JPH07207064A - Reactive resin particle and its production - Google Patents

Abstract

PURPOSE:To obtain a reactive resin particles having a specified active oxygen content and a specified particle diameter and being capable of a reaction among particles or with an external substrate by effecting the emulsion polymerization or nonaqueous dispersion polymerization of an unsaturated monomer having an organic peroxide bond group and an unsaturated monomer copolymerizable therewith. CONSTITUTION:This particles have organic peroxide bond groups of an active oxygen content of 0.005-4.0% within the resin particle and have a mean particle diameter of 0.01-100mum. It is desirable that the reactive resin particles are internally cross-linked ones. These particles are produced by effecting the emulsion polymerization or nonaqueous dispersion polymerization of an unsaturated monomer having an organic peroxide bond (a compound having both a radical- polymerizable C-C double bond and an organic peroxide bond group in the molecule, e.g. a ketone peroxide corresponding to an ester of (meth)acrylic acid, itaconic acid or the like) and an unsaturated monomer copolymerizable therewith.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel reactive resin particle containing an organic peroxide-bonding group in a resin particle, more specifically, a coating material, ink, adhesive, polymer modifier, medical treatment,
The present invention relates to a reactive resin particle useful in the fields of medical materials, cosmetics, fragrances, polymer flocculants, molding materials and the like, and a method for producing the same.

[0002]

2. Description of the Related Art Reactive resin particles are used as flow control agents in industrial fields such as paints, inks, adhesives and polymer modifiers.
It is widely used as a bulking agent or an additive for improving physical properties, and also as a functional carrier material for medical treatment, pharmaceuticals, cosmetics, fragrances and the like, and has been attracting attention.

For the purpose of imparting such a function of the reactive resin particles, a method of introducing a reactive functional group such as a hydroxyl group, a carboxyl group, an amino group, an epoxy group or an isocyanate group into the resin particles has been known for a long time. There is. However, as the reactive functional groups that have been conventionally introduced, only functional groups whose main purpose is mainly a reaction between the reactive resin particles and a reaction between the reactive resin particles and an external substrate are known.

Therefore, the reaction between the particles and the reaction between the particles and an external substrate are possible, and further, a reaction having a new function such as newly polymerizing a monomer in the reactive resin particles. The development of resin particles is desired.

[0005]

DISCLOSURE OF THE INVENTION The object of the present invention is to enable a mutual reaction between particles and a reaction with an external substrate, and further to newly polymerize a monomer in a resin particle. Another object of the present invention is to provide a reactive resin particle and a method for producing the same.

Another object of the present invention is to increase the amount of residual active oxygen in the resulting reactive resin particles,
Another object of the present invention is to provide a method for producing reactive resin particles capable of adjusting the amount of active oxygen contained in a desired range.

[0007]

According to the present invention, the resin particles have an organic peroxide-bonding group so that the amount of active oxygen in the resin particles is 0.005 to 4.0%, and Provided is a reactive resin particle having an average particle diameter of 0.01 to 100 μm.

Further, according to the present invention, there is provided a method for producing the above-mentioned reactive resin particles, which comprises an unsaturated monomer containing an organic peroxide bond group and an unsaturated monomer copolymerizable therewith. There is provided a method for producing reactive resin particles, which comprises polymerizing the resin by an emulsion polymerization method or a non-aqueous dispersion polymerization method.

The present invention will be described in detail below. The reactive resin particle of the present invention has a specific amount of the organic peroxide-bonding group in the resin particle and has a specific average particle diameter. Having the organic peroxide-bonding group in the resin particles means that hydrogen abstraction reaction, radical initiation ability, etc., enable mutual reaction between particles or reaction with an external substrate, and a new monomer It suffices that an organic peroxide-bonding group is present so that the body can be polymerized, and it is preferably a structure in which the organic peroxide-bonding group is chemically bonded to the polymer chain itself constituting the resin particle. As such an organic peroxide-bonding group, for example, an organic peroxide-bonding group-containing unsaturated monomer described below and introduced into the polymer chain when the unsaturated monomer copolymerizable therewith is copolymerized Preferred examples thereof include organic peroxide-bonding groups. The content of the organic peroxide-bonding group in the reactive resin particles is 0.005 to 4.0%, preferably 0.
It is in the range of 005 to 1.0%. When the content of the organic peroxide-bonding group is less than 0.005% in terms of the amount of active oxygen, the amount of the organic peroxide-bonding group contained in the obtained resin particles is too small and the reactive resin It is difficult to sufficiently exhibit the function as particles, and when it exceeds 4.0%, the organic peroxide-bonding groups introduced into the obtained resin particles undergo radical decomposition or extreme gelation during the reaction. There is a possibility that it will cause aging.

The reactive resin particles of the present invention may be internally crosslinked if necessary, and the internal crosslinking means a monomer having two or more polymerizable double bonds in the molecule described later. It is meant that the reactive resin particles themselves are not crosslinked by polymerization, but that the reactive resin particles themselves have a crosslinked structure.

The average particle diameter of the reactive resin particles is 0.0
It is in the range of 1 μm to 100 μm. Average particle size is 0.01
When it is less than μm, the viscosity during production becomes high and the workability is deteriorated. On the other hand, when it exceeds 100 μm, good smoothness cannot be obtained when it is used for paints or inks, and the sedimentation stability is further deteriorated.

In the method for producing the reactive resin particles of the present invention, the organic peroxide-bonded group-containing unsaturated monomer and the unsaturated monomer copolymerizable therewith are prepared by a known emulsion polymerization method or It can be obtained by polymerizing according to a water dispersion polymerization method.

The unsaturated monomer containing an organic peroxide-bonding group has a carbon-carbon double bond exhibiting radical polymerizability, such as a vinyl group, and an organic peroxide-bonding group in the same molecule. Specifically, for example, ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, perester corresponding to esters such as (meth) acrylic acid, itaconic acid, maleic acid or fumaric acid. Oxydicarbonates, peroxyesters and the like; ketone peroxides having allyl groups, methallyl groups, allyloxy groups, metalyloxy groups, etc., peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, peroxy Esters, etc .; Styrene, vinyl Examples include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, and peroxyesters derived from nuclear-substituted styrenes such as ruene, dimethylstyrene, and ethylstyrene. In the reaction, they can be used alone or as a mixture.

Further, as a particularly preferable example of the unsaturated monomer containing an organic peroxide-bonding group, Japanese Patent Publication No. 3-67526
The compounds described in JP-B No. 4-26325 and the like, specifically, for example, the monomers represented by the following general formula 1 or 2 can be mentioned, and in the reaction, they are used alone or as a mixture. Can be used.

[0015]

[Chemical 1]

(In the formula, R ¹ is a hydrogen atom or a carbon number of 1 to 4
Is an alkyl group, R ² is a hydrogen atom or a methyl group, R ³ and R ⁴ are the same or different groups and represent an alkyl group having 1 to 4 carbon atoms, and R ⁵ is 1 to 12 carbon atoms. Represents an alkyl group, a phenyl group, an alkyl-substituted phenyl group, or a cycloalkyl group having 3 to 12 carbon atoms. N ₁ represents 1 or 2. )

[0017]

[Chemical 2]

(In the formula, R ⁶ is a hydrogen atom or a carbon number of 1 to 4
R ⁷ is a hydrogen atom or a methyl group, R ⁸ and R ⁹ are the same or different groups and represent an alkyl group having 1 to 4 carbon atoms, and R ¹⁰ is 1 to 12 carbon atoms. Represents an alkyl group, a phenyl group, an alkyl-substituted phenyl group, or a cycloalkyl group having 3 to 12 carbon atoms. N ₂ represents an integer of 0 to 2. ) Examples of the compound represented by the general formula 1 include t
-Butylperoxy (meth) acryloyloxyethyl carbonate, t-amylperoxy (meth) acryloyloxyethyl carbonate, t-hexylperoxy (meth) acryloyloxyethyl carbonate, 1,
1,3,3-Tetramethylbutylperoxy (meth) acryloyloxyethyl carbonate, cumylperoxy (meth) acryloyloxyethyl carbonate, p-isopropylcumylperoxy (meth) acryloyloxyethyl carbonate, t-butylperoxy (Meth) acryloyloxyethoxyethyl carbonate, t-amylperoxy (meth) acryloyloxyethoxyethyl carbonate, t-hexylperoxy (meth) acryloyloxyethoxyethyl carbonate, 1,1,3,3
3-tetramethylbutylperoxy (meth) acryloyloxyethoxyethyl carbonate, cumylperoxy (meth) acryloyloxyethoxyethyl carbonate, p-isopropylcumylperoxy (meth) acryloyloxyethoxyethyl carbonate, t-butylperoxy ( (Meth) acryloyloxyisopropyl carbonate, t-amylperoxy (meth) acryloyloxyisopropyl carbonate, t-hexylperoxy (meth) acryloyloxyisopropyl carbonate,
1,1,3,3-tetramethylbutylperoxy (meth) acryloyloxyisopropyl carbonate, cumylperoxy (meth) acryloyloxyisopropyl carbonate, p-isopropylcumylperoxy (meth) acryloyloxyisopropyl carbonate, etc. be able to.

The compound represented by the general formula 2 is, for example, t-butylperoxyallylcarbonate, t-amylperoxyallylcarbonate or t-butylperoxyallylcarbonate.
Hexyl peroxyallyl carbonate, 1,1,3
3-tetramethylbutyl peroxyallyl carbonate, p-menthane peroxyallyl carbonate, cumyl peroxyallyl carbonate, t-butyl peroxy methallyl carbonate, t-amyl peroxy methallyl carbonate, t-hexyl peroxy methallyl carbonate, 1,1, 3,3-Tetramethylbutylperoxymethallyl carbonate, p-menthane peroxymethallyl carbonate, cumylperoxymethallyl carbonate, t-butylperoxyaryloxyethyl carbonate, t-amylperoxyallyloxyethyl carbonate, t-hexylperoxyari Roxyethyl carbonate, 1,1,3,3-tetramethylbutylperoxyallyloxyethyl carbonate, p-menthane peroxyallyloxye Le carbonate, cumyl peroxy allyloxyethyl carbonate, t- butyl peroxy meth Lilo carboxyethyl carbonate, t-amyl peroxy meth Lilo carboxyethyl carbonate, t-hexyl peroxy meth Lilo carboxyethyl carbonate, 1,1,
3,3-Tetramethylbutylperoxymetallyloxyethyl carbonate, p-menthane peroxymetallyloxyethyl carbonate, cumylperoxymetallyloxyethyl carbonate, t-butylperoxyallyloxyisopropyl carbonate, t-amylperoxyallyloxyisopropyl carbonate, t- Hexyl peroxyallyloxy isopropyl carbonate, t-butyl peroxy metalryloxy isopropyl carbonate, t
-Amyl peroxy metal ryloxy isopropyl carbonate, t-hexyl peroxy metal ryloxy isopropyl carbonate, etc. can be mentioned. Particularly, t-butylperoxy (meth) acryloyloxyethyl carbonate, t-butylperoxyallyl carbonate, t-
Butyl peroxymethallyl carbonate can be mentioned most preferably.

In the production method of the present invention, since the above-mentioned unsaturated monomer containing an organic peroxide-bonding group is used as a raw material component, in the reaction when preparing the reactive resin particles, the unsaturated monomer containing an organic peroxide-bonding group is used. The carbon-carbon double bond exhibiting radical polymerizability of the monomer participates in the reaction to form the polymer chain in the reactive resin particle, in which case the organic peroxide-bonding group does not participate in the reaction at all, Since the state is maintained, the amount of active oxygen contained in the reactive resin particles obtained can be designed before the reaction by adjusting the charged amount of the organic peroxide-bonding group-containing unsaturated monomer.

The amount of the unsaturated monomer containing an organic peroxide-bonding group charged is 0.
1 to 60% by weight, particularly 0.1 to 15% by weight is preferable.
If the amount is less than 0.1% by weight, the amount of organic peroxide-bonded groups in the obtained reactive resin particles is too small, and it is difficult to sufficiently exhibit the function as the reactive resin particles, which is not preferable. On the other hand, if it exceeds 60% by weight, the organic peroxide-bonding group introduced into the resulting reactive resin particles causes an undesirable reaction such as radical decomposition or extreme gelation during the reaction, which is not preferable.

Examples of the unsaturated monomer copolymerizable with the unsaturated monomer containing an organic peroxide-bonding group include (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid and esters thereof. Styrene,
Nucleus-substituted styrenes such as vinyltoluene, dimethylstyrene, and ethylstyrene, acrylonitrile, and vinyl acetate may be included. When (meth) acrylic acid esters are used here, the following general formula 3
Preferred examples thereof include esters represented by:

[0023]

[Chemical 3]

(Wherein R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² represents an organic group containing a saturated hydrocarbon group of 1 to 15, a hydroxyl group, an epoxy group or the like) The ester represented by the general formula 3 As the class, when R ¹² in the formula is a saturated hydrocarbon group, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
Examples thereof include lauryl (meth) acrylate. In the formula, when R ¹² is a hydroxyl group or an epoxy group, for example, 2-hydroxyethyl (meth) acrylate, (meth)
Examples thereof include hydroxypropyl acrylate and glycidyl (meth) acrylate.

The amount of the unsaturated monomer copolymerizable with the unsaturated monomer containing an organic peroxide-bonding group is 40 to 99.9% by weight, based on the total weight of the starting monomers. Especially 8
5 to 99.9% by weight is preferable.

When the internally cross-linked reactive resin particles are prepared, for example, a monomer having two or more radically polymerizable polymerizable double bonds in the molecule is mixed and polymerized. Can be crosslinked.

The monomer having two or more polymerizable double bonds in the molecule is, for example, a polymerizable unsaturated monocarboxylic acid ester of polyhydric alcohol, a polymerizable unsaturated alcohol ester of polybasic acid, or Examples thereof include aromatic compounds substituted with two or more vinyl groups, and specifically, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di ( (Meth) acrylate, pentaerythritol di (meth) acrylate Pentaerythritol tri (meth)
Acrylate, pentaerythritol tetra (meth) acrylate, glycerol di (meth) acrylate, glycerol allyloxy di (meth) acrylate, 1,
1,1-trishydroxymethylethane di (meth) acrylate, 1,1,1-trishydroxymethylethane tri (meth) acrylate, 1,1,1-trishydroxymethylpropane di (meth) acrylate, 1,1,
Examples thereof include 1-trishydroxymethylpropane tri (meth) acrylate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diallyl terephthalate, diallyl phthalate and divinylbenzene.

2 in the molecule in the case of the internal cross-linking
The amount of the monomer or the like having a polymerizable double bond capable of radical polymerization of not less than 0.1 is 0.1% by weight or more, particularly 0.1 to 50% by weight, based on the total weight of the raw material monomers. Is preferred. If it is less than 0.1% by weight, there is no difference in the physical properties of the reactive resin particles as compared with the case of uncrosslinked, which is not preferable.

In order to copolymerize the respective monomers as the raw materials by the emulsion polymerization method or the non-aqueous dispersion polymerization method, for example, thermal decomposition of the organic peroxide-bonding group of the unsaturated monomer containing the organic peroxide-bonding group is carried out. It is preferable to use a polymerization initiator that minimizes the polymerization. At this time, the polymerization reaction temperature is 20 ° C. or more lower than the 10-hour half-life temperature of the organic peroxide-bonding group of the unsaturated monomer containing an organic peroxide-bonding group to be used, particularly 30 ° C. or more lower temperature, and further 40 ° C. It is preferable that the temperature is lower than the above, and it is preferable to select a polymerization initiator or the like that can be polymerized at such a polymerization reaction temperature. When the polymerization reaction temperature is higher than the above temperature, the amount of the organic peroxide-bonding group introduced into the reactive resin particles to be obtained is decreased, and in addition, there is a problem due to the radical initiation ability of the organic peroxide-bonding group-containing monomer. Turbid polymerization occurs and the yield of the reactive resin particles themselves decreases, which is not preferable. The polymerization time is preferably 1 to 24 hours.

Examples of the polymerization initiator capable of polymerization at a relatively low temperature and the polymerization initiator system include inorganic polymerization initiators such as ammonium persulfate, potassium persulfate, sodium persulfate, persulfuric acid and hydrogen peroxide. Initiation of polymerization by combining these inorganic polymerization initiators with ferrous sulfate such as ferrous sulfate, ferrous chloride, ferrous acetate, or reducing agents such as acidic sodium sulfite, sodium thiosulfate, Rongalit Agent system; 2,2'-azobisisobutyronitrile, 2,
2'-azobis-2,4-dimethylvaleronitrile,
4,4'-azobis-4-cyanovaleric acid, 1-azobis-1-cyclohexanecarbonitrile, dimethyl-2,
Azo compounds such as 2'-azobisisobutyrate; t-butyl hydroperoxide, cumene hydroperoxide,
Diisopropylbenzene hydroperoxide, acetyl peroxide, lauroyl peroxide, 3,5,5-
Trimethylhexanoyl peroxide, succinic acid peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-toluyl peroxide, dicumyl peroxide, di-t-butyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, 1,1-bis (t- Butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy)-
Organic peroxides such as 3,3,5-trimethylcyclohexane; these organic peroxides and dimethylaniline, sulfuric acid first
A system of polymerization initiators in combination with iron, ferrous chloride such as ferrous chloride and ferrous acetate, or a reducing agent such as acidic sodium sulfite, sodium thiosulfate and Rongalit; isobutyryl peroxide, diisopropylperoxy Examples thereof include low-temperature decomposable organic peroxides such as dicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propylperoxydicarbonate, t-butylperoxyneodecanate and cumylperoxyneodecanate. it can. Especially in the case of emulsion polymerization, inorganic polymerization initiators such as ammonium persulfate, potassium persulfate, sodium persulfate, persulfuric acid and hydrogen peroxide, and ferrous sulfate, ferrous chloride, ferrous acetate, etc. A system of polymerization initiators in combination with a reducing agent such as ferrous iron salt, acidic sodium sulfite, sodium thiosulfate and Rongalit; hydroperoxides such as t-butyl hydroperoxide, cumene hydroperoxide and diisopropylbenzene hydroperoxide; A polymerization initiator system in which a ferrous salt such as ferrous sulfate, ferrous chloride, ferrous acetate, etc., and a reducing agent such as dimethylaniline, sodium acid sulfite, sodium thiosulfate, Rongalit, etc., are preferably used. Can be mentioned. In the non-aqueous dispersion polymerization method, 2,2'-azobis-2,4-dimethylvaleronitrile, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, acetyl peroxide, which are low-temperature decomposable azo compounds, Lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, succinic acid peroxide, benzoyl peroxide,
2,4-dichlorobenzoyl peroxide, m-toluyl peroxide, dicumyl peroxide, di-t-butyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t -Butylperoxy) -3,3,5-trimethylcyclohexane and other organic peroxides, ferrous sulfate, ferrous chloride, ferrous acetate and other ferrous salts, dimethylaniline, sodium acid sulfite, thiol A system of polymerization initiators in combination with a reducing agent such as sodium sulfate and Rongalit; isobutyryl peroxide, diisopropyl peroxydicarbonate,
Preferable examples include di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, t-butyl peroxyneodecanate and cumylperoxyneodecanate.

The amount of the polymerization initiator used is preferably 0.001 to 20 parts by weight with respect to 100 parts by weight of all the monomers as raw materials.

Further, in order to adjust the particle size of the reactive resin particles to an average particle size of 0.01 to 100 μm within the above range, for example, the type of surfactant, dispersion stabilizer and polymer surfactant to be used, It can be carried out by appropriately selecting the synthesis conditions such as the amount used, the dispersion medium, the type of the monomer, the system of the polymerization initiator, the dropping rate and the polymerization temperature.

To use the reactive resin particles of the present invention,
For example, it is possible to apply an emulsion-polymerized water or non-aqueous solvent dispersion as it is to an aqueous or organic solvent-based composition, and further after the solvent conversion or solvent removal step, aqueous or organic solvent-based composition. It is also possible to apply to non-solvent type compositions, such as paints, inks, adhesives, polymer modifiers,
It can be used in the fields of medical care, medical materials, cosmetics, fragrances, polymer flocculants, molding materials and the like.

[0034]

INDUSTRIAL APPLICABILITY The reactive resin particles of the present invention are capable of mutual reaction between particles or reaction with an external substrate due to the function of the contained organic peroxide-bonding group, namely hydrogen abstraction reaction and radical initiation ability. It is also possible to newly polymerize the monomer inside the particles. Therefore, it can be widely used for paints, inks, adhesives, polymer modifiers, medical care, pharmaceuticals, cosmetics, fragrances, molding materials and the like. Further, in the production method of the present invention, since an organic peroxide-bonded group-containing unsaturated monomer is used, the amount of active oxygen contained in the reactive resin particles obtained can be adjusted within a desired range by adjusting the charged amount. Can be designed.

[0035]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

[0036]

Example 1 Deionized water 830 was placed in a reaction vessel equipped with a stirrer, a cooler, a temperature control device, a nitrogen introducing pipe and a dropping funnel.
Parts by weight, 4.5 parts by weight of sodium dioctylsulfosuccinate, 0.7 parts by weight of Rongalit, 3.5 parts by weight of trisodium phosphate dodecahydrate, 0.3 parts by weight of sodium tetraethylenediaminetetraacetate, and then nitrogen. The mixture was stirred while being introduced, the temperature was raised, and the temperature was kept at 40 ° C. Then, an aqueous solution prepared by dissolving 0.2 part by weight of ferrous sulfate heptahydrate in 44 parts by weight of deionized water and 0.5 parts of t-butyl hydroperoxide.
After charging an aqueous solution in which 44 parts by weight of deionized water was dissolved, 384.44 parts by weight of butyl acrylate and t-
A mixture of 8.76 parts by weight of butyl peroxymethacryloyloxyethyl carbonate and 43.80 parts by weight of 1,4-butanediol dimethacrylate was added dropwise over 3 hours. After the dropping of the monomer mixture was completed, the temperature was raised to 60 ° C., and stirring was continued for 2 hours to complete the reaction. The heating residue of the resin particle-dispersed aqueous solution thus obtained, the average particle size of the resin particles, the amount of active oxygen in the resin particles, and the residual rate with respect to the charged amount were measured according to the following methods. The results are shown in Table 1.

Method for measuring active oxygen (1) Phase conversion of resin particles into organic solvent dispersion system: The obtained resin particle-dispersed aqueous solution was charged into a separatory funnel, and then the same weight of methyl as the resin particle-dispersed aqueous solution was charged. 6/4 (weight ratio) of isobutyl ketone and isopropyl alcohol
The mixed solvent was added, and the mixture was shaken vigorously and left standing for 3 hours. As a result, the resin particles were phase-transformed from the aqueous dispersion system to the organic solvent dispersion system, and thus the organic phase was separated from the aqueous phase to obtain an organic solvent dispersion solution of the resin particles. The proportion of resin particles in the dispersion solution was determined by the heating residue.

(2) Method for measuring the amount of active oxygen Regarding the organic solvent dispersion solution of the resin particles obtained in (1), 1,4-dioxane and 1 part of an acetic acid solution of 0.0002% ferric chloride hexahydrate were used. It was determined by performing iodine reduction titration using a mixed solvent of 1/1 (weight ratio) as a reaction solvent and crystalline sodium iodide as a source of iodide ions. The amount of active oxygen per resin particle was converted from the obtained amount of active oxygen and the value of the heating residue obtained in (1). Further, by comparing the amount of active oxygen calculated from the charged amount of the monomer with the measured value, the residual ratio of the active oxygen amount of the charged unsaturated monomer containing an organic peroxide-bonding group was determined.

[0039]

Examples 2 to 5, Comparative Examples 1 and 2 Nitrogen was introduced after the initial charge shown in Table 1 was charged into a reaction vessel equipped with a stirrer, a cooler, a temperature controller, a nitrogen introducing pipe, and a dropping funnel. While stirring, the temperature was raised and the temperature was maintained at 50 ° C. Then, an aqueous solution of the initial polymerization initiator shown in Table 1 and 1/10 weight of the monomer mixture were charged, and it was confirmed that a polymerization reaction had occurred. Then, the rest of the monomer mixture was added dropwise over 3 hours. Additional catalysts shown in Table 1 were sequentially added every 30 minutes from the time when the dropping of the monomer mixture was started. Furthermore, 50
The reaction was completed by continuing stirring at ℃ for 3 hours. Each physical property of the resin particle-dispersed aqueous solution thus obtained was measured in the same manner as in Example 1. The results are shown in Table 1.

[0040]

[Table 1]

As shown in Table 1, in the examples of the present invention,
The polymerization of the monomers used as raw materials is almost complete,
Further, it can be seen that 90% or more of the active oxygen amount of the used organic peroxide-bonded group-containing unsaturated monomer remains. Further, in the examples of the present invention, since a specific organic peroxide-bonding group-containing unsaturated monomer is used as a raw material component, the calculated value of the active oxygen amount (%) converted from the charged amount shown in Table 1 , And the measured values are almost the same. Therefore, the amount of active oxygen in the reactive resin particles can be designed to a desired content.

Claims (3)

[Claims] 1. The amount of active oxygen in the resin particles is 0.005.
Reactive resin particles having an organic peroxide-bonding group in the resin particles so as to be 4.0% and having an average particle size of 0.01 to 100 μm. 2. The reactive resin particle according to claim 1, wherein the reactive resin particle is internally crosslinked. 3. A method for producing the reactive resin particles according to claim 1, wherein an unsaturated monomer containing an organic peroxide bond group and an unsaturated monomer copolymerizable therewith are used. A method for producing reactive resin particles, which comprises polymerizing by an emulsion polymerization method or a non-aqueous dispersion polymerization method.