JP5279314B2 - Polyolefin resin dispersion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyolefin resin dispersion not deteriorating characteristics of a polyolefin resin, having excellent mixture stability with both of water and various organic solvents, and allowing reduction in viscosity for improvement in ease of handling. <P>SOLUTION: The polyolefin resin dispersion comprises a polyolefin resin (A) containing unsaturated carboxylic acid units in an amount of 0.01-25 mass%, a basic compound (B), a lactam compound (C), and water (D), and the mass ratio (C)/(D) of the lactam compound (C) to the water (D) is from 99.5/0.5 to 50/50. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a polyolefin resin dispersion.

A non-aqueous dispersion in which a polyolefin resin is dispersed in an organic solvent is very important as a binder for solvent-based paints, inks, and adhesives.
As a method for producing such an organic solvent dispersion of polyolefin resin, after dissolving polyolefin resin once in an organic solvent called good solvent by an operation such as heating, an organic solvent called poor solvent is added, or cooling conditions are devised. In other words, methods (precipitation methods) for depositing polyolefin resin particles have been proposed (Patent Documents 1 to 5). In addition, the present inventors have proposed a method of dispersing a polyolefin resin containing a specific amount of an unsaturated carboxylic acid unit in a specific ratio of an amphiphilic organic solvent (Patent Document 6).
Japanese Patent Laid-Open No. 05-086203 Japanese Patent Laid-Open No. 06-065387 Japanese Patent Application Laid-Open No. 06-057006 Japanese Patent Laid-Open No. 07-258423 JP 2001-207033 A JP 2005-008813 A

  However, in the methods described in Patent Documents 1 to 3, since dispersion aids such as emulsifiers and dispersants are used, these non-volatile compounds remain in the resin after drying, and the original resin has There is a risk of deteriorating the characteristics. In particular, there is a problem that the water resistance of the coating film is significantly reduced. Further, the dispersing aid may bleed out, and not only changes in physical properties with time but also is unfavorable in terms of environment and hygiene. Furthermore, since the particle diameter of the polymer fine particles obtained by the production method using the dispersing aid is as large as 1 μm or more, there are problems in dispersion stability and mixing stability.

  Patent Documents 4 and 5 describe a method of producing polyolefin resin particles in a non-aqueous solvent without using a dispersion aid, but the former has a very complicated deposition condition of polymer fine particles, In the latter, the physical properties of the polyolefin resin are greatly limited. Furthermore, the average particle diameter of the polymer fine particles obtained by these methods is also as large as 1 μm or more.

  The dispersion obtained by the method of Patent Document 6 proposed by the present inventors has solved these problems, but a composition in which the proportion of water in the medium is further reduced is required. Further, the viscosity of the dispersion having a low ratio of water becomes high, and further improvement is demanded.

  In view of these problems, the present invention does not impair the properties of the polyolefin resin, is excellent in mixing stability with both water and various organic solvents, and has low handling capability due to its low viscosity. It is an object to provide an improved polyolefin resin dispersion.

  As a result of intensive studies to solve the above problems, the present inventors can finely and stably disperse a polyolefin resin containing a specific amount of an unsaturated carboxylic acid unit by using a lactam compound and water as a medium. In addition, the inventors have found that the content of water can be reduced and the viscosity can be reduced by including a lactam compound, and the present invention has been achieved.

That is, the polyolefin resin dispersion of the present invention comprises a polyolefin resin (A) having an unsaturated carboxylic acid unit content of 0.01 to 25% by mass, a basic compound (B), a lactam compound (C), Water (D), the basic compound (B) is ammonia or an organic amine compound having a boiling point of 300 ° C. or less, and the mass ratio (C) / (Lactam compound (C) to water (D) D) is 99.5 / 0.5 to 50/50, and the viscosity at a temperature of 25 ° C. and a shear rate of 20.40 s ⁻¹ when the content of the polyolefin resin (A) is 20 mass% is 500 mPa · s. The number average particle diameter of the polyolefin resin (A) is 0.8 μm or less.

  Since the polyolefin resin dispersion of the present invention uses a lactam compound and water as a medium, it is not necessary to include a non-volatile dispersion aid in the dispersion, and this completely impairs the performance of the polyolefin resin. A coating film without any problems can be formed. In addition, it is excellent in mixing stability with both water and various organic solvents, and since it has low viscosity, it is excellent in mixing stability of powder materials, so it is suitable for applications such as binders, inks, paints, and adhesives. .

Hereinafter, the present invention will be described in detail.
In the polyolefin resin dispersion of the present invention, a polyolefin resin (A) containing a specific amount of an unsaturated carboxylic acid unit is contained in a medium containing a basic compound (B), a lactam compound (C), and water (D). Are distributed.

  The polyolefin resin (A) used in the present invention needs to contain 0.01 to 25% by mass of an unsaturated carboxylic acid unit. If the content of the unsaturated carboxylic acid unit is less than 0.01% by mass, it becomes difficult to disperse (liquefy) the resin. On the other hand, if the content exceeds 25% by mass, the water resistance and alkali resistance are reduced or dispersed. The stability of the body may deteriorate. From these points, the content of the unsaturated carboxylic acid unit is preferably 0.05 to 22% by mass, more preferably 0.1 to 15% by mass, further preferably 0.5 to 10% by mass, and 1 to 8%. Mass% is particularly preferable, and 1 to 7 mass% is most preferable.

  The unsaturated carboxylic acid unit is introduced by an unsaturated carboxylic acid or an anhydride thereof. Specific examples of these include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid and the like, as well as unsaturated dicarboxylic acid half esters, half amides, and the like. . Of these, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferable, and acrylic acid and maleic anhydride are particularly preferable. Moreover, the unsaturated carboxylic acid unit should just be copolymerized in polyolefin resin (A). The form is not limited, and examples thereof include random copolymerization, block copolymerization, and graft copolymerization.

  Examples of the olefin component that is the main component of the polyolefin resin include ethylene hydrocarbons having 2 to 6 carbon atoms such as ethylene, propylene, isobutylene, 1-butene, 1-pentene, and 1-hexene.

  Preferred examples of the polyolefin resin containing the unsaturated carboxylic acid unit and the olefin component include those containing an acrylic acid ester or a methacrylic acid ester in addition to the unsaturated carboxylic acid unit. From the viewpoint of easy dispersion of the resin, adhesion to various substrates, water resistance and alkali resistance of the coating film, in particular, the olefin component (L) and the acrylate ester or methacrylate ester (M). The mass ratio is preferably in the range of (L) / (M) = 65/35 to 99/1 in view of the balance of performance, more preferably 70/30 to 97/3, and 75/25 to Particularly preferred is 97/3. When the ratio of (M) to [(L) + (M)] is less than 1% by mass, it becomes difficult to disperse the polyolefin resin, and it is difficult to obtain a good dispersion. On the other hand, when the ratio of (M) to [(L) + (M)] exceeds 35% by mass, the properties as a polyolefin resin due to the olefin component (L) are lost, adhesion to various substrates, heat Performance such as sealing performance and water resistance is reduced.

  Specific examples of the acrylic ester or methacrylic ester (M) include acrylics such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, and butyl methacrylate. An esterified product of an acid or methacrylic acid and an alcohol can be mentioned. Among these, methyl acrylate, methyl methacrylate, ethyl acrylate, and ethyl methacrylate are preferable.

  Examples of the polyolefin resin (A) include an ethylene-acrylic acid ester-maleic anhydride terpolymer and an ethylene-methacrylic acid ester-maleic anhydride terpolymer. Among these, ethylene-acrylic acid ester-maleic anhydride is more preferable. Here, the acrylic ester unit may be converted into an acrylic acid unit by hydrolyzing a small part of the ester bond during the dispersion of the resin described later. It is only necessary that the ratio of each constituent component considering the change is within the above-described range.

  Moreover, as preferable polyolefin resin (A), the resin in which an olefin component contains a propylene and / or butene is mentioned. The content of propylene and / or butene is preferably 50 to 98% by mass, more preferably 60 to 98% by mass, still more preferably 70 to 98% by mass, and particularly preferably 80 to 98% by mass. Examples of the butene component include 1-butene and isobutene. The polyolefin resin containing propylene and / or butene preferably further contains 2 to 50% by mass of an ethylene component. A particularly preferred configuration is one containing three components, a propylene component, a butene component, and an ethylene component, as the olefin component, and the composition ratio is such that when the total of these three components is 100 parts by mass, the propylene component is 8-90. They are a mass part, a butene component 8-90 mass parts, and an ethylene component 2-50 mass parts. Thus, by containing an ethylene component, the dispersibility of the resin and the coating film performance are improved. In the polyolefin resin, the copolymerization form of each component is not limited, and examples thereof include random copolymerization and block copolymerization. Among these, random copolymerization is preferable from the viewpoint of easy polymerization.

  Further, the polyolefin resin (A) may further contain other components of about 10% by mass or less based on the whole polyolefin resin. Such components include 1-pentene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-hexene, 1-octene, norbornene and other alkenes and dienes; (meth) acrylic acid (Meth) acrylic acid esters such as methyl, ethyl (meth) acrylate and butyl (meth) acrylate; maleic acid esters such as dimethyl maleate, diethyl maleate and dibutyl maleate; (meth) acrylic acid amides Alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate and vinyl versatate; and obtained by saponifying vinyl esters with basic compounds, etc. Vinyl alcohol, 2-hydroxyethyl acrylate , And the like glycidyl (meth) acrylate. Mixtures of these can also be used.

  In addition, when the unsaturated carboxylic acid unit constituting the polyolefin resin (A) is an unsaturated carboxylic anhydride unit such as a maleic anhydride unit, an acid anhydride in which the adjacent carboxyl group is dehydrated and cyclized in the dry state of the resin Although a structure is formed, particularly in a medium containing a basic compound, a part or all of the ring is opened to facilitate the formation of a carboxylic acid or a salt thereof.

  A small amount of other monomers may be copolymerized in the polyolefin resin (A). Examples of other monomers mentioned here include dienes, (meth) acrylonitrile, styrene, vinyl halides, vinylidene halides, carbon monoxide, and sulfur dioxide.

  Although the molecular weight of polyolefin resin (A) is not specifically limited, It is preferable that the melt flow rate in 190 degreeC and 20.2N (2160g) load used as the standard of molecular weight is 0.01-10000g / 10min. More preferably, it is 0.5-1000 g / 10min, More preferably, it is 1-500g / 10min, Most preferably, it is 1-300g / 10min. When the melt flow rate of the polyolefin resin (A) is less than 0.01 g / 10 minutes, it is difficult to disperse the resin. On the other hand, when the melt flow rate of the polyolefin resin (A) exceeds 10,000 g / 10 minutes, the resulting coating film becomes brittle and its mechanical strength decreases.

  In addition, the synthesis method of polyolefin resin (A) is not specifically limited. In general, it is obtained by high-pressure radical copolymerization of a monomer constituting the polyolefin resin in the presence of a radical generator. Further, the unsaturated carboxylic acid unit may be graft copolymerized (graft-modified).

The number average particle diameter (hereinafter referred to as “mn”) of the polyolefin resin particles dispersed in the dispersion of the present invention is 0.8 μm or less from the viewpoint of improving the storage stability of the dispersion. Is required , 0.005-0.5 μm is more preferable, 0.005-0.3 μm is more preferable, and 0.005-0.2 μm is most preferable.

The dispersion of the present invention needs to contain a basic compound (B). The basic compound (B), must be in terms of volatilization during film formation, also the water resistance of the coating film surface or these alkali-resistant, organic amine compound ammonia or boiling point of 300 ° C. or less It is . When the boiling point exceeds 300 ° C., it becomes difficult to disperse the organic amine compound from the resin coating film by drying, and the water resistance and alkali resistance of the coating film may deteriorate.

  Specific examples of the organic amine compound include triethylamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine, diethylamine, and 3-ethoxypropylamine. , 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, 3-methoxypropylamine, monoethanolamine, morpholine, N-methylmorpholine, N-ethylmorpholine and the like.

  The addition amount of the basic compound (B) is preferably 0.6 to 3.0 times equivalent, more preferably 0.8 to 2.5 times equivalent to the carboxyl group in the polyolefin resin (A). 1.0-2.0 times equivalent is particularly preferable. When the amount is less than 0.6 times equivalent, the effect of adding the basic compound (B) is not recognized, and when the amount exceeds 3.0 times equivalent, the viscosity of the dispersion may increase.

  In the present invention, in order to stably disperse the polyolefin resin (A) having the specific composition described above under the condition that the proportion of water in the medium is 50% by mass or less and to obtain a low-viscosity dispersion, a lactam compound It is necessary to use (C) as a medium. Specific examples of the lactam compound (C) include 2-pyrrolidone, N-methyl-2-pyrrolidone (hereinafter abbreviated as “NMP”), N-vinyl-2-pyrrolidone and the like. Among these, NMP is most preferable for reasons such as handleability and price.

Any water (D) may be used in the present invention, and examples thereof include pure water, distilled water, ion exchange water, tap water, soft water, and hard water.
In the present invention, it is very important to add water (D) when the polyolefin resin (A) is dispersed in the lactam compound (C). At this time, the lactam compound (C) and water (D) are added. And the mass ratio (C) / (D) must be in the range of 99.5 / 0.5 to 50/50. When the content of water in the mixed medium of the lactam compound (C) and water (D) is less than 0.5% by mass, the polyolefin resin can be dispersed, but the stability of the dispersion ( Storage stability) is significantly reduced. Moreover, since mixing stability with various organic solvents will deteriorate when water content exceeds 50 mass%, it cannot be used for a solvent-type use. In balancing the two, (C) / (D) is preferably 99/1 to 60/40, more preferably 99/1 to 65/35, and 99/1 to 70/30. It is more preferable that it is 99 / 1-80 / 20.

  An organic solvent other than the lactam compound (C) may be added to the polyolefin resin dispersion of the present invention. Specifically, diethyl ketone (3-pentanone), methyl propyl ketone (2-pentanone), methyl isobutyl ketone (4-methyl-2-pentanone), 2-hexanone, 5-methyl-2-hexanone, 2-to Ketones such as butanone, 3-heptanone, 4-heptanone, cyclopentanone, cyclohexanone, acetone, methyl ethyl ketone, cyclohexanone; aromatic hydrocarbons such as toluene, xylene, benzene, Solvesso 100, Solvesso 150; butane, pentane Aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane, nonane; methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chlorobenzene, o-dichlorobenzene , M-dichlorobenzene, -Halogen-containing compounds such as dichlorobenzene; ethyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, 3-methoxybutyl acetate, methyl propionate, ethyl propionate, diethyl carbonate, γ- Esters such as butyrolactone and isophorone; methanol, ethanol, n-propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, alcohols such as tert-amyl alcohol, 1-ethyl-1-propanol, n-hexanol and cyclohexanol; ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and dioxane; ethylene Glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol ethyl ether acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol ethyl ether acetate, Glycol derivatives such as propylene glycol, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol methyl ether acetate; and further, 3-methoxy-3-methylbutanol, 3-methoxybutanol, acetonitrile, dimethylform Bromide, dimethyl acetamide, diacetone alcohol, ethyl acetoacetate, and the like. Among them, those having a boiling point of 30 to 300 ° C are preferable, and those having a boiling point of 50 to 250 ° C are particularly preferable. These organic solvents may be used as a mixture of two or more. In addition, when the boiling point of the organic solvent is less than 30 ° C., the ratio of volatilization when the resin is dispersed increases, and it may be difficult to disperse the resin. An organic solvent having a boiling point exceeding 300 ° C. is difficult to be scattered from the resin coating film by drying, and the water resistance of the coating film may deteriorate.

Although there is no restriction | limiting in particular of the addition amount of an organic solvent, In order to maintain the effect of a lactam compound, it is preferable that it is less than the equivalent of a lactam compound.
The dispersion of the present invention can be made a stable dispersion even when a non-volatile dispersion aid is added. However, the dispersion of the present invention can stably maintain the polyolefin resin in the medium with a number average particle diameter of 0.8 μm or less without using this. On the other hand, if added, the non-volatile dispersion aid remains in the polyolefin resin even after the formation of the coating film, and plasticizes the coating film to thereby improve the properties of the polyolefin resin, such as water resistance and adhesion to the substrate. It may worsen sex. For this reason, it is preferable not to contain a non-volatile dispersion | distribution adjuvant. However, in applications that do not require performance such as water resistance, the content may be about 0.01 to 20% by mass relative to the polyolefin resin.

  Here, the “dispersion aid” is a drug or compound added for the purpose of promoting dispersion or stabilizing the dispersion in the production of the dispersion, and “nonvolatile” means normal pressure. Or a high boiling point (for example, 300 ° C. or higher) at normal pressure.

  Examples of the non-volatile dispersion aid include an emulsifier, a compound having a protective colloid action, an acid-modified compound having a high acid value, and a water-soluble polymer.

  Examples of the emulsifier include a cationic emulsifier, an anionic emulsifier, a nonionic emulsifier, and an amphoteric emulsifier. In addition to those generally used for emulsion polymerization, surfactants are also included. For example, anionic emulsifiers include higher alcohol sulfates, higher alkyl sulfonates, higher carboxylates, alkyl benzene sulfonates, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, vinyl sulfosuccinates. And the like. Nonionic emulsifiers include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol fatty acid esters, ethylene oxide propylene oxide block copolymers, polyoxyethylene fatty acid amides, ethylene oxide-propylene oxide copolymers, and the like. Examples thereof include compounds having an oxyethylene structure and sorbitan derivatives such as polyoxyethylene sorbitan fatty acid esters. Examples of amphoteric emulsifiers include lauryl betaine and lauryl dimethylamine oxide.

  Compounds having protective colloid action, acid-modified compounds with high acid value, water-soluble polymers include polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, modified starch, polyvinyl 2-pyrrolidone, poly Acrylic acid and its salt, acrylic acid-maleic anhydride copolymer and its salt, styrene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid copolymer, isobutylene-maleic anhydride alternating copolymer , (Meth) acrylic acid- (meth) acrylic acid ester copolymer and other unsaturated carboxylic acid unit content of 26 mass% or more carboxyl group-containing polymer and salts thereof, polyitaconic acid and salts thereof, and amino groups Water-soluble acrylic copolymer Body, gelatin, gum arabic, casein, generally compounds which are used as dispersion stabilizer of fine particles.

  The resin content in the dispersion of the present invention can be appropriately selected depending on the film forming conditions, the thickness and performance of the target resin coating film, and is not particularly limited. However, it is preferably 1 to 60% by mass, more preferably 3 to 50% by mass, and more preferably 5 to 40% by mass in terms of maintaining the viscosity of the coating composition moderately and expressing good coating film forming ability. Is more preferable, and 7 to 35% by mass is particularly preferable.

The viscosity of the dispersions of the invention, from the viewpoint of mixing stability with various additives is improved, the content of the polyolefin resin (A) at 20 mass%, the temperature 25 ° C., a shear rate 20.40S ^{- 1} , it is necessary to be less than 500 mPa · s. 5-300 mPa · s is more preferred, 10-200 mPa · s is more preferred, and 10-100 mPa · s is most preferred. If it exceeds 500 mPa · s, it may be difficult to stably disperse or mix the powder material.

Next, the manufacturing method of the polyolefin resin dispersion of this invention is demonstrated.
The production method for obtaining the polyolefin resin dispersion of the present invention is not particularly limited. For example, the components described above, that is, a polyolefin resin (A) having a specific composition, a basic compound (B), a lactam compound ( A method in which a medium in which C) and water (D) are mixed at a specific ratio is preferably heated and stirred in a sealable container. This method is most preferred. At this time, it is very important to add water (D), and the mass ratio (C) / (D) of the lactam compound (C) to water (D) is set to 99.5 / 0. It is necessary to set it as 5-50 / 50. According to this method, the polyolefin resin (A) having a specific composition can be satisfactorily formed into a dispersion without substantially adding a non-volatile dispersion aid.

  Further, in the present invention, after obtaining the dispersion, the organic solvent and / or the lactam compound (C) / water (D) may be in the range of 99.5 / 0.5 to 50/50 in quality ratio. Alternatively, water can be added.

  The container for heating and stirring the raw material may be any container provided with a tank into which a liquid can be charged so that the mixture of the medium and the resin powder or granular material charged in the tank can be appropriately stirred. As such a device, a device widely known to those skilled in the art as a solid / liquid stirring device or an emulsifier can be used. Among these, it is preferable to use an apparatus that can pressurize 0.1 MPa or more. The stirring method and the rotation speed of stirring are not particularly limited, but high-speed stirring (for example, 1000 rpm or more) is not essential because sufficient dispersion can be achieved even with low-speed stirring that allows the resin to float in the medium. . For this reason, the dispersion can be produced even with a simple apparatus.

  The above raw materials are put into a tank of this apparatus, and preferably stirred and mixed at a temperature of 40 ° C. or lower. Next, the polyolefin resin is sufficiently dispersed by keeping stirring in the tank at a temperature of 60 to 200 ° C., preferably 80 to 200 ° C., more preferably 100 to 180 ° C., and preferably stirring for 5 to 120 minutes. And then cooled to 40 ° C. or lower, preferably with stirring, to obtain a dispersion. At this time, when the temperature in the tank is less than 60 ° C., it becomes difficult to disperse the polyolefin resin. On the other hand, when the temperature in the tank exceeds 200 ° C., the molecular weight of the polyolefin resin may decrease. As a heating method in the tank, heating from the outside of the tank is preferable. For example, the tank can be heated using oil or water, or a heater can be attached to the tank for heating. Examples of the cooling method in the tank include a method of naturally cooling at room temperature and a method of cooling using oil or water at 0 to 40 ° C.

  After this, jet pulverization may be further performed as necessary. Jet pulverization here refers to a fluid such as a polyolefin resin dispersion that is ejected from a pore such as a nozzle or slit under high pressure to cause resin particles to collide with each other, By colliding, it means that the resin particles are further refined by mechanical energy. Specific examples of the apparatus for that purpose include A.I. P. V. Examples thereof include a homogenizer manufactured by GAULIN, and a microfluidizer M-110E / H manufactured by Mizuho Industry.

  As described above, the dispersion of the present invention is prepared by dispersing or dissolving the polyolefin resin (A) in a medium to prepare a uniform liquid. Here, the uniform liquid state means that, in terms of appearance, a portion in which the solid content concentration such as precipitation, phase separation, and skinning is locally different from other portions is not found in the dispersion. Say.

  Even if undispersed resin remains in the resulting dispersion, it can be used as a dispersion in subsequent steps if such resin is removed by filtration through a filter during the manufacturing process. It is.

  According to the present invention, the dispersion of the polyolefin resin (A) is generally very good, although it may decrease slightly depending on conditions. That is, almost no resin remains and the dispersion can be satisfactorily achieved.

  In the dispersion of the present invention, in order to further improve various coating film performances such as water resistance and solvent resistance, 0.01 to 100 parts by mass of a crosslinking agent is added to 100 parts by mass of the resin in the dispersion. , Preferably 0.1-60 mass parts can be added. When the addition amount of the crosslinking agent is less than 0.01 parts by mass, the degree of improvement in the coating film performance is small, and when it exceeds 100 parts by mass, the performance such as workability is deteriorated. As the crosslinking agent, a crosslinking agent having self-crosslinking property, a compound having a plurality of functional groups that react with a carboxyl group in the molecule, a metal complex having a polyvalent coordination site, and the like can be used. For example, isocyanate compounds, melamine compounds, urea compounds, epoxy compounds, carbodiimide compounds, oxazoline group-containing compounds, zirconium salt compounds, silane coupling agents and the like are preferable. Moreover, you may use combining these crosslinking agents.

  The dispersion of the present invention is excellent in mixing stability, and the polyolefin resin (A) contained therein is excellent in adhesiveness and binding properties with various substrates, so that it can be used as an adhesive, a binder for paints, and a binder for electrodes. Can be suitably used.

  Examples of the substrate that can be used as the adhesive include metal, glass, plastic, paper, and the like, and the shape thereof is not limited.

  The dispersion of the present invention can be made into a paint by adding a pigment or a dye, and a pigment dispersant as required. Furthermore, it can also be added to commercially available paints (whether aqueous or oily), thereby imparting direct laminate suitability to the paint.

  Examples of the electrode binder include a secondary battery electrode binder and a capacitor electrode binder.

  Furthermore, the dispersion of the present invention can be used as a coating agent or paint by adding various agents such as inorganic particles, leveling agents, antifoaming agents, anti-waxing agents, and UV absorbers to the dispersion of the present invention as necessary. Can be used. At this time, a high boiling point solvent generally used for adjusting the drying conditions may be added. It is also possible to add organic or inorganic compounds other than those described above to the dispersion as long as the stability of the dispersion is not impaired.

Next, a method for using the dispersion of the present invention will be described.
Since the dispersion of the present invention is excellent in film forming ability, known film forming methods such as gravure roll coating, reverse roll coating, wire bar coating, lip coating, air knife coating, curtain flow coating, spray coating, dipping Uniformly coat the surface of various base materials by coating, brushing, etc., set it near room temperature as necessary, and then subject it to heat treatment for drying or drying and baking. It can be formed in close contact with various substrate surfaces. As a heating device at this time, a normal hot air circulation type oven, an infrared heater, or the like may be used. In addition, the heating temperature and the heating time are appropriately selected according to the characteristics of the substrate to be coated, the type of curing agent described later, the blending amount, etc., but considering the economy, the heating temperature is It is preferable that it is 50-250 degreeC, 90-230 degreeC is more preferable, and 100-200 degreeC is especially preferable. The heating time is preferably 1 second to 120 minutes, more preferably 10 seconds to 60 minutes, and particularly preferably 15 seconds to 30 minutes. When a crosslinking agent is added, the heating temperature and time are appropriately selected depending on the type of the crosslinking agent in order to sufficiently promote the reaction between the carboxyl group in the polyolefin resin (A) and the crosslinking agent or the self-reaction of the crosslinking agent. It is desirable to do.

  The thickness of the resin coating film formed using the dispersion of the present invention is appropriately selected depending on the application, but is preferably 0.01 to 100 μm, more preferably 0.01 to 50 μm. 0.01 to 30 μm is particularly preferable. If the film is formed so that the thickness of the resin coating film falls within the above range, a resin coating film having excellent uniformity can be obtained.

Hereinafter, the present invention will be described specifically by way of examples. However, the present invention is not limited to these.
Various characteristics in the following examples and comparative examples were measured or evaluated by the following methods.

(1) Composition of polyolefin resin In orthodichlorobenzene (d ₄ ), ¹ H-NMR and ¹³ C-NMR analysis (analyzer manufactured by Varian, 300 MHz) was performed at 120 ° C. to obtain. ^{In 13} C-NMR analysis, measurement was performed using a gated decoupling method in consideration of quantitativeness. Further, the content of the unsaturated carboxylic acid unit was determined using the method (1-A) or method (1-B) shown below.

(1-A)
The acid value of the polyolefin resin was measured according to JIS K5407, and the content (graft ratio) of the unsaturated carboxylic acid was determined from the value by the following formula.

Content (mass%)
= (Mass of grafted unsaturated carboxylic acid) / (mass of raw material polyolefin resin)
× 100

(1-B)
It was obtained by performing infrared absorption spectrum analysis using a Perkin Elmer Co., Ltd., System-2000 Fourier transform infrared spectrophotometer, resolution 4 cm ⁻¹ ).

(2) Melt flow rate of polyolefin resin It measured by the method (190 degreeC, 20.2N (2160g) load) of JISK6730.

(3) Melting | fusing point of polyolefin resin It measured by DSC (The Perkin Elmer company make, DSC-7) at the temperature increase rate of 10 degree-C / min.

(4) Solid content concentration of polyolefin resin dispersion An appropriate amount of polyolefin dispersion was weighed and heated at 150 ° C. until the mass of the residue (solid content) reached a constant weight, and the solid content concentration of polyolefin resin was determined from the mass. It was.

(5) Average particle diameter of polyolefin resin particles The number average particle diameter (mn) was calculated | required using the Nikkiso Co., Ltd. make and micro track particle size distribution analyzer UPA150 (MODEL No. 9340). The refractive index of the resin used for particle diameter calculation was 1.50.

(6) Appearance of the dispersion The color tone of the dispersion was evaluated by visual observation.

(7) Viscosity and shear rate
Measurement was carried out at a temperature of 25 ° C. using a BROOKFIELD DIAL VISCOMETER Model LVT (Spindle 18) manufactured by BROOKFIELD ENGINEERING LABORATORIES, INC.

  The shear rate was converted by multiplying the rotor speed (60 rpm) by 1.34.

(8) Stability of mixing of polyolefin resin dispersion with water and organic solvent 5 g each of water, isopropanol, methyl ethyl ketone, and toluene were individually added to 10 g of polyolefin resin dispersion, and then mixed for 1 day at room temperature. From the appearance of the liquid, it was evaluated in the following two stages.

○: No change in appearance.
X: Solidification or generation of a large amount of agglomeration or precipitate is observed.

(9) Coating film adhesion evaluation The dispersion was coated on a glass plate (made by Onishi Glass Mfg. Co., Ltd., parallel plate glass plate, thickness 3 mm) with a Mayer bar so that the coating thickness after drying was 1 μm, and 150 ° C. For 30 minutes. Next, after affixing an adhesive tape (manufactured by Nichiban Co., Ltd., TF-12) to the coating surface, the tape was peeled off vigorously. And the state of the coating-film surface was observed visually and evaluated as follows.

○: No peeling at all.
X: Peeling partly occurred.

Table 1 shows the composition and properties of the polyolefin resins used in the following examples and comparative examples. In detail,
The polyolefin resin (A) is Bondine HX-8290 manufactured by Arkema,
The polyolefin resin (I) is Bondine HX-8210 manufactured by Arkema,
The polyolefin resin (U) is Primacol 5980I manufactured by Dow Chemical Company.

Example 1
Using a stirrer equipped with a heat-resistant 1 L glass container equipped with a heater, 100.0 g of polyolefin resin (A) shown in Table 1 (A) (Arkema, Bondine HX-8290, ethylene- Maleic anhydride copolymer resin, 2% by weight maleic anhydride copolymer), 355.5 g NMP as lactam compound (C), and 5 g basic compound (B) (anhydrous in resin (A)) Triethylamine (1.0 times equivalent to the carboxyl group of maleic acid) (hereinafter abbreviated as “TEA”) and 39.5 g of distilled water as water (D) were charged into a glass container, and a stirring blade The stirring speed was 300 rpm. As a result, no sedimentation of resin particles was observed at the bottom of the container, confirming that it was in a floating state.

  Therefore, while maintaining this state, the heater was turned on after 10 minutes to start heating. Then, the system temperature was kept at 120 ° C., and the mixture was further stirred for 20 minutes. Then, it cooled to room temperature (about 25 degreeC), stirring by air cooling and rotating speed 300rpm. Subsequently, pressure filtration (air pressure 0.2 MPa) was performed with a 300-mesh stainless steel filter (wire diameter 0.035 mm, plain weave) to obtain a light brown uniform polyolefin resin dispersion. Various properties of this dispersion and the coating film obtained therefrom are shown in Table 2.

Examples 2-4
Compared to Example 1, the mixing ratio of NMP as the lactam compound (C) and distilled water as the water (D) was changed as shown in Table 2. Otherwise, a dispersion was obtained in the same manner as in Example 1. Various properties of this dispersion and the coating film obtained therefrom are shown in Table 2.

Example 5
Compared to Example 1, the type of amine as the basic compound (B) to be added was changed to N, N-dimethylethanolamine (hereinafter abbreviated as “DMEA”), and the charge composition was as shown in Table 2. I made it. Otherwise, a dispersion was obtained in the same manner as in Example 1. Various properties of this dispersion and the coating film obtained therefrom are shown in Table 2.

Example 6
Compared to Example 2, the lactam compound (C) was changed to 2-pyrrolidone, and the type of amine added was changed to DMEA. The charge composition was as shown in Table 2. Otherwise, a dispersion was obtained in the same manner as in Example 2. Various properties of this dispersion and the coating film obtained therefrom are shown in Table 2.

Example 7
Compared to Example 5, (a) (Bondaine HX-8210, manufactured by Arkema, ethylene-maleic anhydride copolymer resin, 3% by weight maleic anhydride copolymer) shown in Table 1 is used as the polyolefin resin (A). It was. Otherwise, a dispersion was obtained in the same manner as in Example 5. Various properties of this dispersion and the coating film obtained therefrom are shown in Table 2.

Example 8
Compared to Example 6, using (U) (Dow Chemical Co., Primacol 5980I, ethylene-acrylic acid copolymer resin, acrylic acid 20% by mass copolymerization) shown in Table 1 as the polyolefin resin (A), The charged composition was as shown in Table 2. Otherwise, a dispersion was obtained in the same manner as in Example 6. Various properties of this dispersion and the coating film obtained therefrom are shown in Table 2.

Comparative Examples 1 and 2
Compared to Example 1, the mixing ratio of lactam compound (C) and water (D) was changed as shown in Table 3. Other than that, examination was performed in the same manner as in Example 1. The results are shown in Table 3.

Comparative Example 3
Compared to Example 1, the mixing ratio of each raw material was changed as shown in Table 3. Other than that, examination was performed in the same manner as in Example 1. The results are shown in Table 3.

Comparative Example 4
Compared to Example 4, absolute ethanol (hereinafter abbreviated as “EA”) was used in place of the lactam compound (C). Other than that, examination was performed in the same manner as in Example 4. The results are shown in Table 3.

Comparative Example 5
Compared to Example 1, 2-ethyl-1-butanol (hereinafter abbreviated as “E-BA”) was used in place of the lactam compound (C). Other than that, examination was performed in the same manner as in Example 1. The results are shown in Table 3.

Comparative Example 6
Compared to Example 1, isobutyl acetate (hereinafter abbreviated as “IBAc”) was used in place of the lactam compound (C). Other than that, examination was performed in the same manner as in Example 1. The results are shown in Table 3.

Comparative Example 7
Compared to Example 1, a resin not containing an unsaturated carboxylic acid unit was used as the polyolefin resin. That is, polyethylene (Sumitomo Chemical Co., Ltd., Sumikasen L211, melt flow rate 12 g / 10 min, hereinafter abbreviated as “L211”) was used as the resin. Other than that, examination was performed in the same manner as in Example 1. The results are shown in Table 3.

Comparative Example 8
TEA which is a basic compound (B) was not added. Other than that, examination was performed in the same manner as in Example 1. The results are shown in Table 3.

Comparative Example 9
Compared with Example 1, EA was used instead of the lactam compound (C), and the mixing ratio of EA and water (D) was as shown in Table 3. Other than that, examination was performed in the same manner as in Example 1. The results are shown in Table 3.

Comparative Example 10
Compared to Example 2, isopropyl alcohol (hereinafter abbreviated as “IPA”) was used in place of the lactam compound (C). Other than that, examination was performed in the same manner as in Example 2. The results are shown in Table 3.

While using a lactam compound (C) like Examples 1-8, the mixing ratio (C) / (D) [mass ratio] of a lactam compound (C) and water (D) is made into the range of the present invention. Thus, a fine and good polyolefin resin dispersion could be obtained. The dispersion also had good mixing stability with water and various organic solvents. These dispersions had a viscosity of less than 500 mPa · s at a temperature of 25 ° C. and a shear rate of 20.40 s ⁻¹ .

  On the other hand, when the water (D) of Comparative Example 1 was not added, there was no problem in the state of dispersion at 120 ° C., but the viscosity increased significantly during cooling and solidified at room temperature. When the lactam compound (C) of Comparative Example 2 was not added, a large amount of resin remained, and a resin dispersion was not substantially obtained. When the mixing ratio of the lactam compound (C) and water (D) in Comparative Example 3 is outside the range of the present invention (the ratio of water is high), the resin remains and is remarkably increased in the process of cooling. Thickened and solidified at room temperature. When organic solvents other than the lactam compound (C) of Comparative Examples 4 to 6 were used, practical dispersions could not be obtained. That is, in Comparative Example 4, a large amount of the remaining resin was visually observed, and substantially no resin dispersion was obtained. In Comparative Examples 5 and 6, there was no problem in the state of dispersion at 120 ° C., but the viscosity increased significantly during cooling and solidified at room temperature. Furthermore, when the polyolefin resin containing no unsaturated carboxylic acid unit of Comparative Example 7 was used, a large amount of the resin remained and a resin dispersion was not substantially obtained. When the basic compound (B) of Comparative Example 8 was not added, a large amount of resin remained, and a resin dispersion could not be obtained substantially. The dispersion obtained in Comparative Example 9 was excellent in storage stability and adhesion, but EA was used instead of the lactam compound (C), and the water content in the medium was high. Since it was outside the scope of the present invention, when it was mixed with methyl ethyl ketone or toluene, it immediately increased in viscosity and solidified, and was unsuitable for solvent-based applications. Since the dispersion obtained in Comparative Example 10 used IPA instead of the lactam compound (C), it was excellent in storage stability, adhesion, and mixing stability with various media. The viscosity was higher than in Examples 1 to 8.

Claims (4)

A polyolefin resin (A) having an unsaturated carboxylic acid unit content of 0.01 to 25% by mass, a basic compound (B), a lactam compound (C), and water (D), and a base Compound (B) is ammonia or an organic amine compound having a boiling point of 300 ° C. or less, and the mass ratio (C) / (D) of the lactam compound (C) to water (D) is 99.5 / 0.5. When the content of the polyolefin resin (A) is 20% by mass, the viscosity at a temperature of 25 ° C. and a shear rate of 20.40 s ⁻¹ is less than 500 mPa · s, and the polyolefin resin (A) A polyolefin resin dispersion having a number average particle diameter of 0.8 μm or less.   The polyolefin resin dispersion according to claim 1, wherein the lactam compound (C) is N-methyl-2-pyrrolidone.   The polyolefin resin dispersion according to claim 1 or 2, wherein the polyolefin resin (A) is an ethylene-acrylic acid ester-maleic anhydride terpolymer.   The polyolefin resin dispersion according to any one of claims 1 to 3, which is substantially free of a non-volatile dispersion aid.