JP7265683B2 - reactive composition - Google Patents

Description

The present invention relates to reactive compositions used to make polymeric matrix bodies containing volatile materials.

Traditionally, volatile substances dissolved in solvents such as water are dissolved or solubilized in water-based solvents, or air fresheners, volatile insect repellents, and volatile fungicides in which active ingredients are carried in volatile solvents. Volatile formulations such as agents are known.

Among these, for example, fragrances are widely used for automobiles as well as for households. A large amount of volatile substances are volatilized in the car air freshener because the temperature of the sunlit part of the car parked under the scorching sun is close to 40 to 80°C. The amount of volatilization in a volatile formulation depends on the rate of volatilization of the volatile substance itself or the volatile solvent used as the carrier. As a result, there is a problem that the amount of volatile substance volatilized far exceeding the required amount in a given space.

In order to suppress the significant increase in the amount of volatile substances volatilized under such high-temperature conditions, the rate of volatilization can be controlled by combining a thermosensitive polymer that causes thermoreversible aggregation or gelation with volatile substances. There is a volatilization adjustment type liquid fragrance (Patent Document 1). However, in order to prevent the excessive release of volatile substances in the early stages, providing a barrier or a gelling structure will reduce the amount of volatile substances released in the latter half more than necessary. There was a fear of not fulfilling the Furthermore, there is a problem that volatile substances tend to bleed out and the storage stability is poor.

Perfumes, deodorants, insect repellents, repellents, attractants, insecticides, fungicides, growth regulators, herbicides, fumigants, and other volatile substances are retained in the polymer matrix body, and are used in indoor and other atmospheres. It is also known that when left inside, the volatile substances gradually volatilize into the atmosphere, exhibiting effects such as fragrance and deodorization. These products also tend to cause bleed-out of volatile substances and have problems in storage stability.

JP-A-06-207162

The present invention suppresses bleed-out of volatile substances, does not require heating during production, and has good storage stability of volatile substances, and has excellent properties such as low toxicity, odorlessness, transparency, and breathability. It is an object of the present invention to provide a reactive composition capable of forming a polymer matrix body having a

The present invention is as follows.
[1] A reactive composition containing (a) two or more monomers polymerizable by light irradiation and (b) a volatile substance,
The Hansen Solubility Parameter (HSP) is calculated for each of the monomer (a) and the volatile substance (b), and the HSP distance (Ra) between the monomer (a) and the volatile substance (b) is 8 MPa ^1/2 or less. , the components are adjusted so that the relative energy difference RED (RED = Ra / volatile substance dissolving sphere radius R ₀ ) is less than 1,
The HSP distance Ra' between the polymer (a') and the volatile substance (b) after the reaction of the reactive composition is 8 MPa ^1/2 or less, and the relative energy difference RED' (RED1 =Ra'/radius of volatile substance dissolving sphere _R0 and RED2=Ra'/radius of dissolving sphere of polymer _R1 ) are both 0.6 or less.
[2] The reactive composition according to [1], wherein the reactive composition undergoes a polymerization reaction by irradiating the droplets with light.
[3] The reactivity according to [1] or [2], wherein the monomer is a radically polymerizable compound having an ethylenically unsaturated bond at the molecular chain end or a compound having both an ethylenically unsaturated bond and an epoxy group. Composition.
[4] The radically polymerizable compound is an acrylate compound, a urethane acrylate compound, an epoxy acrylate compound, a polyether acrylate compound, or an oligoester acrylate compound having an acryloyl group or a methacryloyl group at the molecular chain end [ 3].
[5] The reactive composition according to any one of [1] to [4], wherein the content of the volatile substance in the reactive composition is 0.5 to 30% by weight.

In the present invention, blending is adjusted in the direction of reducing the difference in Hansen solubility parameter between the polymerizable material (monomer material) and the volatile substance, and a volatile substance-containing polymer matrix is obtained by a polymerization method using light irradiation. To provide a polymer matrix body capable of obtaining a desired volatilization rate without causing bleed-out even if the volatilization rate of the volatile substance is adjusted to a desired level by increasing the content of the volatile substance. can be done. Controlling the Hansen Solubility Parameter not only enhances the compatibility of each material and prevents bleed out, but also leads to an increase in the amount of volatile substance that can be filled.

In addition, a matrix base material containing a radically polymerizable compound having an ethylenically unsaturated bond that is curable at room temperature is used and polymerized at room temperature by light irradiation and cured in a short period of time. There is no loss due to volatilization or deterioration of volatile substances. Furthermore, the radically polymerizable compound having an ethylenically unsaturated bond is low in toxicity, odorless, and harmless to the human body.

FIG. 1 is a diagram showing Hansen solubility parameters of Hansen space volatile substances and radically polymerizable monomers or oligomers. FIG. 2 is a schematic diagram showing the relationship between the HSP distance (Ra) and the interaction radius (R ₀ ) between the volatile substance in the Hansen space and the radically polymerizable monomer or oligomer. FIG. 3 is a schematic diagram showing an apparatus for producing beads in the dropping method of the present invention. FIG. 4 is a schematic diagram of beads obtained by the dropping method. FIG. 5 is a schematic diagram showing the overlapping of volatile substance-dissolving spheres (s) and post-reaction polymer-dissolving spheres (s') in the Hansen space.

When the reactive composition of the present invention is irradiated with light, a polymerization reaction proceeds to form a polymer matrix body. As used herein, the term "polymer matrix body" refers to a state in which polymerized polymers are linked three-dimensionally. It can be a mass of gel, granules or beads, or a sheet having a certain thickness. In this specification, examples based on the shape of beads are mainly shown, but it can be easily expected that the same effect of the invention can be obtained from the polymerization method even in other shapes. The polymer matrix body contains various volatile substances and an oily liquid component obtained by dissolving or uniformly dispersing a solubilizer, a volatilization retention agent, and a filler in the volatile substance, if necessary. there is

The reactive composition of the present invention contains (a) two or more monomers capable of being polymerized by light irradiation and (b) a volatile substance, wherein each of the monomer (a) and the volatile substance (b) Calculate the Hansen Solubility Parameter (HSP) to the HSP distance (Ra) between the monomer (a) and the volatile substance (b) is 8 MPa ^1/2 or less, and the relative energy difference RED (RED = Ra/volatility The components are adjusted so that the substance dissolving sphere radius R ₀ ) is less than 1, and the HSP distance between the polymer (a′) and the volatile substance (b) in the reactive composition is Ra′, and the polymer (a ') and the relative energy difference RED'(RED1=Ra'/radius of volatile substance dissolving sphere _R0 and RED2=Ra'/radius of dissolving polymer sphere _R1 ) are both 0.6 or less. there is
The contents are explained below.

The two or more monomers (a) polymerizable by light irradiation, which constitute the polymer matrix body of the present invention, are exemplified by radically polymerizable compounds having an ethylenically unsaturated bond at the molecular end. A (meth)acrylate compound having an acryloyl group or a methacryloyl group at the molecular chain end, an unsaturated polyester composed of an unsaturated dicarboxylic acid such as fumaric acid or maleic acid and a polyhydric alcohol such as ethylene glycol or propylene glycol is preferably used. be done. In the present specification, the term "monomer" means a low-molecular-weight compound having a polymerizable functional group, but it also includes multimers of monomers generally called oligomers. Also, the definition of "two or more types of monomers" means a mixture of two different types of monomers.

In this specification, the term "(meth)acryloyl group" indicates either acryloyl group or methacryloyl group, and the term "(meth)acrylate" indicates either acrylate or methacrylate. The (meth)acrylate compound used in the present invention includes urethane (meth)acrylate having one or more urethane bonds in one molecule and having a (meth)acryloyl group at the end, epoxy synthesized from an epoxy resin ( (Meth)acrylic compounds such as meth)acrylates, polybutadiene (meth)acrylates with polybutadiene as the backbone, oligoester (meth)acrylates with ester linkages as the main chain, and polyether (meth)acrylates with ether linkages as the main chain Oligomers, mono(meth)acrylate monomers having one (meth)acryloyl group, and polyfunctional (meth)acrylate monomers having two or more (meth)acryloyl groups are preferably used. A urethane (meth)acrylate can be synthesized, for example, from a polyol component, an isocyanate component, and a (meth)acrylate component having a hydroxyl group for introducing a terminal acryloyl group. The polyol component applied to the synthesis of such urethane (meth)acrylates is a synthetic polymer compound having two or more hydroxyl groups in the molecule, such as polyether polyol compounds, polyester polyol compounds, polyurethane polyol compounds, Polyhydroxy polyolefin compounds and the like are exemplified. Epoxy (meth)acrylate is synthesized from epichlorohydrin, a polyol component and a (meth)acrylate component having a hydroxyl group. Examples of mono(meth)acrylate monomers having one (meth)acryloyl group include usual acrylic acid, methacrylic acid, and acid esters thereof (eg, methyl (meth)acrylate, ethyl (meth)acrylate, etc.). A polyfunctional (meth)acrylate monomer having two or more (meth)acryloyl groups is obtained by introducing (meth)acryloyl groups into both terminal hydroxyl groups of the polyol component described above. Preferred (meth)acrylate compounds for the polymer matrix body of the present invention include (meth)acrylate monomers (oligomers), urethane-modified urethane (meth)acrylate monomers (oligomers), and epoxy-modified epoxy ( meth)acrylate monomers (oligomers).

Examples of the above (meth)acrylate monomers or oligomers include propoxylated ethoxylated bisphenol A di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, polyglycerin monoethylene oxide poly(meth)acrylate, polyglycerin polyethylene Glycol poly(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, ethoxylated glycerin tri(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate ) acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol poly(meth)acrylate, and the like.

Examples of the polyether polyol compound include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polybutylene glycol, polytetramethylene glycol and polyhexamethylene glycol, or alkylene oxides such as ethylene oxide, propylene oxide and tetrahydrofuran, and ethylene glycol. , diethylene glycol, propylene glycol, dipropylene glycol, glycerol, trimethylolpropane, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,2,6-hexanetriol, Examples include polyether polyols obtained by addition to polyhydric alcohols such as pentaerythritol.

Examples of the above polyester polyol compounds include phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrachlorophthalic acid, tetrabromophthalic acid, hexahydrophthalic acid, succinic acid, maleic acid, adipic acid, sebacic acid, and dodecenylsuccinic acid. , trimellitic acid or other polybasic acids or their anhydrides, and polyester polyols obtained by condensation reaction with the aforementioned polyhydric alcohols.

Polyurethane polyol compounds include polyurethane polyols obtained by an addition reaction between a polyisocyanate compound or a polymer thereof and an excess polyhydric alcohol; Polyurethane polyols obtained by the compound are exemplified.

Furthermore, examples of polyhydroxy polyolefin compounds include acrylic polyol, polybutadiene polyol, polyisoprene polyol, hydrogenated polybutadiene polyol, and hydrogenated polyisoprene polyol.

Examples of isocyanate components applied to synthesis of urethane (meth)acrylates include ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, phenylene diisocyanate, xylene diisocyanate, diphenylmethane-4,4'-diisocyanate, naphthylene-1,5-diisocyanate, isophorone diisocyanate, 1-methyl-2 ,4-diisocyanatocyclohexane, 1-methyl-2,6-diisocyanatocyclohexane, dicyclohexylmethane diisocyanate and the like.

Furthermore, as the (meth)acrylic acid ester component having a hydroxyl group for introducing a terminal (meth)acryloyl group applied to the synthesis of urethane (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl ( meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, ε-caprolactone-modified hydroxy (meth) acrylate, etc. exemplified.

<Photoinitiator>
Examples of the photopolymerization initiator of the present invention include phosphine oxide compounds, benzoylformate compounds, thioxanthone compounds, oxime ester compounds, hydroxybenzoyl compounds, benzophenone compounds, ketal compounds, α-aminoalkylphenone compounds, and the like. Phosphine oxide compounds include bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Benzoyl formate compounds include methyl benzoyl formate and the like. The thioxanthone compound includes isopropylthioxanthone and the like. Hydroxybenzoyl compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone and benzoin alkyl ether. Examples of benzophenone compounds include Michler's ketone and benzophenone.

Among these, phosphine oxide compounds, hydroxybenzoyl compounds and α-aminoalkylphenone compounds are preferred from the viewpoint of curability and coloring of the cured product. A photoinitiator may be used individually by 1 type, or may use 2 or more types together.

The amount of the photopolymerization initiator used is preferably 2 to 15% by weight, more preferably 2 to 10% by weight, based on the weight of the monomer component, from the viewpoint of curability and coloring of the cured product.

<Volatile substance>
As the volatile substance used in the present invention, when left in the atmosphere, it gradually volatilizes into the atmosphere and exerts an effect as a desired active ingredient such as fragrance and deodorant. Fragrances, deodorants, insect repellents, repellents, attractants, insecticides, bactericides, fumigants and the like are used.

Perfumes preferably used include terpenes such as citronellol, geraniol, terpineol, benzyl alcohol, dihydromyrcenol, dibenzyl ether, benzaldehyde, cyclamenaldehyde, lyrial, benzyl acetate, limonene, benzyl benzoate, terpenyl acetate, Examples include alcohol-based, aldehyde-based, ketone-based, ester-based, phenol-based natural and synthetic fragrances, and compounded fragrances which are mixtures thereof.

Examples of deodorants include α,β-unsaturated carboxylic acids and their esters such as fumaric acid, crotonic acid and citraconic acid, and active methylene compounds such as acetylacetone, ethyl acetoacetate and malonic acid. Examples of insect repellents include naphthalene, camphor, p-dichlorobenzene and the like. Examples of repellents include neem extract, 1,8-cineole, and phthalates.

In addition to the above, empentrin, transfluthrin, profluthrin, and the like are preferably used as insect repellents.

In addition to the above, repellents include empenthrin, transfluthrin, allethrin, phenothrin, profluthrin, metofruthrin, eminence, dichlorvos, diazinon, fenitrothion, malathion, N,N-diethyl-m-toluamide (DEET), dimethylphthalate, Dibutyl phthalate, 2-ethyl-1,3-hexanediol, di-n-propylisocincomeronate, p-dichlorobenzene, di-n-butylsuccinate, carane-3,4-diol, 1-methylpropyl- 2-(2-hydroxyethyl)-1-piperidine carboxylate, isopropyl myristate, isobornyl thiocyanoacetate, diphenyl, diphenylmethane, dibenzyl, benzylphenyl ether, benzylphenyl ethyl ether, benzophenone, benzylphenyl ketone, dibenzyl ketone, benzal Acetophenone, β-phenylethyl benzoate, γ-phenylpropyl benzoate, phenyl phenylacetate, benzylphenylacetate, β-phenylethylphenylacetate, phenylcinnamate, benzylcinnamate, β-phenylethylcinnamate, β-phenylpropyl Cinnamate, cinnamyl cinnamate, diphenylcarbinol, phenylbenzylcarbinol, dibenzylcarbinol, n-amyl benzoate, isoamyl benzoate, hexyl benzoate, heptyl benzoate, octyl benzoate, nonyl benzoate, cis-3-hexenyl benzoate , n-amyl salicylate, isoamyl salicylate, hexyl salicylate, cis-3-hexenyl salicylate, benzyl propionate, benzyl-n-butyrate, benzo-iso-butyrate, benzyl-n-valerate, benzyl isovarate, benzyl capro Terpene compounds such as ate, benzylheptanoate, benzylcaprylate, pentyldanilate, eugenol, methyleugenol, isoeugenol, α,β-pinene, α,β-terpinol, limonene, citronellal, linalool, citral; Menthol, vetiver oil, patchouli oil, clove oil, plant essential oils such as essential oils of cedar, cypress, Taiwan cypress, and hiba, pressed liquids, extracts, and distillates of plants belonging to the genus Fir of the family Pinaceae, and the like. A seed may be used individually and can also be used in combination of 2 or more types.

Attractants include an extract obtained by boiling a mixture of dried sardine powder, dried bonito powder, brewer's yeast, bread crumbs, etc., coconut oil, acetoin, diacetyl, acetone, ethyl acetate, phenethyl alcohol, 3-methyl-1-butanol, etc. exemplified.

Insecticides such as carboxylic acid hydrazides, methyl 1-naphthyl-N-carbamate, 4-bromo-2-(4-chlorophenyl)-1-ethoxymethyl-5-trifluoromethylpyrrole-3-carbonitrile, pyrethrin, etc. , and mixtures thereof.

Carbamic acid etc. are illustrated as a disinfectant.

Examples of fumigants include chloropicrin, 1,3-dichloropropene, dichlorodiisopropyl ether, methyl isothiocyanate and the like.

Volatile substances are used by dissolving them in a solvent as necessary. The choice of solvent depends on the nature of the volatile matter. As the solvent, an alcohol-based solvent, a ketone-based solvent, an ester-based solvent, or the like, which has good compatibility between the volatile substance and the curable resin, can be appropriately used. Some of these solvents are also used as perfumes.

Examples of solvents include benzyl alcohol, dibenzyl ether, benzyl acetate, methyl benzoate, benzyl benzoate, diethyl phthalate, dipropylene glycol, ethyl carbitol, hexylene glycol, 3-methoxy-3-methylbutanol, 3-methyl-3- Methoxybutyl acetate, citronellol, dihydromyrcenol, dihydroterpineol, geraniol, terpineol, benzaldehyde, cyclamenaldehyde, hydroxycitronellal, geranyl acetate, linalyl acetate, limonene and the like. Among these, benzyl benzoate, diethyl phthalate, dipropylene glycol, ethyl carbitol, hexylene glycol and the like are more preferably used.

The amount of the volatile substance in the polymer matrix body of the present invention is preferably 0.5 to 30% by weight, more preferably 0.5 to 20% by weight, based on the total weight of the polymer matrix body. If the content of the volatile substance is less than 0.5% by weight based on the total weight of the polymer matrix body, it is difficult to obtain the properties of the volatile substance, specifically, effects such as fragrant, deodorant, and insect repellent properties. If the amount exceeds 30% by weight, the amount of the polymer matrix becomes relatively small, making it difficult to obtain a suitable matrix. If it is up to 30% by weight, a polymer matrix body whose components are adjusted within the range of the present invention can be obtained.

The molecular weight of the volatile substance is, for example, 200-1000, preferably 200-500. If the molecular weight of the volatile substance exceeds the above range, the compatibility of the volatile substance with the polymer may decrease. On the other hand, if the molecular weight of the volatile substance is less than the above range, the volatile substance may remain in the reaction solution during the manufacturing process, and may precipitate and solidify.

<Other ingredients>
In the present invention, an antistatic agent or an antifogging agent may be appropriately added to the monomer composition and/or the polymer composition in order to suppress aggregation due to static electricity in the polymer matrix body after polymerization. .

Antistatic agents or antifogging agents include silica gel, polyoxyalkylene ether, partial ester of polyhydric alcohol, partial ester of alkylene oxide adduct of polyhydric alcohol, poly(oxyethylene)alkylamine, poly(oxyethylene). ) alkylamides, higher alcohol sulfate alkali metal salts, alkylarylsulfonates, quaternary ammonium salts, and the like. More specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol monopalmitate, polyethylene glycol monostearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan mono Palmitate, Glycerin Monolaurate, Glycerin Monopalmitate, Glycerin Monostearate, Glycerin Monooleate, Pentaerythritol Monolaurate, Sorbitan Monopalmitate, Sorbitan Monobehenate, Sorbitan Monostearate, Sorbitan Distearate, Diglycerin monooleate, triglycerol diolate, lauryl diethanolamine, N,N-bis(2-hydroxyethyl) stearylamine, polyoxyethylene laurylamine capryl ester, stearyl diethanolamine monostearate, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, Sodium butylnaphthalenesulfonate, cetyltrimethylammonium chloride, trimethylbenzylammonium chloride, triethylcetylammonium iodide, dodecylamine hydrochloride, laurylamidoethyl laurate phosphate, oleylaminodiethylamine hydrochloride, dodecylpyridinium sulfate, etc. can be done.

The molded article obtained by the polymerization reaction of the reactive composition of the present invention may be of any shape such as beads without partition walls, granules, sheets, rods, and bulk materials of irregular shape.

In the case of beads, the average particle size is usually 0.5-20 mm, and in order to obtain the optimum effect of the present invention, the particle size is preferably 0.5-5 mm.

<Method of Forming Beads in Photopolymerization Reaction by Dropping Method>
The reactive composition of the present invention is capable of forming small spheres (ie, beads) by photopolymerization reaction by the so-called dropping method. FIG. 3 shows a schematic diagram showing a bead manufacturing apparatus in the dropping method of the present invention. As shown in FIG. 3, it can be manufactured by the submerged dropping method using a conventionally known capsule manufacturing technology apparatus equipped with a single layer nozzle (1). Specifically, as shown in FIG. 3, a mixture (2) of a monomer (a) and a volatile substance (b) used in the present invention is passed through a single layer nozzle (1) into a carrier fluid (6). Beads can be produced by methods such as those involving the step of dripping.

It should be noted that the carrier fluid (6) desirably has a polarity different from that of the forming composition. pyrrolidone, (modified) starch, carboxymethylcellulose, methylcellulose, ethylcellulose, sodium alginate, pectin, locust bean gum, tamarind seed gum, xanthan gum, glycerol, (poly)ethylene glycol, (poly)propylene glycol, etc.) aqueous solution or water is preferred. When the forming composition is aqueous (hydrophilic), it is preferably a liquid oily (hydrophobic) substance (liquid oil), such as olive oil, jojoba oil, corn oil, rapeseed oil, lard, beef tallow, Whale oil, castor oil, soybean oil, rice oil, rice germ oil, coconut oil, palm oil, cacao oil, avocado oil, macadamia nut oil, squalane, mink oil, turtle oil, hydrocarbons with 8-30 carbon atoms, lanolin , liquid paraffin, vaseline, silicone oil, fatty acids with 4 to 30 carbon atoms, esters of fatty acids with 4 to 30 carbon atoms and sucrose, esters of fatty acids with 4 to 30 carbon atoms and glycerol, Fatty alcohols having 4 to 30 carbon atoms, esters of fatty acids having 4 to 30 carbon atoms and fatty alcohols having 4 to 30 carbon atoms (e.g., stearyl palmitate, cetyl 2-ethylhexanoate, methyl laurate, myristic acid isopropyl palmitate, 2-ethylhexyl palmitate, octyldodecyl myristate, methyl stearate, butyl stearate, 2-ethylhexyl stearate, isotridecyl stearate, myristyl myristate, stearyl stearate, etc.), combinations thereof, etc. is mentioned.

The bead formation method of the first embodiment will be specifically described with reference to FIG. Single-layer beads can be manufactured by a submerged dropping method using a capsule manufacturing apparatus equipped with a single-layer nozzle (1) shown in FIG. It is desirable that the single-layer nozzle (1) is arranged with the ejection port facing downward in the vertical direction. Moreover, it is desirable to arrange the discharge port of the nozzle inside the forming tube. The carrier liquid (6) is circulated through the device preferably at a constant speed by driving means such as a pump (8). After thoroughly stirring the radically polymerizable monomer or oligomer mixture (polymerization initiator-added solution) and the volatile substance through the single-layer nozzle (1), they are simultaneously extruded (injected) into the carrier fluid through the nozzle hole (2). ). A monolayer jet stream is then formed due to the interfacial tension acting between the carrier fluid (6) and the forming composition. The jet stream then forms spherical droplets (bead precursors) under the action of gravity. At this time, by applying vibration to the jet stream, it is possible to make the particle sizes of the droplets uniform.

A light source (4) is then used to illuminate the bead precursor. The irradiation of the bead precursors with light may be carried out at any stage. may be after separation. Thus, the beads (9) shown in FIG. 4 can be obtained. The beads are characterized by the volatile substance (10) being uniformly retained in the reactive composition.

The light source (4) is not particularly limited as long as it can irradiate light with a wavelength of about 200 nm to about 800 nm, such as a mercury lamp, fluorescent lamp, Zenon lamp, carbon arc lamp, metal halide lamp, etc., and can be used. It can be appropriately selected according to the photocurable component. In addition, when a photosensitizer is added to the above-described forming composition, the photocurable component can be cured by visible light. The irradiation time varies depending on the intensity and distance of the light source, but generally it can be formed in 1 second to 10 minutes. Since the necessary irradiation time varies greatly depending on the embodiment such as the particle size and the content of the volatile substance, complete curing can be achieved by extending the irradiation time with an external device as necessary.

The reactive composition is preferably a composition that does not cause lumps or uneven appearance after sufficiently mixing the mixture of the monomer (a) and the volatile substance (b) before dropping. Specifically, the Hansen Solubility Parameters are used for the desired compositional design.

<Explanation of Hansen Solubility Parameter>
The Hansen Solubility Parameters are determined by Charles M. et al. It was published by Mr. Hansen and is known as an index of solubility between substances. The Hansen solubility parameters are composed of the following three numerical values D, P, and H, and these three parameters are expressed as coordinates in a three-dimensional space (Hansen space).
D: (atomic) dispersion force P: (molecular) polarization force H: (molecular) hydrogen bonding force The closer they are to each other, the easier they dissolve, and the farther they are, the harder they dissolve. In addition, the Hansen solubility parameter can be used not only for judging solubility, but also as an index for judging how easily a certain substance exists in another certain substance, that is, how good the dispersibility is.

The Hansen solubility parameters of the monomer (a), the volatile substance (b), and the polymer formed by polymerization (a') can be calculated from the results of solubility or swelling experiments in known solvents. In this case, the software HSPiP (Hansen Solubility Parameters in Practice: Windows (registered trademark) software for efficiently handling HSPs) developed by Hansen et al.

To obtain the Hansen Solubility Parameters, the desired substance is dissolved (mixed) in multiple solvents with known Hansen Solubility Parameters, and the Hansen Solubility Parameters of the solvents in which the target substance dissolves and those in which it does not dissolve are plotted in the Hansen space. The center of a sphere (Hansen's dissolving sphere) formed by a collection of plots of dissolving solvents is taken as the Hansen solubility parameter of the target substance. These can be calculated using the software HSPiP.

The RED value (Relative Energy Difference) of the monomer (a) to the volatile substance (b) is the distance of the Hansen solubility parameter Ra between the two substances, and the interaction radius, which is the radius of the volatile substance dissolving sphere. is represented _by RED=Ra/ _R0 . FIG. 1 is a diagram plotting the Hansen solubility parameter a of the monomer (a) and the Hansen solubility parameter b of the volatile substance (b) in the Hansen space. If the RED value of the mixture of monomers (or oligomers) relative to the volatile substance is less than 1, then inside the melting sphere s of volatile substance (b), the Hansen solubility parameter a is located, and the volatile substance (b) and the monomer (a) are readily soluble in each other. FIG. 2 further illustrates these relationships in an easy-to-understand manner. FIG. 2 shows the situation when the RED value is less than one. It can be said that the smaller the RED value, the shorter the distance between the two points and the higher the compatibility between the two substances.

<Calculation of Hansen Solubility Parameter and Interaction Radius of Volatile Substances>
The interaction radius R ₀ and Hansen solubility parameter of volatile substances were calculated by the following procedure.
(1) Dissolution test Prepare 13 types of test solvents with known Hansen solubility parameters shown in Table 1, and add the test solvent and volatile substance at a volume ratio of 1:1 to a screw tube with a capacity of 10 ml. After sufficiently stirring, the mixture was allowed to stand for 5 minutes, and the state of the liquid was confirmed and scored.
1: Dissolution (colorless and transparent, transparent)
0: cloudiness, separation (2) Calculation of Hansen solubility parameter and interaction radius _R0 , which is the radius of the volatile substance dissolving sphere Using software HSPiP, Hansen solubility parameter and interaction radius _R0 based on the evaluation results of (1) can be calculated.

<Calculation of the Hansen Solubility Parameter of a Mixture of Monomers or Oligomers>
The Hansen solubility parameter of each single monomer (a) was calculated in the same manner as described above. The Hansen solubility parameter of the monomer (or oligomer) mixture (monomer (a)) used as the actual composition is the volume ratio at the time of mixing, multiplied by the Hansen solubility parameter of each component, and the value calculated for each component. was used (volume-weighted average value).

<How to calculate the HSP distance Ra>
The HSP distance Ra is the distance separating the volatile substance (b) from the monomer (a). The formula for calculating the HSP distance is described below.
Ra={4×(δ ^ad _−δ ^b _d ) ² +(δ ^a _p −δ ^b _p ) ² +(δ ^a _h −δ ^b _h ) ² } ^0.5
δ ^ad _, δ ^ap , δ ^ah _are the Hansen solubility parameters of _the mixture ( _a ) ^of the monomer (or _oligomer ) before ^the radical ^{polymerization} reaction _; Hansen Solubility Parameter. Each parameter value was substituted into this formula to calculate the HSP distance between two points.

<Calculation method of relative energy difference (RED value)>
The HSP distance Ra, which is the distance of each Hansen solubility parameter calculated above, and the dissolving sphere radius _R0 of the volatile substance calculated as the interaction radius are used. The formula for calculating the RED value is described below.
RED=Ra/R ₀
It can be said that the smaller this value, the easier the monomer (a) and the volatile substance (b) dissolve. In the range of RED value>1, it can be said that the compatibility between the two substances is poor.

A mixed solution was prepared by adjusting the component ratio of the monomer (a) and the volatile substance (b) to the conditions described in Table 2, and the state after stirring the mixed solution and the state after UV curing (curability, 30 Occurrence of bleeding out due to standing still for days) was confirmed. 30 parts by weight of the volatile substance was mixed with 100 parts by weight of the whole.

From the above results, it was confirmed that the RED value<1 is the condition under which lumps and unevenness in appearance do not occur in the mixture of the volatile substance and the monomer (or oligomer) before radical polymerization. However, when Ra>8 MPa ^1/2 and RED value<1, the volatile substance cannot be retained in the polymer after UV curing, and so-called bleed-out occurs. It was found that by setting Ra≦8 MPa ^1/2 as the condition under which these phenomena do not occur, it is possible to produce a radically polymerizable composition that exhibits good curability and does not cause bleeding out.

Next, the compatibility between the polymer (a') and the volatile substance (b) after UV curing under four conditions prepared in Table 2 was confirmed using Hansen solubility parameters. The test method is as follows.

<Calculation of Hansen Solubility Parameter and RED Value of Radically Polymerizable Reactive Composition (Polymer)>
The Hansen solubility parameter Ra' of the radical polymerizable compound was calculated by the following procedure.
(1) Dissolution (swelling) test A mixture of monomers (or oligomers) adjusted to each condition was irradiated with a UV irradiation machine (LED H-16VCII-C manufactured by HOYA) with an output of 100%, an irradiation distance of 4.5 cm, and an irradiation time. After irradiation for 10 seconds, a film of 1.5 mm long, 3 mm wide and 1 mm thick was obtained.

The resulting films were immersed in the test solvents of Table 1. It was allowed to stand at normal temperature for 5 days, and the degree of dissolution of the test sample in each test solvent was confirmed by the change from the initial weight.

When measuring the weight, the solvent adhering to the surface was completely wiped off with a wipe, and then the weight was measured. A change of ±5% or more from the initial weight was given a score of 1 (dissolved), and no change was given a score of 0 (not dissolved).

(2) Calculation of Hansen Solubility Parameters Using the software HSPiP, Hansen solubility parameters were calculated based on the evaluation results in (1).
Using the Hansen solubility parameter of the polymer calculated in (2), the HSP distance to the volatile substance and the RED value were calculated. Table 3 shows the relationship between the HSP distance and the RED value between the polymer (a') and the volatile substance (b) after UV curing.

As shown in Table 3, even in the polymer (a') and the volatile substance (b) after UV curing, the compatibility is good at the levels where the components are adjusted within the ranges of Ra'≦8 MPa ^1/2 and RED<1. bleed out was suppressed. In addition, the optimum conditions after UV curing are Ra' ≤ 8 MPa ^1/2 , RE D1 ≤ 0.6, and RE D2 ≤ 0.6. It could be confirmed.

It can be said that this is a means for obtaining a reactive composition in which the bleed-out suppression range after curing can be predicted before curing and the composition can be adjusted, and the increase in the amount of volatile substances and bleed-out are suppressed efficiently.

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

<Procedure for preparing a radically polymerizable reactive composition containing a volatile substance>
A mixed solution of a mixture of a radically polymerizable monomer (or oligomer) and a volatile substance, which will be described in Examples and Comparative Examples, is prepared. A mixture of monomers (or oligomers) and acylphosphine oxide-based photopolymerization initiator A (manufactured by IGM Resins B.V., product name: Omnirad 907) 0.5 parts by weight using a supermixer, acylphosphine oxide-based After 2 parts by weight of photopolymerization initiator B (IGM Resins B.V., product name: Omnipol TX) was stirred and the polymerization initiator was completely dissolved, a volatile substance was added and stirring was continued. Stirring was continued until a uniform liquid (no lumps or unevenness in appearance) was obtained. Poured into a mold of 50 mm × 50 mm × 2 mm, using a UV irradiation machine (HOYA LED H-16VC2-C, maximum wavelength 365 nm, irradiation distance 4.5 cm, illuminance 150 mW / cm ² ) at 100% output for 5 seconds per side Each sample was irradiated for a total of 10 seconds to obtain a test piece.

<Bleed-out evaluation procedure>
Bleed-out evaluation of volatile substances was performed using the test piece.
For the bleed-out evaluation, a hole was made at the tip of the plate sample, a hanging hook was attached, the plate sample was placed in a constant temperature air oven at 40° C., and the bleed-out condition was checked for every predetermined number of days. The bleed-out condition was evaluated in 4 stages and indicated by the following criteria.
4: Bleed-out is not observed at all.
3: A small amount of bleed-out was observed on the surface.
2: Bleed-out was observed a little.
1: A very large amount of bleeding out was observed.

(Example 1)
Acrylate compound (manufactured by Kyoeisha Chemical Co., Ltd., product name: Light Acrylate 14EG-A) as a monomer, urethane acrylate compound (manufactured by Kyoeisha Chemical Co., Ltd., product name: UA-306H) as an oligomer, and volatile substance (Ogawa Koryo Co., Ltd. ) product name: peppermint oil AA13094) was selected. They were mixed at a weight ratio of 48:32:20 and cured to obtain a radically polymerizable reactive composition. The distance between the HSPs between the monomer/oligomer mixture and the volatile substance was Ra = 0.79, and the relative energy difference (RED value) = 0.07 when the volatile substance dissolving sphere radius R ₀ was taken as the interaction radius. . HSP distance Ra' to the polymer after curing = 0.07, relative energy difference (RED value) when the volatile substance dissolving sphere radius R ₀ is the interaction radius = 0.07, polymer dissolving sphere radius R ₁ is the interaction radius, the relative energy difference (RED value) was 0.09.

(Example 2)
Acrylate compound (manufactured by Kyoeisha Chemical Co., Ltd., product name: Light Acrylate DCP-A) as a monomer, urethane acrylate compound (manufactured by Kyoeisha Chemical Co., Ltd., product name: UA-510H) as an oligomer, and volatile substance (Ogawa Koryo Co., Ltd. ) product name: peppermint oil AA13094) was selected. They were mixed at a weight ratio of 65:15:20 and cured to obtain a radically polymerizable reactive composition. The distance between the HSPs between the monomer/oligomer mixture and the volatile substance Ra = 2.64, the relative energy difference (RED value) = 0.22 when the volatile substance dissolving sphere radius R ₀ is the interaction radius. . HSP distance Ra' to the polymer after curing = 3.65, relative energy difference (RED value) when the volatile substance dissolving sphere radius R ₀ is the interaction radius = 0.25, polymer dissolving sphere radius R ₁ is the interaction radius, the relative energy difference (RED value) was 0.36.

(Example 3)
Acrylate compound (manufactured by Kyoeisha Chemical Co., Ltd., product name: Light Acrylate 14EG-A) as a monomer, urethane acrylate compound (manufactured by Kyoeisha Chemical Co., Ltd., product name: UA-306H) as an oligomer, and volatile substance (Fuji Film Wako Jun Yaku Co., Ltd. product name: d-limonene) was selected. They were mixed at a weight ratio of 48:32:20 and cured to obtain a radically polymerizable reactive composition. The distance between the HSPs between the monomer/oligomer mixture and the volatile substance Ra = 7.82, the relative energy difference (RED value) = 0.73 when the volatile substance dissolving sphere radius R ₀ is the interaction radius. . HSP distance Ra' to the polymer after curing = 7.12, relative energy difference (RED value) when the volatile substance dissolving sphere radius R ₀ is the interaction radius = 0.58, polymer dissolving sphere radius R ₁ is the interaction radius, the relative energy difference (RED value) was 0.59.

(Example 4)
Acrylate compound (manufactured by Kyoeisha Chemical Co., Ltd., product name: Light Acrylate 14EG-A) as a monomer, urethane acrylate compound (manufactured by Kyoeisha Chemical Co., Ltd., product name: UA-306H) as an oligomer, and volatile substance (Fuji Film Wako Jun Yaku Co., Ltd. product name: d-limonene) was selected. They were mixed at a weight ratio of 42:28:30 and cured to obtain a radically polymerizable reactive composition. The distance between the HSPs between the monomer/oligomer mixture and the volatile substance Ra = 7.82, the relative energy difference (RED value) = 0.73 when the volatile substance dissolving sphere radius R ₀ is the interaction radius. . HSP distance Ra' to the polymer after curing = 7.12, relative energy difference (RED value) when the volatile substance dissolving sphere radius R ₀ is the interaction radius = 0.58, polymer dissolving sphere radius R ₁ is the interaction radius, the relative energy difference (RED value) was 0.59.

(Example 5)
Acrylate compound (manufactured by Kyoeisha Chemical Co., Ltd., product name: Light Acrylate 14EG-A) as a monomer, glycidyl acrylate as epoxy acrylate, urethane acrylate compound (manufactured by Kyoeisha Chemical Co., Ltd., product name: UA-306H) as an oligomer, volatile substances (trade name: d-limonene manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was selected as the They were mixed at a weight ratio of 35:7:28:30 and cured to obtain a radically polymerizable reactive composition. The distance between the HSPs between the monomer/oligomer mixture and the volatile substance Ra = 7.80, the relative energy difference (RED value) = 0.69 when the volatile substance dissolving sphere radius R ₀ is the interaction radius. . HSP distance Ra′ to the polymer after curing = 7.09, relative energy difference (RED value) when the volatile substance dissolving sphere radius R ₀ is the interaction radius = 0.55, polymer dissolving sphere radius R ₁ is the interaction radius (RED value) = 0.55.

(Comparative example 1)
Acrylate compound (manufactured by Kyoeisha Chemical Co., Ltd., product name: Light Acrylate 14EG-A) as a monomer, urethane acrylate compound (manufactured by Kyoeisha Chemical Co., Ltd., product name: UA-306H) as an oligomer, and volatile substance (Ogawa Koryo Co., Ltd. ) product name: vanilla oil GL53038) was selected. They were mixed at a weight ratio of 48:32:20 and cured to obtain a radically polymerizable reactive composition. The distance between the HSPs between the monomer/oligomer mixture and the volatile substance Ra = 6.99, the relative energy difference (RED value) = 1.21 when the volatile substance dissolving sphere radius R ₀ is the interaction radius. . HSP distance Ra' to the polymer after curing = 7.33, relative energy difference (RED value) when the volatile substance dissolving sphere radius R ₀ is the interaction radius = 0.59, polymer dissolving sphere radius R ₁ is the interaction radius, the relative energy difference (RED value) was 1.1.

(Comparative example 2)
Acrylate compound (manufactured by Kyoeisha Chemical Co., Ltd., product name: Light Acrylate 4EG-A) as a monomer, urethane acrylate compound (manufactured by Kyoeisha Chemical Co., Ltd., product name: UA-510H) as an oligomer, volatile substance (Ogawa Koryo Co., Ltd. ) product name: vanilla oil GL53038) was selected. They were mixed at a weight ratio of 40:40:20 and cured to obtain a radically polymerizable reactive composition. The distance between the HSPs between the monomer/oligomer mixture and the volatile substance Ra = 9.06, the relative energy difference (RED value) = 1.56 when the volatile substance dissolving sphere radius R ₀ is the interaction radius. . HSP distance Ra′ to the polymer after curing = 9.80, relative energy difference (RED value) when the volatile substance dissolving sphere radius R ₀ is the interaction radius = 0.78, polymer dissolving sphere radius R ₁ is the interaction radius (RED value) = 1.51.

(Comparative Example 3)
Acrylate compound (manufactured by Kyoeisha Chemical Co., Ltd., product name: Light Acrylate DCP-A) as a monomer, urethane acrylate compound (manufactured by Kyoeisha Chemical Co., Ltd., product name: UA-510H) as an oligomer, and volatile substance (Ogawa Koryo Co., Ltd. ) product name: vanilla oil GL53038) was selected. They were mixed at a weight ratio of 15:65:20 and cured to obtain a radically polymerizable reactive composition. The distance between the HSPs between the monomer/oligomer mixture and the volatile substance Ra = 10.04, the relative energy difference (RED value) = 0.90 when the volatile substance dissolving sphere radius R ₀ is the interaction radius. . HSP distance Ra' to the polymer after curing = 10.6, relative energy difference (RED value) when the volatile substance dissolving sphere radius R ₀ is the interaction radius = 0.78, polymer dissolving sphere radius R ₁ is the interaction radius (RED value) = 0.91.

(Comparative Example 4)
Acrylate compound (manufactured by Kyoeisha Chemical Co., Ltd., product name: Light Acrylate 14EG-A) as a monomer, urethane acrylate compound (manufactured by Kyoeisha Chemical Co., Ltd., product name: UA-306H) as an oligomer, and volatile substance (Ogawa Koryo Co., Ltd. ) product name: vanilla oil GL53038) was selected. They were mixed at a weight ratio of 54:36:10 and cured to obtain a radically polymerizable reactive composition. The distance between the HSPs between the monomer/oligomer mixture and the volatile substance Ra = 6.99, the relative energy difference (RED value) = 1.21 when the volatile substance dissolving sphere radius R ₀ is the interaction radius. . HSP distance Ra' to the polymer after curing = 7.33, relative energy difference (RED value) when the volatile substance dissolving sphere radius R ₀ is the interaction radius = 0.59, polymer dissolving sphere radius R ₁ is the interaction radius, the relative energy difference (RED value) was 1.1.

(Comparative Example 5)
Acrylate compound (manufactured by Kyoeisha Chemical Co., Ltd., product name: Light Acrylate 14EG-A) as a monomer, urethane acrylate compound (manufactured by Kyoeisha Chemical Co., Ltd., product name: UA-306H) as an oligomer, and volatile substance (Fuji Film Wako Jun Yaku Co., Ltd. product name: d-limonene) was selected. They were mixed at a weight ratio of 41:27:32 and cured to obtain a radically polymerizable reactive composition. The distance between the HSPs between the monomer/oligomer mixture and the volatile substance Ra = 7.82, the relative energy difference (RED value) = 0.73 when the volatile substance dissolving sphere radius R ₀ is the interaction radius. . HSP distance Ra' to the polymer after curing = 7.12, relative energy difference (RED value) when the volatile substance dissolving sphere radius R ₀ is the interaction radius = 0.58, polymer dissolving sphere radius R ₁ is the interaction radius, the relative energy difference (RED value) was 0.59.

Distance Ra between HSPs before curing in Examples 1 to 5 and Comparative Examples 1 to 5, relative energy difference RED value when volatile substance dissolving sphere radius is used, blending ratio of perfume in total composition (% by weight), HSP distance Ra' to polymer after curing, relative energy difference (RED value) when volatile substance dissolving sphere radius _R0 is the interaction radius, polymer dissolving sphere radius _R1 interaction Table 4 shows the relative energy difference (RED value) with respect to the radius.

From the results in Table 4, under pre-curing conditions, the distance between HSPs Ra ≤ 8 MPa ^1/2 and the RED value (value where the volatile substance dissolving sphere radius R ₀ is the interaction radius) < 1, and under the reactive composition conditions The effect of suppressing bleed-out is in the range of distance Ra' ≤ 8 MPa ^1/2 and RED' value (value where each of the volatile substance dissolving sphere R ₀ and the polymer dissolving sphere radius R ₁ is the interaction radius) ≤ 0.6 I found out. Especially in Example 1, good results were obtained.

According to the present invention, when there _is a large overlap between the volatile substance dissolving spheres s and the polymer dissolving spheres _s ' as shown in FIG. It was confirmed that a reactive composition which is excellent in retention of reactive substances and which does not cause bleeding out or discoloration for a long period of time can be obtained.

It was found that the reactive composition of the present invention can suppress bleed out for a long period of time and is excellent in appearance.

The reactive composition containing a volatile substance of the present invention can contain a desired volatile substance, has excellent holding power, and can provide a reactive composition excellent in appearance.

In addition, in the present invention, when the total reactive composition is 100% by weight, a maximum of 30% by weight of volatile substances can be blended, and a reactive composition with a high content of volatile substances can be easily provided. There is an advantage.

Furthermore, the reactive composition containing the volatile substance of the present invention has the advantage of being able to suppress bleeding out and maintain fluidity for a long period of time.

Therefore, the reactive composition containing the volatile substance of the present invention has high utility value, and may be provided as an application tool that can be utilized in all industrial fields.

a HSP value of the mixture of monomers (and oligomers),
b HSP value of volatile substances,
s volatile matter dissolving spheres,
s′ post-reaction polymer dissolving spheres,
1 single layer nozzle,
2 a mixture of two or more monomers (or oligomers) and volatile substances,
3 forming tube,
4 a light source,
5 separation means,
6 carrier fluid;
7 carrier fluid recovery liquid,
8 driving means;
9 post-radical polymerization reactive composition,
10 volatile substances

Claims (3)

A reactive composition containing (a) two or more monomers polymerizable by light irradiation and (b) a volatile substance,
The Hansen Solubility Parameter (HSP) was calculated for each of said monomer (a) and said volatile substance (b), and the HSP distance (Ra) between said monomer (a) and said volatile substance (b) was 8 MPa ^{1/ 2} or less, and the components are adjusted so that the relative energy difference RED (RED=Ra/volatile substance dissolving sphere radius R ₀ ) is less than 1,
The HSP distance (Ra') between the polymer (a') after the reaction of the reactive composition and the volatile substance (b) is 8 MPa ^1/2 or less, and the relative energy with the polymer (a') The difference RED'(RED1=Ra'/radius of volatile substance dissolving sphere _R0 and RED2=Ra'/radius of polymer dissolving sphere _R1 ) is both 0.6 or less.
The monomer (a) is a radically polymerizable compound having an ethylenically unsaturated bond at the molecular chain end,
The content of the volatile substance (b) in the reactive composition is 0.5 to 30% by weight,
The cured product of the reactive composition is not a gel-like product,
A reactive composition characterized by: 2. The reactive composition according to claim 1, wherein the reactive composition undergoes a polymerization reaction by irradiating the liquid droplets with light. The radically polymerizable compound is an acrylate compound having an acryloyl group or a methacryloyl group at the molecular chain end, and the acrylate compound is a urethane acrylate compound, an epoxy acrylate compound, a polyether acrylate compound, or an oligoester acrylate compound. 3. A reactive composition according to claim 1 or claim 2, characterized in that.

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