JP2013108071A - Method for producing polymer of compound having olefinically unsaturated bond - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an emulsion or polymer particles which are excellent in storage stability, coating properties and work efficiency, and excellent in water resistance, transparency and adhesion of a formed coating film.SOLUTION: In the method for producing an emulsion, a compound having an olefinically unsaturated bond is dispersed in water medium in the presence of an emulsifier and emulsion polymerization is carried out in the presence of 3-methoxy-3-methyl-1-butanol. In the method for producing polymer particles, a compound having an olefinically unsaturated bond is dispersed in water medium in the presence of a dispersant and suspension polymerization is carried out in the presence of 3-methoxy-3-methyl-1-butanol to produce a particulate product of a polymer of the compound having an olefinically unsaturated bond.

Description

  The present invention relates to a method for producing a polymer of a compound having an olefinically unsaturated bond. Specifically, the present invention relates to a process for producing an emulsion by emulsion polymerization of a compound having an olefinically unsaturated bond in the presence of 3-methoxy-3-methyl-1-butanol, and a compound having an olefinically unsaturated bond. The present invention relates to a method for producing polymer particles by suspension polymerization. The emulsion or polymer particles obtained by the production method of the present invention are useful for applications such as pressure-sensitive adhesives / adhesives, paints, toners, and resin surface modifiers.

Emulsions obtained by emulsion polymerization of compounds having olefinic unsaturated bonds, or polymer particles obtained by suspension polymerization are widely used as adhesives, adhesives, paints, toners, resin surface modifiers, etc. Has been. For applications such as pressure-sensitive adhesives, adhesives, paints, and the like, conventionally, a solution type resin composition dissolved in an organic solvent has been often used. However, in recent years, from the viewpoint of safety and hygiene, an alternative study to an aqueous resin composition such as an aqueous emulsion that does not use an organic solvent has been actively promoted. The aqueous emulsion is usually obtained by dispersing a compound having an olefinically unsaturated bond in water and emulsion polymerization. It is known that an emulsifier is added during production in order to maintain the polymerization stability when producing such an aqueous emulsion, the storage stability of the obtained aqueous emulsion, and the smoothness and transparency when formed into a coating film. (See Patent Documents 1, 2, and 3 and Non-Patent Document 1).
On the other hand, polymer particles obtained by suspension polymerization of a compound having an olefinically unsaturated bond are used in applications such as a toner, a resin surface modifier, and an adhesive. In suspension polymerization, a compound having an olefinically unsaturated bond is usually dispersed in water and polymerized, and then polymer particles can be obtained by a sedimentation operation or a filtration operation. In this suspension polymerization, it is known to add a dispersing agent such as an aqueous polymer in order to suppress aggregation between polymer particles and to reduce the particle size distribution of the particles (see Patent Documents 4 and 5). .

JP-A-2-73803 Japanese Patent Laid-Open No. 7-3233 JP 2007-297417 A JP 58-23801 A JP 63-112602 A

Experimental Chemistry Course, 5th Edition, Volume 26, Page 39

However, the emulsifier and the dispersant remain in a coating film obtained from an aqueous emulsion or polymer particles, a film-formed adhesive, a pressure-sensitive adhesive, or fine particles, and have a problem that water resistance and appearance are impaired. . For example, particles may be refined to improve coating properties for coating applications, transparency of coating films, and adhesion to substrates for adhesive applications. In such cases, a large amount of emulsifier / dispersant These problems may become prominent. In addition, the water-based emulsion has a problem that the emulsion freezes below the freezing point of water, and the workability particularly in winter and in a cold region is lowered as compared with a solution-type resin composition using an organic solvent. .
Therefore, an object of the present invention is to provide a method for producing a polymer of a compound having an olefinically unsaturated bond, which can solve the above problems.

According to the present invention, the above object is
[1] A method for producing a polymer of a compound having an olefinically unsaturated bond, comprising polymerizing a compound having an olefinically unsaturated bond in the presence of 3-methoxy-3-methyl-1-butanol;
[2] A compound having an olefinic unsaturated bond is dispersed in an aqueous solvent in the presence of an emulsifier, and emulsion polymerization is carried out in the presence of 3-methoxy-3-methyl-1-butanol, thereby producing an olefinic unsaturated bond. A process for producing a polymer emulsion of a compound having the following:
[3] A compound having an olefinically unsaturated bond is dispersed in an aqueous solvent in the presence of a dispersant, and suspension polymerization is carried out in the presence of 3-methoxy-3-methyl-1-butanol. A production method of [1], wherein a particulate product of a polymer of a compound having a saturated bond is produced;
[4] A mixed liquid of a compound having an olefinically unsaturated bond and 3-methoxy-3-methyl-1-butanol, or a compound having an olefinically unsaturated bond and 3-methoxy-3-methyl-1-butanol The production method of [2] or [3], wherein each is independently and simultaneously added to a reaction system containing water;
[5] The method according to any one of [1] to [4], wherein the polymerization is performed in the presence of a radical polymerization initiator;
[6] The compound having an olefinically unsaturated bond is a monomer that is copolymerizable with (meth) acrylic acid ester, or (meth) acrylic acid ester and (meth) acrylic acid ester. Any of the production methods of
[7] A polymer emulsion of a compound having an olefinically unsaturated bond obtained by the production method of [2];
[8] An adhesive obtained using the emulsion of [7];
[9] A paint obtained using the emulsion of [7];
[10] Polymer particles of a compound having an olefinically unsaturated bond obtained by the production method of [3];
[11] A resin surface modifier containing polymer particles according to [10];
[12] A paint containing polymer particles of [10]; and [13] a toner containing polymer particles of [10];
Is achieved by providing

  The production method of the present invention, preferably an emulsion obtained by emulsion polymerization, or a polymer particle obtained by suspension polymerization, is obtained by making the polymer particles fine, and there is little aggregation between the particles, and the particle size distribution is narrow. . Therefore, the coating film obtained by using such emulsion or polymer particles is excellent in water resistance, transparency, adhesion, etc., and is suitable in fields such as pressure-sensitive adhesives, adhesives, paints, toners, and resin surface modifiers. Can be used. In addition, since an emulsion having a low freezing point can be obtained, workability in winter and cold regions is improved and coating properties and storage stability are excellent.

2 is an SEM image (2000 times) of the emulsion of Example 1; 2 is an SEM image (10,000 times) of the emulsion of Example 1; 2 is an SEM image (2000 magnification) of the emulsion of Example 2. 2 is an SEM image (10,000 times) of the emulsion of Example 2. 3 is an SEM image (2000 times) of the emulsion of Comparative Example 1. 2 is an SEM image (10,000 times) of the emulsion of Comparative Example 1.

In the production method of the present invention, the greatest feature is that a compound having an olefinically unsaturated bond is polymerized in the presence of 3-methoxy-3-methyl-1-butanol. 3-methoxy-3-methyl-1-butanol is used in various applications such as various cleaning agents, cleaners, paints, and the like, and has the following properties.
(1) A colorless and transparent liquid with low odor.
(2) Since it has amphiphilic properties and is compatible with water in any composition, it has performance as a surfactant aid.
(3) It functions to lower the freezing point of water.
(4) Volatilizes with water to form an azeotrope with water.
(5) Low toxicity and biodegradability.
In addition, 3-methoxy-3-methyl-1-butanol is commercially available, and a trade name “Solfit” of Kuraray Co., Ltd. can be mentioned.

When a compound having an olefinically unsaturated bond is polymerized in the presence of 3-methoxy-3-methyl-1-butanol having the above properties, preferably by emulsion polymerization or suspension polymerization, use of an emulsifier or dispersant Even if the amount is reduced, the polymer particle size in the resulting emulsion or the polymer particle size obtained by suspension polymerization is refined and the aggregation of particles is suppressed, so that polymerization stability and storage stability are achieved. Thus, an emulsion or polymer particles having excellent coating properties and transparency can be obtained. Moreover, when the production method of the present invention is applied, the freezing point of the resulting emulsion can be lowered due to the presence of 3-methoxy-3-methyl-1-butanol. For this reason, the emulsion which is excellent in workability | operativity especially in winter and a cold region can be obtained. Further, 3-methoxy-3-methyl-1-butanol volatilizes with water when the emulsion is dried to form a coating film, and does not remain in the coating film, thus affecting the water resistance of the coating film. It also has the advantage of not giving.
In the following, embodiments of the present invention will be specifically described below, in particular, an emulsion production method by emulsion polymerization and a polymer particle production method by suspension polymerization, but the embodiments of the present invention are limited thereto. For example, a production method for obtaining a polymer of a compound having an olefinically unsaturated bond by performing solution polymerization using, for example, 3-methoxy-3-methyl-1-butanol as at least one component of a solvent is also disclosed. Needless to say, it is within the scope of the invention.

  Examples of the compound having an olefinically unsaturated bond that can be used in the production method of the present invention include vinyl halide compounds such as vinyl chloride, vinyl bromide, and vinyl fluoride; vinylidene halide compounds such as vinylidene chloride and vinylidene fluoride. Ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1 An α-olefin compound having preferably 20 or less carbon atoms, such as nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene; isobutylene, β-pinene, 8,9- Olefins such as p-mentene, dipentene, methylene norbornene and 2-methylenetetrahydrofuran Vinyl ester such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl caprate, vinyl benzoate; acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, monobutyl maleate, fumaric acid, itacone Unsaturated carboxylic acids such as acids or their anhydrides; metal salts of acrylic acid, metal salts of methacrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth) Isopropyl acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, (meth) Neopentyl acrylate, cyclopentyl (meth) acrylate, (meth) acrylic acid n-he Sil, (meth) acrylic acid isohexyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid n-heptyl, (meth) acrylic acid n-octyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid n- Nonyl, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, n-pentadecyl (meth) acrylate, (meth) Linear, branched or cyclic alkyl having 1 to 20 carbon atoms, preferably n-hexadecyl acrylate, n-heptadecyl (meth) acrylate, n-octadecyl (meth) acrylate, isobornyl (meth) acrylate, etc. (Meth) acrylic acid alkyl ester having a group; (meth) acrylic acid 2-hydroxyethyl, ( T) 2-hydroxypropyl acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, ( Such as 2-methoxyethyl (meth) acrylate, trifluoromethyl (meth) acrylate, glycidyl (meth) acrylate, trimethylsilyl (meth) acrylate, 2- (N, N-dimethylamino) ethyl (meth) acrylate, etc. (Meth) acrylic acid ester containing a functional group; (meth) acrylic acid ester containing an aromatic group such as phenyl (meth) acrylate and benzyl (meth) acrylate; 1,4-butanediol di (meth) Acrylate, 1,6-hexanediol di (meth) acrylate, triol (e.g. Multifunctional (meth) acrylates having two or more (meth) acrylates such as (meth) acrylic acid esters (eg glycerol) and tetrols (eg pentaerythritol); methacrylamide, N-methylmethacrylamide, N- Ethyl methacrylamide, N-isopropyl methacrylamide, N, N-dimethyl methacrylamide, N, N-diethyl methacrylamide, acrylamide, N-methyl acrylamide, N-ethyl acrylamide, N-isopropyl acrylamide, N, N-dimethyl acrylamide, (Meth) acrylamide such as N, N-diethylacrylamide and (meth) acrylic acid N-methylolamide; N-vinylpyrrolidone; (meth) acrylonitrile such as acrylonitrile and methacrylonitrile Styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, vinylnaphthalene, vinylanthracene, pt-butylstyrene, 2,4-dimethylstyrene, 2,4,6-trimethylstyrene, p-methoxy Vinyl aromatic compounds such as styrene, monofluorostyrene, monochlorostyrene, dichlorostyrene, indene, diphenylethylene; butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene , Conjugated diene compounds such as piperylene and 1,3-octadiene; maleimide compounds such as N-methylmaleimide, N-phenylmaleimide and N-cyclohexylmaleimide; vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmeth Vinylsilane compounds such as silane; N-vinylcarbazole; alkyl vinyl ether compounds such as methyl vinyl ether; 3-methyl-3-buten-1-ol, 3-buten-1-ol, methallyl alcohol, allyl alcohol, octa-2, And α-olefin compounds containing a functional group such as a hydroxyl group, preferably having 20 or less carbon atoms, such as 7-dienyl alcohol. These compounds having an olefinically unsaturated bond may be used singly or in combination of two or more.

  Examples of polymers obtained by polymerization using the above compound having an olefinically unsaturated bond include, for example, polyvinyl chloride resins (copolymerization of vinyl chloride and vinyl chloride such as vinyl ethers, acrylonitrile, and maleimides). Including polyvinyl alcohol) polyvinyl acetate resin; styrene resin such as acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin, maleic anhydride-styrene resin; (meth) acrylic acid ester-based (co) polymer, etc. Acrylic resin; and the like, but are not limited thereto.

  The amount of the compound having an olefinically unsaturated bond is usually preferably in the range of 20 to 70% by mass, preferably 30 to 60% by mass with respect to the total mass of the reaction mixture when performing the polymerization reaction. A range is more preferable. If it is higher than 70% by mass, the viscosity of the polymerization reaction mixture may increase, making it difficult to produce an emulsion. If it is lower than 20% by mass, the emulsion is used as a paint, adhesive, or adhesive. In such a case, the effects of the present invention may not be sufficiently achieved.

  In the production method of the present invention, mercaptans such as lauryl mercaptan, octyl mercaptan, dodecyl mercaptan, 2-mercaptoethanol, octyl thioglycolate, 3-mercaptopropionic acid and thioglycerin, or α-methylstyrene dimer, etc. A compound having chain transfer ability may be added as a molecular weight modifier.

  In the production method of the present invention, polymerization stability and storage stability of the resulting emulsion, and suppression of aggregation of polymer particles, and smoothness of the coating film when a coating film is prepared using the emulsion or polymer particles, From the viewpoint of maintaining transparency, an emulsifier and a dispersant are used. Usually, an emulsifier is used for emulsion polymerization, and a dispersant is used for suspension polymerization. However, the production method of the present invention is not limited thereto. For example, in addition to the emulsifier during emulsion polymerization, A dispersant may be used in combination, or an emulsifier may be used in combination with the dispersant when performing suspension polymerization.

  Examples of emulsifiers that can be used in the production method of the present invention, preferably a method of producing an emulsion by emulsion polymerization, include polyoxyethylene alkyl ethers (commercially available products: for example, Emulgen 120, Emulgen 150, Emulgen 1108S manufactured by Kao Corporation, etc.) ), Nonionic emulsifiers such as polyoxyethylene alkyl phenyl ether, polyoxyethylene sorbitan alkylate, oxyethylene oxypropylene block copolymer, polyglycerin ester, polyoxyethylene alkylamine; sodium polyoxyethylene alkyl ether sulfate (commercially available product) : Lamuru E-150, Latemul E-118B, etc. manufactured by Kao Corporation), polyoxyethylene alkyl ether sulfate triethanolamine, polyoxyethylene alkyl ether sulfate Ionic systems such as ammonium, sodium alkylbenzene sulfonate, sodium alkyl sulfate, triethanolamine alkyl sulfate, ammonium alkyl sulfate, sodium naphthalene sulfonate formalin condensate, dialkyl sulfosuccinate or fatty acid sodium, fatty acid potassium, fatty acid amine, alkyl trimethyl ammonium chloride Emulsifiers. In addition, allyloxypolyoxyethylene sulfonate (commercially available product: for example, Adekaria soap SR-10, SR-20, SR1025, etc. manufactured by Asahi Denka Kogyo Co., Ltd.), allyloxypolyoxyethylene, (meth) acryloxypolyoxyethylene Alkyl succinic acid alkenyl ether salts (commercially available products such as LATEMUL S-180A and S-180 manufactured by Kao Corporation) and the like can also be used. You may use these individually by 1 type or in combination of 2 or more types.

  Examples of the dispersant that can be used in the production method of the present invention, preferably polymer particles by suspension polymerization, include ammonium polyacrylate, sodium polyacrylate, lithium polyacrylate, and polyacrylic. Neutralized polycarboxylic acids including polyacrylates such as potassium acid; acrylamides such as polyacrylamide; cellulose derivatives such as methylcellulose, sodium carboxymethylcellulose, sodium carboxymethylcellulose, quaternized amine-substituted cellulose derivatives; polyvinyl alcohols; anhydrous Mention may be made of maleic acid-styrene copolymer; maleic anhydride-methyl vinyl ether copolymer; gelatin and the like. One of these dispersants may be used alone, or two or more thereof may be used in combination.

  In the production method of the present invention, the use amount of the emulsifier or the dispersant is not strictly limited, but the total mass of the compound having an olefinically unsaturated bond, water and 3-methoxy-3-methyl-1-butanol On the other hand, 0.01-5 mass% is preferable normally, More preferably, it is 0.1-3 mass%. If the amount of the emulsifier or dispersant added is less than 0.01% by mass, the polymerization stability and storage stability become insufficient, and the polymer particles dispersed in the resulting emulsion may aggregate or separate and settle. It tends to be. On the other hand, when it is more than 5% by mass, the water resistance and appearance of a coating film prepared from the obtained emulsion tend to be impaired.

  In the production method of the present invention, it is preferable to employ a radical polymerization reaction as the polymerization reaction and perform the polymerization in the presence of a radical polymerization initiator. Examples of the radical polymerization initiator that can be used in the production method of the present invention include hydroperoxide compounds such as t-butyl hydroperoxide, cumene hydroperoxide, and 2,5-dimethylhexane-2,5-dihydroperoxide. Dicumyl peroxide, di-t-butyl peroxide, t-butyl peroxyisobutyrate, t-butyl-α-cumyl peroxide, di-α-cumyl peroxide, α, α'-bis (t- Butylperoxy) -p-diisopropylbenzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) -hexyne-3, etc. Dialkyl peroxide compounds; acetyl peroxide, succinic acid peroxide, diisobutyryl peroxide, Acyl peroxides such as rhoyl peroxide and benzoyl peroxide; peroxide esters such as t-butyl peroxyacetate, t-butyl peroxyisobutyrate, di-isobutyl peroxydicarbonate, t-butylperoxyisopropyl carbonate; Organic peroxides such as ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; 2,2′-azobisisobutyronitrile, dimethyl = 2,2′-azobisisobutyrate, dimethyl azobisisobutyrate, 2 , 2′-azobis (2-methylbutyronitrile), 2,2′-azobis (isobutylamidine) dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] and its Disulfate, 2,2'-azobis (2-methyl Luamide oxime) azo compounds such as dihydrochloride; persulfates such as potassium persulfate, sodium persulfate, ammonium persulfate; hydrogen peroxide; ammonium persulfate, potassium persulfate, t-butyl hydroperoxide, benzoyl peroxide And various redox initiators used in combination of oxidizing agents such as cumene hydroperoxide and hydrogen peroxide and reducing agents such as sodium sulfite, acidic sodium sulfite, Rongalite and ascorbic acid. One of these radical polymerization initiators may be used alone, or two or more thereof may be used in combination.

  The amount of radical polymerization initiator used is the type and amount of the compound having an olefinically unsaturated bond used in the polymerization reaction (the type and total amount used when two or more types are copolymerized), chain transfer agent, polymerization Although it can be suitably selected according to the polymerization conditions such as temperature, it is usually preferably in the range of 0.03 to 5% by mass, more preferably, relative to the total mass of the compound having an olefinically unsaturated bond used in the polymerization reaction. Is in the range of 0.05 to 3 mass%. If the amount is less than 0.03% by mass, the progress of the polymerization reaction may be insufficient. On the other hand, if the amount is more than 5% by mass, the stability of the resulting emulsion or polymer particles tends to decrease. Become.

  In the production method of the present invention, the amount of 3-methoxy-3-methyl-1-butanol used is in the range of 0.1 to 30% by mass relative to the total mass of the compound having an olefinically unsaturated bond. Preferably, it is in the range of 1 to 20% by mass. If the amount is less than 0.1% by mass, the effect of the present invention cannot be obtained. On the other hand, if it exceeds 30% by mass, the stability of the polymer during the polymerization reaction and the stability of the resulting emulsion or polymer particles are impaired.

There is no restriction | limiting in particular in specific embodiment of the manufacturing method of this invention. For example, when an emulsion is produced by emulsion polymerization, a solution in which an emulsifier, water and, if necessary, a dispersant are mixed is set to a predetermined temperature, and a compound having an olefinically unsaturated bond, 3-methoxy- Method of polymerizing a mixture of 3-methyl-1-butanol and a radical polymerization initiator by batch addition or sequential addition; compound having olefinically unsaturated bond, 3-methoxy-3-methyl-1-butanol, emulsifier and water And a method of preparing a dispersion (pre-emulsion) by emulsifying and dispersing in advance using a dispersion apparatus or the like, and continuously adding the dispersion and a radical polymerization initiator in water to perform polymerization. On the other hand, in the case of producing polymer particles by suspension polymerization, a solution in which a dispersant and water and, if necessary, an emulsifier are further mixed is set to a predetermined temperature, and this solution has a compound having an olefinically unsaturated bond, A method in which a mixture of 3-methoxy-3-methyl-1-butanol and a radical polymerization initiator is added all at once or sequentially, and a compound having an olefinically unsaturated bond is polymerized while being dispersed in water by a stirrer or a dispersing device. Is mentioned. 3-methoxy-3-methyl-1-butanol is present when a compound having an olefinically unsaturated bond is emulsified and dispersed, or when dispersed in water using a stirrer or a dispersing device in suspension polymerization. However, it is important from the viewpoint of obtaining effects such as refinement of polymer particles to be obtained and suppression of aggregation.
As the dispersing device, known devices such as a high-speed rotating homogenizer, a high-pressure homogenizer, an ultrasonic homogenizer, an optimizer, and a nanomizer can be used.

  Moreover, when performing suspension polymerization, the average particle diameter of a polymer particle can be adjusted by adjusting superposition | polymerization conditions. Polymerization conditions generally refer to the stirring speed, reactor volume, baffle plate, shape and number of stirring blades, etc., and by selecting these appropriately, fine particles having a desired average particle diameter can be obtained (“suspension” Polymer particle size control in polymerization "by Masato Tanaka, issued by IPC Corporation on June 20, 1993).

  The reaction temperature for carrying out the production method of the present invention, preferably emulsion polymerization or suspension polymerization, is preferably in the range of 0 to 100 ° C from the viewpoint of using water as the dispersion solvent, and in the range of 50 to 90 ° C. More preferably. Regarding the reaction time, the type and amount of the compound having an olefinically unsaturated bond, the amount of emulsifier or dispersant used, the amount of water and 3-methoxy-3-methyl-1-butanol used, the reaction temperature, and the strength of stirring. It depends on various conditions such as the length and can be set as appropriate. For example, when performing a polymerization reaction, the remaining amount of the compound having an olefinically unsaturated bond is measured by gas chromatography or the like, and the polymerization reaction is performed for the time when the compound having an olefinically unsaturated bond does not remain in the reaction solution. The polymerization reaction may be continued.

The polymer obtained by the production method of the present invention, preferably the polymer obtained by emulsion polymerization or suspension polymerization, is usually fine particles. In the case of emulsion polymerization, the particle size of the polymer dispersed in the resulting emulsion is preferably in the range of 0.001 to 10 μm, more preferably in the range of 0.01 to 1 μm. When the particle size of the polymer dispersed in the emulsion is smaller than 0.001 μm or larger than 10 μm, the storage stability of the emulsion tends to be lowered. On the other hand, in the case of suspension polymerization, the particle diameter of the polymer particles obtained is preferably in the range of 0.01 μm to 100 μm, more preferably in the range of 0.1 μm to 50 μm. When the particle diameter of the obtained polymer particles is smaller than 0.01 μm or larger than 100 μm, the stability during polymerization tends to be low and the particles tend to aggregate.
The particle diameter can be measured by using a known method such as a laser diffraction method or a dynamic light scattering method, or by directly observing the particles with a scanning electron microscope (SEM).

  In the production method of the present invention, the viscosity of the emulsion obtained by emulsion polymerization is usually preferably in the range of 10 mPa · s to 100 Pa · s, and more preferably in the range of 50 mPa · s to 10 Pa · s. When it is lower than 10 mPa · s, the storage stability of the emulsion tends to be lowered, and when it is higher than 100 Pa · s, workability tends to be impaired. As a method for measuring the viscosity of the emulsion, for example, a Brookfield viscometer can be preferably used.

  Polymers, preferably emulsions or polymer particles obtained by the production method of the present invention are suitably used as paints, pressure-sensitive adhesives, adhesives, toners, resin surface modifiers, light scattering agents, cosmetic raw materials and the like. be able to. Further, additives such as a film-forming aid, a plasticizer, a pigment, a thickener, an antifoaming agent, a pH adjuster, a leveling agent, and a tackifying resin may be blended depending on the application.

  Here, as tackifying resin, what is conventionally used as resin which provides adhesiveness can be used without a restriction | limiting especially. For example, rosin resins such as gum rosin, tall oil rosin, wood rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, glycerin ester, rosin ester such as pentaerythritol ester, α-pinene, β-pinene, dipentene, etc. Terpene resins such as terpene resins, aromatic modified terpene resins, hydrogenated terpene resins, terpene phenol resins, etc .; (hydrogenated) aliphatic (C5) petroleum resins, (hydrogenated) aromatic (C9) Petroleum resin, (hydrogenated) copolymerized (C5 / C9) petroleum resin, (hydrogenated) dicyclopentadiene-based petroleum resin, alicyclic saturated hydrocarbon resin, etc. α-methylstyrene, α-methylstyrene / styrene copolymer, styrene monomer / aliphatic monomer copolymer, styrene monomer / α Styrene resins such as methylstyrene / aliphatic monomer copolymer, styrene monomer copolymer, styrene monomer / aromatic monomer copolymer other than styrene monomer, phenolic resin, xylene resin, coumarone-indene Synthetic resins such as resin based on the above. These may be used alone or in combination of two or more. When the tackifying resin is contained, the amount thereof is preferably 100 parts by mass or less with respect to 100 parts by mass of the compound having an olefinically unsaturated bond, and more preferably 80 parts by mass or less from the viewpoint of heat resistance. preferable. Examples of the method of blending such tackifier resin include a method of blending an emulsion type tackifier resin during or after emulsion polymerization, and a method of performing emulsion polymerization or suspension polymerization by dissolving a solid type tackifier resin. It is done. 3-methoxy-3-methyl-1-butanol also has the effect of increasing the solubility of these tackifying resins. In addition, about the softening point of tackifying resin, the thing of 50 to 150 degreeC is preferable from a heat resistant viewpoint, and 100 to 150 degreeC is more preferable.

  EXAMPLES Hereinafter, although an Example and a comparative example (henceforth an Example etc.) demonstrates this invention further in detail, this invention is not limited to this Example etc. In addition, evaluation of the emulsion obtained by the Example etc. was performed with the following method.

(1) Solid Content Concentration About 1 g of the emulsion obtained in Examples and the like was weighed and the solid content concentration was calculated from the weight of the residue after being left in a dryer at 120 ° C. for 3 hours (Formula 1).
Solid content concentration (% by mass) = (emulsion mass after drying) / (emulsion mass before drying) × 100 (Formula 1)
(2) Viscosity After leaving 200 g of the emulsion obtained in Examples etc. at 30 ° C. for 5 hours, the viscosity at a rotational speed of 20 rpm was measured with a Brookfield viscometer.
(3) Particle observation (cryo-SEM)
The emulsion obtained in Examples and the like was snap-frozen with liquid nitrogen, a fracture surface was created by breaking one side of the obtained solid, and then a sample for SEM observation was created by performing platinum deposition. While maintaining the sample at -130 ° C, the emulsion was observed using an FBI FBI-SEM apparatus Helios NanoLab 600 at an acceleration voltage of 1 kV, a magnification of 2000 times and a magnification of 10,000 times.
(4) Particle size The particle size of the polymer constituting the emulsion was determined from the SEM image obtained in (3).
(5) Standing stability The emulsions obtained in Examples and the like were allowed to stand at 25 ° C. for 1 month, and the state of separation and precipitation of solids was visually observed.
(6) Water Resistance of Emulsion Coating Film Using the emulsion obtained in Examples and the like, the emulsion was poured into a mold so that the thickness after drying was 500 μm, and allowed to stand at 23 ° C. for 1 week to form a cast film. The obtained coating film was cut into a size of 1 cm × 1 cm, mass a was measured, and then immersed in water at 20 ° C. for 24 hours. Thereafter, the mass b of the coating film obtained by removing the coating film from water and lightly wiping water was measured, and the mass c was measured by leaving it in a thermostatic bath at 105 ° C. for 5 hours. The water absorption and elution rate of the coating film were measured from the obtained masses a to c (Equation 2 and Equation 3).
Water absorption (%) = (mass b−mass a) / mass a × 100 (Formula 2)
Elution rate (%) = (mass a−mass c) / mass a × 100 (formula 3)
(7) Melting point of emulsion coating film Using the film obtained in (6) above as a sample, the temperature was raised from −100 ° C. to 10 ° C./min using a differential scanning calorimeter (DSC “EXSTAR DSC6200” manufactured by Seiko Instruments Inc.). The endothermic peak temperature at this time was taken as the melting point.

<Example 1>
(1) 120 g of 2-ethylhexyl acrylate as a compound having an olefinically unsaturated bond, 120 g of n-butyl acrylate and 10 g of acrylic acid, 2.5 g of 1-dodecanethiol as a molecular weight regulator, and Emulgen 118S-70 (Kao as an emulsifier) 2.5 g of active ingredient 70%) and 2.9 g of Latemul E-118B (manufactured by Kao Corporation 26% of active ingredient), 78.1 g of ion-exchanged water and 3-methoxy-3-methyl-1-butanol as a solvent (Kuraray Co., Ltd .: trade name “Solfit”) 25 g (10% by mass with respect to the total amount of the compound having an olefinically unsaturated bond) was put in a 500 mL container, and after bubbling with nitrogen for 30 minutes, Stir at 7000 rpm for 30 minutes using a high-speed rotating homogenizer, It was manufactured.
(2) 137.9 g of ion-exchanged water is placed in a 1 L container equipped with a stirrer, reflux condenser, thermometer, dropping funnel, metering pump, and nitrogen inlet, and heated to 80 ° C. with stirring at 400 rpm under a nitrogen stream. did. While maintaining the internal temperature at 80 ° C., 10% by mass of the pre-emulsion prepared in (1) was added all at once. After 5 minutes, 0.5 g of 10% ammonium persulfate aqueous solution was added all at once to initiate polymerization. After stirring the reaction mixture at 80 ° C. for 30 minutes, the remaining pre-emulsion was continuously added over 2 hours using a dropping funnel and 4.5 g of 10% aqueous ammonium persulfate solution using a metering pump. After completion of addition, 0.5 g of 10% aqueous ammonium persulfate solution was further added at once and stirred at 80 ° C. for 30 minutes. Thereafter, the reaction mixture was cooled to 40 ° C., and the pH was adjusted to 7.5 to 8.5 with a 25% aqueous ammonia solution to obtain an emulsion. The evaluation results of the emulsion are shown in Table 1. SEM images are shown in FIG. 1 (magnification 2000 times) and FIG. 2 (magnification 10000 times).

<Example 2>
In Example 1, the amount of ion-exchanged water 78.1 g used in the preparation of the pre-emulsion was 90.6 g, 3-methoxy-3-methyl-1-butanol 12.5 g (compound having an olefinically unsaturated bond) Except for the change to 5% by mass with respect to the total amount of the monomer, the same operation as in Example 1 was performed to obtain an emulsion. The evaluation results of the emulsion are shown in Table 1. SEM images are shown in FIG. 3 (magnification 2000 times) and FIG. 4 (magnification 10000 times).

<Comparative Example 1>
In Example 1, the same amount as in Example 1 except that 3-methoxy-3-methyl-1-butanol was not added to 103.1 g of the amount of ion-exchanged water 78.1 g used in preparing the pre-emulsion. Operation was performed to obtain an emulsion. The evaluation results of the emulsion are shown in Table 1. SEM images are shown in FIG. 5 (magnification 2000 times) and FIG. 6 (magnification 10000 times).

In the emulsions obtained in Examples 1 and 2, as shown in FIGS. 1 to 4, almost no aggregation of particles is observed, the particle diameter is small, and the distribution width of the particle diameter is also small. On the other hand, in the emulsion obtained in Comparative Example 1, particles are aggregated as shown in FIGS. 5 and 6, the particle size is slightly larger than those in Examples 1 and 2, and the distribution range of the particle size is large.
In addition, regarding the stability of the emulsion, the emulsions obtained in Examples 1 and 2 were stable with no separation and precipitation of solids observed even when left at 25 ° C. for 1 month, whereas those obtained in Comparative Example 1 were obtained. In the emulsion, separation and sedimentation of solids were observed. From this result, it can be seen that a highly stable emulsion can be obtained by producing an emulsion by polymerizing in the presence of 3-methoxy-3-methyl-1-butanol.
Furthermore, as shown in Table 1, the coating film prepared from the emulsions obtained in Examples 1 and 2 has a lower melting point than the coating film prepared from the emulsion obtained in Comparative Example 1. From this, it can be seen that an emulsion excellent in workability in winter and cold regions can be obtained by carrying out polymerization in the presence of 3-methoxy-3-methyl-1-butanol to produce an emulsion.
On the other hand, Examples 1 and 2 and Comparative Example 1 are equivalent in terms of water resistance of the coating film, and the obtained emulsion and emulsion were used even when polymerization was performed in the presence of 3-methoxy-3-methyl-1-butanol. It can also be seen that the water resistance of the coating film obtained is not affected.

  The emulsion or polymer particles obtained by the production method of the present invention are excellent in storage stability, coating property, workability in winter and cold regions, and excellent in water resistance, transparency and adhesion of the coating film to be produced. Accordingly, it can be suitably used for applications such as pressure-sensitive adhesives, adhesives, paints, toners, and resin surface modifiers.

Claims (13)

  A method for producing a polymer of a compound having an olefinically unsaturated bond, comprising polymerizing a compound having an olefinically unsaturated bond in the presence of 3-methoxy-3-methyl-1-butanol.   A compound having an olefinically unsaturated bond by dispersing a compound having an olefinically unsaturated bond in an aqueous solvent in the presence of an emulsifier and performing emulsion polymerization in the presence of 3-methoxy-3-methyl-1-butanol The production method according to claim 1, wherein an emulsion of the polymer is produced.   A compound having an olefinic unsaturated bond is dispersed in an aqueous solvent in the presence of a dispersant, and suspension polymerization is carried out in the presence of 3-methoxy-3-methyl-1-butanol, thereby removing the olefinic unsaturated bond. The production method according to claim 1, wherein a particulate product of a polymer of the compound having the compound is produced.   A mixed liquid of a compound having an olefinically unsaturated bond and 3-methoxy-3-methyl-1-butanol, or a compound having an olefinically unsaturated bond and 3-methoxy-3-methyl-1-butanol are each independently The method according to claim 2 or 3, wherein the reaction system is simultaneously added to a reaction system containing water.   The production method according to claim 1, wherein the polymerization is performed in the presence of a radical polymerization initiator.   The compound having an olefinically unsaturated bond is (meth) acrylic acid ester or a monomer copolymerizable with (meth) acrylic acid ester and (meth) acrylic acid ester. The manufacturing method as described.   An emulsion of a polymer of a compound having an olefinically unsaturated bond, obtained by the production method according to claim 2.   A pressure-sensitive adhesive obtained by using an emulsion of a polymer of a compound having an olefinically unsaturated bond according to claim 7.   A paint obtained by using an emulsion of a polymer of a compound having an olefinically unsaturated bond according to claim 7.   Polymer particles of a compound having an olefinically unsaturated bond, obtained by the production method according to claim 3.   The resin surface modifier containing the polymer particle | grains of the compound which has an olefinically unsaturated bond of Claim 10.   The coating material containing the particle | grains of the polymer of the compound which has an olefinically unsaturated bond of Claim 10.   11. A toner comprising polymer particles of a compound having an olefinically unsaturated bond according to claim 10.