JP5059668B2 - Resin composition and method for producing the same - Google Patents

Description

The present invention relates to a solid resin composition using a vinyl polymer, a production method thereof, a resin emulsion obtained by dissolving the resin composition in water, and use thereof.

Resin emulsions are those in which resin particles are dispersed in water using the electrostatic repulsive force of an electric double layer by a surfactant, and are widely used in the production of adhesives such as adhesive tapes and adhesive sheets. ing.

As a method of producing a resin emulsion, as a mechanical emulsification method for refining the dispersed phase by mechanical force, for example, a high pressure emulsification method for refining the dispersed phase by applying a high shear force by passing through a narrow gap under high pressure. Dispersion by applying pressure dispersion in a dispersion medium using an ultrasonic emulsification method that refines the dispersed phase using the cavitation force generated when ultrasonic waves are applied to the liquid, and a porous film having a uniform pore size A membrane emulsification method for refining phases is known.

In addition, as an emulsification method using the physicochemical power of a surfactant, for example, a phase inversion emulsification method in which an emulsifier is dissolved in an oil phase, a water phase is gradually added, and a continuous phase is inverted from an oil phase to an aqueous phase. Utilizing the temperature dependence of the hydrophilic-lipophilic balance of nonionic surfactants, phase inversion temperature emulsification method in which the continuous phase is inverted by temperature change, disperse and hold the dispersed phase in the liquid crystal, and the interfacial tension at that time A liquid crystal emulsification method using a decrease in the viscosity and the orientation of surfactant molecules is known.

Here, when a vinyl polymer such as petroleum resin, rosin resin, or terpene resin is selected as the resin particle of the resin emulsion, these resins are solid or semi-solid at room temperature. A large amount of power is required for stirring and the like, and the resin viscosity is restricted in terms of equipment during emulsification.

In order to remove this viscosity restriction, a method is used in which a resin is dissolved in an organic solvent to lower the melt viscosity of the resin, emulsified by the above-described method, and then recovered by vacuum distillation. However, it is difficult to completely remove the organic solvent from the emulsion obtained by this method, and a resin emulsion that does not use an organic solvent has been demanded from the viewpoint of environmental measures in recent years.

On the other hand, as a method of converting a solid or semi-solid resin at room temperature into a resin emulsion without using an organic solvent, for example, a method of lowering the viscosity of a thermoplastic resin by a phase inversion emulsification method in a high temperature and high pressure environment is known. (For example, refer to Patent Documents 1 and 2).

Also known is a method of melt kneading an olefin resin and an aqueous solution of partially saponified polyvinyl alcohol having a specific saponification degree with a multi-screw extruder (see, for example, Patent Document 3).

However, the water contained in the resin emulsion obtained by these means represents 30% or more of the product, and most of it is removed during the product processing. That is, the resin emulsion requires a great deal of cost for storage and transportation.

By further reducing the water content of these resin emulsions, a solid resin can be obtained. However, even if the solid resin thus obtained was dispersed again in water, the composition of the resin composition itself was changed, and the original resin emulsion could not be obtained.

Also, a method in which a thermoplastic resin, a surfactant and a small amount of water are previously melt-kneaded to obtain a solid resin composition in which the surfactant and water are in a continuous phase, and then the solid resin composition and water are mixed. (For example, see Patent Document 4).
1995 Patent Publication No. 155576 1999 Patent Publication No. 209477 1981 Patent Publication No. 002149 Japanese Patent Application No. 2007-305292

Provided are a solid resin composition that can be stored for a long period of time without requiring special equipment, and a resin emulsion having a small particle diameter comprising the resin composition and water.

The present invention relates to 100 parts by mass of a vinyl polymer having a glass transition temperature of 0 to 140 ° C. and a weight average molecular weight of 300 to 10,000, and 1 to 20 parts by mass of a nonionic surfactant having an HLB value of 12 to 20 determined by the Griffin method. And a solid resin composition containing 0.1 to 20 parts by mass of water. The vinyl polymer of the resin composition is preferably adjacent as a dispersed phase having an average particle size of 0.1 to 1.0 μm via a continuous phase in which a surfactant and water are mixed. It is preferably at least one selected from resins and terpene resins.

In order to produce a resin composition, 100 parts by mass of a vinyl polymer, 1 to 20 parts by mass of a surfactant, and 0.1 to 20 parts by mass of water are kneaded with a melt kneader, What is necessary is just to cool below to glass transition temperature.
The resin composition can be made into a resin emulsion by dissolving in 35 to 10000 parts by mass of water with respect to 100 parts by mass of the resin composition.
Resin emulsions can be used as pressure-sensitive adhesives, adhesives, paints, printing inks, and coating agents. These can be used for pressure-sensitive adhesive tapes, pressure-sensitive adhesive sheets, pressure-sensitive adhesive film materials, paper, plastic films, cement, mortar and metals. It can be used as a surface coating agent.

Provided are a solid resin composition that can also be referred to as an emulsion precursor, and a resin emulsion comprising the resin composition and water, which can obtain a resin emulsion without requiring special equipment. And the resin composition of this invention has an effect that long-term storage is possible especially.

The resin composition of the present invention is obtained by kneading a vinyl polymer, a surfactant, and water under a specific composition and specific conditions. The resin composition is a solid composition in which a vinyl polymer is preferably dispersed as a dispersed phase having an average particle size of 0.1 to 1.0 μm through a continuous phase in which a surfactant and water are mixed. It is.

The vinyl polymer used as a raw material for the resin composition has a glass transition temperature of 0 to 140 ° C. and a weight average molecular weight of 300 to 10,000. For example, a C5 fraction-based petroleum resin or a C9 fraction-based petroleum resin is used. Rosin resin, rosin ester resin, rosin phenol resin, disproportionate rosin resin such as petroleum resin, C5 and C9 fraction copolymer petroleum resin, dicyclopentadiene petroleum resin, styrene petroleum resin, hydrogenated petroleum resin, etc. Α-pinene resin, β-pinene resin, terpene phenol resin, hydrogenated terpene resin, etc. as other terpene resins, such as alkylphenol resin, xylene resin, hydrogenated rosin resin, hydrogenated rosin resin, aromatic modified terpene resin, etc. Coumarone indene resin, ketone resin and the like are preferably used.
These vinyl polymers may be used alone or in combination of two or more.

Since a vinyl polymer having a glass transition temperature exceeding 140 ° C. and a vinyl polymer having a weight average molecular weight exceeding 10,000 are high in viscosity, in a general-purpose kneading equipment, the vinyl polymer is placed in a continuous phase composed of a surfactant and water. It is difficult to disperse uniformly, and a resin composition having the intended composition cannot be obtained.
The glass transition temperature is preferably 100 ° C. or lower, and the weight average molecular weight is preferably 5000 or lower. By setting it as this range, a vinyl polymer can be uniformly disperse | distributed in the said continuous phase with general purpose equipment, and the resin composition obtained will also become more stable.
In addition, since the vinyl polymer having a glass transition temperature of less than 0 ° C. and the vinyl polymer having a weight average molecular weight of less than 300 are semi-solid or liquid at room temperature, the resulting resin composition does not become solid.

By setting the average particle size of the vinyl polymer as a dispersed phase in the resin composition in the range of 0.1 to 1.0 μm, the storage stability of the resin emulsion obtained by dissolving the resin composition in water is improved. It is preferable because it improves.
The average particle diameter of the vinyl polymer in the resin composition can be adjusted by the type of vinyl polymer selected and the shearing force of the apparatus for kneading the vinyl polymer. That is, by selecting a vinyl polymer having a low average molecular weight and increasing the shearing force to promote the dispersion of the surfactant and water, the average particle size of the vinyl polymer in the resin composition can be reduced. .
Moreover, it can be adjusted depending on the kind and amount of the surfactant to be selected.
For example, the average particle size of the vinyl polymer in the resin composition can be reduced by increasing the blending amount of the surfactant, and conversely, the average particle size can be increased by decreasing the blending amount. be able to.

The continuous phase in which the surfactant and water in the resin composition are mixed needs to be continuously present so as to enclose the vinyl polymer resin particles which are the dispersed phase in the resin composition. The means for doing so is not particularly limited. For example, the vinyl polymer, the surfactant, and water are once mixed by a blender such as a Henschel mixer, and then mixed with a single screw extruder or What is necessary is just to knead | mix using a twin-screw extruder, a kneader, a Banbury mixer, a planetary mixer, a kneading roll, etc. It is preferable that the kneading apparatus use equipment having a sealing mechanism, or set the temperature in the kneading part to 100 ° C. or less and knead under the condition that the blended water does not evaporate.

The surfactant used as the raw material of the resin composition is preferably a nonionic surfactant having an HLB value of 12 to 20 determined by the Griffin method. Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene myristyl ether, polyoxyethylene alkylene alkyl ether, polyoxylethylene derivatives, polyoxyethylene polyoxypropylene block polymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid Ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene oleic acid ester, polyoxyethylene alkylamine, alkyl alkanolamide, polyoxyethylene nonylphenyl ether and the like are preferably used.
These nonionic surfactants may be used alone or in combination of two or more.

When the HLB value of the surfactant used as the raw material of the resin composition is less than 12, the long-term storage stability of the resin composition is inferior and does not dissolve in water after long-term storage.
A preferred range for the HLB value is 14-17. By setting it as this range, even after long-term normal temperature storage in the state of the resin composition, it dissolves in water and a resin emulsion is obtained.

The addition amount is 1 to 20 parts by mass, preferably 2 to 10 parts by mass, and more preferably 3 to 8 parts by mass with respect to 100 parts by mass of the vinyl polymer. If the addition amount of the surfactant is less than 1 part by mass, the effect of improving the storage stability of the obtained resin composition cannot be obtained. If the addition amount exceeds 20 parts by mass, the resin composition is dissolved in water. When the resin emulsion obtained in this way is used as a pressure-sensitive adhesive or an adhesive, its water resistance decreases.

Water used as a raw material for the resin composition is present as a continuous phase between resin particles of the vinyl polymer via a surfactant. Water is not particularly limited, but pure water such as distilled water or ion exchange water is preferably used.
The amount of water added is 0.1 to 20 parts by mass, preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the vinyl polymer. If it is less than 0.1 parts by mass, a stable resin emulsion cannot be obtained when the obtained solid resin composition is dissolved in water, and if it exceeds 20 parts by mass, it is difficult to uniformly disperse in the resin composition. .

A commonly used plasticizer may be added to the resin composition in order to impart a plasticizing effect to the vinyl polymer to facilitate the kneading operation. Examples of the plasticizer include phthalic acid ester, adipic acid ester, phosphoric acid ester, trimellitic acid ester, citric acid ester, epoxy, and polyester.

When the plasticizer is added in an amount of 40 parts by mass or less, preferably 10 parts by mass or less, more preferably 5 parts by mass or less with respect to 100 parts by mass of the vinyl polymer, the properties of the resulting resin composition are not impaired. Therefore, it is preferable.

In the kneading step, the resin composition is further blended with a desired stabilizer, antioxidant, weathering agent, ultraviolet absorber, lubricant, pigment, dye, crosslinking agent, filler, plasticizer, crosslinking accelerator, and the like. You can also

The shape of the solid resin composition obtained by kneading the vinyl polymer, surfactant, water and additives to be added as necessary is not particularly limited, but is kneaded with an extruder and stranded. When the mixture is extruded into a shape and cut into pellets to obtain small particles such as resin pellets, the dissolution time when mixed with water to form a resin emulsion can be shortened.
Examples of the apparatus for cutting the resin composition into pellets include known strand cut methods and hot cut methods.
The strand cut method is a method in which a kneaded product extruded in a strand shape by an extruder is cooled, guided to a pelletizer, cut into a pellet shape, and collected.
The hot cut method is a method in which a kneaded product extruded in a strand shape by an extruder is cut into a pellet shape and collected by a rotary cutter attached to the tip of the extruder.

Whichever method is used for pelletization, it is desirable that the strand-shaped resin composition extruded from the extruder is cooled to a temperature not higher than the glass transition temperature of the vinyl polymer used.
By cooling, the entire strand can be solidified and the dispersed vinyl polymer fine particles can be prevented from recombining with each other. Thereby, the solid resin composition excellent in storage stability can be obtained. This resin composition can be dissolved in water even after long-term storage to obtain a stable resin emulsion.
Further, as another method of using the resin composition as resin pellets, there is a method of kneading with a kneader, a Banbury mixer, an extruder, etc., forming a plate with two rolls, etc., and then using resin with a dicer.
Even in this case, it is desirable to cool the resin composition to a temperature equal to or lower than the glass transition temperature after making it into a plate shape with two rolls or the like, or after forming into resin pellets.

The resin composition can be made into a resin emulsion simply by putting it in water and allowing it to stand. Furthermore, dissolution time can be shortened by mixing and stirring after throwing in water. A known apparatus can be used for mixing and stirring, and is not particularly limited. However, a magnetic stirrer, three-one motor, homogenizer, media mill, colloid mill, homomixer, planetary mixer, inline mixer, pipe There are line mixers.

The water temperature at which the resin composition is dissolved in water is not particularly limited, and can be arbitrarily changed according to the purpose of use.

Various additives can be added to the water in which the resin composition is dissolved, as long as the effects of the present invention are not impaired. Examples of additives include preservatives, antifungal agents, antioxidants, light stabilizers, pH adjusters, and the like.

In the obtained resin emulsion, an antifoaming agent, an antiseptic agent, an antifungal agent, a rust inhibitor, a permeability adjuster, a viscosity viscosity adjuster, a pH adjuster, a flame retardant, a dispersant, an inorganic filler, if necessary. Various additives such as aggregates such as silica sand, pigments, and other emulsions can be added. Further, a water-soluble polymer such as hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, a conventionally known anionic, cationic or nonionic surfactant may be added.

The resin emulsion can be made into a pressure-sensitive adhesive, an adhesive, a paint, an ink, or a coating agent by mixing with an emulsion of synthetic resin or synthetic rubber, other emulsions or additives. The synthetic resin and the synthetic rubber are not particularly limited. For example, polyolefin resins such as polyethylene and polypropylene, acrylic resins, urethane resins, bisphenol type epoxy resins, phenol novolac type epoxy resins, alicyclic epoxy resins, Epoxy resins such as heterocyclic epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, halogenated epoxy resins, polybenzimidazole, polybenzoxazole, polybenzthiazole, polyoxadiazole, polypyrazole, polyquinoxaline, Polyquinazolinedione, polybenzoxazinone, polyindolone, polyquinazolone, polyindoxyl, silicone resin, silicone-epoxy resin, phenol resin, melamine resin, urea resin, Japanese polyester, polyamino bismaleimide, diallyl phthalate resin, fluororesin, polyimide, polyamideimide, polyetherimide, nylon resin, polyamide such as amorphous nylon, polyester such as polybutylene terephthalate and polyethylene terephthalate, polyphenylene sulfide, modified polyphenylene ether, Polyarylate, wholly aromatic polyester, polysulfone, liquid crystal polymer, polyether ether ketone, polyether sulfone, polycarbonate, maleimide modified resin, ABS resin, AAS (acrylonitrile / acrylic rubber / styrene) resin, AES (acrylonitrile / ethylene / propylene / propylene) Diene rubber-styrene) resin, butyl rubber, acrylic rubber, ethylene propylene rubber Polymerization of elastomers such as silicone rubber, polyester elastomer, polybutadiene, chloroprene, styrene-butadiene rubber, acrylonitrile-butadiene rubber, natural rubber, polyisoprene, and monomers such as acrylic acid, styrene and acrylonitrile based on elastomer Resin.

The pressure-sensitive adhesive, adhesive, paint, ink, and coating agent contain various additives as necessary. Such additives are not particularly limited, for example, antifoaming agents, antiseptics, antifungal agents, rust inhibitors, permeability adjusters, viscosity viscosity modifiers, anti-aging agents, thickeners, flame retardants, There are dispersants, inorganic fillers, aggregates such as silica sand, pigments and the like. Further, if necessary, a water-soluble polymer such as hydroxyethyl cellulose, methyl cellulose, or carboxymethyl cellulose, a conventionally known anionic, cationic or nonionic surfactant may be used.

Adhesives and adhesives are suitable for bonding of the same or different types of paper, wood, cloth, leather, jersey, leather, rubber, plastic, foam, earthenware, glass, mortar, cement material, ceramic, metal, etc. is there. With respect to the construction method at the time of bonding, brush coating, trowel coating, spray coating, roll coater coating and the like are possible.

The paint and ink and the coating agent can be used as a surface coating agent for paper, wood, cloth, leather, rubber, plastic, foam, earthenware, glass, mortar, cement material, ceramic, metal and the like. In addition, as a coating method on the surface of a substrate such as paper, brush coating, trowel coating, dipping, spray coating, roll coater coating, and the like are possible.

An adhesive tape, an adhesive sheet, an adhesive film, etc. can be obtained by applying the obtained adhesive to a support and drying it.

The support is, for example, a plastic sheet and foam such as polypropylene resin, polyethylene resin, polystyrene resin, vinyl chloride resin, Japanese paper, kraft paper, coated paper, fine paper, synthetic paper, cloth, nonwoven fabric, etc. Examples thereof include porous substances, composites thereof, and multilayer laminates.

The surface of the support can be coated with a primer or corona treated. Moreover, in order to adjust the adhesive strength of the pressure-sensitive adhesive composition, a release agent can be applied to the pressure-sensitive adhesive application back surface.

The pressure-sensitive adhesive tape, pressure-sensitive adhesive sheet, and pressure-sensitive adhesive film are completed by applying a pressure-sensitive adhesive to the support, drying it, and cutting it into predetermined dimensions. Examples of the method for applying the adhesive to the support include a direct gravure method, a reverse direct gravure method, an offset gravure method, a knife coater, a roll coater, a comma coater, a lip coater, and a die coater. Also, the primer and release agent can be applied in the same manner.

The thickness of the pressure-sensitive adhesive layer is not particularly limited. For example, when the thickness is in the range of 1 to 100 μm, preferably 10 to 50 μm, the necessary adhesive force is exhibited, and the coating performance and drying properties are improved. Therefore, it is preferable.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, these Examples do not limit this invention. In the following description, “part” and “%” are based on mass unless otherwise specified.

（式中、Ｎは不揮発分（％）、ｍ_０は平底皿の質量（ｇ）、ｍ_１は平底皿と試料との合計質量（ｇ）、ｍ_２は平底皿と蒸発残留分との合計の質量（ｇ）を表す。）
［平均粒子径］
レーザ回折／散乱式粒度分布測定装置ＬＡ-９２０（ 株式会社堀場製作所社製）を用いレーザ回折法で樹脂エマルジョン中の樹脂粒子のメジアン径測定を実施した。評価は、平均粒子径と樹脂エマルジョンの安定性の関係を考慮し、０．５μｍ未満のものを優、０．５〜１．０μｍのものを良、１．０μｍを超えるものを不可とした。
[樹脂組成物の貯蔵安定性]
ペレット状の樹脂組成物をガラス瓶に入れて密栓し、２３℃のオーブン中で２ヶ月および６ヶ月貯蔵したサンプルについて貯蔵安定性試験を実施した。試験は、サンプルを上記乳化性の試験と同様の手順で不揮発分を算出した。評価は、不揮発分が４０％以上のものを優、不揮発分１５％以上４０％未満のものを良、不揮発分１５％未満のものを不可とした。 [Example 1]
Petroleum resin as a vinyl polymer (glass transition temperature 42 ° C., weight average molecular weight 1400, trade name Escoretz 2101; manufactured by ExxonMobil) and polyoxyethylene lauryl ether (HLB value 16.8, product) as a surfactant Name Emulgen 123P (manufactured by Kao Corporation) 5.0 parts of distilled water and 5.0 parts of distilled water were kneaded at 100 rpm with a twin-screw melt extruder with a cylinder set at 90 ° C. (TEX-30α; manufactured by Nippon Steel) Then, the kneaded material discharged from the die at 94 ° C. was cooled until the resin temperature became 30 ° C. or lower to obtain a strand. The moisture content of the strands was measured with a Karl Fischer moisture meter (MKC-210; Kyoto Electronics), and was used as the actual blending amount of water in the resin composition. The obtained strand was cut into pellets by a strand cut method to obtain a resin composition.
The resin composition thus obtained was solid, and could be packed, stored and transported with ordinary paper bags or polyolefin bags.
[HLB value of surfactant]
The HLB value of a surfactant is a value that represents the ratio of relative affinity of a surfactant to water and an organic compound that is insoluble in water, and can be determined by various methods. Used to calculate. The Griffin method is defined based on the formula weight and molecular weight of the hydrophilic group of the surfactant, and is represented by the following formula.
HLB value = 20 × total formula weight of hydrophilic part / molecular weight
[Glass-transition temperature]
Measurement was performed according to JIS K7121 9.3, and extrapolated glass transition start temperature was calculated.
[Weight average molecular weight]
The weight average molecular weight was measured under the size exclusion chromatography measurement conditions described below.
Device name: SYSTEM-21 Shodex (manufactured by Showa Denko)
Column: 3 PL gel MIXED-B in series Temperature: 40 ° C
Detection: Differential refractive index Solvent: Tetrahydrofuran Concentration: 2% by mass
Calibration curve: produced using standard polystyrene (PS) (manufactured by PL), and the weight average molecular weight was expressed in terms of PS.
[Emulsifying]
A white resin emulsion is obtained by putting 100 parts of the resin composition pellets in 100 parts of distilled water at 25 ° C. and allowing to stand for 1 hour. The nonvolatile content of this resin emulsion was calculated according to JIS K6828-1. The measurement was performed according to the following procedure. Weigh 1.0 g of resin emulsion that does not contain resin composition pellets in a flat bottom dish and dry it in an oven at 105 ° C. (ACR gear oven; manufactured by Toyo Seiki Seisakusho) for 1 hour. The balance was calculated by the following general formula (Formula 1). In the evaluation, those having a nonvolatile content of 45% or more were excellent, those having a nonvolatile content of 15% or more and less than 45% were good, and those having a nonvolatile content of less than 15% were not acceptable.

(Where N is the non-volatile content (%), m ₀ is the mass (g) of the flat bottom pan, m ₁ is the total mass (g) of the flat bottom pan and the sample, and m ₂ is the sum of the flat bottom pan and the evaporation residue. Represents the mass (g) of
[Average particle size]
The median diameter measurement of the resin particles in the resin emulsion was performed by a laser diffraction method using a laser diffraction / scattering particle size distribution measuring apparatus LA-920 (manufactured by Horiba, Ltd.). In consideration of the relationship between the average particle diameter and the stability of the resin emulsion, the ones of less than 0.5 μm are excellent, the ones of 0.5 to 1.0 μm are good, and the ones exceeding 1.0 μm are not acceptable.
[Storage stability of resin composition]
The pellet-shaped resin composition was put in a glass bottle and sealed, and a storage stability test was performed on samples stored in an oven at 23 ° C. for 2 months and 6 months. In the test, the non-volatile content of the sample was calculated in the same procedure as the above emulsifiability test. In the evaluation, those having a nonvolatile content of 40% or more were excellent, those having a nonvolatile content of 15% or more and less than 40% were good, and those having a nonvolatile content of less than 15% were not acceptable.

[Example 2]
Tested in the same manner as in Example 1 except that the surfactant used in Example 1 was changed to polyoxyethylene lauryl ether (HLB value 12.1, trade name Emulgen 108; anionic surfactant manufactured by Kao Corporation). And Example 2 was carried out. In addition, the resin temperature at the time of discharge was 94 degreeC.

[Example 3]
The test was carried out in the same manner as in Example 1 except that the surfactant used in Example 1 was changed to polyoxyethylene lauryl ether (HLB value 18.4, trade name Emulgen 150; manufactured by Kao Corporation). It was set to 3. In addition, the resin temperature at the time of discharge was 96 degreeC.

[Example 4]
Similar to Example 1 except that the surfactant used in Example 1 was changed to polyoxyethylene styrenated phenyl ether (HLB value 13.0, trade name Neugen EA-137; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). The test was carried out to give Example 4. In addition, the resin temperature at the time of discharge was 95 degreeC.

[Example 5]
Similar to Example 1 except that the surfactant used in Example 1 was changed to polyoxyethylene styrenated phenyl ether (HLB value 14.8, trade name Neugen EA-177; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). The test was carried out and was taken as Example 5. In addition, the resin temperature at the time of discharge was 95 degreeC.

[Example 6]
Similar to Example 1 except that the surfactant used in Example 1 was changed to polyoxyethylene styrenated phenyl ether (HLB value 15.6, trade name Neugen EA-197; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). The test was carried out to give Example 6. In addition, the resin temperature at the time of discharge was 95 degreeC.

[Example 7]
The test was carried out in the same manner as in Example 1 except that the surfactant used in Example 1 was changed to polyoxyethylene olein ether (HLB value 14.5, trade name Pegnol O-16A; manufactured by Toho Chemical Industry Co., Ltd.) Example 7 was made. In addition, the resin temperature at the time of discharge was 95 degreeC.

[Example 8]
The test was carried out in the same manner as in Example 1 except that the surfactant used in Example 1 was changed to polyoxyethylene nonylphenol ether (HLB value 15.8, trade name Nonal 530; manufactured by Toho Chemical Industry Co., Ltd.) Example 8 was adopted. In addition, the resin temperature at the time of discharge was 95 degreeC.

[Example 9]
The test was carried out in the same manner as in Example 1 except that the surfactant used in Example 1 was changed to polyoxyethylene alkyl ether (HLB value 16.3, trade name Leocol TD-200; manufactured by Lion Corporation). Example 9 was taken. In addition, the resin temperature at the time of discharge was 95 degreeC.

[Example 10]
The test was conducted in the same manner as in Example 1 except that the thermoplastic resin used in Example 1 was changed to petroleum resin (glass transition temperature 65 ° C., weight average molecular weight 4100, trade name G-115; manufactured by Nippon Zeon Co., Ltd.). Example 10 was made. In addition, the resin temperature at the time of discharge was 118 degreeC.

[Example 11]
Similar to Example 1 except that the thermoplastic resin used in Example 1 was changed to a hydrogenated petroleum resin (glass transition temperature 50 ° C., weight average molecular weight 1500, trade name P-100; manufactured by Arakawa Chemical Industries, Ltd.). The test was conducted and was referred to as Example 11. In addition, the resin temperature at the time of discharge was 97 degreeC.

[Example 12]
The test was carried out in the same manner as in Example 1 except that the thermoplastic resin used in Example 1 was changed to a terpene resin (glass transition temperature 50 ° C., weight average molecular weight 1200, trade name PX-1000; manufactured by Yasuhara Chemical Co., Ltd.). Example 12 was used. In addition, the resin temperature at the time of discharge was 102 degreeC.

[Example 13]
The test was conducted in the same manner as in Example 1 except that the thermoplastic resin used in Example 1 was changed to a rosin ester resin (glass transition temperature 57 ° C., weight average molecular weight 1100, trade name RE-100L; manufactured by Arizona Chemical Co.). Example 12 was carried out. In addition, the resin temperature at the time of discharge was 100 degreeC.

[Comparative Example 1]
A test was carried out in the same manner as in Example 1 except that the surfactant used in Example 1 was changed to polyoxyethylene lauryl ether (HLB value 9.6, trade name Emulgen 104P; manufactured by Kao Corporation). It was set to 1. In addition, the resin temperature at the time of discharge was 95 degreeC.

[Comparative Example 2]
A test was carried out in the same manner as in Example 1 except that the surfactant used in Example 1 was changed to polyoxyethylene lauryl ether (HLB value 10.5, trade name Emulgen 106; manufactured by Kao Corporation). 2. In addition, the resin temperature at the time of discharge was 95 degreeC.

[Comparative Example 3]
Similar to Example 1 except that the surfactant used in Example 1 was changed to polyoxyethylene styrenated phenyl ether (HLB value 10.6, trade name Neugen EA-87; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). The test was performed and it was set as Comparative Example 3. In addition, the resin temperature at the time of discharge was 94 degreeC.

[Comparative Example 4]
The test was carried out in the same manner as in Example 1 except that the surfactant used in Example 1 was changed to polyoxyethylene olein ether (HLB value 9.6, trade name Peganol O-6; manufactured by Toho Chemical Industry Co., Ltd.) Comparative Example 4 was obtained. In addition, the resin temperature at the time of discharge was 94 degreeC.

[Comparative Example 5]
The test was carried out in the same manner as in Example 1 except that the surfactant used in Example 1 was changed to polyoxyethylene olein ether (HLB value 11.2, trade name Nonal 208; manufactured by Toho Chemical Industry Co., Ltd.) It was set as Comparative Example 5. In addition, the resin temperature at the time of discharge was 94 degreeC.

[Comparative Example 6]
A test was conducted in the same manner as in Example 1 except that the surfactant used in Example 1 was changed to polyoxyethylene alkyl ether (HLB value 10.2, trade name TD-50; manufactured by Lion Corporation). Example 6 was adopted. In addition, the resin temperature at the time of discharge was 95 degreeC.

As can be seen from Tables 1 to 3, a solid resin composition that can be stored for a long period of time from the present invention, and a resin emulsion having a small particle diameter composed of the resin composition and water were obtained.

In Tables 1 to 3, details of the thermoplastic resin are shown in Table 4, and details of the surfactant are shown in Table 5, respectively.

Claims (3)

100 parts by mass of a vinyl polymer that is at least one selected from petroleum resins, rosin resins, and terpene resins having a glass transition temperature of 0 to 140 ° C. and a weight average molecular weight of 300 to 10,000, and an HLB value determined by the Griffin method of 12 to 20 A solid resin composition containing 1 to 20 parts by mass of a nonionic surfactant and 0.1 to 20 parts by mass of water. A vinyl polymer that is at least one selected from petroleum resin, rosin resin, and terpene resin is used as a dispersed phase having an average particle diameter of 0.1 to 1.0 μm through a continuous phase obtained by mixing a surfactant and water. The solid resin composition according to claim 1, which is adjacent to each other. 100 parts by mass of at least one vinyl polymer selected from petroleum resins, rosin resins, and terpene resins , 1-20 parts by mass of a nonionic surfactant having an HLB value determined by the Griffin method of 12-20, and water 0 A method for producing a resin composition, comprising kneading 1 to 20 parts by mass with a kneading apparatus and then cooling to a glass transition temperature or less of the vinyl polymer.