JP6268513B2 - Method for producing crosslinked resin particles - Google Patents

Description

The present invention relates to a method for producing crosslinked resin particles capable of uniformly controlling the molecular weight and particle size of a resin and capable of producing resin particles having excellent solvent resistance and mechanical properties.

Organic resin particles are used in toners for electrophotography, matting, colorants and the like by utilizing flexibility, adhesion, and processability, which are characteristics of polymers.
However, for example, in the field of bonding materials for electronic parts, the organic resin particles have insufficient heat resistance, and there is a problem that they are melted and deformed when mixed with other materials or in a heating process. In addition, the solvent resistance is inferior to that of inorganic fine particles.

On the other hand, in order to achieve excellent properties of the inorganic material and the organic material at the same time, a composite material of both is used. However, the compatibility between the inorganic material and the organic material is generally not sufficient.
Moreover, the method of improving heat resistance and solvent resistance is performed by bridge | crosslinking an organic monomer.
For example, in Patent Document 1 and Patent Document 2, a crosslinked resin particle is produced by adding a radical polymerization catalyst to an acrylic monomer, a styrene monomer or the like and polymerizing it in a medium containing water as a main component. A polymerization method (1) or a dispersion polymerization method (2) in which resin particles are produced by adding a radical polymerization catalyst to an acrylic monomer, a styrene monomer or the like and polymerizing in a medium in which the monomer is dissolved but the polymer is not dissolved. ) Is described.
However, the crosslinked resin particles formed in the production method (1) are not uniform in molecular weight or particle diameter, or the crosslinking is not uniform, so that sufficient heat resistance and solvent resistance cannot be obtained. There was a problem. In addition, the crosslinked resin particles formed in the production method (2) have a uniform particle diameter, but because of simple radical polymerization, the molecular weight is not uniform. When a crosslinkable monomer is used, There was a problem that the particles could not be combined to obtain desired spherical fine particles.

JP 2009-029951 A JP 2006-335977 A

An object of the present invention is to provide a method for producing crosslinked resin particles capable of uniformly controlling the molecular weight and particle diameter of a resin and capable of producing resin particles having excellent solvent resistance and mechanical properties. And

The present invention performs living polymerization using a crosslinkable allene monomer having two or more allenyl groups per molecule and crosslinks a resin obtained by living polymerization using the crosslinkable allene monomer. the crosslinking Allen monomers are Jiarenmonoma over, the di Allen monomer represented by the following formula (1), in the manufacturing method of the crosslinked resin particle having a structure represented by the following formula (2) or the following formula (3) is there.
In formulas (1) to (3), R ¹ represents any linking group represented by the following formula (13).
The present invention is described in detail below.

As a result of intensive studies, the present inventors have uniformly controlled the molecular weight and particle diameter of the resin by conducting living polymerization using an allene monomer and producing crosslinked resin particles by crosslinking the resin. In addition, the inventors have found that resin particles having excellent solvent resistance and mechanical properties can be produced, and have completed the present invention.

The manufacturing method of the crosslinked resin particle of this invention has the process of performing living polymerization using an allene monomer, and bridge | crosslinking resin.
The living polymerization and the crosslinking of the resin may be performed simultaneously, or after the step of performing the living polymerization, a step of crosslinking the resin may be performed.
In the present invention, it is preferable to perform living polymerization using a crosslinkable allene monomer having two or more allenyl groups per molecule and to crosslink the resin.

The living polymerization refers to polymerization in which a molecular chain grows without the polymerization reaction starting from an initiator being hindered by a side reaction such as a termination reaction or a chain transfer reaction.
In particular, in the present invention, a method in which the living polymerization is performed by dispersion polymerization is preferable.
In the present invention, by using such living polymerization, a polymer having a uniform molecular weight can be obtained if the polymerization reaction starts simultaneously. For example, when precipitation polymerization is used, the timing at which particle nuclei are generated is aligned. Therefore, it is possible to obtain crosslinked resin particles having a uniform particle diameter composed of a polymer chain having a regulated molecular weight and primary structure.

The living polymerization is not particularly limited, and for example, living anionic polymerization, living radical polymerization, living cation polymerization, living coordination polymerization and the like can be employed.
Of these, living coordination polymerization is preferred.

As the initiator used in the living polymerization, for example, various transition metal catalysts including a π-allyl nickel catalyst can be used.
The π-allyl nickel catalyst is composed of allyl compounds such as allyl halide and allyl acetate, organic nickel such as bis (1,5-cyclooctadiene) nickel (hereinafter referred to as Ni (COD) ₂ ), triphenylphosphine. And phosphine such as tributylphosphine, triphenoxyphosphine, triethoxyphosphine, and the like.

In the living polymerization, a dispersion stabilizer may be used. Examples of the dispersion stabilizer used include polyvinyl pyrrolidone, polyvinyl alcohol, methyl cellulose, ethyl cellulose, poly (meth) acrylic acid, poly (meth) acrylic acid ester, and polyethylene glycol.

The polymerization solvent used in the living polymerization is not particularly limited. For example, in addition to nonpolar solvents such as hexane, cyclohexane, octane, toluene, xylene, water, methanol, ethanol, propanol, butanol, acetone, methyl ethyl ketone, methyl isobutyl. High polar solvents such as ketone, tetrahydrofuran, dioxane, N, N-dimethylformamide can be used. These solvents may be used alone or in combination of two or more. Among these, it is preferable to use water, methanol, and ethanol in an appropriate mixture.
The polymerization temperature is preferably 0 to 90 ° C. from the viewpoint of the reaction rate.

Specific examples of the living polymerization include a method in which a solvent and a crosslinkable allene monomer are added to a π-allyl nickel catalyst prepared in advance in a nitrogen-substituted polymerization vessel and stirred for several hours at room temperature.

The crosslinkable allene monomer has two or more allenyl groups per molecule. Thus, by having two or more allenyl groups per molecule, the crosslinking density of the particle surface is increased with a small amount of introduction, and the resulting crosslinked resin particles have a high degree of crosslinking and are polymerized through living polymerization. In addition, a polymer having a uniform molecular weight can be obtained. Moreover, it becomes possible to form bridge | crosslinking uniformly by superposing | polymerizing through living polymerization.
The number of allenyl groups is not particularly limited as long as it is 2 or more per molecule, but those having 2 to 4 per molecule are preferable.
Examples of the crosslinkable allene monomer include a dialene monomer represented by the following formulas (1) to (3), a trialene monomer represented by the following formulas (4) to (7), and the following formulas (8) to (12). And the tetraarene monomer shown. Among these, crosslinkable allene monomers represented by the following formulas (3), (7), and (12) are more preferable because the reactivity of the monomers is good.

In formulas (1) to (3), R ¹ represents any linking group represented by the following formula (13), and in formulas (4) to (7), R ² represents any of the following formula (14). In the formulas (8) to (12), R ³ represents any one of the linking groups represented by the following formula (15).

Examples of the crosslinkable allene monomer having two or more allenyl groups per molecule include 1,4-dialenoxybenzene, 1,4-dialenylbenzene, bisphenol A dialenyl ether (various bisphenol compounds) ), 1,4-butanediol diarenyl ether, dihydroxynaphthalenediallenyl ether, 1-allenoxy-4-allenylbenzene, and other diols and polyfunctional alcohols (for example, polyurethanes and polycarbonates). Raw materials for synthesis) and the like.
1,4-dialenoxybenzene, 1,4-diarenylbenzene because the reactivity of the monomer is good and particles with little aggregation are obtained and the hardness of the obtained particles is hard. Bisphenol A dialenyl ether, 1,4-butanediol diarenyl ether, dihydroxynaphthalenediallenyl ether, and 1-allenoxy-4-allenylbenzene are preferred.

The allenyl group in the crosslinkable allene monomer is an unsaturated group in which two double bonds are continuous between three carbons. The other part bonded to the allenyl group may be anything, but in order to increase the reactivity of the allenyl group to the polymerization catalyst, the allenyl group and the other part are preferably bonded with oxygen.

The preferable lower limit of the addition amount of the crosslinkable allene monomer is 5 mol% with respect to all the allene monomers. When the addition amount of the crosslinkable allene monomer is less than 5 mol%, it may be difficult to form a crosslink.
The more preferable lower limit of the addition amount of the crosslinkable allene monomer is 8 mol%.
Moreover, a preferable upper limit is 50 mol%. If it is 50 mol% or less, fine particles with little aggregation can be obtained in a high yield. A more preferred upper limit is 40 mol%.

In the present invention, other allene monomers may be added as necessary in the step of performing the living polymerization. Specific examples include a hydrocarbon-based allene monomer, a functional group-containing allene monomer, an allene monomer having an unsaturated bond other than a carbon-carbon bond, and an allene monomer having a photodimerizable functional group.
If an allene monomer having an unsaturated bond other than the carbon-carbon bond or an allene monomer having a functional group to be photodimerized is used, good crosslinked resin particles can be obtained through a crosslinking step described later.
In particular, by using an allene monomer having an unsaturated bond other than a carbon-carbon bond and an allene monomer having a functional group to be photodimerized in combination with the above-mentioned crosslinkable allene monomer, Further, crosslinked resin particles having a higher crosslinking density can be obtained.

Examples of the hydrocarbon-based allene monomer include phenoxyallene, allene (1,2-propadiene), methylallene, ethylallene, propylallene, butylallene, isopropylallene, hexylallene, phenylallene, benzylallene, dimethylallene, and diethyl. Examples include allene, dihexyl allene, diphenyl allene, substituted alkyl butadiene ether, arenic acid ester, polyoxyethylene allenyl alkyl ether, and the like. Examples of the phenoxyallene include phenoxyallene, (4-tert-butylphenoxy) allene, (4-nitrophenoxy) allene, and (4-acetylphenoxy) allene.

Examples of the functional group-containing allene monomer include allenic acid, carboxymethyl allene, 2-carboxyethyl allene, dicarboxylmethyl allene, 2,2-dicarboxyethyl allene, aminomethyl allene, 2-aminoethyl allene, and cyanomethyl. Allene, 2-cyanoethyl allene, hydroxymethyl allene, hydroxyethyl allene and the like can be mentioned.

As the allene monomer having an unsaturated bond other than the carbon-carbon bond, an allene monomer having an alkoxy group is preferably used.
Examples of the allene monomer having an alkoxy group include naphthoxyallene, methoxyallene, phenoxyallene, and the like.

Examples of the allene monomer having a functional group to be photodimerized include coumarin group-modified allene, anthracene group-modified allene, cinnamate ester group-modified allene, maleimide modification, and thymine modification. Specific examples include 7-arenyloxy-4-methylcoumarin.

As a manufacturing method of the crosslinked resin particle of the present invention, after performing a living polymerization using a crosslinkable allene monomer having two or more allenyl groups per molecule or performing a living polymerization, You may perform the process of bridge | crosslinking resin.
By performing such a crosslinking step, crosslinked resin particles having a uniform particle diameter and molecular weight and excellent heat resistance and solvent resistance can be obtained without aggregation of the particles.

As the crosslinking step, for example, when an allene monomer having an unsaturated bond other than a carbon-carbon bond is used as the other allene monomer, a method of treating with a strong acid can be used.
Moreover, when using the allene monomer which has a functional group photodimerized as said other allene monomer, the method of irradiating light can be used.

Examples of the strong acid include sulfuric acid, phosphoric acid, hydrogen fluoride, boron trifluoride, hexafluorophosphoric acid, methanesulfonic acid and trifluoromethanesulfonic acid.
Further, a material that generates the strong acid by light or heat may be used.
The strong acid may be added all at once or in divided portions.

The addition amount of the strong acid in the crosslinking step is preferably 1 to 20 parts by weight with respect to 100 parts by weight of the allene monomer having an unsaturated bond other than the carbon-carbon bond. By setting it within the above range, crosslinking can be efficiently performed without damaging the particles. More preferably, it is 3 to 10 parts by weight with respect to 100 parts by weight of the allene monomer having an unsaturated bond other than the carbon-carbon bond.

Examples of the method of irradiating with light include electromagnetic wave irradiation, infrared irradiation, ultraviolet irradiation, and the like, preferably ultraviolet irradiation. The ultraviolet irradiation can be performed by using a UV lamp or the like.

The above-mentioned crosslinked resin particles have a preferable lower limit of the average particle diameter of 0.01 μm and a preferable upper limit of 10 μm. When the average particle size is less than 0.01 μm, the solvent resistance may be lowered. When the average particle diameter exceeds 10 μm, aggregation may easily occur. A more preferable lower limit of the average particle diameter is 0.05 μm, and a more preferable upper limit is 5 μm.
In addition, the average particle diameter of the said crosslinked resin particle means the average value of the diameter obtained by observing the 50 crosslinked resin particles selected at random using an optical microscope or an electron microscope.

The molecular weight distribution (= weight average molecular weight / number average molecular weight) of the polymer constituting the crosslinked resin particles obtained by the method for producing crosslinked resin particles of the present invention is 2.0 or less.
When the molecular weight distribution is larger than 2.0, the particle size distribution is widened, and when the block copolymer is synthesized using two or more kinds of monomers, the variation in the composition ratio of each block increases. Preferably it is 1.0-1.5.

The crosslinked resin particles obtained in the present invention can be suitably used as electronic materials such as spacers, surface modifiers, matting agents, paints, toners, and other conductive particles for anisotropic conductive films.

ADVANTAGE OF THE INVENTION According to this invention, the molecular weight and particle diameter of resin can be controlled uniformly, and the manufacturing method of the crosslinked resin particle which can manufacture the resin particle which is excellent in solvent resistance and a dynamic characteristic can be provided.

2 is a photomicrograph of the crosslinked resin particles obtained in Example 1. 2 is a photomicrograph after a solvent resistance test of the crosslinked resin particles obtained in Example 1. FIG. 2 is a photomicrograph of the crosslinked resin particles obtained in Example 2. 2 is a photomicrograph after a solvent resistance test of the crosslinked resin particles obtained in Example 2. FIG. 6 is a photomicrograph of the crosslinked resin particles obtained in Reference Example 8. It is a microscope picture after the solvent resistance test of the crosslinked resin particle obtained in Reference Example 8. 2 is a photomicrograph of resin particles obtained in Comparative Example 1. 2 is a photomicrograph after a solvent resistance test of resin particles obtained in Comparative Example 1.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

Example 1
0.00105 g of poly (N-vinylpyrrolidone) (Mw = 40,000) was added as a dispersion stabilizer to a rubbed test tube fitted with a three-way cock, and nitrogen substitution was performed. 0.15 mL of toluene solution (0.010 M) of bis (cyclooctadiene) nickel, 22.5 μL of toluene solution of allyl trifluoroacetate (1.0 M), and toluene solution of triphenylphosphine (1.0 M) Were sequentially added, and toluene was distilled off under reduced pressure. Here, 1.5 mL of dry ethanol was added as a polymerization medium to prepare a π-allyl nickel catalyst solution. 0.198 g (1.5 mmol) of phenoxyallene was added to the catalyst solution thus prepared, and polymerization was carried out by stirring at room temperature for 24 hours. Next, as a crosslinkable allene monomer having two or more allenyl groups per molecule, 0.0279 g (0.15 mmol) of 1,4-dialenoxybenzene dissolved in 1.5 mL of dry ethanol is added. Then, copolymerization was performed and the reaction was performed for about 24 hours to obtain crosslinked resin particles.

(Example 2)
Crosslinked resin particles were obtained in the same manner as in Example 1 except that the amount of 1,4-dialenoxybenzene added was changed to 0.0558 g (0.30 mmol).

(Example 3)
Crosslinked resin particles were obtained in the same manner as in Example 1 except that the amount of 1,4-dialenoxybenzene added was changed to 0.0837 g (0.45 mmol).

Example 4
Crosslinked resin particles were obtained in the same manner as in Example 1 except that the amount of 1,4-dialenoxybenzene added was changed to 0.1395 g (0.75 mmol).

(Comparative Example 1)
Crosslinked resin particles were obtained in the same manner as in Example 1 except that 1,4-dialenoxybenzene was not added.

(Example 5)
0.00105 g of poly (N-vinylpyrrolidone) (Mw = 40,000) was added as a dispersion stabilizer to a rubbed test tube fitted with a three-way cock, and nitrogen substitution was performed. To this, 0.15 mL of a toluene solution (0.01 M) of bis (cyclooctadiene) nickel, 22.5 μL of a toluene solution of allyl trifluoroacetate (1.0 M), and a toluene solution of triphenylphosphine (1.0 M) Were sequentially added, and toluene was distilled off under reduced pressure. Here, 0.5 mL of dry ethanol was added as a polymerization medium to prepare a π-allyl nickel catalyst solution. To the catalyst solution thus prepared, 0.198 g (1.5 mmol) of phenoxyallene and 0.0279 g (0.15 mmol) of 1,4-dialenoxybenzene were dissolved in 1.0 mL of dry ethanol. In one step, the copolymerization was carried out by stirring for 24 hours at room temperature to obtain crosslinked resin particles.

(Example 6)
Crosslinked resin particles were obtained in the same manner as in Example 5 except that the amount of 1,4-dialenoxybenzene added was changed to 0.0558 g (0.30 mmol).

(Example 7)
Crosslinked resin particles were obtained in the same manner as in Example 5 except that the amount of 1,4-dialenoxybenzene added was changed to 0.0837 g (0.45 mmol).

( Reference Example 8)
To the π-allylnickel catalyst solution obtained in Example 1, 0.273 g (1.5 mmol) of naphthoxyallene and 1.5 mL of dry ethanol were added, and polymerization was performed for 24 hours.
Thereafter, BF ₃ (boron trifluoride) was added and stirred for 24 hours to obtain crosslinked resin particles.

( Reference Example 9)
0.00105 g of a polyethylene glycol-polypropylene glycol-polyethylene glycol triblock copolymer was added as a dispersion stabilizer to a rubbed test tube fitted with a three-way cock, followed by nitrogen substitution. To this, 0.15 mL of a toluene solution (0.01 M) of bis (cyclooctadiene) nickel, 22.5 μL of a toluene solution of allyl trifluoroacetate (1.0 M), and a toluene solution of triphenylphosphine (1.0 M) Were sequentially added, and toluene was distilled off under reduced pressure. Here, 1.5 mL of tetrahydrofuran was added as a polymerization medium to prepare a π-allyl nickel catalyst solution. To the catalyst solution thus prepared, 0.321 g (1.5 mmol) of 7-arenyloxy-4-methylcoumarin was added and polymerization was carried out by stirring at room temperature for 24 hours.
Thereafter, using a high pressure mercury lamp, ultraviolet rays having a wavelength of 310 nm were irradiated for 60 minutes to obtain crosslinked resin particles.

(Example 10)
Instead of 1,4-dialenoxybenzene, crosslinked resin particles were obtained in the same manner as in Example 3 except that 0.0747 g (0.45 mmol) of 1,4-butanediol diarenyl ether was used.

(Example 11)
Crosslinked resin particles were obtained in the same manner as in Example 3 except that 0.0693 g (0.45 mmol) of 1,4-bisallenylbenzene was used in place of 1,4-dialenoxybenzene.

(Example 12)
Crosslinked resin particles were obtained in the same manner as in Example 3 except that 0.0765 g (0.45 mmol) of 1-allenoxy-4-allenylbenzene was used instead of 1,4-dialenoxybenzene.

(Comparative Example 2)
To the separable flask, 1.0 g of poly (N-vinylpyrrolidone) (Mw = 40,000) was added as a dispersion stabilizer, and 100 g of ethanol was added thereto to prepare a dispersion solution. By adding 0.15 g of azobisisobutyronitrile, 7.0 g of styrene, and 3.0 g of divinylbenzene as a crosslinkable monomer, the mixture is heated to 70 ° C. and stirred for 24 hours to carry out polymerization, whereby crosslinked resin particles are obtained. Got. The obtained crosslinked resin particles were massive aggregates.

(Comparative Example 3)
To the separable flask, 1.0 g of poly (N-vinylpyrrolidone) (Mw = 40,000) was added as a dispersion stabilizer, and 100 g of ethanol was added thereto to prepare a dispersion solution. To this, 0.15 g of azobisisobutyronitrile and 10.0 g of methyl methacrylate were added, the temperature was raised to 70 ° C., and the mixture was stirred for 24 hours for polymerization to obtain resin particles.

(Comparative Example 4)
To the separable flask, 1.0 g of polyvinyl alcohol was added as a dispersion stabilizer, and 100 g of ion-exchanged water was added thereto to prepare a dispersion solution. To this was added 0.15 g of azobisisobutyronitrile, 7.0 g of styrene, and 3.0 g of divinylbenzene as a crosslinkable monomer, emulsified and dispersed using a homogenizer, then heated to 70 ° C. and stirred for 24 hours. Then, cross-linked resin particles were obtained by performing polymerization.

(Comparative Example 5)
To the separable flask, 1.0 g of polyvinyl alcohol was added as a dispersion stabilizer, and 100 g of ion-exchanged water was added thereto to prepare a dispersion solution. To this was added 0.15 g of azobisisobutyronitrile, 7.0 g of styrene, and 3.0 g of 1,4-dialenoxybenzene as a crosslinkable monomer, emulsified and dispersed using a homogenizer, and then raised to 70 ° C. The polymerization was carried out by warming and stirring for 24 hours. However, the polymerization reaction did not proceed and was stopped during the reaction.

(Evaluation)
(1) Measurement of average particle diameter The obtained crosslinked resin particles were dried in a vacuum dryer at 50 ° C. for 24 hours to obtain crosslinked resin particle powders.
Arbitrary 50 particles of the obtained powder were observed with a scanning electron microscope, and the number average particle diameter (Dn) measured with a caliper was measured. Moreover, the weight average particle diameter (Dw) was measured by the following formula.
Dw = Σ (particle diameter of each particle × volume of each particle) / Σ (volume of each particle)
And ratio (Dw / Dn) of the weight average particle diameter (Dw) and the number average particle diameter (Dn) was calculated.

(2) Solvent resistance The obtained crosslinked resin particles were dried in a vacuum dryer at 50 ° C. for 24 hours to obtain crosslinked resin particle powders. The obtained powder was collected in a 0.05 g glass petri dish, 1.0 g of toluene was added, and the mixture was allowed to stand for 24 hours, and then dried at 50 ° C. for 24 hours in a vacuum dryer, to obtain a crosslinked resin particle powder (toluene). After). About the obtained crosslinked resin particle powder (after toluene), the number average particle diameter was measured by the same evaluation method as described above, and was defined as Dnx. And Dnx / Dn was calculated and evaluated according to the following criteria.
Dnx / Dn is not less than 0.00 and less than 0.80 ×
Dnx / Dn is 0.80 or more and less than 0.90 ○
Dnx / Dn is 0.90 or more and less than 1.10.
Dnx / Dn is 1.10 or more and less than 1.20 ○
Dnx / Dn is 1.20 or more ×

(3) Strength The obtained crosslinked resin particles were dried in a vacuum dryer at 50 ° C. for 24 hours to obtain crosslinked resin particle powder. 0.1 g of the obtained powder, 20 g of zirconia balls having a diameter of 1 mm (“YTZ-10” manufactured by ASONE) and 10 g of toluene were placed in a 50 mL beaker (inner diameter 5.5 cm), and a three-one motor stirrer (HEIDON) The product was stirred at 25 ° C. for 10 minutes at 500 rpm. Next, the crosslinked resin particles after stirring were filtered, washed and dried, and observed with a scanning electron microscope at a magnification of 5000 times.
From the obtained microscopic image, the shortest diameter and the longest diameter of the particles were measured using calipers, and the sphericity A1 was evaluated. The same operation was performed on arbitrary 20 particles, and the average sphericity An of A1 to A20 was calculated.
Sphericality = Smallest particle diameter / Longest particle diameter An is less than 0.85 ×
An is 0.85 or more ○

In addition, the microscope picture of the resin particle obtained in Example 1 was shown in FIG. 1, and the microscope picture after a solvent resistance test was shown in FIG. In addition, the micrographs of the resin particles obtained in Example 2, Reference Example 8 and Comparative Example 1 and the micrographs after the solvent resistance test are also shown in FIGS.

ADVANTAGE OF THE INVENTION According to this invention, the molecular weight and particle diameter of resin can be controlled uniformly, and the manufacturing method of the crosslinked resin particle which can manufacture the resin particle which is excellent in solvent resistance and a dynamic characteristic can be provided.

Claims (6)

Living polymerization is performed using a crosslinkable allene monomer having two or more allenyl groups per molecule, and the resin obtained by living polymerization using the crosslinkable allene monomer is crosslinked.
The crosslinking Allen monomers are Jiarenmonoma over,
The said dialene monomer has a structure represented by following formula (1), following formula (2), or following formula (3), The manufacturing method of the crosslinked resin particle characterized by the above-mentioned.
In formulas (1) to (3), R ¹ represents any linking group represented by the following formula (13).
The method for producing crosslinked resin particles according to claim 1, wherein the addition amount of the crosslinkable allene monomer is 5 to 50 mol% with respect to all the allene monomers. The method for producing crosslinked resin particles according to claim 1, wherein an allene monomer having an unsaturated bond other than a carbon-carbon bond is added as the allene monomer. 2. The method for producing crosslinked resin particles according to claim 1, wherein an allene monomer having a functional group to be photodimerized is added as the allene monomer. 4. The method for producing crosslinked resin particles according to claim 3, wherein the crosslinked resin particles are crosslinked by treatment with a strong acid. The method for producing crosslinked resin particles according to claim 4, wherein crosslinking is performed by irradiating light.