include aromatic compounds substituted with more than one vinyl group, specifically ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,3-butylene gelicoldi(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentylglycol di(meth)acrylate,
1.6-hexanethiol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerol di(meth)acrylate, glycerol allyloxy dimethacrylate, 1゜1.1-trishydroxymethylethane di(meth)acrylate, 1,1.1-trishydroxymethylethane tri(meth)acrylate, 1,1゜1-trishydroxymethylpropane di(meth)acrylate, l, 1 .1-trishydroxymethylpropane tri(meth)acrylate, triallyl cyanurate,
Examples include triallyl isocyanurate, triallyl trimellitate, diallyl terephthalate, diallyl phthalate, and divinylbenzene.

Since the reactive resin particles of the present invention carry a chelate group, they can be used for various purposes by reacting with the above-mentioned compounds that react with the chelate group to form chemical bonds. In order to carry out the reaction at a low temperature, it is preferable to use a compound having an amino group, an aldehyde group, etc., or a compound having an unsaturated ester group in the presence of a basic catalyst. Furthermore, since the reaction proceeds quantitatively at low temperatures in both aqueous and nonaqueous media, the reactive resin particles of the present invention can be applied to any aqueous or organic solvent composition.

<Effects of the Invention> The reactive resin particles of the present invention greatly improve the drawbacks of conventional reactive resin particles, and can react at low temperatures even in an aqueous medium or an organic medium, so they can be used in paints. ,ink,
It is extremely useful as a flow regulator for adhesives, a filler, or an additive for improving physical properties, and as a functional carrier material and polymer flocculant for medical and pharmaceutical products.

<Example> The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited in any way by these examples.

Note that parts in one example indicate parts by weight.

725.1 ml of deionized water was added to a 2Q reaction vessel equipped with a forklift stirrer, condenser, temperature control device, nitrogen inlet tube and dropping funnel.
6. The temperature was raised under a nitrogen gas stream and maintained at 80°C.
Next, an aqueous solution of 3.0 parts of potassium persulfate and 59.7 parts of deionized water was charged, followed by 1 part of methyl methacrylate.
16.1 parts and 8. ethylene glycol dimethacrylate.
The mixture with 9 parts was filtered down over 2.5 hours. Thereafter, a mixture of 18.5 parts of acetoacetoxyethyl methacrylate and 1.1 parts of ethylene glycol dimethacrylate was passed through the solution over 30 minutes. After the monomer mixture starts running upstream, add 0.6 parts of potassium and 1 part of deionized water every 30 minutes.
An aqueous solution of 2.0 parts was added sequentially in 6 portions. After the seven-mer mixture had gone upstream, stirring was continued for 2 hours at 80°C to complete the reaction, and the heating residue was 14.3% by weight.
, the average particle size was 0.35 μm under zero reaction conditions and heating residue.

The results of the average particle diameter and gelation time, which is a measure of reactivity, are shown in Table 1, and the method for measuring the gelation time is shown below.

20 g of the aqueous dispersion containing the reactive resin particles obtained in Example 1 was placed in a 100-hour beaker, and hexamethylene diamine was added so that the concentration in water was 0.2 mol/Q. added to. Next, the beaker was immersed in hot water at 50° C., and after fixing the beaker so that the water level in the beaker and the hot water level matched, stirring was started, and the time until the contents gelled was measured.

By measuring the gelation time, the reactivity of the obtained resin particles can be confirmed.

830 parts of deionized water,
4.5 parts of sodium dioctyl sulfosuccinate, 0.7 part of Rongalite, 3.5 parts of trisodium phosphate dodecahydrate, and 0.3 parts of tetrasodium ethylenediaminetetraacetate were charged, and the temperature was raised to 40°C under a nitrogen gas stream. After charging an aqueous solution of 0.2 part of ferrous sulfate heptahydrate dissolved in 44 parts of deionized water and an aqueous solution of 0.5 part of t-butyl hydroperoxide dissolved in 44 parts of deionized water. A mixture of 304.4 parts of methyl methacrylate, 131.4 parts of acetoacetoxyethyl methacrylate, and 2.2 parts of ethylene glycol dimethacrylate was poured down over 3 hours. After finishing the percolation of the 7-mer mixture, the temperature was lowered to 60°C.
When the temperature was raised to ℃ and stirring was continued for 2 hours to complete the reaction, the heating residue was 29.9% by weight and the average particle size was 0.16μ.
The results of the reaction conditions, heating residue, average particle size, and gelation time are shown in Table 1.

480 parts of deionized water was added to a 1Ω reaction vessel equipped with a stirrer, a condenser, a temperature control device, a nitrogen inlet tube, and a dropping funnel.
Prepare 0.8 dioctyl sodium sulfosuccinate,
The temperature was raised under a nitrogen stream and maintained at 60°C. Next, after charging an aqueous solution of 0.3 parts of sodium thiosulfate and 15 parts of deionized water and an aqueous solution of 0.25 parts of potassium persulfate and 15 parts of deionized water, 103 parts of methyl methacrylate and 44 parts of acetoacetoxyethyl methacrylate were added. 4 parts of ethylene glycol dimethacrylate and 0.75 parts of ethylene glycol dimethacrylate were mixed to obtain a 7-mer mixture. 1,710 parts of the monomer mixture was charged. After confirming that a polymerization reaction had occurred, the remaining monomer mixture was heated for 3 hours. It was transparent. 1 of each aqueous solution of 0.3 parts of lithium and 15 parts of deionized water and 0.25 parts of potassium persulfate and 15 parts of deionized water. /7 amounts were added sequentially. After the monomer mixture had gone upstream, stirring was continued for 3 hours at 60°C to complete the reaction, and the heating residue was 20.5% by weight, and the average particle size was 0.103.
Table 1 shows the results of the reaction conditions, heating residue, average particle size, and gelation time in μm.

Except that a monomer mixture having the composition shown in Table 1 was used instead of the monomer mixture prepared in Daiarashi Goto Example 3.

Reactive resin particles were obtained in exactly the same manner as in Example 3.

Claims (1)

[Claims] 1) Resin particles having an average particle diameter of 0.01 to 100 μm, the resin particles having the following general formula (I) ▲ mathematical formula, chemical formula, table, etc. ▼...(I) (formula R_1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X represents an oxygen atom, a sulfur atom, or -NR_2-
, where R_2 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group. and n is an integer of 1 to 3). 2) The reactive resin particles according to claim 1, wherein the reactive resin particles are crosslinked.