KR20200131825A - Hollow particle dispersion - Google Patents

Abstract

A hollow particle dispersion containing a shell formed of at least one or more layers, an acidic compound and an organic solvent, wherein at least one of the layers contains a nitrogen atom and a carbon atom, and the content of the acidic compound is the hollow particle And the total amount of the acidic compound is 0.01 to 70 parts by mass, and the content of the hollow particles is 0.01 to 30 parts by mass based on 100 parts by mass of the hollow particle dispersion.

Description

Hollow particle dispersion

The present invention relates to a hollow particle dispersion. According to the hollow particle dispersion of the present invention, a cured product having abrasion resistance and high transparency can be obtained by curing the curable resin composition having high dispersibility in the curable resin and containing the hollow particles.

Particles having pores therein are used as microcapsule particles by embedding various substances in the pores. In addition, particles having voids therein are also referred to as hollow particles, and are used as a light scattering material, a low reflection material, a heat insulating material, a low dielectric constant material, and the like. These materials are, for example, added to a thermosetting or thermoplastic resin and molded into a plate shape, or added to an ultraviolet curable resin to form a film, thereby being used as a light scattering film, a low reflection film, a heat insulating film, a low dielectric constant film, or the like.

However, when the hollow particles are added to the thermosetting or thermoplastic resin to be molded, or added to the curable resin composition and cured, there has been a problem that the mechanical strength of the molded product or the cured product, especially the scratch resistance of the surface, is lowered. Techniques for solving this problem are proposed in JP 2010-084017 A (Patent Document 1), JP 2010-084018 A (Patent Document 2), and JP 5411477 A (Patent Document 3). . In these patent documents, after surface-treating with an alkoxysilane, the hollow particle which surface-treated with a silane coupling agent which has a radical polymerizable group further is described.

Japanese Unexamined Patent Publication No. 2010-084017 Japanese Unexamined Patent Publication No. 2010-084018 Japanese Patent No. 5411477

However, also in the hollow particles of the above patent document, since the dispersibility in an organic solvent or a curable resin is low, a molded article or cured article having sufficient scratch resistance and transparency cannot be obtained.

As described above, according to the present invention, as a hollow particle dispersion containing a hollow particle having a shell formed of at least one or more layers, an acidic compound and an organic solvent,

At least one of the layers contains a nitrogen atom and a carbon atom,

Hollow particles in which the content of the acidic compound is 0.01 to 70 parts by mass with respect to 100 parts by mass of the total of the hollow particles and the acidic compound, and the content of the hollow particles is 0.01 to 30 parts by mass with respect to 100 parts by mass of the hollow particle dispersion A dispersion is provided.

According to the present invention, a hollow particle dispersion suitable for producing a molded article having sufficient scratch resistance can be provided.

According to the present invention, in the case of having any of the following aspects, a hollow particle dispersion suitable for producing a molded article having more sufficient scratch resistance can be provided.

(1) The acidic compound shows an acid value of 10 to 300 mgKOH/g.

(2) The hollow particle|grains show the average particle diameter of 30-120 nm, and the porosity of 10-70% is shown.

(3) The hollow particle satisfies the relationship of 0.01≦N/C≦0.2 in the abundance N of nitrogen atoms and the abundance C of carbon atoms in XPS measurement.

(4) The hollow particle satisfies the relationship of 0.001≦Si/C≦0.1 in the abundance ratio Si of silicon atoms and the abundance C of carbon atoms in XPS measurement.

(5) the ratio of the hollow particles, the absorbance (A1720) of the absorbance (A810) and 1720㎝ ^-1 in 810㎝ ^-1 in the infrared absorption spectrum obtained by measuring as ATR-FTIR (α) (the absorption ratio (α) : When A810/A1720) is calculated, it shows the absorbance ratio (α) of 0.015-0.50.

(6) The acidic compound is selected from inorganic acids, carboxylic acid compounds, alkyl ester compounds of acids, sulfonic acid compounds, phosphoric acid ester compounds, phosphonic acid compounds and phosphinic acid compounds.

(7) The organic solvent is selected from alcohol-based solvents, ketone-based solvents, ester-based solvents, glycol ether-based solvents, and glycol ester-based solvents.

(A) Hollow particle dispersion

The hollow particle dispersion contains at least hollow particles, an acidic compound, and an organic solvent for dispersing the hollow particles. The hollow particles may be contained in an amount of 0.01 to 30 parts by mass based on 100 parts by mass of the hollow particle dispersion.

The organic solvent is not particularly limited as long as the hollow particles are not dissolved, and both aqueous and oily media can be used. For example, alcohol-based solvents such as ethanol and isopropyl alcohol, hydrocarbon-based solvents such as toluene, xylene, and cyclohexane, ketone-based solvents such as methyl ethyl ketone and methyl isobutyl ketone, and esters such as ethyl acetate and butyl acetate Solvents, ether solvents such as diisopropyl ether, 1,4-dioxane, glycol solvents such as ethylene glycol and diethylene glycol, glycol ether solvents such as propylene glycol monomethyl ether, propylene glycol monobutyl ether, Glycol ester solvents such as ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, diglyme solvents such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, halogenated perchlorethylene, 1-bromopropane, etc. Solvent, dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, etc. are mentioned. Among them, alcohol-based solvents, ketone-based solvents, ester-based solvents, glycol ether-based solvents, and glycol ester-based solvents are preferred from the viewpoint of handling properties. Further, water or one or more different organic solvents may be added to the organic solvent as necessary.

The hollow particle dispersion contains an acidic compound as a dispersant. By including the acidic compound, the dispersibility of the hollow particles can be further improved. The acid groups constituting the acidic compound interact with the lone pair of nitrogen atoms contained in the hollow particles, thereby improving dispersibility in the organic solvent. As a result, it is possible to impart higher scratch resistance and higher transparency to a molded product or a cured product obtained by using the hollow particle dispersion. In addition, it is possible to improve the surface smoothness of a molded product or a cured product. The acidic compound can be selected from, for example, inorganic acids such as nitric acid, phosphoric acid, sulfuric acid and carbonic acid, or carboxylic acid compounds, alkyl ester compounds of inorganic acids, sulfonic acid compounds, phosphoric acid ester compounds, phosphonic acid compounds and phosphinic acid compounds. Among them, the acidic compound is preferably an alkyl ester compound of sulfuric acid, a sulfonic acid compound, a phosphoric acid ester compound, a phosphonic acid compound, and a phosphinic acid compound which can further improve the dispersibility of the hollow particles.

The acidic compound preferably exhibits an acid value of 10 to 300 mgKOH/g. When the acid value is less than 10 mgKOH/g, the improvement in the dispersibility of the hollow particles becomes insufficient, and the scratch resistance of the molded article obtained using the hollow particle dispersion may be insufficient. When it is larger than 300 mgKOH/g, the dispersibility of the hollow particles in an organic solvent may be lowered. Acid values are 10 mgKOH/g, 15 mgKOH/g, 20 mgKOH/g, 50 mgKOH/g, 100 mgKOH/g, 150 mgKOH/g, 200 mgKOH/g, 250 mgKOH/g and 300 mgKOH/g can be taken. The acid value is preferably 15 to 300 mgKOH/g, more preferably 20 to 250 mgKOH/g.

The content of the acidic compound is 0.01 to 70 parts by mass based on 100 parts by mass in total of the hollow particles and the acidic compound. When the content is less than 0.01 parts by mass, good dispersibility may not be obtained. When it is more than 70 parts by mass, the scratch resistance of the molded article obtained by using the hollow particle dispersion may be insufficient. The content may take 0.01 parts by mass, 0.1 parts by mass, 0.5 parts by mass, 1 part by mass, 2 parts by mass, 5 parts by mass, 10 parts by mass, 30 parts by mass, 50 parts by mass and 70 parts by mass. The content is preferably 1 to 50 parts by mass, more preferably 2 to 30 parts by mass.

In addition, the hollow particle dispersion may contain an arbitrary binder.

The binder is not particularly limited, and a known binder resin can be used as the binder. Examples of the binder resin include thermosetting resins, thermoplastic resins, and more specifically, fluorine resins, polyamide resins, acrylic resins, polyurethane resins, acrylic urethane resins, butyral resins, and the like. . These binder resins may be used alone or in combination of two or more. Further, the binder resin may be a single reactive monomer homopolymer or a copolymer of a plurality of monomers. Moreover, you may use a reactive monomer as a binder.

For example, as reactive monomers, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl ( Meth)acrylate, pentyl (meth)acrylate, (cyclo)hexyl (meth)acrylate, heptyl (meth)acrylate, (iso)octyl (meth)acrylate, nonyl (meth)acrylate, (iso)decyl (Meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, lauryl (meth)acrylate, tetradecyl (meth)acrylate, ( (Meth)acrylic acid such as iso)stearyl (meth)acrylate, phenoxyethylene glycol (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, and 2-ethylhexyl (meth)acrylate, and 1 to 25 carbon atoms Monofunctional reactive monomers such as esters of alcohols of

Trimethylolpropane tri(meth)acrylate, tripropylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, Pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropanetri(meth) )Acrylate, ditrimethylolpropanetetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, tripentaerythritol octa(meth)acrylate, tetrapentaerythritoldeca(meth)acrylate, isocyanate Nuulic acid tri(meth)acrylate, isocyanuric acid di(meth)acrylate, polyester tri(meth)acrylate, polyester di(meth)acrylate, bisphenol di(meth)acrylate, diglycerin tetra(meth) Acrylate, adamantyldi(meth)acrylate, isobornyldi(meth)acrylate, dicyclopentanedi(meth)acrylate, tricyclodecanedi(meth)acrylate, ditrimethylolpropanetetra(meth)acrylate Polyfunctional reactive monomers, such as a rate, are mentioned.

In addition, when using these reactive monomers, a polymerization initiator that initiates a curing reaction by ionizing radiation may be included in the hollow particle dispersion. As a polymerization initiator, for example, imidazole derivatives, bisimidazole derivatives, N-arylglycine derivatives, organic azide compounds, titanocenes, aluminate complexes, organic peroxides, N-alkoxypyridinium salts, thioxanthone derivatives And the like.

In addition, as the binder, for example, an inorganic binder such as a hydrolyzate of silicon alkoxide may be used. Silicon alkoxides include, for example, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 2- Hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3- Hydroxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, allyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldime Oxysilane, 3-methacryloxytrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyl Methyldimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl Triethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-(meth)acryloxypropyltrimethoxy Silane, 3-(meth)acryloxypropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane And diethyldiethoxysilane.

Further, the hollow particle dispersion may contain other additives such as a curing agent, a colorant, an antistatic agent, and a leveling agent.

The substrate to be coated of the hollow particle dispersion is not particularly limited, and a substrate according to the application may be used. Examples of the substrate to be coated include transparent substrates such as glass substrates and transparent resin substrates in optical applications.

(Hollow particles)

Hollow particles have a shell formed of at least one layer. The layer constituting the shell may be composed of one or two or more layers.

At least one of the layers constituting the shell contains a nitrogen atom and a carbon atom. In addition, it is preferable that at least one of the layers constituting the shell contains a vinyl resin. The vinyl-based resin is a resin containing a portion composed of a vinyl-based monomer. In particular, a vinyl resin composed of a vinyl monomer having no aromatic ring is preferable because it has high weather resistance and can suppress yellowing and the like over time. The entire shell may be made of a vinyl resin. The vinyl resin is preferably a polymer obtained by crosslinking a polymer of radical reactive monomers having at least one epoxy group or oxetane group with a crosslinkable monomer such as a polyamine compound.

The hollow particles preferably have a nitrogen atom abundance N and a carbon atom abundance C satisfying the relationship of 0.01≦N/C≦0.2 in the measurement by XPS (X-ray photoelectron spectroscopy). When N/C is less than 0.01, the crosslinking density becomes low, and the binder component of low molecular weight may easily penetrate into the hollow interior. In addition, it becomes difficult to interact with the acidic compound, and sufficient dispersibility may not be provided in some cases. When it exceeds 0.2, since the crosslinking density is too high, pinholes are liable to occur, and a low-molecular binder component may easily penetrate into the hollow interior. N/C can take 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1 and 0.2. N/C is more preferably 0.01 to 0.15, and even more preferably 0.02 to 0.1.

Further, at least one or more layers may be a layer containing a phosphorus atom and/or a sulfur atom. When these atoms are contained in at least one layer, the dispersibility of the hollow particles in the curable resin can be improved, or the physical strength of the hollow particles can be improved, thereby providing sufficient scratch resistance and transparency to the molded article. The presence of phosphorus atoms and/or sulfur atoms in at least one or more layers can be confirmed by fluorescence X-ray analysis or XPS. A phosphorus atom and/or a sulfur atom may be contained in at least one or more layers by using a monomer containing a phosphorus atom and/or a sulfur atom in the vinyl resin itself. In particular, it is preferable to make at least one layer contain a phosphorus atom and a sulfur atom by performing a surface treatment with a surface treatment agent containing a phosphorus atom and a sulfur atom described below. Moreover, the whole shell may be a layer containing a phosphorus atom and/or a sulfur atom, and only a part of the layer may contain a phosphorus atom and/or a sulfur atom. It is preferable that the content of a phosphorus atom or a sulfur atom is 0.2 to 5.00 mass%. When the content is less than 0.2% by mass, sufficient scratch resistance may not be imparted to a molded article containing hollow particles. If it is more than 5.00 mass%, the dispersibility of the hollow particles in the curable resin may decrease, or the hardness of the molded product may become too high, resulting in a decrease in scratch resistance. The content can take 0.2% by mass, 0.3% by mass, 0.5% by mass, 1.00% by mass, 2.00% by mass, 3.00% by mass, 4.00% by mass and 5.00% by mass. The content is more preferably 0.2 to 4.00 mass%, and still more preferably 0.3 to 3.00 mass%. Phosphorus atom and sulfur atom may contain only one atom or both atoms in at least one or more layers. When both atoms are contained, the content can be set to 0.2 to 10.0 mass%. The content can take 0.2% by mass, 0.5% by mass, 1.00% by mass, 3.00% by mass, 5.00% by mass, 7.00% by mass and 10.00% by mass.

In addition, hollow particles of non-ATR-FTIR (infrared spectroscopy ATR) Absorbance (A810) and the absorbance (A1720) at 1720㎝ ^-1 in 810㎝ ^-1 from the infrared absorption spectrum obtained by measuring the hollow particles by ( When α) (absorbance ratio (α): A810/A1720) is calculated, it is preferably a particle having an absorbance ratio (α) of 0.015 to 0.50. Absorbance (A810) is an absorbance corresponding to an absorption spectrum resulting from the out-of-plane variable angle vibration of vinyl group CH. Further, the absorbance A1720 is an absorbance corresponding to an absorption spectrum resulting from the C=O stretching vibration of a carbonyl group. The absorbance ratio (α) can be used as an index indicating the degree of the amount of radical reactive groups introduced in the hollow particles. Specifically, as the absorbance ratio (α) increases, there is a tendency that the radical reactive groups introduced into the particles increase. By introducing a radical reactive group into the particles, dispersibility in the curable resin and adhesion to the resin after curing are improved, and a molded article having high scratch resistance is easily obtained. When the absorbance ratio (α) is less than 0.015, the dispersibility or adhesion of the hollow particles is lowered, so that a molded article having low scratch resistance can be obtained. Basically, the larger the absorbance ratio (α) is, the higher the scratch resistance is obtained, so it is preferable that the absorbance ratio (α) is larger, but when it is greater than 0.50, the radical reactive groups introduced into the hollow particles react with time and Can cause aggregation. The absorbance ratio α may take 0.015, 0.020, 0.050, 0.10, 0.20, 0.30, 0.40 and 0.50. The absorbance ratio (α) is more preferably 0.015 to 0.400, and even more preferably 0.020 to 0.300.

It is preferable that at least one of the layers constituting the shell contains a silicon atom. Further, it is preferably an organic-inorganic hybrid vinyl resin (Si-containing resin) containing a silicon component. In this specification, "organic-inorganic" means using silicon as an inorganic component and resin other than silicon as an organic component.

Si-containing resin is a copolymer obtained by polymerization or copolymerization of at least one monomer having radical reactive functional groups such as vinyl group, (meth)acryloyl group, allyl group, maleoyl group, fumaroyl group, styryl group, cinnamoyl group, etc. Si-containing resins in which the polymer is crosslinked with a crosslinkable monomer such as a polyamine compound is preferred.

The Si-containing resin is preferably a copolymer obtained by crosslinking a copolymer comprising a radical reactive monomer having at least one epoxy group or an oxetane group and a radical reactive monomer having at least one silyl group with a crosslinkable monomer such as a polyamine compound. Do. In addition, an epoxy group, an oxetane group, and a silyl group are combined, and it is also called a non-radical reactive functional group.

In addition, the hollow particles preferably have a silicon atom abundance Si and a carbon atom abundance C satisfying the relationship of 0.001≦Si/C≦0.1 in XPS measurement. When Si/C is less than 0.001, the crosslinking density becomes low, so that the binder component of low molecular weight may easily penetrate into the interior of the hollow particles. When it exceeds 0.1, pinholes are liable to occur because the crosslinking density is too high, and a low-molecular binder component may easily infiltrate the interior of the hollow particles. Si/C can take 0.001, 0.002, 0.005, 0.01, 0.03, 0.05, 0.08 and 0.1. It is more preferable that it is 0.002-0.05, and, as for Si/C, it is still more preferable that it is 0.002-0.02.

In addition, in the hollow particle, at least one layer contains at least one of a silicon atom, a sulfur atom, and a phosphorus atom, and a carbon atom, and the abundance M of the sum of silicon atoms, sulfur atoms, and phosphorus atoms in XPS of the hollow particles and It is preferable that the abundance C of carbon atoms has the abundance M of the sum of silicon atoms, sulfur atoms and phosphorus atoms satisfying the relationship of 0.001≦M/C≦0.2. When the M/C is less than 0.001, the strength of the particles may be insufficient, and thus collapsed particles may be liable to occur. Even if it exceeds 0.2, collapse of particles may occur. It is more preferable that it is 0.001 to 0.15, and, as for NM/C, it is still more preferable that it is 0.001 to 0.1.

Further, it is preferable that the hollow particles exhibit an average particle diameter of 30 to 120 nm. Hollow particles having an average particle diameter of less than 30 nm may cause aggregation of the hollow particles, resulting in poor handling properties. When hollow particles larger than 120 nm are kneaded with a coating agent or a resin, irregularities on the surface and scattering at the particle interface become large, and whitening may occur. The average particle diameter can take 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 100 nm, and 120 nm. It is more preferable that it is 30-100 nm, and, as for the average particle diameter, it is still more preferable that it is 30-80 nm.

It is preferable that the hollow particles exhibit a porosity of 10 to 70%. If it is less than 10%, the hollow portion is small, and desired properties may not be obtained. If it is greater than 70%, the hollow portion may become too large and the strength of the hollow particles may be lowered. The void ratio can take 10%, 15%, 20%, 25%, 30%, 40%, 50%, 60% and 70%. The void ratio is more preferably 20 to 60%, and still more preferably 25 to 50%.

In the hollow particle dispersion, the hollow particle preferably has a CV value of 30% or less, which is an index of monodispersity evaluation, more preferably 25% or less, and still more preferably 20% or less. When the CV value exceeds 30%, scratch resistance may decrease due to the presence of coarse particles. CV values can take 30%, 25%, 20%, 15%, 10% and 5%.

It is preferable that the shell has few pinholes. When there are many pinholes of the shell, when these particles are used in a member for which thermal conductivity is required to be adjusted, a binder component of a low molecular weight is likely to infiltrate the interior of the hollow particles. For this reason, when hollow particles are used for a low refractive index material, sufficient low refractive index may not be achieved, or when used as a thermal conductivity modifier, thermal conductivity may not be adjusted.

(1) radical reactive monomer having an epoxy group or an oxetane group

The radical reactive monomer having at least one epoxy group or oxetane group has an epoxy group or an oxetane group and a radical reactive functional group.

The radical reactive functional group is not particularly limited as long as it is an ethylenically unsaturated group (a vinyl group or a vinyl group-containing functional group) reacting by radical polymerization. For example, a vinyl group, a (meth)acryloyl group, an allyl group, a maleoyl group, a fumaroyl group, a styryl group, a cinnamoyl group, etc. are mentioned. Among these, a vinyl group, a (meth)acryloyl group, and an allyl group are preferable from the viewpoint of easy reactivity control.

The epoxy group or oxetane group is a functional group that reacts with a compound having an amino group, a carboxyl group, a chlorosulfone group, a mercapto group, a hydroxyl group, an isocyanate group, and the like to form a polymer.

The reactive monomer having a radical reactive functional group and an epoxy group or an oxetane group is not particularly limited. For example, p-glycidyl styrene, glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, (3-ethyloxetan-3-yl) methyl (meth) Acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and the like. These monomers may be used alone or in combination of two or more.

(2) radical reactive monomer having a silyl group

The radical reactive monomer having at least one silyl group has a silyl group and a radical reactive functional group.

The radical reactive functional group is not particularly limited as long as it is an ethylenically unsaturated group reacted by radical polymerization. For example, vinyl group, (meth)acryloyl group, allyl group, maleoyl group, fumaroyl group, styryl group, cinnamoyl group, etc. are mentioned. Among them, a vinyl group, a (meth)acryloyl group, and an allyl group that can easily control reactivity are preferable.

The reactive monomer having a silyl group and a radical reactive functional group is not particularly limited. For example, vinyl trichlorosilane, vinyl trimethoxysilane, vinyl triethoxysilane, p-styrylmethoxysilane, 3-methacryloxypropyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3 -Methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 8-methacryloxyoctyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, and the like. These monomers may be used alone or in combination of two or more.

(3) Copolymer consisting of a radical reactive monomer having an epoxy group or an oxetane group and a radical reactive monomer having a silyl group

In the above copolymer, the ratio (mass ratio) of the component derived from the radical reactive monomer having an epoxy group or an oxetane group and the radical reactive monomer having a silyl group (mass ratio) is preferably 1:100 to 0.001. When the proportion of the component derived from the radical reactive monomer having a silyl group is less than 0.001, the strength of the shell decreases, and the hollow particles may be broken or the hollow particles may not be obtained. When it is larger than 100, the shell becomes too weak to easily generate pinholes, so that it may be difficult to increase the thermal insulation properties of the film. The ratio (mass ratio) of the components may be 1:100, 1:50, 1:10, 1:5, 1:1, 1:0.1, 1:0.01 and 1:0.001. A more preferable ratio is 1:10 to 0.001, and a more preferable ratio is 1:1 to 0.01.

(4) monofunctional monomer

The polymer comprising a radical reactive monomer having an epoxy group or an oxetane group may contain a component derived from a monofunctional monomer having only one reactive functional group. Examples of monofunctional monomers include styrene, esters of (meth)acrylic acid and alcohols having 1 to 25 carbon atoms.

As an ester of (meth)acrylic acid and an alcohol having 1 to 25 carbon atoms, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, iso Butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, (cyclo) hexyl (meth) acrylate, heptyl (meth) acrylate, (iso) octyl (meth) acrylate, Nonyl (meth)acrylate, (iso)decyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, lauryl (meth)acrylic Rate, tetradecyl (meth)acrylate, (iso)stearyl (meth)acrylate, phenoxyethylene glycol (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, 2-ethylhexyl (meth)acrylate And the like.

The monofunctional monomer may be used alone or in combination of two or more.

The content of the component derived from the radical reactive monomer having an epoxy group or an oxetane group and the radical reactive monomer having a silyl group is preferably 10% by mass or more of the entire component derived from the reactive monomer. If the content is less than 10% by mass, hollow particles may not be formed. The content can take 10 mass%, 20 mass%, 30 mass%, 40 mass%, 50 mass%, 60 mass%, 70 mass%, 80 mass%, 90 mass%, and 100 mass%. The content of the component derived from the radical reactive monomer having an epoxy group or an oxetane group and the radical reactive monomer having a silyl group is more preferably 30% by mass or more, and still more preferably 50% by mass or more.

(5) crosslinkable monomer

The vinyl resin may contain components derived from crosslinkable monomers such as polyamine compounds.

As a polyamine compound, for example, ethylenediamine and its adducts, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tetraethylenepentamine, dimethylaminopropylamine, diethylaminopropylamine, dibutyl Aminopropylamine, hexamethylenediamine and its modified products,

N-aminoethyl piperazine, bis-aminopropyl piperazine, trimethylhexamethylenediamine, bis-hexamethylenetriamine, dicyandiamide, diacetoneacrylamide, various modified aliphatic polyamines, aliphatic amines such as polyoxypropylenediamine, 3 ,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 3-amino-1-cyclohexylaminopropane, 4,4'-diaminodicyclohexylmethane, isophoronediamine, 1,3-bis Alicyclic amines such as (aminomethyl)cyclohexane, N-dimethylcyclohexylamine, and bis(aminomethyl)norbornane, and modified products thereof,

4,4'-diaminodiphenylmethane (methylenedianiline), 4,4'-diaminodiphenylether, diaminodiphenylsulfone, m-phenylenediamine, 2,4'-toluylenediamine, m- Aromatic amines such as toluylenediamine, o-toluylenediamine, metaxylylenediamine, and xylylenediamine and their modified products, and other special amine modified products,

Polyamidoamines such as amidoamine and aminopolyamide resin, dimethylaminomethylphenol, 2,4,6-tri(dimethylaminomethyl)phenol, tri-2-ethylhexan salt of tri(dimethylaminomethyl)phenol, etc. Tertiary amines, etc. are mentioned.

Only one type of crosslinkable monomer may be used, or two or more types may be used in combination.

(6) Surface treatment agent

The hollow particles may have a surface treated with a compound having at least one or more anionic groups. The surface treated with this compound imparts heat resistance to the hollow particles, dispersibility in an organic solvent, and properties that a low-molecular binder component is less likely to enter the hollow interior.

Compounds having an anionic group include hydrochloric acid, organic diacid anhydride, oxo acid (e.g., inorganic acids such as nitric acid, phosphoric acid, sulfuric acid, carbonic acid, or carboxylic acid compounds, alkyl ester compounds of sulfuric acid, sulfonic acid compounds, phosphoric acid ester compounds, phosphonic acid. Compounds and organic acids such as phosphinic acid compounds). It is preferable that these compounds are compounds containing a phosphorus atom and/or a sulfur atom as a constituent component.

The carboxylic acid compound is not particularly limited as long as it is a compound containing a carboxyl group. For example, linear carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid and stearic acid; Pivalic acid, 2,2-dimethylbutyric acid, 3,3-dimethylbutyric acid, 2,2-dimethylvaleric acid, 2,2-diethylbutyric acid, 3,3-diethylbutyric acid, 2-ethylhexanoic acid, 2-methyl Branched-chain carboxylic acids such as heptanoic acid, 4-methyloctanoic acid, and neodecanoic acid; Cyclic carboxylic acids, such as naphthenic acid and cyclohexanedicarboxylic acid, etc. are mentioned. Among these, in order to effectively increase the dispersibility in an organic solvent, a straight-chain carboxylic acid having 4 to 20 carbon atoms, a branched-chain carboxylic acid, and the like are preferable.

In addition, as the carboxylic acid compound, a carboxylic acid having radical reactive functional groups such as vinyl group, (meth)acryloyl group, allyl group, maleoyl group, fumaroyl group, styryl group, cinnamoyl group, etc. can also be used. For example, acrylic acid, methacrylic acid, 2-acryloyloxyethylsuccinic acid, 2-methacryloyloxyethylsuccinic acid, 2-acryloyloxyethylhexahydrophthalic acid, 2-methacryloyloxyethylhexahydro And phthalic acid, 2-acryloyloxyethylphthalic acid, 2-methacryloyloxyethylphthalic acid, and vinylbenzoic acid.

Dodecyl sulfuric acid etc. are mentioned as an alkyl ester compound of sulfuric acid.

The sulfonic acid compound is not particularly limited as long as it is a compound containing a sulfo group. For example, p-toluenesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, methylsulfonic acid, ethylsulfonic acid, vinylsulfonic acid, allylsulfonic acid, metalylsulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid, and the like.

The phosphoric acid ester compound is not particularly limited as long as it is an ester compound of phosphoric acid. For example, dodecyl phosphate and polyoxyethylene alkyl ether phosphoric acid represented by the following formula (a) are mentioned.

In the above formula, R ₁ is an alkyl group having 4 to 19 carbon atoms or an allyl group (CH ₂ =CHCH ₂ -), a (meth)acryl group, and a styryl group. Examples of the C4-C19 alkyl group include a butyl group, a pentyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, and a stearyl group. These groups may be linear or branched. Moreover, these may use 1 type or multiple types together.

R ₂ is H or CH ₃ .

n is the number of moles added of the alkylene oxide, and when the whole is made 1 mole, it is a value in the range necessary to give the number of added moles of 0 to 30.

The combination of a and b is a combination of 1 and 2 or 2 and 1.

In addition, KAYAMER PM-21 of Japanese explosives can also be used.

Further, as the oxo acid, a polymer having an acid group can also be used. For example, Disper Big 103, Disper Big 110, Disper Big 118, Disper Big 111, Disper Big 190, Disper Big 194N, Disper Big 2015 (manufactured by Big Chemical), Solspur 3000, Solspur 21000, Solspur 26000, Solspurs 36000, Solspurs 36600, Solspurs 41000, Solspurs 41090, Solspurs 43000, Solspurs 44000, Solspurs 46000, Solspurs 47000, Solspurs 53095, Solspurs 55000 (manufactured by Lubrizol), EFKA4401, EFKA4550 (Manufactured by Fcar Additives), Floren G-600, Floren G-700, Floren G-900, Floren GW-1500, Floren GW-1640 (manufactured by Kyoeisha Chemical Co., Ltd.), Disparon 1210, Disparon 1220, Disparon 2100, Disparon 2150, Disparon 2200, Disparon DA-325, Disparon DA-375 (manufactured by Kusumoto Hwasung), Azisper PB821, Azisper PB822 , Azisper PB824, Azisper PB881, Azisper PN411 (manufactured by Ajinomoto Fine Techno), and the like, but are not limited thereto.

Further, if necessary, surface treatment may be performed with a surface treatment agent such as a silane-based coupling agent, a titanate-based coupling agent, an aluminate-based coupling agent, a zirconate-based coupling agent, or an isocyanate-based compound.

Examples of the silane coupling agent include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n -Propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, trifluoropropyltrime Alkoxysilane such as oxysilane, silazane such as hexamethyldisilazane, chlorosilane such as trimethylsilyl chloride, vinyl trimethoxysilane, vinyl triethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltri Methoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p- Styryltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane Silane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-( Trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfur Silane-based coupling agents such as feed and 3-isocyanate propyltriethoxysilane.

In addition to the silane-based coupling agent, a silane-based coupling agent represented by the following formula (I) is also mentioned.

In formula (I), R ¹ each independently represents a substituted or unsubstituted C 1 to C 6 alkyl group, a C 2 to C 4 alkoxyalkyl group or a phenyl group.

Each of R ² independently represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 4 carbon atoms, or a phenyl group.

R ³ represents a divalent organic group having 1 to 30 carbon atoms.

R ⁴ represents a hydrogen atom or a methyl group.

m represents the integer of 0-2.

Among R ¹ and R ² , methyl, ethyl, propyl, butyl, pentyl and hexyl are exemplified as the C 1 to C 6 alkyl group. If possible, structural isomers are included in these alkyl groups.

Among R ¹ and R ² , examples of the alkoxyalkyl group having 2 to 4 carbon atoms include methoxymethyl, methoxyethyl, ethoxymethyl, methoxybutyl, ethoxyethyl and butoxymethyl. Structural isomers are included in these alkoxyalkyl groups whenever possible.

Examples of the substituents for R ¹ and R ² include halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), hydroxy group, amino group, phenyl group, and the like.

Among R ³ , as a divalent organic group having 1 to 30 carbon atoms, methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, Alkanediyl groups, such as tridecamethylene and tetradecamethylene, are mentioned. The alkanediyl group may have a branched structure substituted with an alkyl group.

As a specific example of the silane coupling agent represented by formula (I),

3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxy Silane, 4-(meth)acryloxybutyltrimethoxysilane, 4-(meth)acryloxybutyltriethoxysilane, 4-(meth)acryloxybutylmethyldimethoxysilane, 4-(meth)acryloxybutylmethyl Dietoxysilane, 5-(meth)acryloxypentyltrimethoxysilane, 5-(meth)acryloxypentyltriethoxysilane, 5-(meth)acryloxypentylmethyldimethoxysilane, 5-(meth)acryloxy Pentylmethyldiethoxysilane, 6-(meth)acryloxyhexyltrimethoxysilane, 6-(meth)acryloxyhexyltriethoxysilane, 6-(meth)acryloxyhexylmethyldimethoxysilane, 6-(meth) Acryloxyhexylmethyldiethoxysilane, 7-(meth)acryloxyheptyltrimethoxysilane, 7-(meth)acryloxyheptyltriethoxysilane, 7-(meth)acryloxyheptylmethyldimethoxysilane, 7-( Meth)acryloxyheptylmethyldiethoxysilane, 8-(meth)acryloxyoctyltrimethoxysilane, 8-(meth)acryloxyoctyltriethoxysilane, 8-(meth)acryloxyoctylmethyldimethoxysilane, 8 -(Meth)acryloxyoctylmethyldiethoxysilane, 9-(meth)acryloxynonyltrimethoxysilane, 9-(meth)acryloxynonyltriethoxysilane, 9-(meth)acryloxynonylmethyldimethoxysilane , 9-(meth)acryloxynonylmethyldiethoxysilane, 10-(meth)acryloxydecyltrimethoxysilane, 10-(meth)acryloxydecyltriethoxysilane, 10-(meth)acryloxydecylmethyldimethe Toxoxysilane, 10-(meth)acryloxydecylmethyldiethoxysilane, 11-(meth)acryloxyundecyltrimethoxysilane, 11-(meth)acryloxyundecyltriethoxysilane, 11-(meth)acrylic Oxyundecylmethyldimethoxysilane, 11-(meth)acryloxyundecylmethyldiethoxysilane, 12-(meth)acryloxidodecyltrimethoxysilane, 12-(meth)acryloxidodecyltriethoxysilane, 12-(meth)acryloxydodecylmethyldimethoxysilane, 12-(meth)acryloxydodecylmethyldiethoxysilane, 13-(meth)acryloxytridecyltrimethoxysilane, 13-(meth)acryloxytri Decyltriethoxysilane, 13-(meth)acryloxytridecylmethyldimethoxysilane, 13-(meth)acryloxytridecylmethyldiethoxysilane, 14-(meth)acryloxytetradecyltrimethoxysilane, 14-(meth)acryloxytetradecyltriethoxysilane, 14-(meth)acryloxytetra Decylmethyldimethoxysilane, 14-(meth)acryloxytetradecylmethyldiethoxysilane, etc. are mentioned.

The silane-based coupling agent used in the present invention is not limited to these. On the other hand, the silane-based coupling agent can be obtained, for example, from a silicone manufacturing company such as Shin-Etsu Silicone.

Among the above silane coupling agents, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane , 8-methacryloxyoctyltriethoxysilane and 3-acryloxypropyltrimethoxysilane are preferred.

As the titanate-based coupling agent, Ajinomoto Fine Techno Corporation's Plan Act TTS, Plan Act 46B, Plan Act 55, Plan Act 41B, Plan Act 38S, Plan Act 138S, Plan Act 238S, Plan Act 338X, Plan Act 44, Plenact 9SA and Plenact ET may be mentioned, but the titanate-based coupling agent used in the present invention is not limited thereto.

The aluminate-based coupling agent may include Planact AL-M manufactured by Ajinomoto Fine Techno, but the aluminate-based coupling agent used in the present invention is not limited thereto.

As the zirconate-based coupling agent, Matsumoto Fine Chemical's Orgatics ZA-45, Orgatics ZA-65, Orgatics ZC-150, Orgatics ZC-540, Orgatics ZC-700, Orgatics ZC-580 , Orgatics ZC-200, Orgatics ZC-320, Orgatics ZC-126 and Orgatics ZC-300, but the zirconate-based coupling agent used in the present invention is not limited thereto.

As the isocyanate-based compound, ethyl isocyanate, propyl isocyanate, isopropyl isocyanate, butyl isocyanate, tert-butyl isocyanate, hexyl isocyanate, dodecyl isocyanate, octadecyl isocyanate, cyclohexyl isocyanate, benzyl isocyanate, phenyl isocyanate, 4-butyl phenyl isocyanate , 2-isocyanate ethyl methacrylate, 2-isocyanate ethyl acrylate, and 1,1-(bisacryloyloxymethyl) ethyl isocyanate, but the isocyanate compound used in the present invention is not limited thereto.

Only 1 type may be used for the said surface treatment agent, and 2 or more types may be used together.

(7) other additives

To the extent that the effect of the present invention is not impaired, the hollow particles include other additives such as pigment particles (pigments), dyes, stabilizers, ultraviolet absorbers, antifoaming agents, thickeners, heat stabilizers, leveling agents, lubricants, and antistatic agents as necessary. You can do it.

The pigment particle is not particularly limited as long as it is a pigment particle used in the art. For example, iron oxide pigments such as mica-like iron oxide and iron black; Oxide-linked pigments such as lead and yellow lead; Titanium oxide pigments such as titanium white (rutile type titanium oxide), titanium yellow, and titanium black; Cobalt oxide; Zinc oxide pigments such as zinc sulfur; Particles, such as a molybdenum oxide type pigment, such as molybdenum red and molybdenum white, are mentioned. The pigment particles may be used alone or in combination of two or more.

(8) Use of hollow particle dispersion

The hollow particle dispersion is useful as a raw material for additives for paints, papers, information recording papers, heat insulating films, and thermoelectric conversion materials, which are applications requiring improved scratch resistance. In addition, the hollow particle dispersion is an additive of a coating agent (coating composition) used for a light diffusion film (optical sheet), a light guide plate ink, an antireflection film, a light extraction film, etc., an additive of a master pellet for forming a molded body such as a light diffusion plate and a light guide plate, It is also useful as a raw material for cosmetic additives.

(a) master pellet

The master pellet contains hollow particles and a base resin.

The base resin is not particularly limited as long as it is an ordinary thermoplastic resin. For example, a (meth)acrylic resin, an alkyl (meth)acrylate-styrene copolymer resin, a polycarbonate resin, a polyester resin, a polyethylene resin, a polypropylene resin, a polystyrene resin, and the like can be mentioned. In particular, when transparency is required, a (meth)acrylic resin, an alkyl (meth)acrylate-styrene copolymer resin, a polycarbonate resin, and a polyester resin are preferable. These base resins may be used alone or in combination of two or more. On the other hand, the base resin may contain a trace amount of additives such as an ultraviolet absorber, a heat stabilizer, a colorant, and a filler.

The master pellet can be produced by melt-kneading hollow particles and a base resin by molding methods such as extrusion molding and injection molding. The blending ratio of the hollow particles in the master pellet is not particularly limited, but is preferably about 0.1 to 60% by mass, more preferably about 0.3 to 30% by mass, and still more preferably about 0.4 to 10% by mass. If the blending ratio exceeds 60% by mass, production of master pellets may become difficult. Moreover, if it is less than 0.1 mass %, the effect of this invention may fall.

The master pellet becomes a molded article by extrusion molding, injection molding, or press molding, for example. Further, a base resin may be newly added during molding. The addition amount of the base resin is preferably added so that the blending ratio of the hollow particles contained in the finally obtained molded body is about 0.1 to 60% by mass. On the other hand, during molding, a trace amount of additives such as an ultraviolet absorber, a heat stabilizer, a colorant, and a filler may be added.

(b) cosmetic

Specific cosmetics in which hollow particles can be blended include solid cosmetics such as powder and foundation, powder cosmetics such as baby powder and body powder, liquid cosmetics such as lotion, emulsion, cream, and body lotion. The hollow particle dispersion is blended into these cosmetics after removing the medium as necessary. In the case of a liquid cosmetic, the hollow particle dispersion may be blended into the cosmetic as it is without removing the medium.

The blending ratio of the hollow particles to these cosmetics varies depending on the type of cosmetics. For example, in the case of solid cosmetics such as powder and foundation, 1 to 20% by mass is preferable, and 3 to 15% by mass is particularly preferable. Further, in the case of powdery cosmetics such as baby powder and body powder, 1 to 20% by mass is preferable, and 3 to 15% by mass is particularly preferable. In the case of liquid cosmetics such as lotions, emulsions, creams, liquid foundations, body lotions, and pre-shave lotions, 1 to 15% by mass is preferable, and 3 to 10% by mass is particularly preferable.

In addition, these cosmetics include inorganic compounds such as mica and talc, pigments for coloring such as iron oxide, titanium oxide, ultramarine blue, persimmon blue, carbon black, or synthetic dyes such as azo in order to improve the optical function or the touch. Can be added. In the case of a liquid cosmetic, the liquid medium is not particularly limited, but water, alcohol, hydrocarbon, silicone oil, vegetable, animal fat or the like may be used. In addition to the above other ingredients, various functions may be added to these cosmetics by adding a moisturizing agent, an anti-inflammatory agent, a whitening agent, a UV care agent, a disinfectant, an antiperspirant, a refreshing agent, a fragrance, and the like, which are generally used in cosmetics.

(c) insulation film

The heat insulating film contains at least the above hollow particles. A film or a sheet-like article containing the above hollow particles can be used as a heat insulating film since they have an air layer inside the hollow particles. In addition, since the particle diameter of the hollow particles is small, a heat insulating film having high transparency is obtained, and since the binder hardly penetrates the inside of the hollow particles, a heat insulating film having high heat insulating properties is easily obtained. The heat insulating film can be obtained by applying the coating agent to a substrate by a known method such as dip method, spray method, spin coating method, spinner method, roll coating method, etc., dried, and further heated, irradiated with ultraviolet rays, or fired as necessary. have.

(d) antireflection film

The antireflection film contains at least the above hollow particles. The film or sheet-like article containing the hollow particles can be used as an antireflection film because the refractive index is lowered by the air layer inside the hollow particles. Further, since the hollow particles have high heat resistance, an antireflection film having high heat resistance is obtained. The antireflection film can be obtained by applying the coating agent to a substrate by a known method such as dip method, spray method, spin coating method, spinner method, roll coating method, etc., dried, and further heated, irradiated with ultraviolet rays, or fired as necessary. have.

(e) a substrate on which an antireflection film is formed

The substrate on which the anti-reflection film is formed is on the surface of the substrate such as glass, polycarbonate, acrylic resin, plastic sheet such as PET, TAC, plastic film, plastic lens, plastic panel, cathode ray tube, fluorescent display tube, liquid crystal panel, etc. An antireflection film was formed. Depending on the application, the film may be formed alone, or a protective film, a hard coating film, a planarization film, a high refractive index film, an insulating film, a conductive resin film, a conductive metal fine particle film, a conductive metal oxide fine particle film, etc. It is formed in combination with a primer film and the like used accordingly. On the other hand, when used in combination, the antireflection film need not necessarily be formed on the outermost surface.

(f) light extraction film

The light extraction film contains at least the above hollow particles. In LED or organic EL lighting, since the difference in refractive index between the air layer and the light emitting layer is large, the emitted light is likely to be trapped inside the device. For this reason, a light extraction film is used for the purpose of improving luminous efficiency. Since the refractive index of the film or sheet-like article containing the hollow particles is lowered by the air layer inside the hollow particles, it can be used as a light extraction film. Further, since the hollow particles have high heat resistance, a light extraction film having high heat resistance is obtained. The light extraction film is obtained by applying the above-described coating agent to a substrate by a known method such as dip method, spray method, spin coating method, spinner method, roll coating method, etc., dried, and additionally heated, irradiated with ultraviolet rays, and baked as necessary. I can.

(g) substrate on which the light extraction film is formed

The substrate on which the light extraction film is formed is specified on the surface of the substrate such as glass, polycarbonate, acrylic resin, plastic sheet such as PET, TAC, plastic film, plastic lens, plastic panel, etc., cathode ray tube, fluorescent display tube, liquid crystal panel, etc. One light extraction film was formed. Depending on the application, the film may be formed alone, or a protective film, a hard coating film, a planarization film, a high refractive index film, an insulating film, a conductive resin film, a conductive metal fine particle film, a conductive metal oxide fine particle film, etc. It is formed in combination with a primer film and the like used accordingly. On the other hand, when used in combination, the light extraction film is not necessarily formed on the outermost surface.

(h) low dielectric constant film

The low dielectric constant film contains at least the above hollow particles. Since the film or sheet-like article containing the hollow particles has an air layer inside the hollow particles, it can be used as a low dielectric constant film. Further, since the hollow particles have a small particle diameter, a low dielectric constant film with high transparency is obtained, and since the binder is difficult to penetrate into the hollow interior, a low dielectric constant film with a low relative dielectric constant is easily obtained. Further, since the hollow particles are excellent in alkali resistance, it is easy to obtain a low dielectric constant film having high alkali resistance. The low dielectric constant film can be obtained by applying the coating agent to a substrate by a known method such as dip method, spray method, spin coating method, spinner method, roll coating method, etc., dried, and further heated, irradiated with ultraviolet rays, and baked as necessary. have.

(9) Method for producing hollow particle dispersion

The hollow particle dispersion is not particularly limited, for example, a step of producing polymer particles containing a non-reactive solvent (polymerization step), a step of phase-separating a non-reactive solvent from the polymer particles (phase separation step), and non-reactive It can be manufactured by going through a process of removing a solvent (solvent removal process), and a process of dispersing in a medium (dispersion process) if necessary.

In the conventional method for producing hollow particles, the shell is formed by polymerizing a reactive monomer once, and phase separation between the organic solvent (non-reactive solvent) and the shell is performed simultaneously with the polymerization. The inventors of the present invention thought that in this method, the step of simultaneously performing phase separation and polymerization causes the occurrence of pinholes and lowering of monodispersity. In addition, it was thought that the pinhole of the shell inhibited the reduction of the thermal conductivity of the film and the decrease of the reflectance of the film when hollow particles were used as the thermal conductivity modifier. Accordingly, the inventors thought that if the polymer particles were once formed before the phase separation of the non-reactive solvent, and then phase separated, the occurrence of pinholes could be suppressed and the monodispersity could be improved.

Specifically, polymer particles are prepared by polymerizing a reactive monomer having a radical reactive functional group and a non-radical reactive functional group based on either of the bifunctional groups. The non-reactive solvent is mixed with a reactive monomer in advance or absorbed after preparing the polymer particles to be contained in the polymer particles. Subsequently, the polymer and the non-reactive solvent are phase-separated by polymerization of the other functional group remaining in the bifunctional group, thereby obtaining microcapsules containing the non-reactive solvent. After that, hollow particles are obtained by removing the non-reactive solvent.

The manufacturing method is by separating polymerization and phase separation,

・There is no gap between the polymers of the shell existing in the conventional manufacturing method, and the occurrence of pinholes in the resulting shell can be suppressed.

Hollow particles with high monodispersity are easy to obtain because the shape of the hollow particles does not depend on oil droplets, but depends on the shape and particle size distribution of the polymer particles before phase separation.

Has an advantage. Hereinafter, description of the manufacturing method is described.

(9-1) polymerization process

In the polymerization step, polymer particles are prepared by polymerizing a reactive monomer having a radical reactive functional group and a non-radical reactive functional group based on either of the bifunctional groups. The non-reactive solvent is mixed with a reactive monomer in advance or absorbed after preparing the polymer particles to be contained in the polymer particles.

(a) Method for producing polymer particles

As a method for producing the polymer particles, any method may be employed among known methods such as a bulk polymerization method, a solution polymerization method, a dispersion polymerization method, a suspension polymerization method, and an emulsion polymerization method. Among them, a suspension polymerization method or an emulsion polymerization method is preferable since the polymer particles can be produced relatively easily. In addition, the emulsion polymerization method is more preferable because polymer particles having high monodispersity are easily obtained.

The polymer particles are obtained by polymerizing a radical reactive functional group or a non-radical reactive functional group.

It is preferable to perform polymerization by adding a compound which polymerizes the functional group to be polymerized.

(i) When polymerizing a radically reactive functional group, a polymerization initiator can be used for this compound. The polymerization initiator is not particularly limited, for example, persulfates such as ammonium persulfate, potassium persulfate, sodium persulfate, cumene hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, benzoyl peroxide, laur Loryl peroxide, dimethylbis(tert-butylperoxy)hexane, dimethylbis(tert-butylperoxy)hexine-3, bis(tert-butylperoxyisopropyl)benzene, bis(tert-butylperoxy)trimethylcyclo Organic peroxides such as hexane, butyl-bis (tert-butylperoxy) valerate, 2-ethylhexaneperoxy acid tert-butyl, dibenzoyl peroxide, paramentane hydroperoxide, and tert-butyl peroxybenzoate , 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] Disulfate dihydrate, 2,2'-azobis(2-amidinopropane)dihydrochloride, 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]hydrate, 2, 2'-azobis{2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane}dihydrochloride, 2,2'-azobis[2-(2-imidazoline) -2-yl)propane], 2,2'-azobis(1-imino-1-pyrrolidino-2-ethylpropane) dihydrochloride, 2,2'-azobis {2-methyl-N-[ 1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide}, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 4,4' -Azobis (4-cyanopentanoic acid), 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methyl-butyronitrile), 2,2'-azobis (2- Isopropylbutyronitrile), 2,2'-azobis (2,3-dimethylbutyronitrile), 2,2'-azobis (2,4-dimethylbutyronitrile), 2,2'-azobis (2-methylcapronitrile), 2,2'-azobis (2,3,3-trimethylbutyronitrile), 2,2'-azobis (2,4,4-trimethylvaleronitrile), 2, 2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-ethoxyvaleronitrile), 2,2'-azobis (2,4 -Dimethyl-4-n-butoxyvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleroni Tril), 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], 2,2'-azobis(N-butyl-2-methylpropionamide), 2,2' -Azobis (N-cyclohexyl-2-methylpropionamide), 1,1'-azobis (1-acetoxy-1-phenylethane), 1,1'-azobis (cyclohexane-1-carbonitrile) ), dimethyl-2,2'-azobis(2-methylpropionate), dimethyl-2,2'-azobisisobutyrate, dimethyl-2,2'-azobis(2-methylpropionate), 2 Azo compounds, such as -(carbamoyl azo) isobutyronitrile and 4,4'-azobis (4-cyanovaleric acid), are mentioned. Only one type of polymerization initiator may be used, and two or more types may be used in combination.

In addition, the polymerization initiator of the persulfates and organic peroxides, sodium sulfoxylate formaldehyde, sodium hydrogen sulfite, ammonium hydrogen sulfite, sodium thiosulfate, ammonium thiosulfate, hydrogen peroxide, sodium hydroxymethanesulfinate, L-ascorbic acid And a redox initiator in which a reducing agent such as a salt, a cuprous salt, or a ferrous salt is combined may be used as the polymerization initiator.

When the polymerization is emulsion polymerization, the polymerization initiator is preferably a water-soluble polymerization initiator capable of emulsion polymerization in an aqueous medium. The water-soluble polymerization initiator is not particularly limited, and examples thereof include persulfates such as ammonium persulfate, potassium persulfate and sodium persulfate, 2,2'-azobis[2-(2-imidazolin-2-yl) Propane]dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane]disulfate dihydrate, 2,2'-azobis(2-amidinopropane)dihydrochloride, 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] hydrate, 2,2'-azobis{2-[1-(2-hydroxyethyl)-2-imine Dazolin-2-yl]propane}dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis(1-imino-1 -Pyrrolidino-2-ethylpropane)dihydrochloride, 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide}, 2 And azo compounds such as 2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide] and 4,4'-azobis(4-cyanopentanoic acid).

(ii) It is preferable that the polymer particle has an unreacted non-radical reactive functional group in the polymer by first polymerizing a radical reactive functional group. If the non-radical reactive functional group is first polymerized, absorption of the non-reactive solvent may become difficult.

It is preferable that the polymer particle has an unreacted other reactive functional group in the polymer by polymerizing one reactive functional group of a radical reactive functional group and a non-radical reactive functional group. However, there is no major problem even if the entire amount of the functional group to be polymerized during the production of the polymer particles is not polymerized and partially polymerized, and even if the other reactive functional group partially polymerizes, there is no major problem. For example, when polymer particles having an epoxy group are prepared by polymerizing the radical reactive functional group of glycidyl methacrylate, the unreacted radical reactive functional group may remain, or the epoxy group may partially ring-open (in other words, the polymer The amount of epoxy groups that can be phase-separated should remain in the particles).

(iii) You may use a chain transfer agent at the time of polymerization of a reactive monomer. The chain transfer agent is not particularly limited, for example, alkyl mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, t-octyl mercaptan, n-dodecyl mercaptan, and t-dodecyl mercaptan, α -Phenol compounds such as methylstyrene dimer, 2,6-di-t-butyl-4-methylphenol, styrenated phenol, allyl compounds such as allyl alcohol, halogenated hydrocarbon compounds such as dichloromethane, dibromomethane, and carbon tetrachloride Can be mentioned. Chain transfer agents may be used alone or in combination of two or more.

The upper limit of the amount of the chain transfer agent used is 50 parts by mass per 100 parts by mass of the reactive monomer.

(b) absorption of non-reactive solvent

Absorption of the non-reactive solvent to the polymer particles can be carried out during or after the production of the polymer particles. In addition, absorption of the non-reactive solvent can be performed in the presence or absence of a dispersion medium incompatible with the non-reactive solvent. Conducting in the presence of a dispersion medium is preferable because absorption of the non-reactive solvent can be performed efficiently. In the case of using a medium for producing the polymer particles, the medium may be used as it is as a dispersion medium, and once the polymer particles are isolated from the medium, they may be dispersed in the dispersion medium.

A non-reactive solvent that is not compatible with the dispersion medium is added to the dispersion medium containing the polymer particles, and the non-reactive solvent can be absorbed by the polymer particles by stirring or the like for a certain period of time.

In addition, absorption of the non-reactive solvent during the production of the polymer particles can be realized by selecting a dispersion medium and a non-reactive solvent suitable for production of the polymer particles. For example, when polymer particles are prepared by emulsion polymerization under an aqueous medium, a non-reactive solvent incompatible with water is added to the aqueous medium in advance, and the reactive monomer is polymerized to produce polymer particles and absorption of the polymer particles. Can be performed at the same time. If the polymer particles are prepared and the polymer particles are absorbed at the same time, the time taken for absorption of the non-reactive solvent can be reduced.

(i) dispersion medium

The dispersion medium is not particularly limited as long as it is a liquid that does not completely dissolve the polymer particles. For example, water; Alcohols such as ethyl alcohol, methyl alcohol, and isopropyl alcohol; Alkanes such as butane, pentane, hexane, cyclohexane, heptane, decane, and hexadecane; Aromatic hydrocarbons such as toluene and xylene; Ester solvents such as ethyl acetate and butyl acetate; Ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; Halogen solvents, such as methyl chloride, methylene chloride, chloroform, and carbon tetrachloride, are mentioned. These may be used alone or in combination of two or more.

(ii) non-reactive solvent

The non-reactive solvent is not particularly limited as long as it is a liquid substance not compatible with the dispersion medium. Here, "not compatible with the dispersion medium" means that the solubility (at 25°C) of the non-reactive solvent in the dispersion medium is 10% by mass or less. For example, when water is used as the dispersion medium, non-reactive solvents that can be used include butane, pentane, hexane, cyclohexane, heptane, decane, hexadecane, toluene, xylene, ethyl acetate, butyl acetate, and methyl ethyl ketone. , Methyl isobutyl ketone, 1,4-dioxane, methyl chloride, methylene chloride, chloroform, and carbon tetrachloride. These may be used alone or in combination of two or more.

The amount of the non-reactive solvent to be added is not particularly limited, but is 20 to 5000 parts by mass per 100 parts by mass of the polymer particles. If it is less than 20 parts by mass, the hollow portion of the obtained hollow particles becomes small, and desired properties may not be obtained. When it exceeds 5000 parts by mass, the hollow part becomes too large, and the strength of the obtained hollow particles may decrease.

(9-2) Phase separation process

Subsequently, the remaining reactive functional groups are polymerized to phase separate the polymer and the non-reactive solvent. By phase separation, microcapsule particles containing a non-reactive solvent are obtained. On the other hand, in the present invention, the hollow of the hollow particle means not only the case where air is present in the hollow portion, but also includes microcapsule particles in which a non-reactive solvent or other dispersion medium is present in the hollow portion.

The compound added to polymerize the remaining reactive functional group may be the same as the polymerization initiator for polymerizing the radical reactive functional group described in the above polymerization step and the crosslinking agent for polymerizing the non-radical reactive functional group.

(9-3) Solvent removal (substitution) step

If necessary, by removing or replacing the non-reactive solvent contained in the microcapsule particles, it is possible to obtain hollow particles in which air or other solvent is present in the hollow portion. The method of removing the non-reactive solvent is not particularly limited, and a drying method under reduced pressure may be mentioned. Conditions for the vacuum drying method include, for example, a pressure of 500 Pa or less, 30 to 200°C, and 30 minutes to 50 hours. In addition, a non-reactive solvent can be substituted by a solvent substitution operation. For example, by adding a suitable dispersion medium to microcapsule particles or dispersions thereof containing a non-reactive solvent, and performing agitation or the like, the non-reactive solvent inside the particles is replaced with the dispersion medium. Thereafter, the non-reactive solvent can be replaced by removing the excess non-reactive solvent and the dispersion medium by a vacuum drying method, a centrifugal separation method, an ultrafiltration method, or the like. Solvent substitution may be performed only once or may be performed multiple times.

(9-4) (dispersion process)

The hollow particle dispersion may remain, for example, in the state of a microcapsule particle dispersion containing a non-reactive solvent obtained after the phase separation step, or may be a dispersion substituted with another solvent.

In the case of substitution with another solvent, the solvent present after the phase separation process is once removed to take out hollow particles, and the extracted hollow particles can be dispersed in a desired medium.

(9-5) Other processes

The surface of the hollow particles can be treated with a compound having an anionic group by adding and stirring a compound having an anionic group to the hollow particle dispersion after the phase separation process, or by adding and mixing a compound having an anionic group to the hollow particles after the solvent removal process. I can. Among them, after removing the excess crosslinking agent after the phase separation step, it is preferable to add and stir the compound having an anionic group in the hollow particle dispersion. Treatment conditions include, for example, 30 to 200°C and 30 minutes to 50 hours.

The hollow particles may be used as dry powder obtained by drying the hollow particle dispersion as necessary. The method of drying the hollow particles is not particularly limited, and a vacuum drying method and the like are mentioned. On the other hand, in the dry powder, a dispersion solvent, a non-reactive solvent, or the like remaining without drying may remain.

Example

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited thereto. First, details of various measurement methods used in Examples are described below.

(Average particle diameter, porosity)

The average particle diameter and the porosity of the hollow particles were measured as follows.

That is, 10 mass% of the surface-treated hollow particle isopropyl alcohol dispersion or hollow particle methyl isobutyl ketone dispersion was dried for 4 hours in a vacuum dryer at 70° C. (pressure is 100 kPa or less) to obtain dry powder. The hollow particles were taken with a transmission electron microscope (H-7600 manufactured by Hitachi High-Technologies Corporation) under conditions of an acceleration voltage of 80 kV, and a TEM photograph was taken at a magnification of about 100,000 times. At this time, by using ruthenium tetraoxide dyeing or the like, the particles could be more clearly identified. The particle diameter and inner diameter of any 100 or more particles taken in this picture were observed. At this time, five or more particle diameters and inner diameters were measured and averaged so as to pass through the center of the particles to obtain an average particle diameter and an average inner diameter. In addition, the porosity of the hollow particles was determined from the formula of (average inner diameter) ³ /(average particle diameter) ³ ×100.

(Dispersion particle diameter)

The diameter of the hollow particles dispersed in the organic solvent was measured as follows.

That is, the dispersion prepared by diluting a 10% by mass hollow particle isopropyl alcohol dispersion or a hollow particle methyl isobutyl ketone dispersion with isopropyl alcohol and methyl isobutyl ketone to about 0.1% by mass is irradiated with laser light, and isopropyl The intensity of scattered light scattered from the hollow particles dispersed in alcohol was measured with a time change in microseconds. And the Z average particle diameter of colored resin particles was calculated|required by cumulant analysis method for calculating the average particle diameter by applying the scattering intensity distribution resulting from the detected hollow particles to a normal distribution. This Z average particle diameter was taken as the dispersed particle diameter in an organic solvent. The measurement of this Z average particle diameter could be performed conveniently with a commercially available particle diameter measuring device. In the following Examples and Comparative Examples, the Z-average particle diameter was measured using a particle diameter measuring apparatus (brand name "Zetasizer Nano ZS") manufactured by Malvern Instruments Ltd.

(Elemental analysis of hollow particles)

Elemental analysis of the hollow particles was performed as follows.

A 10% by mass surface-treated hollow particle isopropyl alcohol dispersion was dried for 4 hours with a 90°C vacuum dryer (pressure is 100 kPa or less) to obtain dry powder. X-ray photoelectron spectroscopy equipment (XPS) manufactured by Kratos (Young), AXIS-ULTRA DLD was used, and the area of the peak originating in the 2p orbital for nitrogen and carbon atoms was 1s, silicon and sulfur atoms, and Using RSF (Relative Sensitivity Coefficient), the amount of nitrogen atoms constituting the hollow particles N [atom%], the amount of carbon atoms C [atom%], the amount of silicon atoms Si [atom%], the substance of sulfur atoms The amounts of S [atom%] and the substance amount P [atom%] of phosphorus atoms were measured.

X-ray source: monochromatic Al-Kα ray

Photoelectron extraction angle: 90°

Measurement range: 0.3×0.7mm rectangle

Beam output: 75W (15kV-5mA)

Measurement energy: 1200-0eV

Pass energy: 80eV

Neutralization mechanism: ON

Measurement step: 1eV

Measurement time: 100 ms

Number of integration: 4 times

Vacuum degree: Approx. 4×10 ^-9 Torr

By dividing the substance amount M of the sum of the measured substance amount N of the nitrogen atom and the substance amount Si of the silicon atom, the substance amount S of the sulfur atom, and the substance amount P of the phosphorus atom by the substance amount C of the carbon atom, (N/C) and (M/C) ) Was calculated.

(Transmittance of hollow particle dispersion)

The transmittance of the hollow particle dispersion was measured as follows.

That is, 0.4 ml of the hollow particle dispersion prepared in the examples was put into a cell for LUMiSizer (made of polyamide, optical path length 2 mm) manufactured by LUM JAPAN, and the transmittance at a position of 115 mm from the center of the device was determined It was set as the transmittance.

(Haze and scratch resistance)

Haze and scratch resistance of the cured product using hollow particles were evaluated as follows.

In other words, the hollow particle dispersion is easily bonded using a PET substrate (Toray Co., Ltd., IMC-70F0-C type, tensile speed: 10mm/sec) equipped with an applicator with a gap of 12.5㎛. Manufacturing Lumira U34 (thickness 100 µm) was applied to obtain a coating film. After drying the obtained coating film in an oven at 60° C. for 1 minute, it was cured by passing it twice through an ultraviolet irradiation device (J-Cure manufactured by JATEC, type JUC1500, tensile speed: 0.4 m/min, accumulated light amount: 2000 mJ/cm 2 ). , To prepare a cured product containing hollow particles.

Haze was measured in the following procedure according to the method described in JIS K7361-1:1997 "Plastic-Test method of total light transmittance of transparent material-Part 1: Single beam method". That is, after the device light source was stabilized using a haze meter (manufactured by Murakami Color Technology Research Institute, type: HM-150), the prepared substrate on which the light extraction film was formed was measured for individual haze by a light source (D65) and a double beam method. The stability was confirmed by measuring 30 minutes after starting the light source. The number of tests was made into two, and the average of two individual haze was made into haze.

Using #0000 steel wool, it slid 10 times under a load of 250 g, and the surface of the cured product was visually observed, and scratch resistance was evaluated according to the following criteria.

Evaluation standard:

Almost no scratches are found:◎

Some scratches are found:○

A lot of scratches are confirmed:△

The whole surface is sharpened:×

(Preparation of Hollow Particle Dispersion A)

In a 5L stainless beaker, 3600 parts by mass of ion-exchanged water and 0.4 parts by mass of reactive surfactant Aqualon AR-10 (manufactured by Daiichi Pharmaceutical Co., Ltd.), 0.02 parts by mass of anion-modified polyvinyl alcohol Gosenex L-3266 (manufactured by Japan Synthetic Chemical Co., Ltd.) Parts, 6.0 parts by mass of sodium p-styrene sulfonate and 9.5 parts by mass of potassium persulfate were added and dissolved. A mixed solution of 176 parts by mass of glycidyl methacrylate, 24 parts by mass of 3-methacryloxypropyltriethoxysilane, 4.0 parts by mass of n-octyl mercaptan, and 200 parts by mass of toluene was added to a stainless steel beaker, and an internal ultrasonic homoji Prepare an emulsion by stirring for 10 minutes using a Niger (manufactured by BRANSON, type SONIFIER450), put it in a 5L reactor equipped with a stirrer and thermometer to replace nitrogen to make the inside of a nitrogen atmosphere, and then heat up to 70℃ for 2 hours. By performing a polymerization reaction, polymer particles in which an epoxy group remained. Since toluene was added to the emulsion polymerization, the polymer particles in which the epoxy group remained were swollen with toluene.

Next, in order to polymerize the remaining epoxy group, 100 parts by mass of ethylenediamine was added and polymerization was performed at 70°C for 16 hours. When the epoxy groups in the polymer particles react, the polymer and toluene phase separated to obtain a hollow particle dispersion. 4000 parts by mass of the hollow particle dispersion was cross-flow washed with 14,000 parts by mass of ion-exchanged water using a ceramic filter having a pore diameter of 50 nm, and after removing excess ethylenediamine, appropriate concentration or ion exchange so that the solid content became 10% by mass. Water was added to obtain a 10% by mass aqueous dispersion of hollow particles.

After dissolving the surfactant phosphanol RS-710 (manufactured by Toho Chemical Industries, Ltd.), which has 120 parts by mass of a phosphoric acid group, in 2000 parts by mass of isopropyl alcohol, 2000 parts by mass of an aqueous 10% by mass hollow particle dispersion was added, and an internal ultrasonic homogenizer By stirring for 30 minutes, a surface-treated hollow particle dispersion was obtained. Subsequently, the surface-treated hollow particle dispersion was cross-flow washed with 20000 parts by mass of isopropyl alcohol, and appropriately concentrated or added isopropyl alcohol so as to have a solid content of 10% by mass, and a 10% by mass hollow particle isopropyl alcohol dispersion. Got it.

A hollow particle dispersion into which a reactive group was introduced was obtained by adding 100 parts by mass of 3-methacryloxypropyltrimethoxysilane to 2000 parts by mass of a 10% by mass hollow particle isopropyl alcohol dispersion and stirring at 70°C for 16 hours. . The surface-treated hollow particle dispersion was cross-flow washed with 20000 parts by mass of isopropyl alcohol, isopropyl alcohol was added so that the solid content was 10% by mass, and 10% by mass of the surface-treated hollow particle isopropyl alcohol dispersion (hollow particles The dispersion A) was obtained.

The average particle diameter of the obtained hollow particles by a transmission electron microscope was 81 nm, the dispersed particle diameter in isopropyl alcohol according to the dynamic light scattering method was 105 nm, and the porosity was 40%. In addition, N/C of the hollow particles was 0.03, Si/C was 0.02, and M/C was 0.02.

(Preparation of Hollow Particle Dispersion B)

In a 5L stainless beaker, 3600 parts by mass of ion-exchanged water and 0.4 parts by mass of reactive surfactant Aqualon AR-10 (manufactured by Daiichi Pharmaceutical Co., Ltd.), 0.02 parts by mass of anion-modified polyvinyl alcohol Gosenex L-3266 (manufactured by Japan Synthetic Chemical Co., Ltd.) Parts, 8.0 parts by mass of sodium p-styrene sulfonate and 9.5 parts by mass of potassium persulfate were added and dissolved. A mixed solution of 168 parts by mass of glycidyl methacrylate, 32 parts by mass of 3-methacryloxypropyltriethoxysilane, 4.0 parts by mass of n-octyl mercaptan, and 200 parts by mass of toluene was added to a stainless beaker, and an internal ultrasonic homoji Prepare an emulsion by stirring for 10 minutes using a Niger (manufactured by BRANSON, type SONIFIER450), put it in a 5L reactor equipped with a stirrer and thermometer to replace nitrogen to make the inside of a nitrogen atmosphere, and then heat up to 70℃ for 2 hours. By performing a polymerization reaction, polymer particles in which an epoxy group remained. Since toluene was added to the emulsion polymerization, the polymer particles in which the epoxy group remained were swollen with toluene.

Next, in order to polymerize the remaining epoxy group, 100 parts by mass of ethylenediamine was added, and polymerization was performed at 80°C for 16 hours. When the epoxy groups in the polymer particles react, the polymer and toluene phase separated to obtain a hollow particle dispersion. 4000 parts by mass of the hollow particle dispersion was cross-flow washed with 14,000 parts by mass of ion-exchanged water using a ceramic filter having a pore diameter of 50 nm, and after removing excess ethylenediamine, appropriate concentration or ion exchange so that the solid content became 10% by mass. Water was added to obtain a 10% by mass aqueous dispersion of hollow particles.

After dissolving the surfactant Lyfon LH-200 (manufactured by Lion Specialty Chemicals), which has 120 parts by mass of a sulfonic acid group, in 2000 parts by mass of isopropyl alcohol, 2000 parts by mass of an aqueous 10% by mass hollow particle dispersion was added, and an internal ultrasonic homopaper The surface-treated hollow particle dispersion was obtained by stirring for 30 minutes using a niger. Subsequently, the surface-treated hollow particle dispersion was cross-flow washed with 20000 parts by mass of isopropyl alcohol, and appropriately concentrated or added isopropyl alcohol so as to have a solid content of 10% by mass, and a 10% by mass hollow particle isopropyl alcohol dispersion. Got it.

A hollow particle dispersion into which a reactive group was introduced was obtained by adding 200 parts by mass of 3-methacryloxypropyltrimethoxysilane to 2000 parts by mass of a 10% by mass hollow particle isopropyl alcohol dispersion and stirring at 70°C for 16 hours. . The surface-treated hollow particle dispersion was cross-flow washed with 20000 parts by mass of isopropyl alcohol, isopropyl alcohol was added so that the solid content was 10% by mass, and 10% by mass of the surface-treated hollow particle isopropyl alcohol dispersion (hollow particles Dispersion B) was obtained.

The obtained hollow particles had an average particle diameter of 72 nm by a transmission electron microscope, a dispersed particle diameter of 96 nm in isopropyl alcohol according to the dynamic light scattering method, and a porosity of 40%. In addition, N/C of the hollow particles was 0.04, Si/C was 0.02, and M/C was 0.03.

Example 1

20.0 parts by mass of the hollow particle dispersion A, 0.1 parts by mass of phosphanol RS-710, 1.90 parts by mass of pentaerythritol tetraacrylate (A-TMMT manufactured by Shin-Nakamura Chemical Co., Ltd.), and 0.1 parts by mass of a photopolymerization initiator (Irgacure 127). A hollow particle dispersion was produced by mixing 40.0 parts by mass of a mass part and a methyl isobutyl ketone.

The obtained dispersion had a dispersed particle diameter of 102 nm, a transmittance of 91%, and a dispersion having excellent dispersibility of hollow particles.

In addition, the haze of the cured product was 0.6%, and the surface after the abrasion resistance test was such that some scratches were observed, and it was a cured product having excellent optical properties and physical properties.

Example 2

A hollow particle dispersion was produced in the same manner as in Example 1, except that 0.04 parts by mass of NACURE 5076 and 1.96 parts by mass of pentaerythritol tetraacrylate were used instead of phosphanol RS-710.

The obtained dispersion had a dispersed particle diameter of 104 nm, a transmittance of 90%, and a dispersion having excellent dispersibility of hollow particles.

In addition, the haze of the cured product was 0.7%, and the surface after the abrasion resistance test was such that some scratches were observed, and it was a cured product having excellent optical properties and physical properties.

Example 3

A hollow particle dispersion was produced in the same manner as in Example 1 except that 0.20 parts by mass of BYK-W996 and 1.80 parts by mass of pentaerythritol tetraacrylate were used instead of phosphanol.

The obtained dispersion had a dispersed particle diameter of 109 nm, a transmittance of 87%, and a dispersion having excellent dispersibility of hollow particles.

In addition, the haze of the cured product was 0.7%, and the surface after the abrasion resistance test was such that some scratches were observed, and it was a cured product having excellent optical properties and physical properties.

Example 4

A hollow particle dispersion was produced in the same manner as in Example 1, except that 0.20 parts by mass of Solspurs 41000 and 1.80 parts by mass of pentaerythritol tetraacrylate were used instead of phosphanol RS-710.

The obtained dispersion had a dispersion particle diameter of 110 nm, a transmittance of 87%, and a dispersion having excellent dispersibility of hollow particles.

In addition, the haze of the cured product was 0.7%, and the surface after the abrasion resistance test was such that some scratches were observed, and it was a cured product having excellent optical properties and physical properties.

Example 5

A hollow particle dispersion was produced in the same manner as in Example 1, except that 0.40 parts by mass of KAYAMER PM-21 and 1.60 parts by mass of pentaerythritol tetraacrylate were used instead of phosphanol RS-710.

The obtained dispersion had a dispersed particle diameter of 105 nm, a transmittance of 88%, and a dispersion having excellent dispersibility of hollow particles.

In addition, the haze of the cured product was 0.7%, and the surface after the abrasion resistance test was such that almost no scratches were observed, and it was a cured product having excellent optical properties and physical properties.

Example 6

A hollow particle dispersion was produced in the same manner as in Example 1 except that 0.20 parts by mass of SR9053 and 1.80 parts by mass of pentaerythritol tetraacrylate were used instead of phosphanol RS-710.

The obtained dispersion had a dispersed particle diameter of 106 nm, a transmittance of 88%, and a dispersion having excellent dispersibility of hollow particles.

In addition, the haze of the cured product was 0.7%, and the surface after the abrasion resistance test was such that almost no scratches were observed, and it was a cured product having excellent optical properties and physical properties.

Example 7

20.0 parts by mass of the hollow particle dispersion B, 0.20 parts by mass of SR9053, 1.90 parts by mass of pentaerythritol triacrylate (A-TMM-3LM-N manufactured by Shin-Nakamura Chemical Co., Ltd.), and 0.1 parts by mass of a photopolymerization initiator (Irgacure 127). A hollow particle dispersion was produced by mixing a mass part, 20.0 mass parts of methyl isobutyl ketone, and 20.0 mass parts of butyl acetate.

The obtained dispersion had a dispersed particle diameter of 97 nm, a transmittance of 92%, and a dispersion having excellent dispersibility of hollow particles.

In addition, the haze of the cured product was 0.4%, and the surface after the abrasion resistance test was such that almost no scratches were observed, and it was a cured product having excellent optical properties and physical properties.

Comparative Example 1

A hollow particle dispersion was produced in the same manner as in Example 1 except that Emulgen 123P was used in place of the phosphanol RS-710.

The obtained dispersion was a dispersion having a dispersed particle diameter of 121 nm, a transmittance of 80%, and a low dispersibility of hollow particles.

In addition, the haze of the cured product was 1.1%, and the surface after the abrasion resistance test was such that many scratches were observed, and the cured product had poor physical properties.

Comparative Example 2

A hollow particle dispersion was produced in the same manner as in Example 1 except that cotamine 86W was used in place of phosphanol RS-710.

The obtained dispersion was a dispersion having a dispersed particle diameter of 259 nm, a transmittance of 59%, and a low dispersibility of hollow particles.

In addition, the haze of the cured product was 6.2%, the degree to which the surface after the abrasion resistance test was cut off as a whole, and was a cured product having poor optical properties and physical properties.

Comparative Example 3

A hollow particle dispersion was produced in the same manner as in Example 1 except that 0.20 parts by mass of DISPERBYK-2164 and 1.80 parts by mass of pentaerythritol tetraacrylate were used instead of phosphanol RS-710.

The obtained dispersion was a dispersion having a dispersed particle diameter of 233 nm, a transmittance of 64%, and a low dispersibility of hollow particles.

In addition, the haze of the cured product was 5.4%, the degree to which the surface after the abrasion resistance test was cut out as a whole, and was a cured product having poor optical properties and physical properties.

Comparative Example 4

A hollow particle dispersion was produced in the same manner as in Example 1, except that 0.20 parts by mass of light ester DM and 1.80 parts by mass of pentaerythritol tetraacrylate were used instead of phosphanol RS-710.

The obtained dispersion was a dispersion having a dispersed particle diameter of 332 nm, a transmittance of 54%, and a low dispersibility of hollow particles.

In addition, the haze of the cured product was 8.2%, and the surface after the abrasion resistance test was cut off as a whole, and it was a cured product having poor optical properties and physical properties.

Comparative Example 5

A hollow particle dispersion was produced in the same manner as in Example 1, except that 0.40 parts by mass of light ester M and 1.60 parts by mass of pentaerythritol tetraacrylate were used instead of phosphanol RS-710.

The obtained dispersion was a dispersion having a dispersed particle diameter of 132 nm, a transmittance of 80%, and a low dispersibility of hollow particles.

In addition, the haze of the cured product was 0.7%, and the surface after the scratch resistance test was such that many scratches were observed, and the cured product had poor physical properties.

Meanwhile, the source and physical properties of the drugs of each brand listed in Table 1 are as follows.

Phosphanol RS-710: manufactured by Toho Chemical Industries, Ltd., surfactant having a phosphoric acid group, acid value: 50-75 mgKOH/g

NACURE 5076: manufactured by King Industries, a surfactant having a sulfonic acid group, acid value: 130-149 mgKOH/g (non-volatile content 70%)

BYK-W996: manufactured by Big Chemie Japan, dispersant having a phosphoric acid group, acid value: 71 mgKOH/g (non-volatile content 52%)

Solspur 41000: manufactured by Lubrizol, Japan, dispersant having a phosphate group, acid value: 50±5 mgKOH/g

KAYAMER PM-21: manufactured by Japanese Explosives, Monomer having a phosphoric acid group, acid value: 200 mgKOH/g or less

SR9053: manufactured by Sartomer, a monomer having a phosphoric acid group, acid value: 120-180 mgKOH/g

Emulgen 123P: Kao Corporation, nonionic surfactant

Cotamine 86W: Kao, amine salt type surfactant (non-volatile content 28%)

DISPERBYK-2164: Dispersant having an amino group, manufactured by Big Chemie Japan

Light ester DM: manufactured by Kyoeisha Chemical Co., Ltd., a monomer having an amino group

Light ester M: Kyoeisha Chemical Co., Ltd., nonionic monomer

From the comparison between Examples 1 to 7 in Table 1 and Comparative Examples 1 to 5, it was found that a hollow particle dispersion suitable for producing a film having a small particle diameter and high scratch resistance can be produced.

Example 8 (substrate with antireflection film and antireflection film)

20 parts by mass of the hollow particle dispersion of Example 1, 4 parts by mass of dipentaerythritol polyacrylate (NK ester A-DPH manufactured by Shin-Nakamura Chemical Co., Ltd.), 0.20 parts by mass of a photopolymerization initiator (IRGACURE 1173 manufactured by BASF), and ultrasonic waves Forced stirring for 5 minutes using a homogenizer to obtain a coating agent. 0.5 ml of the coating agent was added dropwise to a slide glass (S1111 manufactured by Matsunami Glass Industries, Ltd.), and applied with a spin coater (manufactured by Kyowa Riken, Model K-359SD1) to obtain a coating film. The obtained coating film was dried at room temperature (about 25°C) and under normal pressure. An antireflection film is formed on a glass substrate by passing the dried coating film twice through an ultraviolet irradiation device (J-Cure manufactured by JATEC, type JUC1500, tensile speed: 0.4m/min, accumulated light amount: 2000mJ/cm2). A substrate on which an antireflection film was formed was prepared.

Example 9 (Substrate with light extraction film and light extraction film)

20 parts by mass of the hollow particle dispersion of Example 1, 4 parts by mass of dipentaerythritol polyacrylate (NK ester A-DPH manufactured by Shin-Nakamura Chemical Co., Ltd.), 0.20 parts by mass of a photopolymerization initiator (IRGACURE 1173 manufactured by BASF), and ultrasonic waves Forced stirring for 5 minutes using a homogenizer to obtain a coating agent. 0.5 ml of the coating agent was added dropwise to a slide glass (S1111 manufactured by Matsunami Glass Industries, Ltd.), and applied with a spin coater (manufactured by Kyowa Riken, Model K-359SD1) to obtain a coating film. The obtained coating film was dried at room temperature (about 25°C) and under normal pressure. A light extraction film is formed on a glass substrate by passing the dried coating film twice through an ultraviolet irradiation device (J-Cure manufactured by JATEC, type JUC1500, tensile speed: 0.4m/min, accumulated light quantity: 2000mJ/cm2). A substrate on which a light extraction film was formed was prepared.

Example 10 (light guide plate ink/light guide plate)

The hollow particle dispersion of Example 1 was washed three times with methyl ethyl ketone to obtain a 10 mass% hollow particle methyl ethyl ketone dispersion. 45 parts by mass of a 10% by mass of hollow particle methyl ethyl ketone dispersion, 10 parts by mass of an acrylic resin (Acridic A-181 manufactured by DIC, 45% solid content), a polyetherphosphate surfactant (Solsper 41000 manufactured by Lubrizol, Japan) ) 1.0 parts by mass were mixed to obtain a light-diffusing composition (light guide plate ink).

The light-diffusing composition was screen-printed on a 5-inch transparent acrylic plate so as to have a dot pitch of 500 μm and a dot diameter of 50 μm to obtain a light guide plate.

Example 11 (low dielectric constant film)

20 parts by mass of a 10% by mass surface-treated hollow particle isopropyl alcohol dispersion prepared in Example 1, 4 parts by mass of dipentaerythritol polyacrylate (NK ester A-DPH manufactured by Shin-Nakamura Chemical Co., Ltd.), a photoinitiator (BASF) Production IRGACURE 1173) 0.20 parts by mass were mixed, and forced stirring for 5 minutes using an ultrasonic homogenizer to obtain a coating agent. 0.5 ml of the coating agent was added dropwise to a slide glass (S1111 manufactured by Matsunami Glass Industries, Ltd.), and applied with a spin coater (manufactured by Kyowa Riken, Model K-359SD1) to obtain a coating film. The obtained coating film was dried at room temperature (about 25°C) and under normal pressure. A low dielectric constant film was produced on a glass substrate by passing the dried coating film twice through an ultraviolet irradiation apparatus (J-Cure manufactured by JATEC, model JUC1500, tensile speed: 0.4 m/min, accumulated light amount: 2000 mJ/cm 2) and cured.

Claims (13)

A hollow particle dispersion containing a hollow particle having a shell formed of at least one or more layers, an acidic compound and an organic solvent,
At least one of the layers contains a nitrogen atom and a carbon atom,
Hollow particles in which the content of the acidic compound is 0.01 to 70 parts by mass with respect to 100 parts by mass of the total of the hollow particles and the acidic compound, and the content of the hollow particles is 0.01 to 30 parts by mass with respect to 100 parts by mass of the hollow particle dispersion. Dispersion. The method of claim 1,
Hollow particle dispersion, wherein the acidic compound exhibits an acid value of 10 to 300 mgKOH/g. The method according to claim 1 or 2,
The hollow particle dispersion, wherein the hollow particles exhibit an average particle diameter of 30 to 120 nm and a porosity of 10 to 70%. The method according to any one of claims 1 to 3,
A hollow particle dispersion in which the abundance ratio N of nitrogen atoms and the abundance C of carbon atoms in the XPS measurement of the hollow particles satisfy the relationship of 0.01≦N/C≦0.2. The method according to any one of claims 1 to 4,
Hollow particle dispersion in which at least one of the layers contains a silicon atom and a carbon atom, and the abundance ratio of the silicon atom Si and the abundance C of the carbon atom in the XPS measurement of the hollow particle satisfies the relationship of 0.001≦Si/C≦0.1 sieve. The method according to any one of claims 1 to 5,
The hollow particles are non-(α) of the absorbance (A810) and absorbance 1720㎝ ^-1 (A1720) in the infrared absorption spectrum in 810㎝ ^-1 according to the obtained measured by ATR-FTIR (absorbance ratio (α): A810 /A1720), a hollow particle dispersion showing an absorbance ratio (α) of 0.015 to 0.50. The method according to any one of claims 1 to 6,
Hollow particle dispersion wherein the acidic compound is selected from inorganic acids, carboxylic acid compounds, alkyl ester compounds of acids, sulfonic acid compounds, phosphoric acid ester compounds, phosphonic acid compounds, and phosphinic acid compounds. The method according to any one of claims 1 to 7,
Hollow particle dispersion wherein the organic solvent is selected from alcohol-based solvents, ketone-based solvents, ester-based solvents, glycol ether-based solvents, and glycol ester-based solvents. The coating agent containing the hollow particle dispersion of any one of Claims 1-8. The hollow particle dispersion for a heat insulating film in any one of Claims 1-8. A hollow particle dispersion for a substrate having the antireflection film and the antireflection film according to any one of claims 1 to 8. A hollow particle dispersion for a substrate on which the light extraction film and the light extraction film of any one of claims 1 to 8 are formed. The hollow particle dispersion for a low dielectric constant membrane according to any one of claims 1 to 8.